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Chemico-nanotreatment methods for the removal of persistent organic pollutants and xenobiotics in water -A review

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Bioresource Technology 324 (2021) 124678
Available online 7 January 2021
0960-8524/© 2021 Elsevier Ltd. All rights reserved.
Review
Chemico-nanotreatment methods for the removal of persistent organic
pollutants and xenobiotics in water A review
Guruviah Karthigadevi
a
,
b
, Sivasubramanian Manikandan
c
, Natchimuthu Karmegam
d
,
Ramasamy Subbaiya
e
, Sivasankaran Chozhavendhan
f
, Balasubramani Ravindran
g
,
Soon Woong Chang
g
, Mukesh Kumar Awasthi
a
,
*
a
College of Natural Resources and Environment, Northwest A&F University, Taicheng Road 3#, Yangling, Shaanxi 712100, China
b
Department of Biotechnology, Sri Venkateswara College of Engineering, (Autonomous), Sriperumbudur TK - 602 117, Tamil Nadu, India
c
Department of Biotechnology, Saveetha School of Engineering, Saveetha Institute of Medical and Technical Sciences (SIMATS), Saveetha Nagar, Thandalam, Chennai -
602 105, Tamil Nadu, India
d
Department of Botany, Government Arts College (Autonomous), Salem - 636 007, Tamil Nadu, India
e
Department of Biological Sciences, School of Mathematics and Natural Sciences, The Copperbelt University, Riverside, Jambo Drive, P.O. Box. 21692, Kitwe, Zambia
f
Department of Biotechnology, V.S.B Engineering College, Karur 639 111, Tamil Nadu, India
g
Department of Environmental Energy and Engineering, Kyonggi University, Youngtong-Gu, Suwon, 16227, South Korea
HIGHLIGHTS GRAPHICAL ABSTRACT
Persistent and xenobiotic compounds
pollution in water sources affect
environment.
Chemical treatments for xenobiotics
removal are practicable and costly.
Nanotechnology provides low-cost
nanomaterials for wastewater
treatments.
Nanomaterials are excellent agents for
eliminating xenobiotics in wastewater.
ARTICLE INFO
Keywords:
Nanomaterials
Persistent pollutants
Photocatalysis
Wastewater treatment
Xenobiotics
ABSTRACT
While the technologies available today can generate high-quality water from wastewater, the majority of the
wastewater treatment plants are not intended to eliminate emerging xenobiotic pollutants, pharmaceutical and
personal care items. Most endocrine disrupting compounds (EDCs) and personal care products (PPCPs) are more
arctic than most regulated pollutants, and several of them have acid or critical functional groups. Together with
the trace occurrence, EDCs and PPCPs create specic challenges for removal and subsequent improvements of
wastewater treatment plants. Various technologies have been investigated extensively because they are highly
persistent which leads to bioaccumulation. Researchers are increasingly addressing the human health hazards of
xenobiotics and their removal. The emphasis of this review was on the promising methods available, especially
nanotechnology, for the treatment of xenobiotic compounds that are accidentally released into the setting. In
* Corresponding author at: College of Natural Resources and Environment, Northwest A&F University, Taicheng Road 3#, Yangling, Shaanxi 712100, China.
E-mail address: mukesh_awasthi45@yahoo.com (M.K. Awasthi).
Contents lists available at ScienceDirect
Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech
https://doi.org/10.1016/j.biortech.2021.124678
Received 3 December 2020; Received in revised form 29 December 2020; Accepted 2 January 2021
Bioresource Technology 324 (2021) 124678
2
terms of xenobiotic elimination, nanotechnology provides better treatment than chemical treatments and their
degradation mechanisms are addressed.
1. Introduction
Owing to the widespread event of persistent organic contaminants
and xenobiotics, knowledge of their occurrence in the environment is
very critical in the past decades. Under the Stockholm Convention 21
organic persistent contaminants with high toxicological risk have been
reported (des Ligneris et al., 2018). The main purpose of the Convention
of Stockholm is to nd the right way of preventing pollutant accumu-
lation and to identify new persistent organic pollutants (POPs). Re-
searchers focus more on cleaning xenobiotics and POPs from
environmental media using different technologies (Pi et al., 2018). The
fact that most POPs and xenobiotics are accumulated in surface water
and drinking water as micropollutant substances present many chal-
lenges to quantication and detection. Recently, EU guidelines have laid
down regulations to periodically track releases of xenobiotics to mini-
mize this step in a wise manner (Sousa et al., 2018). Some pesticides and
pharmaceutical products have been reviewed and updated by the reg-
ulatory authorities based on priority setting. The study shows the pre-
dominance of pesticides and drugs among the xenobiotic compounds
and that their removal is a major concern because of their low degrad-
ability (Liu et al., 2020). On the global stage, the distribution of organic
xenobiotics primarily affects agro and aquatic environments, and so
treatment processes for developing countries are the prerequisites.
Conventional wastewater treatment methods for xenobiotic removal
were initially employed but due to its hydrophilic existence, the efu-
ents were released in a merging environment. Many techniques have
been developed over the decades, such as advanced oxidation, electro-
chemical and photochemical processes (Chakraborty et al., 2020; Lin
and Lee, 2010), but they do not eliminate organic pollutants. To mitigate
or remove releases to the atmosphere, POPs are dened as being based
on reduction, output and accidental production (Stockholm conven-
tion). According to geographical locations, these compounds continue to
inuence the climate, people and animals (Tran et al., 2018). Both soil
and human species expose these compounds to a variety of causes of
disease such as metabolic disorders, kidney injury, insomnia and ner-
vous disorders (George et al., 2017; Garza-Lomb´
o et al., 2018). For the
treatment of POPs and xenobiotics in the earlier decades, chemical
processes such as reduction, oxidation, precipitation, ion exchangers
and adsorption have been used. These are not cost-efcient approaches,
however, and require non-environmentally friendly procedures to
establish environmental sustainability problems (Ramírez-García et al.,
2019).
In recent days, there has been a surge to resolve the problem; sci-
entists are making technological advances to optimize the method of
pollutant cleaning at ‘0levels. Several literature pieces focused upon
safe practices through the use of natural materials, and nano-
technological approaches to extract heavy metals and dyes from
wastewater (Le et al., 2015). Nanomaterials have outstanding properties
because they are capable of transforming their structures into specic
functionalities, which display greater promise in wastewater treatment.
A wide variety of nanomaterials have been tested as reliable, cost-
effective and environmentally safe for the treatment of industrial ef-
uents, soil waters, surface water and drinking water (Kodama et al.,
2015; Pang et al., 2011). Based on the literature research, scientists
make efforts to develop new materials by combining technical innova-
tion with human ecological risk evaluations. Nanotechnology that is
effectively used to disposing of contaminants allows such materials
possible. The current review summarises the multidisciplinary ap-
proaches involved in the design, manufacture, transport and removal of
xenobiotics and the environmental risks associated with them.
