Chemosphere 272 (2021) 129492

Contents lists available at ScienceDirect

Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Environmental and health impacts of contaminants of emerging

concerns: Recent treatment challenges and approaches
Deepak Yadav a, *, S. Rangabhashiyam b, Pramit Verma c, Pardeep Singh d, **, Pooja Devi e,
Pradeep Kumar f, Chaudhery Mustansar Hussain g, Gajendra Kumar Gaurav h,
Kuppusamy Sathish Kumar i
a
Chemical Engineering Department, Harcourt Butler Technical University (Formerly HBTI), Kanpur, India
b
Department of Biotechnology, School of Chemical and Biotechnology, SASTRA Deemed University, Thanjavur, 613401, Tamilnadu, India
c
Integrative Ecology Laboratory (IEL), Institute of Environment & Sustainable Development (IESD), Banaras Hindu University, Varanasi, India
d
Department of Environment Studies, PGDAV College University of Delhi, New Delhi, India
e
CSIR- Central Scientific Instruments Organisation, Sector-30C, Chandigarh, India
f
Department of Chemical Engineering & Technology, IIT (BHU), Varanasi, India
g
Department of Chemistry and Environment Science, New Jersey Institute of Technology, Newark, New Jersey, 07102, USA
h
Ministry of Education Key Laboratory of Integrated Regulation and Resource Developmenton Shallow Lakes and College of Civil, Hohai University, Nanjing,
210098, PR China
i
Key Laboratory of Integrated Regulation and Resource Development of Shallow Lakes,Ministry of Education, College of Environment, Hohai University,
Nanjing, Jiangsu Province, PR China

h i g h l i g h t s

CECs pretence a threat to human health as well as the ecological balance.

Innovative and cost-effective technologies to treat CECs are deliberated.

Deliver acumens on risk assessment and management of CECs.

Multipronged, flexible risk valuation and response strategy essentials to advance.

Solar photocatalysis using TiO2 one of the prospective approaches for handling pharmaceuticals CECs.

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

Article history: In the past few decades, new contaminants of emerging concern (CECs) in the air, water, and soil have
Received 8 August 2020 gained significant attention due to their adverse impact on human health and the environment. The
Received in revised form sources of CECs have been identified in different forms from domestic and industrial activities such as
30 November 2020
personal care products and pharmaceuticals. It has been established that aqueous medium plays a major
Accepted 26 December 2020
Available online 5 January 2021
role in the dissemination of various contaminants, like drinking water, reservoirs, lakes, rivers and waste
with water medium. There remains inadequate technology for the treatment of CECs in the wastewater
Handling Editor: Derek Muir systems. Though different techniques have advanced for the treatment of CECs, they still pose a severe
threat to human health and disturb the ecological balance. In this review, the characteristics, recent
Keywords: technologies, risk assessment and management of CECs have been discussed. The primary aim is to
Contaminants of emerging concern highlight the new innovative and cost-effective technologies for the remediations of CECs in all forms.
Abatement technology Biochar is readily and economically available in abundance and an economical adsorbent with 100%
Cost-effective technology adsorptive removal for H2PO 4 . The bibliometric analysis also performed to understand the emerging
Disruptive endocrine chemical.
research trends on the treatment techniques, which can help in developing a guiding pathway to modern
research in academia and industry.
© 2021 Elsevier Ltd. All rights reserved.

* Corresponding author. 1. Introduction

** Corresponding author.
E-mail addresses: deepakch@hbtu.ac.in (D. Yadav), psingh.rs.apc@itbhu.ac.in
The evolution to a predominantly urbanized civilization has
(P. Singh).

https://doi.org/10.1016/j.chemosphere.2020.129492
0045-6535/© 2021 Elsevier Ltd. All rights reserved.
D. Yadav, S. Rangabhashiyam, P. Verma et al. Chemosphere 272 (2021) 129492

increased rigorous anthropogenic activities, economic growth, ur- Soil is one of the principal sinks for different chemicals. Some of
banization, industrialization, exploitation of natural resources, them are harmless, nocuous and non-threatening, while other are
resulting in massive waste management, disposal problems and the and poisonous to living organisms originating from petroleum
emergence of various contaminants (United Nations, Waste man- refining, pharmaceuticals, personal care, agricultural, domestic
agement). By the end of the 21st century, the world’s population is wastes, dye manufacturing, and industrial products (Teng et al.,
expected to reach its peak of around 11 billion people (United Na- 2014; Xu et al., 2014; Qing et al., 2015; Taheran et al., 2018). The
tions, 2019). Since contamination is a diverse concept, when unplanned disposal of industrial wastes can be a potential hazard to
coupled with globalization, pollution, biodiversity loss, and other the environment (Bender and van der Heijden, 2015). Microplastics,
global issues, it assumes greater importance. Food, air, personal Municaipal Solid Waste and landfill leachate are the major con-
care products, water, and wastewater, soil, vegetation, and agri- taminants of emerging concern that have a high impact on
culture, are among the many other aspects which are influenced by lowering soil productivity and soil organisms (Zhang et al., 2020;
the growing number of emerging contaminants and related prod- Nagarajan et al., 2012; Va
clavík et al., 2016).
ucts (Ferronato and Torretta, 2019). The multitude of sources, Plants are primary producers in the food chain of living organ-
pathways, targets, and effects has led to the development of various isms and an essential element in transporting CECs to the higher
technologies for treatment or removal contaminants. However, trophic levels (Varjani and Sudha, 2018; Zhuang et al., 2009;
because of such advancements, the research into emerging con- Ferronato and Torretta, 2019). For example, a polyhalogenated
taminants has developed into isolated themes. carbazole (persistent and dioxin-like toxicity), biosolid (domestic
The NORMON groups defined emerging pollutants as, “as pol- sewage) and carbamazepine (Pharmaceutically active compound
lutants that are currently not included in routine monitoring pro- (PhACs)) are a group of emerging contaminants found in soil with
grammes, which may be candidates for future regulation, severe implications for the environment, especially plant and hu-
depending on research on their (eco) toxicity, potential health ef- man health (Tao et al. 2019. Biosolids; Mordechay et al., 2018; Li
fects and public perception and on monitoring data regarding their et al. 2015).
occurrence in the various environmental compartments”. Sauve
Several emerging risks due to long term exposure to the par-
et al. (2018), defined Contaminants of Emerging Concern (CECs) as ticulate matter have been recognized, like prenatal mortality, dia-
‘naturally occurring, manufactured or manmade chemicals or ma- betes, neurodevelopment, and cognitive functions (Kelly &Fussel,
terials which have now been discovered or are suspected [to be] 2015; Singh et al., 2019; Kelly and Fussel, 2015; Rychlik et al.,
present in various environmental compartments and whose 2019). Black carbon, organic carbon, secondary inorganic aerosols,
toxicity or persistence is likely to alter the metabolism of a living and ultrafine particulate matter are some of the emerging air
being significantly.’ The toxicity of CECs is a serious concern due to contaminants with severe effects on human health (Segersson
its high resistance to degradation, a quality attributed to its com- et al., 2017; Colbeck and Lazaridis, 2010). Black Carbon has been
plex structure and other factors (Hoskeri et al., 2014; Fatta-Kassinos proved to increase all-cause and cardiovascular and cardiopulmo-
et al., 2011). nary mortality (Singh et al., 2019).
CECs belong to a large variety of chemicals and are characterized The distribution of such chemicals in the environment forms
based on their chemical structure and mode of toxicity to the hu- complex mixtures, which subsequently leads to adverse synergistic
man and environment (Borgert et al., 2004; Raies et al., 2016). concerns and exerts a direct or indirect impact on human health
According to U.S. Environmental Protection Agency, Emerging and the ecosystem (Hai et al., 2017). The primary path of environ-
Contaminants Workgroup (2008) mentioned various groups of the mental contaminants and their allied human health hazards is
compound in the list of CECs such as POPs, pharmaceutical com- described in Table 1 and Table 2. Therefore, preserving total soil,
pounds, personal care products, antibiotics for veterinary EDCs and water, and air quality is an obligation for sustainable growth,
nanomaterials. Endocrine-disrupting chemicals have been reported intending to maintain the sustainability ecosystem supplies and to
to cause a decline in fertility, developmental effects, and other assure the overall human water security (Unesco, 2015).
reproductive problems (Sharma et al., 2020). They were also found
in popular products like flame retardants and metal food cans 1.1. Motivation
(Zhang et al., 2013).
CECs work through various pathways and contaminate the soil, The multitude of sources, pathways, targets, and effects has led
water, and air, thereby affecting the environmental and human to the development of various technologies for treatment or
health (Fig. 1) (Inyinbor Adejumoke et al., 2018). The inefficient removal contaminants. Further research into the treatment tech-
treatment processes of wastewater treatment plants were consid- nologies, detection and mitigation of the impact of CECs on human
ered as the primary sources of CECs in the aquatic environment, and environmental health, would need to build on established
which are responsible for the contamination of the aquatic concepts which have not been the focus of any study yet. This re-
ecosystem by a various range of CECs (EDC, personal care products, view is a step in that direction with the application of the biblio-
pharmaceutical compounds, antibiotics) (Liu et al., 2018; metric approach. The biggest challenge faced today is to mitigate to
Spongberg and Witter, 2008). These are also responsible for the the synergistic effect of CECs cost-effectively. Research into CECs
harmful impact on human health (Tran et al., 2018). gained importance in the last decade and has seen most of its
Water, an essential component of most living beings, has been development in the last 5 years as described in the next section.
dramatically influenced by intensive urbanization leading to However, because of such advancements, the research into
increased water consumption for domestic, agricultural, industrial emerging contaminants has developed into isolated themes. There
uses, and resulting in the generation of a tremendous amount of is a need to collate the existing research on different technologies
wastewater (Agarwal, 2005; Tran et al., 2018; Pal et al. 2014; Guillet used to remove CECs, identify the emerging themes in this field and
et al., 2019). The industries responsible for water contamination create an analytical account of the same.
include petroleum refining, dye manufacturing, plastic, chemical, We have adopted a structured approach in this review. First, a
coking, leather, textile, pharmaceutical industries, paper industries bibliometric analysis was conducted to ascertain the state of
(Rasheed et al., 2018). Wastewater treatment plants have also been research, emerging fields, and the relationship between them. The
found responsible for the emission of ketamine and metham- thematic distribution of concepts was also analyzed with refined
phetamine as aerosols from the aeration tanks (Liu et al., 2018). results for health and environmental impacts following Cobo et al.
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D. Yadav, S. Rangabhashiyam, P. Verma et al. Chemosphere 272 (2021) 129492