1.1. Sources of xenobiotics and POPs
Xenobiotics are diversied manmade chemicals released into the
environment each of which has the potential ability to cause an envi-
ronmental hazard and the dose level may be either higher for one
compound compared to others. The inherent properties of xenobiotics
are different and pollutant nature is expelled from each source. Certain
sources of xenobiotics may release a single deleterious compound or it
could be a mixture of organic pollutants. A single pollutant or combi-
nation of pollutant compounds can be used in xenobiotics, rendering
environmental protection a major activity. Based on the characteristics
of xenobiotics, natural or anthropogenic releases have been categorized
as deliberate or accidental, direct, or indirect releases. Most xenobiotics
are released as volatilized contaminants that are collected in the air from
industries, which spread directly to soil surfaces, and then released into
aquatic areas by precipitation. The origin of xenobiotics must be clas-
sied so that harmful contaminants can be restricted. The sum of re-
leases from a given location should be calculated under the Stockholm
Convention 2009 so that we can quantify the transport potential.
POPs are halogenated xenobiotic compounds to which human beings
are largely exposed through various commodities either through point
or nonpoint sources. These contaminants are extremely toxic com-
pounds in the atmosphere that are highly bio-accumulative and can
disrupt the food supply chain of the microbiome. Under the guidelines of
the Environmental Protection Agency (EPA), the incidence rates of
diseases caused by these contaminants in the marine and coastal eco-
systems are high. People who have now adapted themselves to modern
lifestyles using the articial compounds are purposely released into the
worlds atmosphere. POPs are categorized under 4 levels: (i) the most
dangerous chemicals which are under restriction for production and use,
(ii) the medium level chemicals which are restricted to use in the pro-
duction process, (iii) the discharge of chemicals unintentionally during
the production process, and (iv) the use of chemicals under investiga-
tion. The required steps for pollution control will be taken in the sites,
based on the screening results done by various communitiesinterna-
tional levels. Normal surveillance to estimate the parameters was co-
ordinated, and campaigns were arranged to slacken the production, use
and release of POPs as they are highly persistent in the environment as a
non-degradable pollutant (Daley et al., 2014). These pollutants undergo
bioaccumulation by the organisms which result in changes in toxicity
levels or it disturbs the metabolism of the microbes.
1.2. Ecological risks associated with xenobiotics and POPs
Xenobiotics released from the various industries and agricultural
activities have now become a global issue as it creates a greater impact
on the ecosystem. There has been an outbreak of several diseases that
occurs to the food-producing animals in connection with this contami-
nant release which in turn affects the health of the humans. This mainly
occurs due to the use of organo-chlorinated pesticides which have been
used over years in agricultural elds (Qi et al., 2020). Such compounds
will not be removed completely from the soil and also the use of recy-
cling wastewater containing POPs gets adsorbed into the soil. It affects
the soil microbial populations which lead to the damage of the plant
thereby affecting the symbiotic relationship between plant and micro-
organisms (Meena et al., 2020). So the roles of microbial biosynthetic
mechanisms are altered so the remediation of the pollutants will also get
disturbed completely resulted in poor degradation. It also imbalances
the soil fertility which affects the yield of crops.
Ecological risk data assessment of POPs showed that the adsorption
of compounds will be higher in low-temperature regions. Because POPs
G. Karthigadevi et al.
Bioresource Technology 324 (2021) 124678
3
migrate to the high latitude atmospheres remains to settle in the air and
there is a possibility to transfer to the marine environments. So the
marine areas in polar-regions have high accumulation when compared
to other regions (Zhang et al., 2018). Hence the people who live in these
regions are at greater risk of bioaccumulation of these components as
they depend highly on seafood (Song et al., 2019a). Generally, exposure
to xenobiotic compounds is a continuous action nowadays via food,
water and commercial products as they always pose serious risks to the
living system (Diamanti-Kandarakis et al., 2009). The level of risk varies
according to the type of chemical, their toxicity nature and their inter-
action with the living organisms. The impact of risk on ecology depends
on the genetic factors of the consumers and also based on how long they
are exposed to the particular chemical and their dose levels. The
assessment of risk should be done based on the quantication of indi-
vidual chemicals present in the group of components present in the
mixture which is the major issue due to the bioavailability nature of the
microorganism for the xenobiotic compounds. Based upon the specic
type of the microorganisms, the adsorption, degradation and meta-
bolism of the xenobiotic compounds also vary which leads to compli-
cations in the removal. So the identication of reliable risk assessment
procedures should be done to balance the environmental protection at a
minimal cost.
1.3. POPs and their interrelations with human health
Nowadays, most of the xenobiotic compounds are used in drugs,
cosmetics and agriculture produce inimical effects to the consumers.
There is an inevitable exposure to a variety of chemicals, there is a need
to focus on the evaluation of possible toxicological effects on humans
and animals has to be focussed. As the variation in the composition of
xenobiotic compounds, the effect may be genotoxic, immuno-toxic,
nephrotoxic, neurotoxic and hepatotoxic, the Stockholm Convention
identied 12 major offenders of pesticide residues, synthetic chemicals
and accidental by-products. The Convention took crucial measures to
protect human health and the environment by removing POPs and
eliminating their production and trade. As the POPs persist on lower
doses in the atmosphere, but in the live organisms, they can bio-
accumulate. These can interact through the mouth, inhalation, and
dermal with living systems, but the impacts of those POPs are not
entirely understood. No major health disorders are caused by a limited
amount of exhibition. Continuous exposure to specic chemicals has
recently been exacerbated as many have resulted in developmental
disorders, reproductive defects, cancer and teratogenic effects, animal
and human endocrine disruptors (Sharma et al., 2014) which is sche-
matically explained in Fig. 1.
In recent years, humans who have been exposed to larger quantities
of polystyrene compounds contain minute particles that may translocate
into the human system and have an effect on the population of the im-
mune cells (Wang et al., 2021). The government has made efforts to
minimize the rate of MOPs and regulated risk margins relative to pre-
vious decades. The lethal effects of each organic matter should be
studied because single organic pollutants can cause no effects but a
combination of organic pollutants causes adverse effects. As each POP
has a particular health inuence, exposure to a variety of POPs has
Fig. 1. ADME impact of xenobiotics on human system.
G. Karthigadevi et al.
Bioresource Technology 324 (2021) 124678
4
negative and epidemic; animal research studies are showing harmful
effects on the health of living things. Therefore, various methods of
treatment are required to protect individuals from harmful health con-
ditions such as learning disabilities, birth defects and behavioral defects.
Additionally, the intake of food from such xenobiotic polluted soils gets
accumulated in the human adipose tissues which induce obsogenesis
and also interrupt the metabolism of the human systems (La Merrill
et al., 2013). From the epidemiological studies, it is inferred that even
low-dose POPs have been linked with chronic metabolic disorders (Zhou
et al., 2020).
1.4. Control and removal measures of POPs
Remediation methods are required for the removal of POPs so that
knowledge about the chemical properties of POPs can be obtained.
Several approaches to battle the effects of POPs are available and their
development and application are minimized. The US Government has
adopted legislation banning the use of POPs using many conventions.