Fig. 1. Sources and pathways of CECs (Barbosa et al., 2016).

Table 1
Environmental effects of pharmaceuticals, PCPs and EDCs (Gogoi et al., 2018).

Pollutant Use Adverse effect Reference

Roxithromycin, clarithromycin, tylosin Antibiotics Growth inhibition of algae (Pseudokirchneriellasubcapitata) Ying et al. (2020);
Long et al., 2020
Bisphenol A (BPA), 2OH-benzothiazole Landfill leachates Proven to have estrogenic effects in rats and hormonal effects Nika et al., (2020)
and valsartan which increase breast cancer risk in human Reported to act as
anti-androgen that causes feminisingsideeffects in men.
alkyl-phdroxybenzoate, lipid regulators, anti-microbiological preservatives in Shows weak estrogenic activity Routledge et al.
parabens cosmetics, toiletteries and even (1998); Reichert
foods, and domestic sewage et al., (2020)
Endocrine disrupting compound plasticizers, pesticides, flame Proven to have estrogenic effects in rats and hormonal effects Yang et al., (2020);
retardants, mycotoxins, etc. which increase breast cancer risk in human; Reported to act as
anti-androgen that causes feminizing side effects in men.
triclosan and carbamazepine Disinfectants/antiseptics,.i.e used in Acts as toxic or biocidic agent and cause of microbial resistance (Okumura and
toothpaste, hand soaps, acne cream) Nishikawa 1996);

et al. (2020)
Planello
sodium perfluorohexanesulfonate (PFHxS) Fire-fighting, defoaming additives, Act as toxic agents in aquatic environment; uncertainty over their Guo et al., (2020);
and perfluorooctanoic acid (PFOA), cosmetics and cleaning chemicals toxic effects Zhang et al., (2020)
perfluorooctane sulfonic acid (PFOS) paints, electronics, etc.

(2011). The treatment and detection technologies were discussed, 2020. The keyword phrase of “contaminant”, “emerging” and
followed by the risk assessment and management approaches, “concern” was used in the first step, followed by (“contaminants”
challenges and opportunities, and possible policy recommenda- AND “emerging”) to refine the results where both these terms are
tions. This review focussed on the technological advancements in found together. The first step yielded 1611 results over a time
the detection and removal of CECs and risks assessment approaches period of 1992e2020. The refined results yielded 407 documents
for CEC management. with 1995 keywords-plus (ID) and 1419 author keywords (DE). ID is
a unique feature of the Web of Science database where the articles
are tagged with predefined research areas according to the refer-
2. Research trends on CECs, health and environment ences cited in the article. These are different from the author’s
keywords and hence, provide a consistent, contextual basis of
A bibliometric analysis was performed using the bibliometrix assessment. Science of the total environment published the highest
package in R (ver. 3.5.1) (Aria & Cuccurullo 2017). The documents number of articles in this subject area, followed by the Chemo-
indexed in the Web of Science database for two decades, from 1991 sphere, Environmental toxicology and chemistry, Environmental
to 2020, were considered to ascertain the trend of research. The science and technology and Environmental science and pollution
literature search was limited to articles published up to January 1,
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D. Yadav, S. Rangabhashiyam, P. Verma et al. Chemosphere 272 (2021) 129492

Table 2
Major route of environmental contaminants and their allied health hazards (adapted and modified Bilal et al., 2019a).

Major routes Common contaminants Health risks Reference

Pharmaceuticals (from human/animal Antibiotics Aquatic life disturbance Prevalence of Wang et al. (2019); Long et al., (2020)
excreta) antibiotic resistance
contaminated food and drinking water; perfluoroalkyl carboxylic Human liver cells Haug et al. (2011); Schwanz et al., (2016); Ojo et al.,
indoor air and indoor dust; consumer acids; perfluoroalkane sulfonic (2020)
products acids
Indoor wood burning; Forest fires Polycyclic aromatic toxic, carcinogenic, mutagenic, and Abdel-Shafy and Mansour (2016); Luo et al., (2020);
hydrocarbons (PAH) teratogenic, and cause risks to human Avenbuan and Zelikoff (2020); Faboya et al., (2020)
health
PCPs, Landfill leachate TCS Bisphenols Immune dysfunction, behavioral Li et al. (2015); Nika et al., (2020)
problems
Agriculture Organophosphorous pesticide Carcinogenesis, mutagenicity, nervous Zhu et al. (2018); Punetha and Rose 2018
system problems
Pyrethroids (pesticides) Immuno-toxicity, carcinogenesis, Tang et al. (2018); Zhou et al., (2019)
mutagenicity, Teratogenicity
Textile and Dye industry Azo dyes Genotoxicity, carcinogenesis, Chung (2016); Nurchi et al., (2019)
mutagenicity
Acridine dyes Mutagenicity, carcinogenesis Zubieta et al. (2012); Du et al., (2020)
Nitro dyes Mutagenicity Chequer et al. (2013); van der Horst, C., & Somerset,
V. (2019)

research (Table 3). Wastewater, followed by personal care products, Table 4

pharmaceuticals, water and removal formed the top five keywords- Top ten keyword-plus terms according to the number of articles indexed in
Web of Science database.
plus terms (Table 4).
We focussed on two specific questions, first, what are the core Keyword-plus Number of articles
fields of research in contaminants of emerging concern and the Personal Care Products 412
relationship between them, and second, what are the lesser- Waste Water 322
explored concepts in this field? We have also analyzed docu- Pharmaceuticals 294
Emerging Contaminants 205
ments for health, impact on the environment and treatment tech-
Removal 175
nologies by refining the Web of Science results for with “health”, Drinking Water 157
“environment” and (“treatment” AND “technology”), respectively. Contaminants 141
There are two plots used for this analysis, apart from the summary Waste Water Treatment 132
of results. The first plot is the keyword-cooccurrence plot and the Aquatic Environment 130
Solid Phase Extraction 127
second one the thematic strategic concept plot, both constructed by
using the keyword-plus field from Web of Science article search
results (Cobo et al. 2015; Moral-Munoz et al. 2019). The thematic
evolution of topics in each case been discussed using the Sankey found close to it, and a keyword with a very high number of link-
plot in the Discussion section. ages has more interconnected lines in a cluster. A keyword repre-
sented by a small node, but a high density of links indicates small
frequency but high linkages whenever present; lesser explored but
2.1. State of research
essential.
The keywords were divided into three clusters represented by
The keyword co-occurrence plot (Fig. 2) gives information about
red, green, and blue colour for the overall search result (Fig. 2). We
the frequency of the use of keywords and the relationship between
referred to each cluster by the name of its most frequent keyword
them. The keywords are represented by nodes (circles). The size of
(Van Eck and Waltman, 2014). Wastewater formed the red colour
the nodes represents the frequency of use, the distance and inter-
cluster; the blue colour represented pharmaceuticals, and the green
connecting lines between the circles indicate their relationship and
colour represented toxicity cluster. The wastewater cluster was the
linkages (Van Eck and Waltman, 2014; Nita 2019). The network of
tightest cluster with the highest number of linkages followed by the
nodes can be divided into clusters; the density of interlinking lines
pharmaceuticals and toxicity. The wastewater, personal care
is greater between the nodes of the same cluster (Fahimnia et al.,
products, drinking water, contaminants, risk assessment, and
2015). A keyword has a strong relationship with another keyword
bisphenol-a were the largest nodes in wastewater cluster with high
linkages. However, in the same cluster, treatment plants and
Table 3 sewage treatment plants were found on the periphery indicating
Top ten journals in the field of contaminants of emerging concern according to the their lesser frequency and linkages with other nodes and emerging
number of articles indexed in Web of Science database.
nature from the perspective of CECs. The pharmaceuticals cluster
Journals Number of articles had water, removal, degradation, and fate as its largest nodes.
Science of the Total Environment 203 Interestingly, the aqueous solution node in this cluster was present
Chemosphere 107 at the periphery, however, despite its larger size than the other
Environmental Science and Pollution Research 76 fringe nodes, it had lesser linkages with other themes. Transport,
Environmental Toxicology and Chemistry 73 groundwater and soil were the smallest nodes in this cluster with
Environmental Pollution 72
the least number of linkages. The third cluster was toxicity. It had
Water Research 64
Environmental Science and Technology 62 toxicity, exposure, polycyclic aromatic hydrocarbons and poly-
Abstracts of the papers of the American Chemical Society 51 brominated diphenyl ether as the largest nodes. This cluster had the
Environmental International 48 smallest nodes in the whole plot indicating their lesser frequency.
Chemical Engineering Journal 35
Accumulation, perfluorinated compounds and gas-

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D. Yadav, S. Rangabhashiyam, P. Verma et al. Chemosphere 272 (2021) 129492

Fig. 2. Keyword co-occurrence plot showing frequency and linkages between the major themes (keywords) of contaminants of emerging concern.

chromatography were the smallest clusters. Thus, the keywords the subject field and vice-versa.
along the fringes, with a lesser number of connections, indicated The first quadrant had drinking water and polybrominated
the emergent nature of these concepts as well as the need for more diphenyl ethers signifying their well-developed external linkages
research in these areas. The core and most frequent concepts, (Fig. 3). Drinking water is a source of transport for numerous CECs
however, also provide an opportunity to provide higher discover- into the animal food chain. Polybrominated Diphenyl ethers, on the
ability when used as keywords along with the lesser researched other hand, are a type of Endocrine-disrupting chemicals and an
fields. active constituent of flame retardants, among other uses like
The thematic plot was used to visualize four types of themes electronics, plastic casing, etc. (Kim and Lee 2011). They have been
where each quadrant represented a typology based on centrality found in an increasing amount in aquatic sources, indoor air and
and density of the themes (Della Corte et al., 2019). Following Cobo dust, mother’s milk, etc. (Darnerud et al. 2001). Their toxicity has
et al. (2011), the upper right quadrant (first) represents motor- led to a prohibition on some types of PBDEs, however, they still
themes, with well-developed external linkages. Motor themes are pose a threat to human and environment health. Because of their
essential for the structuring of the research field and have high potential toxicity and occurrence in different soil, air, and water
density and centrality. The upper left quadrant (second) represents components, their nature as a motor theme is justified. The second
highly developed and isolated themes, with good internal con- quadrant had polycyclic aromatic hydrocarbons, oxidative stress
nections, whereas little external impacts. Thus, they are considered and bioaccumulation as highly developed but isolated themes, with
of little importance for the research area. The themes in the lower well-developed internal linkages. Their high centrality indicated
left quadrant (third) represent emerging or disappearing themes. their relationship to other themes in CECs studies, but the low
The lower right quadrant (fourth) represents transverse and un- density indicated their lesser importance. Thus, they were related
derlying themes, which, even though necessary for the subject, are to several other themes, but because of their isolated nature, they
not well developed (Della Corte et al., 2019). Two measures of were of not much use as representative of the emerging contami-
density and centrality are used to classify themes. A high density nants research.
indicates a large frequency of usage of a particular keyword while a The third quadrant had exposure and surface waters as its
high centrality indicates a strong relationship with other themes in constituents. After the refining the Web of Science results, it was

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D. Yadav, S. Rangabhashiyam, P. Verma et al. Chemosphere 272 (2021) 129492

Fig. 3. Thematic strategic plot showing the density and centrality of the major themes in the contaminants of emerging concern search results.

observed that exposure-based studies in CECs gained traction, in 2.3. Effect on the environment
the beginning, the middle of the last decade. This signifies their
emerging nature especially from the perspective of transportation Pharmaceuticals and drinking-water were found the first
of CECs and plant, animal health human health. The surface waters quadrant signifying their importance to the environmental impacts
theme signifies the increasing contamination of water inland water of CECs (Fig. 5). Both these themes had highly developed internal
bodies. Their emerging nature is important to understand and the and external linkages and were frequently the focus of such studies.
role they play in the accumulation of CECs and associated risks Pollution was found in the second quadrant indicated its higher
(Nanusha et al. 2020; Liu and Fang 2020). Exposure formed the external linkages but isolated nature in the environmental impact
basis of studies addressing the issue of health impacts as will be area. This indicates that the impact of CECs on the environment can
seen in the next section. The fourth quadrant had toxicity, waste- be construed as a part of the broader environmental pollution
water and pharmaceuticals. These themes had high density but low phenomenon, however, the environmental impact is more focussed
centrality, indicating their transversal nature and the need for on contamination of environment leading to exposure of the living
better coherence for their development as underlying themes. A organism to harmful CECs. Organic contaminants and exposure
large number of works of literature addresses the personal care were emerging themes in this field. Waste-water was found in the
products and pharmaceutical themes, but their focus can be fourth quadrant. Waste-water has been the focus of many studies
considered diverse and need significant conceptual development. focussing on the environmental impact of CECs however, due to the
They represented underlying themes at best. emerging nature of such contaminants, a robust conceptual
In the next sections, we have discussed the impact of CECs, on framework is needed. Wastewater had very high density indicating
health, environment and treatment technologies with the help of its strong linkages with other themes and frequent usage in many
thematic plot and thematic evolution Sankey plot. studies.

2.4. Treatment technologies

2.2. Health impact
A similar thematic strategic plot was constructed for treatment
The first quadrant of the thematic strategic plot had wastewater, technologies (Fig. 6). The aim was to find out the emerging treat-
indicating its ubiquitous nature in the health impact of CECs (Fig. 4). ment technologies being used. A generic perspective about treat-
Polybrominated diphenyl ethers occupied the second quadrant ment technologies is given in the following lines. A more
indicating their highly developed external linkages but isolated comprehensive description of emerging treatment technologies is
nature. PBDE has come to occupy an important part in under- given in the latter sections.
standing the health impacts of CECs, however, they need to be Solid-phase extraction is increasingly being used for removal of
studied along with other aspects of health impacts, like exposure. contaminant from their aqueous phase and chemical analysis as
Degradation was the only theme in the third quadrant and it is well. Its presence in the first quadrant signifies its importance as a
increasingly being studied in reducing the health impacts of CECs. treatment technology for CECs. After the discovery of endocrine
However, it remains an emerging aspect of this field. The fourth disruptors in the 1990s they have come to gain much importance in
quadrant had exposure as its single occupant. As mentioned earlier, CECs because of their mode of action, transportation and lack of
the role of expose-based studies in the health aspect of CECs is removal technologies in the conventional water and wastewater
gaining importance. However, its position in the fourth quadrant treatment plants (Colborn et al. 1993; Seibert et al. 2020). The
signifies that a better conceptual basis needs to be developed for second quadrant had zerovalent ion and sorption overlapping with
such studies. the third and first quadrant, respectively. Other themes in this
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D. Yadav, S. Rangabhashiyam, P. Verma et al. Chemosphere 272 (2021) 129492

Fig. 4. Keyword co-occurrence plot for the impact of CECs on health.

Fig. 5. Thematic strategic plot showing the thematic development of the major themes of the impact of CECs on health.

quadrant were persistent organic pollutants, liquid chromatog- et al. 2020; Metolina et al. 2020). Groundwater contamination has
raphy, heavy-metal removal and pharmaceutical wastewater. All also increased in recent years especially due to different types of
these themes have developed their niche within the treatment CECs and the lack of water treatment facility to handle multiple
technologies for CECs. It is important to note that these themes are contaminant sources (McCance et al. 2020). That is why ground-
isolated in nature due to the nature of different removal technol- water and its treatment has attained an emerging role in the pre-
ogies required for different contaminants. Removal technologies sent scenario. The fourth quadrant representing transverse themes
have advanced in recent years and some have a shown wide with high density but low centrality was occupied by personal care
application. For example, oxidative processes are widely being products, removal, organic compounds, hydrogen peroxide and
studied for removal of persistent and recalcitrant CECs (Seibert water. Hydrogen peroxide is used in removal technologies for CECs

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D. Yadav, S. Rangabhashiyam, P. Verma et al. Chemosphere 272 (2021) 129492

Fig. 6. Keyword cooccurrence plot for the impact of CECs on the environment.