The Agency for Environmental Protection has made serious efforts to
avoid its release into earth, air and water that decreased nearly 90% of
its releases. As a result, physical, chemical and biological remediation
technologies are being developed (Deng and Tam, 2015). Naturally,
bioremediation processes are carried out in soil using existing environ-
mental microorganisms, but they do not eliminate POPs. Genetic engi-
neering technologies help us improving the capacity of microorganisms
to clean up contaminants (Khan et al., 2016). Several researchers have
shown that bioaugmentation and methods of phytoremediation have
been utilized in a viable manner to rehabilitate polycyclic aromatic
hydrocarbons and many contaminants (Egorova et al., 2017). These
methods are subjected to limitations because of microbial contamina-
tion. The emerging technologies are focused on the elimination of con-
taminants but these have proven to be effective for trace quantities in
the removal. To deal with the removal of high-dose pollutant problems,
the integration of techniques has to be made to nd a possible outcome
(Navaratna et al., 2016). In this study, the techniques of removing
xenobiotic compounds that have accumulated as persistent contami-
nants in the atmosphere in recent decades have been discussed (Table 1).
2. Treatment methods for degradation of POPs and xenobiotics
Around ten million xenobiotic chemicals are released into the
aquatic environment by the factories, containing a large number of
different xenobiotic compounds interacting due to their physical and
chemical properties. There are approximately 129 pollutants screened
by the US Clean Water Act (MERL, USA EPA) under special re-
quirements, which includes heavy metals and organic chemical
products. To degrade the xenobiotic in the water, physical and chemical
methods have been developed over the years, but are unable to elimi-
nate persistent organic contamination. Modern techniques for dening
and quantifying substances based on their molecular dimension, the
solubility of water, polarity and volatility provide major solutions for
extracting POPs from the setting (Megson et al., 2016). Potential ana-
lytic treatment methods for the detection of complex compounds, even
when stored in minimum concentrations, are on the boom. Bio-
treatment approaches arose as an alternative low-cost technology for
high ecological dominance wastewater treatment (Delforno et al.,
2015). In particular, aerobic microorganisms use xenobiotics as a source
of their carbon since they are catabolic, resulting in either degradation
or transformation of the compounds. These remediation approaches can
cause the degradation of most simple organic pollutants, but for decades
the environment has received POPs, such as polyhydroxyalkanoate,
polychlorinated biphenyls, DDT and heterocyclic compounds, as well as
organophosphorus pesticides because of their high biomagnication and
bioaccumulation (Donyinah, 2019). Since chemical concentration
excessively exceeds, microorganisms cannot efciently handle efuents,
and new technologies, such as chemical oxidation methods and nano
treatment methods, are evolving, thereby decreasing toxicity, followed
by biological treatments, to lower levels (Table 2).
2.1. Chemical treatment methods in wastewater treatment
2.1.1. Coagulationocculation for the removal of xenobiotics
Coagulation is typically used for the elimination of xenobiotic com-
pounds by the process of sedimentation and ltration, based on mass
transition, in water treatments. The neutralization of charged particles is
involved in a gelatinous mass, which is ltered by the application of an
agitation process to turn the colloidal particles into occulation and
separated from the solution by the occulation method (Pariatamby and
Kee, 2016). The option of chemical methods is based on compound form,
chemical structure and other organic ingredients. In this process the
removal of inorganic metal compounds and hazardous sludge compo-
nents is difcult. The treatment of contaminants with inorganic co-
agulants is not easy to scaling, replacing natural coagulants. The
efciency of POPs and xenobiotics removal in the coagulation and
occulating processes is determined by the velocity gradient, time, pH,
temperature and retention time. This technology is effectively used to
treat phthalic acid esters, petroleum hydrocarbons and halogenated
compounds (Nascimento et al., 2019). The electro-coagulation method
has been used to remove the endocrine-disrupting chemicals by using
amorphous aluminum oxide as a coagulating agent. Sweep occulation
mechanism promotes the rapid absorption of the soluble organic con-
taminants on the surface of the ocs and it is followed by ltration
Table 1
Various treatment methods employed for xenobiotic degradation.
Method of xenobiotic
treatment
Technologies used Advantages Disadvantages References
Physical methods Membrane ltration
Natural zeolite
Adsorption
Less solid wastes
Less use of hazardous
chemicals
Removal efciency is less
High investment and running
cost
(Asif et al., 2018)
(Kadam et al., 2019)
(Luo et al., 2018)
Chemical methods Chemical precipitation
Chemical coagulation
Electrochemical methods
Simple
High regeneration capacity
Highly selective
Chemical consumption is high
High capital cost
(Abdullah et al., 2020)
(Chen et al., 2020)
Biological methods Phytoremediation
Bioaugmentation
Phytovolatilization
Phytoaccumulation
Rhizodegradation
Bioremediation
phytodegradation
Energy expenditure is low
Environmental friendly
Cost/benet ratio is low (Chen et al., 2011)
(Jung and Ahn, 2016)
(Leong and Chang, 2020)
(Yu et al., 2020)
Nano treatment methods Adsorption and photocatalytic
degradation
High removal capability
High regeneration efciency
Scale-up is difcult (Moharrami and Motamedi,
2020)
(Xiang et al., 2020)
G. Karthigadevi et al.
Bioresource Technology 324 (2021) 124678
5
mechanisms (Cook et al., 2016).
2.1.2. Chemical precipitation method for the removal of xenobiotics
Xenobiotics contained in the personal care products largely contains
a class of emerging contaminants that include synthetic hormones,
parabens, surfactants and antimicrobials. Almost 70% of such contam-
inants showed poor removal efciencies, this has to be treated using
counter ion compounds (Biel-Maeso et al., 2019). Chemical precipita-
tion works primarily by modifying the chemical components of such
POPs to minimize the solubility of these compounds. This can be ach-
ieved by the addition of counter-ions to remove the ionic components
from the solution to precipitate the suspended solids (Pohl, 2020). This
process is used primarily for the treatment of industrial wastewater
containing organic contaminants like phenols or aromatic amines. By
adjusting the pH of a mixture with a high degree of selectivity it is also
possible to isolate heavy metals using this process. The downside is that
reagents are used to adjust the solubility of by-products which ensures
that the production costs are high to satisfy pure requirements.
2.1.3. Ammonium stripping method for the removal of xenobiotics
Ammonium stripping is used for the disposal of the recalcitrant
heavy metals and hydrocarbon that accumulate in particular in the form
of waste dumps. In contrast with other forms of treatment, this stripping
effectively extracts NH
3
-N-compounds with low operating costs. The
removal of ammonia-based nitrogen can be achieved via the separation
process for sludge dewatering. Change of pH, temperature, time, volu-
metric load, reactor conguration and air-liquid ratio can optimize
process magnitude (Kinidi et al., 2018). The major limitation of this
process is the release in the atmosphere of ammonia, which causes a
considerable effect on the environment.