(Zuniga-Benitez et al. 2019; Aseman-Bashiz & Sayyaf 2020). concern. This would depend more on the broader scope of
Based on the bibliometric analysis, we could understand that research and objective.
water plays a major role in disseminating various CECs and the role
of other media are increasingly being explored, especially in the
indoor environment. Certain general conclusions could be drawn 3. Treatment technologies used in detection and
from the above analysis: degradations of CECs

1. The thematic evolution plot (Fig. 7) shows that the research in The research and development of photocatalysts (visible light)
contaminants and emerging substances underwent a period of and phase changing technologies and their applications have
expansion from fewer themes in 1996e2004 time to considerably increased in handling contaminants of emerging
2005e2012. This expansion of themes indicates the increasing concern (CECs). Solar photocatalysis is capable of treating a wide
importance CECs have gained. In the 2013e2020 time, the variety of CEC sources, such as pharmaceuticals, antibiotics, disin-
number of themes reduced, and became integrated to be of fectants, steroids, additives, pesticides and preservatives. Corre-
more relevance for the human health and environmental impact spondingly, solar photocatalysis is used in the treatment of several
due to increase in the scale and diversity of products being chemicals, polycyclic aromatic hydrocarbons (PAHs), heavy metals
consumed by the society (see Fig. 8). and other volatile organic compounds (VOCs) in water and soil
2. Wastewater and pharmaceuticals represented the primary (Birben & Bekbolet et al., 2019). Phase changing technologies work
themes of contaminants of emerging concern, which expands to by transporting contaminants from one phase (e.g., water) into
include drinking water in case of the environment, exposure another (e.g., solid) and they have been reported in the removal of
and polybrominated diphenyl ethers in health impact, removal, CECs like ibuprofen, norfloxacin, ciprofloxacin and paracetamol
solid-phase extraction and endocrine-disrupting chemicals in (Gavrilescu et al., 2015). Adsorption processes using activated car-
treatment technologies. bon, carbon nanotubes, biochar, activated alumina, graphite and
3. In treatment technologies, a large number of isolated and clay mineral have been widely used for the elimination of
transversal themes were found signifying the advancements as numerous diverse pollutants (Makgabutlane et al., 2020; Krasucka
well as the need for integration between such research themes et al., 2020; Zheng et al., 2020; Ashour and Tony., 2020). Particulate
4. The isolated or niche-themes for the contaminants of emerging matter and gas-phase sensors, in the form of active, passive and
concern were different from those for the refined results of whole air sampling, for air contaminant detection are increasingly
health, environment and treatment technology-related being used to monitor air pollutants. However, due to the inherent
research, indicating a need for a holistic as well as specialized characteristic of air pollution, it may vary at very short distances,
approach while dealing with contaminants of emerging and thus, a very robust network of sensors is required (Kelly and
Fussel, 2015). Following is a brief account of such technologies
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D. Yadav, S. Rangabhashiyam, P. Verma et al. Chemosphere 272 (2021) 129492

Fig. 7. Thematic strategic map of the thematic development in the impact of CECs on environment.

The specific filtering properties, like pore size, surface charge and
hydrophobicity, of membranes are imparted by the type material
used in producing them, and that also determines the type of CEC
that can be trapped (Simmons et al., 2011). Membrane technology
is based on hydrostatic pressure. The membrane retains the sus-
pended solids and high molecular weight solutes while the solvent
and low molecular weight solutes are allowed to pass through. The
innovative hybrid process USAMe® which integrates adsorption
(A), ultrasound irradiation (US), and membrane filtration (Me) was
investigated for the removal of CECs from secondary effluents.
Membrane filtration can be classified as ultrafiltration (UF), nano-
filtration (NF), microfiltration (MF), and reverse osmosis (RO). The
details of these four are tabulated Table 5 as below (Shon et al.,
2013).

3.1.2. Biological processes

CEC compounds identified as the predominant contaminants in
Fig. 8. Flow chart for decision making on upgrading conventional WWTPs for CEC the water bodies. CECs used in different forms of synthetic com-
removal (Krzeminski et al., 2018). pounds such as cosmetics, pharmaceutical and personal care
products, steroid hormones, microplastic, pesticides, etc., consid-
ered as primary usage in modern society worldwide (Gomes et al.,
and sampling methods for monitoring and removal of CECs, which 2018; Luo et al., 2014). The toxicity effects of CECs are widely
includes Membrane filtration, biological processes and advanced investigated on the various ecosystem, including the aquatic and
oxidation processes. soil microbiology. The occurrences of such CECs compounds on the
environment impose potential toxic effects on the living system
3.1. Treatment technologies for removal of CECs (Tahir et al., 2019). To combat the adverse effects of CECs on living
systems and environment, the treatment technology with the
Membrane filtration, the biological process, including biodeg- approach of efficient, eco-friendly and sustainability needs to be
radation and ultraviolet irradiation, are some of the phase- considered. Microbial degradations of CECs explored by various
changing techniques. researchers mainly due to the merits associated with the technol-
ogy of attainment of higher performance, low cost and simple
3.1.1. Membrane technology process, free from the generation of toxic residues, etc. In the
Worldwide more than 200 different types of pharmaceutical process of microbe assisted CEC degradation, the indigenous mi-
compounds have been reported in aquatic sources (Hughes et al., crobial strain contributes a significant role in the entire process of
2012; Chander et al., 2016). The U.S. EPA (Environmental Protection CECs degradations (Susanna et al., 2018; Joan et al., 2020). CECs are
Agency) has noticed the intense, protracted toxicity of the above highly persistence in the environment and resist the simple pro-
said CECs and declared themes “priority pollutants” (Husain and cesses used for degradation. The microbial degradation of the
Ulber, 2011). Membrane technology is a type of phase-changing contaminant depends on the several factors such as the inherent
process with diverse application in CECs monitoring and removal. physicochemical characteristics, environmental conditions and
9
D. Yadav, S. Rangabhashiyam, P. Verma et al. Chemosphere 272 (2021) 129492

Table 5
Comparison between MF, UF, NF, and RO (Shon et al., 2013).

Particular UF NF MF RO

Pore size 5e20 nm 1e5 nm 50nm-1mm e

Porous Membrane type Asymmetric Fine Asymmetric/composite isotropic Nonporous Asymmetric/
composite
Mass transfer process Darcy’s law Fick’s law Darcy’s law Fick’s law
Purified water flux (L/ 100e2000 20e200 500e10000 10e100
m2h)
Transfer mechanism Sieving and preferential Sieving/diffusion/electrostatic Sieving and adsorptive Diffusion
adsorption hydration mechanism

microorganisms potential to biodegrade. The degradation of the increase the removal efficiency biodegradation processes of anti-
CECs in microbes occurs through metabolic and co-metabolic biotics and hormones (Cirja et al., 2007; Strenn et al., 2004). This
pathways. The conventional means of subjecting the indigenous further promotes growth and the removal of various other CECs
microbes are not efficient, and therefore biostimulation, bio- comprising diclofenac, erythromycin, etc. (Fernandez-Fontaina
augmentation, and hybrid technology are used for the pollution et al., 2012).
treatment (Sunita and Vivek 2017; Ondrej et al., 2017). High SRTs and reduced F/M ratios coupled with the constituents
Achromobacter One of the significant challenges in the phar- of the solid phase sorption material and diverse uptake perfor-
maceutical industry effluent treatment through biodegradation is mance may increase the vast array of microorganisms (Go € bel et al.,
the larger volume with low C/N ratio (Dong et al., 2020). Sphingo- 2007), which would lead to degradation of more CECs (Gros et al.,
monas sp. reported with the biopolymer production of 19.29 g/L 2010), or, may not influence the elimination of other contami-
mainly consisted of glucose and galacturonic acid, showed their nants (Bernhard et al., 2007). The presence of high biomass con-
significance in bioremediation of ionic liquids and biopolymer centrations enhances biodegradation as it offers higher stability
production (Michalis et al., 2019). The remediation of CEC exam- with resilience against shocks and an augmented contact between
ined through biologically active granular activated carbon-sand and the microbial community and the CECs (Trinh et al., 2016). The lack
anthracite-sand filters in pilot scale. Granular activated carbon- of presence of biodegradable compounds would induce the utili-
sand biofilters demonstrated with higher CEC removal of all the zation of low degradable substance in microbial metabolism due to
contaminants considered. Bioremediation observed effective after the reduced ratio of Food to Microorganism (Verlicchi et al., 2012).
100,000-bed volumes for the low influent concentration. The CEC were classified into three categories according to the seques-
parametric influences on the process are initial CEC concentration, tration performance (Suarez et al. 2010) aerobic and anoxic, aerobic
the charge of CEC, inlet dissolved organic carbon concentration, but insistent under anoxic and stubborn to transformation by
biodegradation rate and hydraulic loading rate (Ben et al., 2018). biological means.
Perfluorooctanesulfonate is highly persistent and bio-
accumulative in the environment. Pseudomonas aeruginosa similar
3.2. Low-cost adsorptions materials for CECs removal
to a mesophilic rod-shaped bacteria. Optimal pH range of 7e9
supported the growth of bacterial strain with 67% removal and 48 h
Biodegradation and adsorption were employed as the most
incubation (Bum et al., 2014). The distribution of organic contam-
crucial component of CEC removal mechanisms in Membrane
inants, especially the pharmaceutical compounds, are the major
Bioreactors (MBR). The small molecular size of the CECs helps them
environmental concerndthe mechanistic removal analysis per-
to pass through the MF (microfiltration) and UF (Ultrafiltration)
formed on metronidazole, bezafibrate, ibuprofen, sulfamethoxa-
MBRs (Radjenovi
c et al., 2008). However, in combination with the
zole, carbamazepine, and ciprofloxacin. The removals of these
sludge deposits formed on MBRs, additional types of CECs can be
contaminants are dominated by sorption and biodegradation. In
trapped and removed. Hydrophobicity is another property utilized
contrast, the mechanisms of volatilization and hydrolysis not sig-
in sorption and removal of CECs. Significantly hydrophobic com-
nificantdthe biodegradation kinetics of first-order rate model used
pounds, for example, diclofenac, azithromycin, triallate and oxa-
to analyze the experimental data. Further biodegradation mecha-
diazon are easily removed by sorption (Phan et al., 2014). However,
nism analyzed using the calculation of geometrical, electrostatic,
due to the limited capacity of sorption on biosolids, biodegradation
and quantum chemical descriptors. The results showed that the
is considered as the preferred mechanism of elimination.
electrophilicity index influenced the biodegradation kinetics
The removal performances have variable trends for persistent
(Xiaobo et al., 2018) significantly.
compounds (Wijekoon et al., 2013). Regardless of the existing
knowledge about removal of contaminants by MBRs, there is still a
gap in understanding the mechanism through which a more sig-
3.1.2.1. Degradations mechanisms through biological processes.
nificant removal is observed with opposite trends for hydrophobic
Biologically compounds among CECs, e.g. pharmaceutical, personal
compounds in comparison to the CECs. This gap also reflects in
care products (PPCPs), cosmetics, biomedical wastes, and
understanding the causes for complete removal of CECs by MBRs
endocrine-disrupting chemicals (EDCs) are of utmost importance.
and their transformation products (Reif et al., 2013). The process
Many of the past and current studies have focused on efficient
factors have a significant influence on the performance of MBRs. Li
removal and contaminant degradation through frequent treatment
et al. (2015) have observed the optimal process conditions of higher
approaches of physical, chemical and biological. CECs, their reme-
SRT, acidic pH, increased rate of nitrogen loading, and anoxic con-
diation processes, efficiency details are compiled in Table 6.
ditions increase the elimination potential for some of the phar-
The fundamental removal mechanisms for CECs are biodegra-
maceutical contaminants through MBRs.
dation, as mentioned earlier and adsorption. The operating con-
straints of the system influence the existence and magnitude i.e.
aerated and not aerated zones, Food to Microorganisms (F/M) ratio, 3.2.1. Biochar used for removal of CECs
pH and temperature. Management of these parameters helps The production of biochar sourced from the biomass residue of
10
D. Yadav, S. Rangabhashiyam, P. Verma et al. Chemosphere 272 (2021) 129492

Table 6
CEC (name) remediation process efficiency reference TiO2.

CEC(Name) Remediation Process Efficiency Reference

soil waste chemicals such as pesticides, polycyclic aromatic bioaccumulation of CEC in the root part is higher than in aerial PAH, ENMs, PPCP, Pullagurala
hydrocarbons, perfluorinated compounds, pharmaceutical parts Pesticides, et al. 2018
and personal care products, and engineered nanomaterials Perflourinatedcompounds
Endocrine disrupting compounds(EDCs), TiO2 Fagan et al.
(2016)
Bacteria by anti-bacterialaction Solar photocatalysis TiO2 Fagan et al.
(2016)
Cyanotoxins or blueegreen algae(blooms) Solar photocatalysis TiO2 Fagan et al.
(2016)
Endocrine disrupting compounds (EDCs) Including compounds Fagan et al.
from the groups of polycyclic aromatic hydrocarbons(PAHs), (2016)
alkyl phenols (APs), organotins (OTs),volatile organic
compounds(VOCs), pesticides, and heavy metals
Hazardous contaminants Immobilized laccase: bio-catalytic laccase-assisted degradation Bilal et al.
Biodegradation of ECs/EDs (2019b)
organochlorine pesticides alkylphenolpolyethoxylates/ Qi et al. 2018
bisphenol analog
8 CECs application of constructed wetlands for the removal of imidacloprid, erythromycin, clarithromyciX, azithromycin, Gorito et al.
priority substances and contaminants of emerging concern diclofenac, estrone (2017)
listed
complex inorganic contaminants and organic contaminants Biochar as a sorbent Li et al. 2015
from water
modification of current technologies of wastewater Taheran et al.
2018
emerging organic contaminants (EOCs) i.e. brominated flame Wang et al.
retardants, phthalates, pharmaceutics and personal care (2016)
products, and per-and polyfluoroalkyl substances
B. Wang et al./Trends in Environmental Analytical Chemistry 12 Phase-change, biological, AOP technologies Rodriguez-
(2016) 13e22 Narvaez et al.
(2017)
pharmaceutical, cosmeceutical, biomedical, personal care enzyme-assisted biodegradation Bilal et al.
products (PPCPs), endocrine-disrupting chemicals (EDCs), (2019a)
and flame-retardants
micropollutants, endocrine disruptors (EDs), pesticides, phase-changing treatment technologies Rasheed et al.,
pharmaceuticals, hormones, toxins, and industrially-related 2018
synthetic dyes and dyes-containing hazardous pollutants
Pharmaceuticals and personal care products and their pharmaceuticals and personal care products and endocrine Noguera-
metabolites, illicit drugs, engineered nanomaterials, and disrupting compounds, and highlighting Oviedo, and
antibiotic resistance genes Aga. (2016)
analygesics, antibiotics, antineoplastics, beta-blockers, plastic micro-/nanoparticles and photochemical Wilkinson
perfluorinated compounds, personal care products and transformation et al. (2017)
plasticizers 60 common pharmaceuticals
drugs and pharmaceuticals residues- new emerging pollutants - newgenerationnano-adsorbents Basheer
endocrine, hormonal and genetic disturbance nature (2018)
Pharmaceutically active compounds (PhACs), personal care Consolidated vs new advanced treatment methods- advanced Rizzo et al.
products, pesticides, synthetic and natural hormones, and oxidation processes (AOPs)) processes/technologies (2018)
industrial chemicals (such as flame retardants, plasticizers,
food additives, among others) -activated carbon (AC)
adsorption, ozonation and membranes. WWTPs - CECs and
secondary (e.g., conventional activated sludge process, CAS)
and tertiary (such as filtration and disinfection)
effluents of wastewater treatment plants (WWTPs) Antibiotic- secondary wastewater treatment methods - conventional Krzeminski
resistant bacteria (ARB) and antibiotic resistance genes activated sludge (CAS), membrane bioreactors et al. (2018)
(ARGs) (MBRs), moving bed biofilm reactors (MBBRs), and nature-
based solutions such as constructed wetlands (CWs)
Inorganic nutrients (ammonia and nitrate) as well as persistent Contaminants of Emerging McCance et al.
organic compounds Concern (CECs) and isotopic tracers 2018
aqueous-phase sorptive removal of emerging contaminants Metaleorganic frameworks (MOFs) (e.g., MIL-53, MIL-100, Coordination
(ECs). MIL-101, UiO-66, and MIL-125) Chemistry
Reviews 2019
reuse of treated wastewater (TWW) for irrigation and the use of Ability of crop plants to uptake and accumulate CECs decrease Christou et al.
biosolids and manures as soil amendment in the order of leafy vegetables > root vegetables > cereals (2018)
and fodder crops > fruit vegetables
personal care products (PCPs), endocrine disrupting compounds biological and chemical treatment techniques Gogoi et al.
(EDCs), pharmaceuticals (PhACs) (2018)
daily personal care products and pharmaceuticals (PPCPs), conventional methods such as Soxhlet, solid-phase extraction Martín-Pozo
flame retardants, endocrine disrupting chemicals (EDCs) and (SPE), pressurized liquid extraction (PLE) or ultrasound- et al. (2018)
nanoparticles (NPs) assisted extraction (UAE), but also other recent techniques,
including novel microextraction techniques such as
microextraction by packed sorbent (MEPS) or solid-phase
micro extraction (SPME)
Emerging pollutants (EPs) encompass a wide range of man- microbes or enzymes capable of degrading endocrine New
made chemicals (such as pesticides, cosmetics, personal and disruptors and other micropollutants. Biotechnology
household care products, pharmaceuticals, among others) 014