2.1.4. Advanced oxidation method for the removal of xenobiotics
Advanced oxidation process (AOP) mainly involves the use of oxi-
dants to degrade organic pollutants that emit reactive oxygen species
(ROS) is needed. This approach refers to contaminants in the soil and
sediments in the water (Cuerda-correa et al., 2020). The degradation
process comprises 4 stages: (i) hydrogen abstraction, (ii) the addition of
free radicals, (iii) the combination of free radicals and molecules, and
(iv) electron transfer (Badmus et al., 2018). Most volatile organic
compounds such as PCBs, Dioxins and PHA are eliminated from the
production of free radicals by advanced oxidation methods. For
example, the electrochemical peroxidation technique uses electricity for
the generation of free radicals. It is an integrated AOP technique that
includes the Fenton, photocatalytic processes along with biological
treatment methods which can, in some respect, eliminate non-
biodegradable contaminants present in the synthetic wastewater (Mor-
eira et al., 2017). Earlier the recalcitrant xenobiotics are removed by
using hydroxyl radical based advanced oxidation process. Now the
recent researchers used sulfate radicals for the removal of ammonia
nitrogen in the wastewater even if it is in traceable amounts (Deng and
Zhao, 2015). Particularly, this AOP is a viable option for the treatment of
landll leachate and efuent organic matters. Radical oxidation of sul-
fate even in the treatment of AOPs is possible apart from this hydroxyl
radical oxidation. The hydroxyl radical dramatically controlled AOP is
used to eliminate inorganic contaminants and recalcitrant organic
matter. The sulfate radical-mediated AOP, which is not effectively
Table 2
Various types of xenobiotics, their impact on environment and degradation mechanisms.
Source of
xenobiotics
Xenobiotics type Xenobiotic
applications
Xenobiotic compound Impact on the soil and
water
Degradation mechanism References
Industrial wastes Chemical
Industries
Plasticizers Phthalate esters di-(2-ethylhexyl)
phthalate (DEHP) and di-n-octyl
phthalate (DOP), dimethyl phthalate
(DMP), diethyl phthalate (DEP), and
dibutyl phthalate (DBP)
i. Genetic aberrations
to the marine
animals
ii. Reproductive
defects in sh
Photocatalytic
degradation
(Pang et al.,
2021)
Textile Industries Acid dyes
Basic dyes
Mordants
Pigments
Additives
Direct Blue 6 Direct Black 38
Azo dyes
Pthaleine dyes
Indigo dyes
Anthraquinone dyes
Nitrosodyes
Synthetic dyes
i. Water contamination Electrochemical
degradation
Biodegradation
(Siddique
et al., 2011)
Pesticide wastes Pesticide
Industries
Pesticide
Herbicide
Insecticide
Organophosphate and organo-chlorine
compounds
Chlorinated hydrocarbons
i. Affect soil microbes
ii. Ground water
pollution
iii. Damage to
successive crop
generations
Microbial degradation (Kumar
et al., 2018)
Pharmaceutical
wastes
Pharmaceutical
industries
Analgesics Ibuprofen,
Paracetamol
i. Surface water
contamination
ii. Risk to aquatic
microbiome
Ozone oxidation
Coagulation
occulatiom
Membrane separation
(˙
Zur et al.,
2018)
Antibiotics Ampicillin, Ciprooxacin, Gatioxacin,
Sparoxacin, and Cepuroxime
i. Eutrophication
ii. Damage to the
microbial diversity
Biotransformation
Bioremediation
(Sharma
et al., 2017)
Anti convulsants Carbamazepine, Phenytoin
Valproic acid, lacosamide, lamotrigine,
oxcarbazepine, topiramate, and
zonisamide.
i. Toxic effects on
earthworms
UV photo-oxidation (Litskas
et al., 2019)
(Silva et al.,
2018)
Cosmetic wastes Personal care
products
Nail polish,
deodorants,
shampoos,
toothpaste, shower
gels
UV lters
Phthalates, triclosan, Parabens,
ethyleneoxide, 1,3 butadiene
i. Bioaccumulation
ii. Teratogenic effects
Carbocatalytic oxidation
and hydrothermal (HT)
hydrolysis
(Kang et al.,
2019)
Food processing
wastes
Food processing
industries
Genotoxins
cytotoxins
nitrosamines (NA), heterocyclic amines
(HCAs), and polycyclic aromatic
hydrocarbons (PAHs)
i. Surface water
contamination
ii. Methane generation
due to landlling
Anaerobic and aerobic
digestion
Bioremediation
(Nogacka
et al., 2019)
G. Karthigadevi et al.
Bioresource Technology 324 (2021) 124678
6
eliminated by the hydroxyl radical-mediated AOP, readily oxidizes
ammonia and nitrogen compounds (Guerra-Rodríguez et al., 2018). The
efciency of the treatment process was dependent on the physical-
chemical properties and operating parameters of organic pollutants.
Many other AOPs for recalcitrant waste treatment have been added,
such as ultrasound-mediated, electronic radiation beam-dependent
AOPs, ozone-dependent AOPs which are based on the 3-phase method
of hydrodynamic cavitations (nucleation, growth and collapse) methods
(Camargo-Perea et al., 2020; Giwa et al., 2021).
2.2. Nano treatment methods in the removal of xenobiotics and POPs
In recent years, the emergence of pollutants in the water environ-
ments are accelerated which possess greater risks to life. As the con-
ventional treatment methods do not effectively remove the pollutants
which are in minor dose levels, the nanomaterials with signicant
physicochemical properties offer a way to rule out all those limitations
(Cai et al., 2018). Various techniques such as adsorption (Manikandan
et al., 2021), photocatalytic degradation (Zhang et al., 2020a, 2020b),
membrane ltration (Chen et al., 2018) and ozonation phenomenon
(Song et al., 2019a, 2019b; Chen et al., 2021) have been explored by the
researchers for the application of engineered nanoparticles and their
specicity in the treatment of such pollutants. The design of various
novel nanomaterials using a variety of sources for the degradation of
pollutants and their mechanisms of reactions have been piled up. As the
nanomaterials possess inherent physiochemical and magnetic proper-
ties, the selection of the nanomaterial should be done accordingly to trap
the specic pollutant. The combination of nanomaterials with either
plant or microorganisms is also effectively involved in the trans-
formation of pollutants to achieve complete elimination from the
ecosystem.
2.2.1. Adsorption method for removal of xenobiotics
Activated carbon has microporous structures that aid in the ef-
ciency of the adsorption process in removing POPs (Pandiarajan et al.,
2018). The diffusion mechanism of the process and the activated carbon
decreases the soils pollutant sorption rate. The surface load density
varies depending on the material type and the electrostatic reaction of
the CA with the contaminant paves the way for the removal. This
approach effectively eliminates wastes based on optimizing pH as an
essential factor in the adsorption of toxins, phenol and trichlorophenol.
Due to its removal efciency, there is an increase in demand for this
technology, but the key limit is the cost incurred for the adsorption
process. So there is a need to nd alternative sources that possess better
adsorption as well as for the regeneration of components. This has been
done by integrating the surface phenomenon with the bioremediation
techniques to remove the aromatic hydrocarbons in the saline waste-
water (Gonz´
alez-Abradelo et al., 2019; Zhang et al., 2020a).
Pharmaceutical-based xenobiotic compounds are usually non-
degradable due to their high solubility nature. In such a case, the
adsorption process remains an effective option due to its process char-
acteristics. Now, the biosorbents are in trend for the treatment of
pharmaceutically active compounds due to their ability to remove the
contaminants completely without releasing any byproducts. Also, the
sorption process is economically feasible due to its high regeneration
capacity as well as its aids in bioaccumulation and biomagnication of
the wastes (Adewuyi, 2020).