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D. Yadav, S. Rangabhashiyam, P. Verma et al. Chemosphere 272 (2021) 129492

different lignocellulosic biomass using thermal treatment under stable at increased temperature, due to dehydration, alkalization,
the limited supply of oxygen result in suitable adsorbents with and demethylation through volatilization of light organic struc-
potential for the removal of wastewater contaminants. Apart from tures, (Cely et al., 2015). The conversion of biomass to biochar is a
the native biochar usage, modification approaches through various potential CEC management solution that helps in utilizing biomass
physical and chemical means enhance the property of adsorbent in the production of a secondary material (biochar), which can be
(Rangabhashiyam, 2019). The physical activation of biochar per- further used in environmental protection (Srinivasan et al., 2015).
formed using carbon dioxide, ammonia, oxygen, air, steam, in While recent decades have seen an increase in the research focused
separate or mixture. The method of chemical activation reported on on the comparison between different types of biochar depending
biochar using acids, alkalis, and salts (Sevilla and Mokaya 2014).To on their production techniques like microwave, conventional
attain the higher yield of biochar with the desired characteristics of techniques, pyrolysis and hydrothermal carbonization (Huang
the high level of carbon content, higher surface area, more pore et al., 2017; Zhu et al., 2014), more research in this aspect needs to
volume, etc., the parameter such as heating rate, pressure, reactor be conducted to determine the properties of different types of
temperature, and biomass particle sizes must be optimized biochar. Biochar is readily and economically available in abundance.
(Tripathi et al., 2016). Conversion of biomass into biochar through Activated alumina, carbon nanotubes, clay mineral etc. are not
pyrolysis technology offers the benefits of elimination of carbon economical as compared to biochar. The 100% adsorptive removal
and lessening the emission of greenhouse gases. The stability of for H2PO 4 .The application of biochar with using different materials
biochar influenced by the occurrence of certain minerals and the and pre-treatments with steam, alkali, acid, and nanomaterial has
presence of higher content of lignin in biomass feedstock with large been observed for wastewater treatment (Ahmed et al.,
particles (Lijian and Huajun 2018). The employment of biomass 2016).Biochar has also been applied to remove heavy metals from
under pyrolysis at the temperature range of 500e700  C forms soil (Zhang and Geiben, 2012) due to mining, industry, and sewage
biochar with rich functional groups, mainly attributed to decom- waste (Anawar et al., 2015). To understand the fate of micro-
position and followed with the distribution of microspores (Zhao pollutants and adsorption systems of biochar, it important to un-
et al., 2016) derstand the properties of the biochar. This would help in selecting
The biomass of rice straw used for the production of biochar, the right material for biochar production according to the type of
considering the effect of temperature at 300, 500, and 700  C and contaminant and better efficiency in CEC removal (Fig. 11).
used for the removal of lead ions. Biochars prepared at higher
temperatures exhibited high pH and surface areas, favoured higher 3.3. Advanced oxidation processes for remediation of CECs
adsorption capacity, and rapid adsorption kinetics (Zhengtao,
2019). The adsorption behaviour of cadmium and lead ions tested 3.3.1. UV radiations
onto biochar in fine granules from coconut shell, Sri Lanka soil, and The UV radiation is required to degrade the CECs content in
a mixture of biochar and soil of 1:1-mixed.The analysis of experi- water and remove/debase organic matter (Rosenfeldt and Linden,
mental data showed that the metal ions adsorption using all the 2004). The organic CECs removal depends on the quantum yield
three adsorbents fitted better with the kinetic model of the pseudo- of the compounds and the quantity of UV radiation absorbed (Kim
second-order kinetics and isotherm model of Langmuir. Instru- et al., 2009). The factors affecting UV irradiation efficiency depends
mental analysis using scanning electron microscopy coupled with on the contact time, dosage and dissolved organic carbon concen-
energy dispersive X-ray represented that cadmium and lead ions tration. Besides, the UV radiation, to remove CECs also has germi-
presented higher adsorption affinity towards soil particles whereas cidal properties and therefore has high potential to be used for
randomly adsorbed to biochar (Paranavithana et al., 2016). multiple purposes as a disinfectant for water (Starling et al., 2019).
Spherical biochar produced using saccharides through pre-
hydrothermal carbonization followed with calculations. The char- 3.3.2. Photocatalytic processes for degradations of CECs
acterization of spherical biochar showed low surface area Andrich Photocatalysis is the “superior photochemical transformation by
functional groups containing oxygen. The spherical biochar utilized the action of a catalyst viz. Fenton’s reagent/TiO2” (Mokhbi et al.,
for the adsorption of lead, copper, and methylene green 5. The 2019), whereas Rutile TiO2, is the utmost frequently used catalyst
uptake of metal ions and methylene green five largely influenced by for photochemical studies. Photocatalysis is the best method for
the initial solution pH of the adsorption system. The predominant high Chemical Oxygen Demand (COD) and complete biological
mechanism of electrostatic attraction involved in the removal of transformation of highly organic pollutant effluents. Photocatalytic
cations and electrostatic repulsion in the case of anionic dye reactions commonly observe the LangmuirHinshelwood (LH) ki-
adsorption (Hai et al., 2017).The removal of endocrine-disrupting netic model, which further reduces to pseudo-first/zero-order ki-
compound (bisphenol A) and pharmaceutical compound (sulfa- netics depending on the operating conditions (Fig. 12) (see Fig. 13).
methoxazole) reported using biochar composite. The biomass of Phenols have an enhanced removal efficiency over UV/TiO2
bamboo employed as feedstock for the production of biochar. Ferric along with H2O2 and COD from fermentation effluent (Zazo et al.,
oxide, zinc oxide, and copper oxide are used in the preparation of 2007). Combing photocatalysis with other mechanisms can
biochar composite through the process of facile one-pot hydro- further increase their targets and enhance removal efficiency. For
thermal. The major mechanisms in the adsorption of bisphenol A example, advanced COD removal has been achieved in penicillin
and sulfamethoxazole using biochar composite showed charge- design waste by combining photocatalysis with ozonation
assisted bonding of hydrogen and interactions of hydrophobic, (Klavarioti et al., 2009). An innovative semiconductor photo-
pep electron donor-acceptor (Jiyong et al., 2019) (see Fig. 10). catalysis formulated by a combination of TiO2 with RuO2eIrO2 as
Biochar is increasingly being used in the removal of CECs. Bio- anode and chloride as an electrolyte has also revealed 95% COD
char is characterized by highly efficient, low-cost, and removal with first-order kinetics.
environment-friendly adsorbent properties. They comprise
different amounts of carbon and inorganic fractions (Zhao et al., 3.3.3. 3 reaction pathway for degradation of CECs by photocatalysis
2016a, b). Their adsorbent properties of the biochar material are processes
determined by pyrolysis temperature, residence time, raw mate- The reaction pathways of pollutant removal require under-
rials, and the thermochemical technology used for their production standing the complexities involved. For example, the photo-
(Bird et al., 2011; Busscher et al., 2010). Biochar becomes more degradation pathway and mechanism for 4-tBP in the absence and
12
D. Yadav, S. Rangabhashiyam, P. Verma et al. Chemosphere 272 (2021) 129492

presence of HO
in aqueous solution has not been observed. To details).

observe this pathway, a study was conducted, which also focussed However, since more resources are being consumed from places
on the transformation products and behaviour of the 4-t-BP under which were hitherto left unexplored, source characterization and
photodegradation. The resultant by-products were identified by LC- sustainability assessment have become very important. Further, a
MS and GC-MS techniques, while the transition products during the need for safe disposal methods is also required since many chem-
experiment were identified by Laser Flash Photolysis (LFP) using icals can become more hazardous if disposed of improperly. Thus,
266 nm laser pulse (Huang et al., 2008; Zhang et al., 2008). apart from the traditional risk management approaches, we have
Furthermore, a detailed study by theoretical calculations was suggested source characterization and nontoxic disposal as a vital
also performed to confirm the chemical structures of byproducts. part of the risk assessment and management tactics for emerging
All these steps helped in finally arriving at the possible mechanism contaminants.
of the 4-t-BP photodegradation mechanism in the presence and Following is a brief account of a conceptual approach towards
absence of HO
in aqueous solution. The advantages, disadvantages risk management and assessment of CEC. Firstly, Hazard charac-
and recommendations for each advanced treatment are assembled terization involves short- and long-term toxicity tests based on
in Table 7. experimental data to regulate the lethality, deviations in imitation,
performances and progress due to the pollutants (Ochoa 2018). The
second step, exposure assessment, aims at the prediction of envi-
4. Risk assessment and management approaches for CECs ronment concentrations. It involves two aspects, first is the emis-
sion assessment, and second is the behaviour and fate of the
The sampling techniques for the CECs have advanced in recent contaminant in the environment, in short, its degradation trail.
decades. However, an essential feature for universal monitoring With the development of passive sampling techniques, exposure
and removal of emerging contaminants is the risk assessment assessment has developed to quantify long term pathways and
based on standard definitions and agreement on CECs (Riva et al., predicted environment concentrations (PEC) of such contaminants.
2019). The description of CECs by the world’s agencies help in the This is followed by the third step, which predicts the dose-response
study of different compounds and their associated risks. Crucial of contaminants based on the contact and reaction of target and
choice of contaminants helps in their management, assessment and control samples. The risk assessment is based on the ratio of two
forming an international agreement on their potential hazards. For standards of PECs and predicted no environment concentrations
example, the lack of a standard definition of EDCs prevented the (PNEC). PNEC is the measure of toxin concentration below which it
assessment of the risk posed by them globally (Fuhrman et al., does not affect the environment (Liu et al., 2018). If the ratio of PEC/
2015). The emergent nature of these contaminants also warrants PNEC is more than (>)1, the contaminant needs to be monitored.
investigation into their assessable toxicity levels. Many of the Prioritization of CECs based on their detected concentrations
chemical compounds, just being recognized as emerging pollut- against their PNEC represents their thresholds of toxicity. This
ants, are found in concentrations which are hard to notice. They approach has been developed by the NORMAN (Dulio, V., van der
may be present in concentrations as low as one ng/Le1 mg/L or even Horst and Somerset, 2019; Alygizakis et al. 2019). The NORMON
at 100 mg/L. Their safety levels for consumption and disposal pose a ECOTOX database provides PNEC values for many CECs identified so
risk of the unknown for the monitoring agencies as well as public far ((https://www.norman-network.com/nds/ecotox/). This
(Pal et al. 2014). approach was applied by Alygizakis et al. (2019) in the character-
Conventionally risk management and assessment have been ization of CECs in wastewater effluents in Danube River using
known as consisting of four phases (Fig. 9), 1. Hazard character- chemical screening, in-vitro bioassays and antibiotic-resistant
ization; 2. Exposure assessment; 3. Dose-response assessment; 4. genes. Apart from identifying the presence of antibiotic-resistant
Risk characterization (see Amiard and Amiard-Triquet, 2015 for

Table 7
Advantages, drawbacks and recommendations for each advanced treatment (Rizzo et al. 2018).

Advanced Advantages Drawbacks Recommendations

Treatment

UV/TiO2
High CEC removal
Low kinetics Not possible to apply until more efficient

Use of solar irradiation
Formation of oxidation transformation products photocatalysts (at least one order of magnitude) will be

Effective as disinfection process too
Catalyst removal developed

Large space requirements for solar collectors
Ozonation
High CEC removal
Formation of by-products (NDMA, bromate) and
Toxicity tests recommended

Full scale evidence on practicability other unknown oxidation transformation
NDMA and bromate should be monitored

Partial disinfection products

Lower energy demand compared to UV/
Need for a subsequent biological treatment (e.g.,
H2O2 and membranes slow sand filtration) to remove organic by-
products
Powdered
High CEC removal
PAC must be disposed Test with different products/process configurations
activated
Full scale evidence on practicability
Post-treatment required (membrane, textile or recommended
carbon
Additional DOC removal sand filter) to prevent discharge of PAC
(PAC)
No formation of by-products
Production of PAC needs high energy

Partial disinfection possible by the
Adsorption capacity may fluctuate with each
combination with membrane filtration (UF) batch
Granular
High CEC removal
Production of GAC needs high energy Test with different products recommended
activated
Full scale evidence on practicability
Still under investigation if more activated carbon
carbon
Additional DOC removal is needed compared to PAC
(GAC)
No formation of by-products
Less flexible in operation than PAC and ozonation

An existing sand filtration can relative easily to react to changes in wastewater composition
be replaced by GAC
Adsorption capacity may fluctuate with each

GAC can be regenerated batch

13
D. Yadav, S. Rangabhashiyam, P. Verma et al. Chemosphere 272 (2021) 129492

Fig. 9. Schematic representation of a simplified treatment route for CECs using column-based reactor.

Fig. 10. Pictorial view of conventional and advanced biological processes (Torresi et al., 2017).

Fig. 11. Type of contaminant and better efficiency in CEC removal. Reprinted from Bilal et al. (2019a) with permission under Creative Commons CC-BY-NC-ND license. Copyright ©
2019 The Authors. Published by Elsevier Ltd.

14
D. Yadav, S. Rangabhashiyam, P. Verma et al. Chemosphere 272 (2021) 129492

5. Challenges and opportunities

There are specific challenges faced in the monitoring and

assessment of emerging contaminants. The first challenge is that
these contaminants are not commonly monitored while at the
same time, they have the potential to affect human and ecological
health. Several emerging effects, like the antibiotic resistance of
aquatic pathogens, make the monitoring and assessment of CEC
more critical in present times (Nawaz and Sengupta 2019). How-
ever, there are certain advancements too in the monitoring and
assessment of CECs with the development of technology and
application of new substances for removal or containment of the
contaminants. Following are some of the broad challenges and
opportunities met in monitoring and assessment of emerging
contaminants.
Experimentation and analysis: The production, disposal and
uses of CECs generating substances and practices change rapidly. It
Fig. 12. Schematic illustration of the photocatalytic process (Banerjee et al., 2015;
Etacheri et al., 2015). is also essential to have an understanding of the pathways and
transformation products of the CECs. The spatial and temporal scale
of monitoring activity for CECs varies depending on their properties
and transporting agent like biological, water or air (McGuire and
genes, they also analyzed the spatial heterogeneity in CECs and McDonnell, 2006). Modelling approaches to validate, calibrate
compared their concentrations against the effect-based trigger- and understand the process of transportation are necessary and
values. The complete results are available at https://norman-data. useful, but, at larger scales, such techniques are subjected to the
eu/EWW_DANUBE. constraints of computational and data requirements (Brunner and
Risk characterization includes the immunotoxicity analysis to Simmons 2012; Aalizadeh et al., 2019). Data availability and vali-
determine the minimum standards for tolerance, i.e., creating dation play a vital role to overcome this challenge. Monitoring
benchmarks for CECs (Arrieta-Cortes et al., 2017). Risk assessment instrumentation and technology, since newer CECs are emerging,
was identified as a significant theme in the thematic plot for the the risk assessment tools, from a perspective of monitoring and
impact of CECs on the environment (Fig. 7). It had high density but detection technology as well as conceptual and methodological
low centrality representing its widespread and regular use but lack understanding, of the risk assessment, need to evolve continually.
of major conceptual keystones and rank in the eco-friendly effect of Sustainability of monitoring and actual utilization results for any
emerging contaminants. Thus, there is a need to recognize the risk assessment framework to continue, it has to be continuously fed
assessment and management as a specific aspect and its evolution back by the results of its application. Since CECs are a global issue,
to consider the existing and future contaminants of emerging there is also a requirement for the development of policies and
concern. rules at the international level to create a common framework for
CECs monitoring and sharing of research and technology. These
assessments are used to further the research and are instrumental

Fig. 13. The sequence of technologies used for the treatment of waste water (Park et al., 2017)