2.2.2. Photocatalytic degradation for removal of xenobiotics
Photocatalysis includes primarily the use of irradiation to produce
photo charges that pass effectively to any surface and cause organic
contaminants to be mineralized (Qin et al., 2020). Due to their low cost,
chemical stability, and structure-dependent electronic properties,
several different semi-conductive materials are used as a photocatalyst
(Kar et al., 2020). To boost the degradation properties of such semi-
conducting materials, researchers tried to change material crystal
structures and surface properties. For the destruction of POPs, TiO
2
is
the commonly approved semiconductor material. The synthesis of
modied structures by combining other semiconductor materials with
ultrasound-assisted electronic deposition methods and techniques for
hydrothermal enhanced photocatalytic activity (Khani et al., 2019).
Furthermore, the heterogeneous photocatalysts play a key role in the
elimination of xenobiotics in water with super-hydrophilicity. The size,
surface, pore structure and pore volume of the semiconductive material
are the parameters that improve catalysis (Dong et al., 2015). Various
nano photocatalysts are set for the degradation of xenobiotics (Table 3).
2.3. Different types of nanomaterials in xenobiotic treatment
2.3.1. Nano-adsorbents in xenobiotics treatment
Carbon-based nano-adsorbents are widely used, such as activated
carbon, porous carbon, graphitized carbon and carbon nanotubes. Due
to hydrophobic, electrostatic, hydrogen bonding and covalent bonding
interactions, the carbon-based nano-adsorbents interact with contami-
nants. Each form has, among other things, several adsorption sites that,
with their exibility and physical chemistry, can absorb organic pol-
lutants (Kurwadkar et al., 2019). Single-walled and multi-walled carbon
nanotubes have been engineered to generate high energy sites in recent
years by modifying their surface chemistry (Rushi, 2019). Magnetic
nanoparticles are used effectively for the removal from usable sorption
sites of toxic compounds that function efciently as porosity increases.
Magnetic carbon nanotubes prepared by a variety of steps may be used
to alter the surface through carbon dots. From the results, a high
adsorption rate with high reuse potential has been observed (Deng et al.,
2019). The sol-gel methods are focused on multiple-walled carbon
nanotubes with a negatively charged surface which is primarily used in
cationic pollution removal (Konicki and Pełech, 2019). Polymeric nano-
adsorbents are porous (Moharrami and Motamedi, 2020) and attached
to magnetic nanoparticles that form core shells. This form of synthesis
resulted in the successful implementation of hybrid structures for
removing high absorption heavy metal ions with a large pH range.
2.3.2. Nano-lters in xenobiotics treatment
Since the implementation of the electrospinning process, ltration
Table 3
Photocatalytic degradation for treatment of wastes using nano-composites.
Category of wastes Photocatalytic agent Light source References
Tetracycline Sulfa-methazine Carbon nitride- Salicylic acid photocatalyst Visible light (Zhou et al., 2019a)
Methyl orange dye TiO
2
activated carbon nanocomposite UV light (Rashed et al., 2017)
Rhodamine B MoS
2
based hybrid photocatalyst SnO
2
/Ag/MoS
2
Visible light (Lu et al., 2017)
Methylene Blue MoS
2
-ZnO heterostructure Solar light (RitikaKaur et al., 2018)
Tetracycline (TTC) Tungsten oxide (WO
3
) on carbon nano-tube (CNT) Visible light (Isari et al., 2020)
Gemioxacin Zn-Co-layered double hydroxide (LDH) nanostructures UV light (Gholami et al., 2020)
Ibuprofen BiOBr/Fe
3
O
4
@SiO
2
Visible light (Khan et al., 2019b)
Petrochemical wastewater TiO
2
and ZnO nanocomposites Visible light/Solar light (Ani et al., 2018)
Rhodamine B TiO
2
/CNTs/rGO composites UVVis light irradiation (Huang et al., 2018)
Indigo dye Graphene WO
3
nanocomposite Visible light (Khan et al., 2019a)
G. Karthigadevi et al.
Bioresource Technology 324 (2021) 124678
7
technology has achieved milestones. Nanolters help to lower the so-
lutions ionic strength, reducing the organic pollutant hardness (Konicki
and Pełech, 2019). Different natural and synthetic polymers are used to
synthesize nanoporous membranes like polyvinyl uoride cellulose ac-
etate, polypropylene, polyacrylonitrile, etc. (Konicki and Pełech, 2019).
Nano-ltration work centered on a pressure-driven method that is ef-
cient in removing components in low molecular weight with size ranges
between 10 and 1 nm. It performs ltration based on hydrodynamics on
the membrane surface and membrane nanopores. The effectiveness of
the ltration depends highly on lter membrane charge, membrane
porosity and the membrane surface concentration polarisation (Abdel-
Fatah, 2018). Using electro-spinner technology for the development of
nano-brous membranes, high-quality interconnected, 3D membranes
are prepared (Vaz et al., 2019). Nanobers reject univalent, divalent and
multivalent ions effectively, so the most useful approach is for treating
arsenic components in potable water. Nano-ltration efciently elimi-
nates almost all dissolved salts under all ltration methods with lower
energy consumption and operating pressure (Le and Nunes, 2016). For
the removal of arsenic compounds, several nano-lter membranes are
available on a commercial scale (Tanne et al., 2019).
Nano-lters prepared with highly charged polyamide facilitate the
removal of arsenic compounds. Separation and elimination are typically
accomplished through physicochemical interactions between mem-
branes and pollutants, however, only nanoltration is possible in the
case of trace components such as pesticides. Nano-lters faced limita-
tions for dissolved organic compounds and uncharged pesticides
because of the spectrum of their molecular weights and the hydropho-
bicity nature of pesticide molecules. The nano-lter membrane was
rejected by 11 different forms of pesticides, including aromatic, hydro-
phobic and phenol compounds, and the polarity of the pesticides
affected membrane ltration capacity. The separation of charged pes-
ticides is effective since it is relatively close to membranes. Thus, the
nanolters with high hydrophilicity are prepared with non-polar
membranes to avoid organic fouling (Abdel-Fatah, 2018; Liu et al.,
2016).
2.3.3. Nano-bers in xenobiotics treatment
Membrane ltration plays an important part in water purication as
traditional methods for water treatment, such as occulation, sedi-
mentation, coagulation and activated carbon cannot remove organic
contaminants to meet the required conditions (Ezugbe and Rathilal,
2020). Diverse natural and synthetic polymers are used for nanopore
membrane syntheses, such as polyvinyl uoride, polypropylene, poly-
acrylonitrile, and these nanobers are effective in the removal of
wastewater micropollutants. Due to their loose bundles compared to
tubes and particles, nanobers have stable adsorption structures. The
adsorption of pesticide contaminants through molecular propagation
mechanisms is especially relevant. Nano-brous membranes used to
adsorb atrazine herbicides are polymerized to pyrrole. Nanobers made
from semi-conducting materials with a photocatalytic property can be
used for the treatment of industrial toxic chemicals. Composite nano-
bers made of titanium dioxide and polymers with graphene have a very
strong photocatalytic effect on various dye compound degradation. The
presence of sodium ions and calcium ions was strongly affected by the
removal of arsenic, as the contact with the membrane changed the ionic
potential of the membrane (Phan, 2020).