15
D. Yadav, S. Rangabhashiyam, P. Verma et al. Chemosphere 272 (2021) 129492

in formulating global and local policies regarding safe levels, removal efficiency for heavy metals (37e100%) and remove noxious
exposure levels, site screening, etc. (Diamond et al., 2015; Nawaz nutrients. Ozonation and powdered activated charcoal remove
and Sengupta 2019) iohexol, iomeprol, and iopromide with an efficiency of >97% and
Execution of the UN’s sustainability objectives, like access to 90% for diatrizoate (Shah et al., 2020). Many (bio)transformation
clean water, is a significant task as it needs empathetic at various (by)products possess different (lower/higher) toxicological finger-
policy and scientific back-up at various strategy building stages prints, which can now also be assessed by advanced modelling.
(Aravindakumar et al. 2019). However, it also provides a chance to Moreover, many of these AOPs are limited commercially by their
conduct similar valuations and a common goal towards which high capital and operating costs (Wacławek et al., 2020). Moreover,
countries can desire. Modelling the transport of contaminants recent changes in the public perception of wastewater has led to
through biotic and abiotic systems can help in their mitigation. several paradigm shifts: (i) water reuse considering wastewater as
Water flow modelling through plant and animal systems is essen- a water resource rather than a hazardous waste, (ii) wastewater-
tial to escalating their accumulation and toxicity. Synergistic effects based epidemiology considering wastewater as a source of infor-
of CECs detection and their analysis in the first stages of their mation regarding the overall health of a population through the
lifecycle, before the formation of any transformation products, analysis of specific biomarkers, (iii) circular economy through the
would help in to prevent further risk to human and ecological implementation of treatment processes aiming at harvesting
health. valuable components such as precious metals or producing valu-
Moreover, for CECs like EDCs, a piece of comprehensive infor- able goods such as biofuel (Villarín and Merel, 2020). Though
mation about various types of contaminants is essential for risk advanced, the cost limitations obstruct their genuine claim in fields.
assessment studies, as these contaminants may interact to cause However, their importance still rests for future research to decrease
synergistic toxic effects on the exposed organisms (Noguera- the cost of such CEC treatment mechanisms (Ribeiro et al., 2015;
Oviedo and Aga, 2016). The chemical nature and use of CEC Barbosa et al., 2016).
determine its risk due to exposure, for example, the exposure
assessment for phthalates is hard because of their extensive use 7. Conclusions and future recommendations
and pervasive occurrence in the environment (Net et al., 2015). The
endocrine-disrupting phenomena is a synergistic effect due to It is concluded that there is a critical need for the enhancement
several EDCs. This synergistic effect requires application of multi- of the efficiency of various treatment technology used for the
residue methods focussed on identifying and isolating the num- removal of CECs from industrial waste and other forms of waste-
ber of EDCs involved in the CEC mix for risk assessment (Jime
nez- water. A variety of treatment techniques are available such as
Díaz et al., 2015). Several analytical methods have detected the physical-chemical, biological and advance oxidations processes are
presence of EDC in drinking water components of cities (Padhye available. There are various limitations available with these pro-
et al., 2014). Exposure to EDCs during various biological phases of cesses such as economic feasibility, eco-friendly, the rising number
animal and humans, like gestation and lactation, is also a critical of more identified CECs, and sometimes intermediate compounds
issue that needs more research. In the coming years, more research are more toxic than the parental compounds. Cost-effective and
into CEC focussing on EDCs would be required especially as the environment-friendly biochar as adsorbent is a viable option to
human activities diversify, due to increased consumption of re- explore in full-scale operations for CECs removal, though further
sources and the resulting waste production. research might be needed in this respect. However, biological
processes are also found eco-friendly and economically feasible,
6. Limitations in the management of CEC but there are some limitations also such climatic conditions, the
load of pollutants, nature of pollutant microbial acclimations.
Due to a large diversity of CECs, their mode of action and the yet Around 3000, different compounds are assessed and used as
to be discovered transformation products, an enormous load is put pharmaceutical constituents, including antibiotics, painkillers, an-
on the management of CECs and in creating policies for their tidiabetics, antidepressants, contraceptives, lipid regulators, beta-
regulation and removal. Therefore, optimization strategies are blockers, and impotence drugs. Only a small subsection of these
required to create a security monitoring and removal mechanism CECs and their impact on the aquatic environment has been pre-
which can handle this load, like adsorbent and flocculants choice, cisely studied. The extensive use of a wide range of pharmaceuticals
selection of membranes, dosing procedures, systems configura- and personal care products has also amplified their presence in
tions, mixing conditions, etc. (Qu et al., 2013; Wand et al. 2019; surface water, groundwater, waste water and storm-water runoff in
Maaz et al., 2019). Thus, information systemization and develop- urban areas (Varjani and Sudha. 2018).
ment of useful tools for modelling CECs behaviour in water, soil and
air medium is essential. Lack of comparison between different 7.1. Future recommendations and management of CEC
mechanisms of CEC removal and in between the conventional and
emergent methods prevents the identification of cost-effective and Based on the risk assessment approaches, remediation and
contaminant specific treatment of remerging contaminants. Site- management of CECs will involve monitoring, their transport, fate
specific characteristics can also play an essential role in deter- and transition products, benchmarking, identifying tracers and
mining the limitations of CEC treatment mechanisms (Krauss et al., indicators, regulation in products, management of contaminated
2019). The relative analysis should also take into account the site- sites, sharing of information and creating regulatory norms at the
specific limitations accounting for the safe disposal or legal limit global scale. Themes and concepts which were identified as
standard for CECs. requiring more research attention in the bibliometric analysis, need
Besides households, hospitals and typical industries, other to be explored. For example, in the case of personal care products,
sources of wastewater appear due to emerging activities like hy- the role of endocrine-disrupting chemicals and antibiotics needs to
draulic fracturing. Certain technologies have been the focus of be explored more in terms of emerging contaminants.
recent studies into the relative performance for CEC removal, like Similarly, the role of organic micropollutants, pesticides and
UV/TiO2, heterogeneous photo-Fenton, photocatalytic ozonation, perfluorinated compounds needs to assessed in water and
photocatalytic membrane processes, electrochemical oxidation and wastewater.
hybrid processes, among others. Algal technologies have excellent CECs are rarely monitored globally, so there is a need of hours to
16
D. Yadav, S. Rangabhashiyam, P. Verma et al. Chemosphere 272 (2021) 129492

studies its existing concentration, transportation and potential Pharmaceutical compounds in drinking water. Journal of xenobiotics 6 (1).
Chequer, F.M.D., de Oliveira, G.A.R., Ferraz, E.R.A., Cardoso, J.C., Zanoni, M.V.B., de
transformation are necessary to understand and restrict the
Oliveira, D.P., 2013. Textile dyes: dyeing process and environmental impact. In
transport of CEC in the hydrological matrix. Identification of po- Eco-friendly textile dyeing and finishing. InTech.
tential tracers and indicators of CECs can help to analyze its threats Christou, A., Papadavid, G., Dalias, P., Fotopoulos, V., Michael, C., Bayona, J.M., Fatta-
along with economic feasibility for identifying such potential Kassinos, D., et al., 2018. Ranking of crop plants according to their potential to
uptake and accumulate contaminants of emerging concern. Environ. Res. 170,
tracers is needed. Characterizations of CECs at source and its proper 422e432.
disposal play a vital role in the mitigation of risk of contamination Cirja, M., Zuehlke, S., Ivashechkin, P., Hollender, J., Sch€ affer, A., Corvini, P.F., 2007.
of surface and subsurface water. Comprehensive technologies for Behavior of two differently radiolabelled 17a-ethinylestradiols continuously
applied to a laboratory-scale membrane bioreactor with adapted industrial
the removal of allied CEC and the effect of additive CEC, affinity and activated sludge. Water Res. 41 (19), 4403e4412.
synergistic behaviour are essential aspects which need to be Colbeck, I., Lazaridis, M., 2010. Aerosols and environmental pollution. Natur-
explored further. wissenschaften 97 (2), 117e131.
Della Corte, V., Del Gaudio, G., Sepe, F., Sciarelli, F., 2019. Sustainable tourism in the
open innovation realm: a bibliometric analysis. Sustainability 11 (21), 6114.
Declaration of competing interest Diamond, J., Munkittrick, K., Kapo, K.E., Flippin, J., 2015. A framework for screening
sites at risk from contaminants of emerging concern. Environ. Toxicol. Chem. 34
(12), 2671e2681.
The authors declare that they have no known competing Dong, H.L., Yongyou, H., Jianhua, C., Yuancai, C., 2020. Simultaneous sulfamethox-
financial interests or personal relationships that could have azole biodegradation and nitrogen conversion in low C/N ratio pharmaceutical
appeared to influence the work reported in this paper. wastewater by Achromobacter sp. JL9. Sci. Total Environ. 703, 135586.
Du, H., Shi, S., Liu, W., Teng, H., Piao, M., 2020. Processing and modification of
hydrogel and its application in emerging contaminant adsorption and in cata-
Acknowledgments lyst immobilization: a review. Environ. Sci. Pollut. Control Ser. 1e28.
Faboya, O.L., Sojinu, S.O., Oguntuase, B.J., Sonibare, O.O., 2020. Impact of forest fires
on polycyclic aromatic hydrocarbon concentrations and stable carbon isotope
Dr. Deepak Yadav received Collaborative Research Scheme compositions in burnt soils from tropical forest, Nigeria. Scientific African,
Project (Project ID 1-5764067271) funding provided by AICTE, Govt. e00331.
of India. Fagan, R., McCormack, D.E., Dionysiou, D.D., Pillai, S.C., 2016. A review of solar and
visible light active TiO2 photocatalysis for treating bacteria, cyanotoxins and
contaminants of emerging concern. Mater. Sci. Semicond. Process. 42, 2e14.
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