In wastewater treatment, these nanobers are effective in the purg-
ing of micro-pollutants which are endocrinologically active in the
environment (Khalil and Sch¨
afer, 2021). Carbon nanobers made of
polyacrylonitrile by the adsorption of pharmaceutical antibiotics using
electrical spinning techniques (Ciproaxin and Bisphenol) are found and
the overall absorbance ability is enhanced by a decrease of molecular
dimensions (Li et al., 2015). Nanobers used for the adsorption of
atrazine herbicide are polymerized on the PA6 nano-bres (Khalil and
Sch¨
afer, 2021). For the preparation of ultra-thin nanolms, the bio-
polysaccharide cellulose obtained from the bacterial cells is used. It
has been covered with a molecule of cyclodextrin and used for water
washing. In this lm, excellent adsorbents are found for removing
different POPs such as phenol, bisphenol A (BPA) and glyphosate (2, 4-
DCP). With excellent reusable property, the product demonstrated
optimal adsorption over a large variety of pH (Khalil and Sch¨
afer, 2021).
2.3.4. Nanocomposites in xenobiotics treatment
Nano-composites are organic matrices that are strongly inuenced in
contrast to micro-composite and monolithic agents by their adsorption
of contaminants (Srivastava et al., 2020). New hybrid matrices were
developed to sequester contaminants and to release toxic payload ef-
ciently through the combination of tunable properties, such as electrical,
mechanical and magnet properties. Due to their recycling ability in
comparison with other materials, nanocomposites acted as attractive
pollutant removal materials (Guerra et al., 2018). Nanocomposites can
be generated through a range of techniques such as co-precipitation
(Sahu et al., 2018), hydrothermal thermal deposition synthesis (Nas-
rollahi et al., 2019), sol-gel synthesis (Jaramillo-Fierro et al., 2020),
microwave synthesis (Omo-Okoro et al., 2020), chemical vapor depo-
sition (Omo-Okoro et al., 2020), surface-modication (Kumar et al.,
2017) and energy-efcient ball milling (Wei et al., 2020). Nano-
composite xenobiotic removal using adsorbents, ion exchangers, or
photocatalysts has many benets, its stability also poses challenges in
applications. There is a possibility of leaching of metal ions from the
nanocomposites occurs; so, the environmental maintenance cost and
production cost limits the commercial production of the nano-
composites. Different types of nanocomposites employed in the degra-
dation of xenobiotics are represented in the Fig. 2.
2.3.4.1. Graphene-based nanocomposites. Graphene is a carbon nano-
composite allotrope used predominantly in the treatment of inorganic
contaminants and oil hydrocarbons. It has many structural variations
and functions based on adsorption. The derivatives from carbon mate-
rials are produced to solve the problems because the activated carbon is
unable to eradicate and it is a persistent organic contaminant. As a
sorption material for the elimination of aromatic pollutants graphene
nanocomposites are fabricated in various forms (Zhou et al., 2019b).
The improved adsorption potential of phenanthrene compounds and
persistent contaminants is seen in nanoporous graphene as shown by the
BET (BrunauerEmmettTeller) performance. This is due to the presence
of delocalized
π
-electron in their structures, which interact with similar
stacking interaction in the aromatic rings of the pollutants. Since gra-
phene has functional oxygen-bearing groups on its surface, cationic
metallic contaminants such as cadmium, chromium and lead adsorption
are affected by their exponential abilities. This in turn also inuences the
adsorption capacity of cationic metallic pollutants such as cadmium,
chromium, and lead exponentially. Fe
3
O
4
-rGO nanocomposites contain
layers of graphene with high surface area helps in the removal of lead
and arsenic compounds (Vuong Hoan et al., 2016). High recyclability
was observed with this nano-composite helps in the removal of rhoda-
mine compounds (Vo et al., 2020). Iron functionalized with graphene
oxide has been used for the adsorption of fulvic acid efciently than
activated carbon (Ray et al., 2017). Amine functionalized graphene
nanocomposites are used for the removal of phenolic pollutants (Nimita
Jebaranjitham et al., 2019). Functionalization of the graphene nano-
composites with various compounds such as thiourea dioxide and iron
(III) oxide and tested for its adsorptive capacity with tetracycline pol-
lutants in the water. It is observed that thiourea possesses increased
adsorption due to the hydrophobic interactions with tetracycline mol-
ecules when compared with the magnetite compound (Lin et al., 2013).
Cellulose-graphene oxide adsorbent has been studied for its adsorption
capacity of the pesticide pollutant ametryn by Zhang and co-workers,
who observed that the adsorption rate was seven times less when
compared with the Fe
3
O
4
-graphene oxide when it is maintained at a
sample pH of about 5 (Zhang et al., 2015). From the results, it is
G. Karthigadevi et al.
Bioresource Technology 324 (2021) 124678
8
observed that the magnetite nanocomposites are effectively doing the
adsorption process when compared with graphene oxide
nanocomposites.
2.3.4.2. Magnetic nanocomposites. Iron (III) oxide is successfully used to
treat photocatalytic degradation of persistent organic pollutant
ibuprofen, impregnated with nanorods of Bi
2
O
4
. This nano-composite
can be recycled magnetically and reused with a higher efciency rate
ve times than other nanocomposites (Xia and Lo, 2016). Magnetic
nanoparticle embedded with activated carbon has been used for the
treatment of dyes in the order of adsorption efciency range for red basic
than nylosan blue and chromazurol (Muntean et al., 2018). For the
removal of the arsenic compounds self-assembled nanocomposites,
prepared using magnetic particles and silica. To prepare TiO
2
/grapheme
oxide/CuFe
2
O
4
reusable nanopropylene, simple ball milling technology
was utilized, adding the magnetic property to the CuFe
2
O
4
compound
that enhances photocatalytic further (Ismael et al., 2020). The photo-
catalyst allows 17 pesticide residues, which remain in the atmosphere
under UV radiation treatment, to be degraded. Polycarrageenine co-
polymers with polyvinyl acetate and Fe
3
O
4
have been tested with a
crystal violet dye solution to generate nanocomposite hydrogels and
their adsorption ability. The ndings show that the adsorption efciency
decreases with the ionic strength of crystal violet solution and increases
with the rise in carrageenin concentration (Mansoori et al., 2016).
2.3.4.3. Polymer clay nanocomposites. The nano polymeric structure
consists of natural or synthetic polymers that serve as a matrix, and
another compound is used to create polymer nanocomposites with a
ller material (clay). The matrix (polymer) used is the determining
factor in the degradation process; because, during chemical reactions
that take place at higher temperatures it is structurally modied (de
Oliveira, 2019). Because of the substantial technological advances, ef-
forts have been made to develop polymers that display excellent
temperature resistance. These thermo-resistant polymers are used to
apply xenobiotic component degradation in the environment (Pathak
and Navneet, 2017). Divinylbenzene was shown to be an extremely
adsorbed polystyrene matrix, lled with phenol, chlorophenol and
nitrophenol. Montmorillonite (MMT)-embedded alginate nano-
composite has been used to extract 4 nitrophenols and copper. The ef-
ciency of the degradation depends on the extent of the ll
encapsulation in the matrix. Polymer Clay (PC) poly(4-vinylepyridin-
costyrene) composite and Poly-di-allyl-Dimethylammonium Chloride
(PDADMAC) polymers are successfully used to minimize the concen-
tration of atrazine pesticide in MMT clay (Kohay et al., 2015). Com-
posite of magnetite/bentonite acts as an adsorbent mixture used for the
removal of pharmaceutical compound nitrofurazone content in the
water to an extent of 50% (Alekseeva et al., 2019). Adsorption is acti-
vated based on the temperature changes maintained during the process
which was studied using MMT (SWy-2)chitosan bio-nano composites
(SWCH) in the treatment of clopyralid from the aqueous solutions. The
removal efciency was higher due to the use of bio-polysaccharide in the
nanocomposite preparations (Alekseeva et al., 2019). Calcium alginate
beads nanocomposites loaded with iron oxide nanoparticles are used for
the adsorption of ortho nitrophenol compounds and maximum adsorp-
tion was taking place at a pH around 2 with a removal efciency of 96%
(Saif et al., 2019). Perlite beads coated with chitosan nanocomposites
have been shown higher adsorption rates at a pH of 7.0 (Parlayici,
2019). Poly (4-vinyl pyridine-co-styrene) and poly diallyl dimethy-
lammonium chloride with MMT nanocomposites were effective for the
adsorption of both trichlorophenol and trinitrophenol pollutant (Ding
et al., 2016).
2.4. Nanosponges in xenobiotic treatment
The earlier studies on cyclodextrin polymers indicate that cyclo-
dextrin polymers have shown that organic and apolar contaminants are
Fig. 2. Types of nanocomposites in pollutant degradation.
G. Karthigadevi et al.
Bioresource Technology 324 (2021) 124678
9
being extracted in sections of one trillion while zeolites and activated CO
in ppm amounts are removed. The cyclodextrin adsorption quality has
insolubility and will thus not improve even if it is recycled a few times.
Cyclodextrin compounds have interstitial pores in the internal cavities
where molecules of the host are bound, and they help to trap the hy-
drophobic molecules. This property supports them in various research
applications, especially for environmental applications. Cyclodextrin
nanosponges are applied for the sorption, even when present at the
smallest concentration, of chlorinated aromatic compounds such as 4-
chlorophenoxyacetic acid and 2,3,4,6-tetrachlorophenol from aquatic
solutions (Salazar et al., 2018). The layering of magnetically engineered
nanoparticles on sponges enhances the polymer properties and can be
obtained after pesticide sequestration is full. Further research has shown
the efciency of cyclodextrin nanosponges, impregnating the polycyclic
aromatic hydrocarbons (PAHs), tri-halogen methanes (THMs), mono-
aromatic hydrocarbons (BTX) and pesticides (simazine) with greater
efciencies on ceramic porous lter membranes. Cyclodextrin de-
rivatives (CDNS) were used to prepare nanosponges that act as rhoda-
mine B sorbents (Li et al., 2020).
CDNSability for adsorption varies depending on the structure of the
dye. The photocatalytic degradation of phenol has been tested in beta
cyclodextrin-nanosponge polyurethanes embedded in titanium-dioxide/
silver nanoparticles (Leudjo Taka et al., 2017). Cyclodextrin nano-
sponges can be strengthened to make composites that are used for
treating wastewater pollutants possible by functioning with nano-
polymeric beads, nano-part, dendrimers, nanomembranes, nanobers,
and carbon nanotubes. Synthetic nanosponge made from pure carbon
nanotubes is used for remediation of oil pollutants from the water. Nano-
sponges retain oil for recovery and reuse. Cyclodextrin-based, highly
cross-linked polymers made of two organo-clays (Dellite 67G and Dellite
43B used for the preparation of nanosponge) are used for the degrada-
tion of triclopyr (3,5,6-trichloro-2-pyridinyloxyacetic acid) with a
removal efciency of about 92% (V´
azquez-Nú˜
nez et al., 2020)
2.5. Nano-zeolites in xenobiotics treatment
Zeolites are natural microporous materials with a high potential for
ion exchange and were considered to be smart alternatives for the
remedy of dye contaminants. Efforts have been made to enhance the
ionic properties of zeolite and to alter its catalytic level and to degrade
waste (Li et al., 2017). But the use of zeolite as an adsorbent is restricted
because of certain characteristics: (i) very low permeability, (ii) loss of
adsorption potential when exposed to humidity in the air, and (iii) dif-
culty in removing highly suspended solids (Moosavifar et al., 2020).
Cadmium ions have been extracted with higher efciency for electro-
spinning of polyvinyl alcohol/zeolite nano adsorbents (Habiba et al.,
2017). The latest studies have shown the ability to extract the inorganic
cation and hydrophobic organic through surface alteration of natural
zeolites (Shi et al., 2018).
2.6. Nanosensors in xenobiotics treatment
Initially, the researchers made an effort to develop sensors for the
identication of pollutants in the atmosphere and the wastewater.
Nanotechnology-based microelectromechanical devices and nano-
contact sensors have been developed in miniature sizes for the detection
of pollutants based on environmental parameters (Willner and Vikes-
land, 2018); Nanotechnology has come to a step forward to degradation
along with the detection of pollutants, through photocatalysis using
semiconductor-based nanostructures (Willner and Vikesland, 2018).
Manganese doped zinc oxide nanowires have been used for the treat-
ment of harmful pesticide pollutants into harmless compounds such as
carbon dioxide, nitrogen and water in presence of visible light (Chen
et al., 2016). A cylindrical photochemical reactor with aqueous TiO
2
dispersions has been used for the degradation of (3,6-dichloro-2-
methoxy benzoic acid) in presence of a solar simulator (Andronic et al.,
2016). Nanolm sensors made of titanium dioxide thin lms have been
used for the degradation of endosulfan upon exposure to UV light within
45 min (Wang et al., 2016). Nanosensors are made of semiconductors
which are having the ability to identify the herbicide pollutants based on
the samples picked from the land. Complete adsorption and degradation
of the pollutants take place upon photodegradation (Saini et al., 2017).
2.7. Metal and metal-oxide nanoparticles in xenobiotics treatment
Metal nanoparticles gained much attraction over years in the treat-
ment of pollutants due to their nontoxic nature towards the environment
(Singh et al., 2018). Metals and metal oxide nanoparticles are broadly
applied in the removal of pesticide pollutants as they are having a large
number of surface reaction sites. They also can absorb the pollutants as
well as convert them into the less hazardous product so that it doesnt
cause any harm to the environment. Particle size plays a major role in
the remediation of the pollutant due to the size quantization property of
the nanomaterials (Chavali and Nikolova, 2019). Graphene oxide
nanoparticles have an ample amount of chemically bonded oxygen on
the surface so that they can able to bind to the metal ions due to elec-
trostatic interactions; this helps to promote the reactivity of graphene
oxide nanoparticles with arsenic metal ion pollutants make them
immobilize to the remediation to occur (Baraga˜
no et al., 2020).
Organophosphorous pesticides are effectively removed by the nano-
metal oxide nanoparticles and alumina (Rani and Shanker, 2018a).
Nonpolar pesticides are removed by C-18 impregnated magnetic nano-
particles. Zinc oxide nanoparticles are highly efcient in the removal of
many organic dyes and zinc oxide nanoparticles are successfully
employed for the complete removal of permethrin compounds through
rapid reactive adsorption mechanisms. Numerous works have been
carried out using different forms of iron oxide nanoparticles in the
removal of As (V) and As (III) pollutants (Rani and Shanker, 2018b).
Additionally, the zerovalent forms of iron oxide nanoparticles have been
applied for the treatment of industrial efuents containing metallic
pollutants such as selenium, arsenic, cadmium, chromium and lead from
the waste streams; nano zerovalent iron also possesses dechlorination of
halogenated pesticides, herbicides, radionuclides and organic com-
pounds. The nitroaromatic compounds such as atrazine, diazinon and
diuron can be converted into corresponding amines into very low con-
centrations with nZVI compounds (Pasinszki and Krebsz, 2020).
TiO
2
nanoparticles exhibit photocatalytic properties when they
interact with UV light irradiations. The hydroxyl radicals are released
upon excitation by the nanoparticles that interact with pesticides. From
the reports, it is studied that dicofol is one kind of chlorinated pesticide
that interacts with the titanium dioxide nanoparticles which will be
converted to less toxic chlorine compounds; almost all the chlorinated
pesticides will be degraded in a shorter duration. Surface modication of
the nanoparticles can be done by changing the size, doping of noble
metals, increasing the surface active sites and the shape of the nano-
particles to improve the adsorption capacity. Another frequently used
nanoparticle with high thermal stability is the nano alumina which is
mainly used for the removal of mercury pollutants. Silver nanoparticles
are designed with antimicrobial properties to nullify the issues that
occur by fouling of the membranes. The nanoparticles can change the
membrane qualities such as hydrophilicity, membrane permeability,
uniformity, the time of separation and fouling resistance (Mahmoudi
et al., 2019). Biogenic nanoparticles possess unique properties that are
successfully employed for the treatment of metal contaminated soil as
well as water without causing any side effects (Fang et al., 2019).
3. Benets and limitations for the adoption of nano-treatment
methods
The adoption of nano-treatment approaches for the removal of
contaminants from wastewater, advantages and limitations are outlined
in Fig. 3. Nanomaterials in the form of sorbents for the treatment of
G. Karthigadevi et al.
Bioresource Technology 324 (2021) 124678
10
contaminants are distinct. Temperature, pH, nano adsorbent doses and
contact time are the key factors affecting the treatment processes. In
recent years, there have been restrictions on the applications of nano-
technology. Each government has identied particular structures and
they are different for each country. Many of the challenges related to
pollution treatment are newly tackled in nanotechnology. The use of
nanomaterials provides bioavailability in the transport and processing
of contaminants in the environment. Biodegradable materials tend to be
a way to prevent bioaccumulation in the preparation of nanomaterials.
The new technology experiments have been performed to concentrate
on pollution capture at the site, as the problems of non-targeted pro-
cedures are avoided. Production of the engineered nanoparticles mainly
for the treatment of contaminants is prepared with special properties
such as targeted pollutant capturing, use of biodegradable raw materials
that can regenerate and recycle nanomaterials. The method of synthesis
should furthermore prevent the formation of agglomerates and stable
nanomaterials. Analysis of potential toxicity, the development of by-
products during synthesis and the costs of recovery should be given
considerable attention. Process design and optimization can be achieved
by knowing these procedures to produce possible nanomaterials for
contaminants removal in the environment.
Various researchers have attempted to remove the halogenated
xenobiotic compounds which are a major threat to the environment. For
this, the existing bioremediation technologies in combination with
nanotechnology approaches are employed to remove such compounds
from the surface layers of the ecosystem. In case of adverse natural
climatic conditions, the concentration levels of the xenobiotic may in-
crease or decrease, organisms become sensitive to eliminate the com-
ponents. Advancements in next-generation biotechnological tools and
the functionalization of nanomaterials and offer a feasible solution to
the remediation of pollutants in such conditions (V´
azquez-Nú˜
nez et al.,
2020). Though the removal has been done, some of the nanomaterials
have been released unintentionally which is undesirable for maintaining
a sustainable environment. On the other side, there is no evidence for
the safety of using the components at nanoscale. However, nano-
bioremediation techniques involve the concept of biological removal
methods which possess an advantage over the chemical treatment
methods in terms of degradation capabilities.
4. Challenges and perspectives
The release of xenobiotic chemicals is increasing in dose levels as the
consumers are increasing every year. Treatment of contaminants at
ground level and the surface water level has been done using conven-
tional techniques but they fail to meet the zero elimination of wastes.
Despite the chemical treatment technologies greater potential for the
removal of a xenobiotic compound, most of the aspects of feasibility and
safety have issues in the point of the economy. After the onset of
nanotechnology principles, there is a rise of innovative treatment op-
tions for the selective removal of wastes. From an environmental point
of view, nanomaterial usage has challenges in manufacturing methods
and applications. Different approaches have been tried to improve the
properties of the nanomaterial using engineering principles to avoid the
release and transport of nanoparticles in the environment.
Until now, most of the barriers faced in the treatment of xenobiotics
have been solved using nanotechnology under laboratory level experi-
ments. From the observations, it was found that the research could be
improved in the following objectives to improve the removal of xeno-
biotic compounds. The major ndings are: (i) surface properties of nano
adsorbents can be altered and it could be effectively utilized for
Fig. 3. Advances and limitations of adopting nano-treatment approaches in POPs and xenobiotic removal.
G. Karthigadevi et al.
Bioresource Technology 324 (2021) 124678
11
contaminant removal from the surface water, (ii) the ability of photo-
catalysts with interface properties for efcient degradation of dye-based
components, and (iii) the improvements could be done in terms of
reusability, material cost and a lifetime of nanomaterials using compu-
tational methods offer the possibility to develop materials with unique
functionalities.
5. Conclusions
In the light of future environmental and health safety legislation in
particular for wastewater restoration and recycling, xenobiotic trace
pollutants should be eliminated. To eliminate these emerging pollutants,
technological and economic factors are critical parameters for choosing
the appropriate treatment scheme. EDCs and PPCPs are degraded to a
great extent by the compound class and method of the treatment pro-
cedure. The government must make people aware of the POPs and make
them realize their deadly consequences. Researchers need to be moti-
vated to design more biodegradable nanomaterials to eliminate POPs in
an environmentally friendly manner in the future.
Declaration of Competing Interest
The authors declare that they have no known competing nancial
interests or personal relationships that could have appeared to inuence
the work reported in this paper.
Acknowledgements
The authors are thankful to The Management of Sri Venkateswara
College of Engineering, Sriperumbudur, India, Saveetha School of En-
gineering (SIMATS), Chennai, India and The Management, Vice-
Chancellor, Dean, SMNS and Head of Biological Sciences, The Copper-
belt University, Kitwe, Zambia for their constant support to complete the
review article. The Shaanxi Introduced Talent Research Funding
(A279021901), China and The Introduction of Talent Research Start-up
fund (No. 00700-Z101022001), College of Natural Resources and
Environment, Northwest A&F University, Yangling, Shaanxi Province
712100, China for the nancial support.
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