Chemosphere 292 (2022) 133380

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

Remediation of noxious wastewater using nanohybrid adsorbent for

preventing water pollution
Pooja Sharma a, *, Kavita Nanda b, Mamta Yadav b, Ashutosh Shukla b, Sudhir Kumar Srivastava c,
Sunil Kumar a, **, Surendra Pratap Singh b, ***
a
CSIR-National Environmental Engineering Research Institute (CSIR-NEERI), Nagpur, 440 020, India
b
Plant Molecular Biology Laboratory, Department of Botany, Dayanand Anglo-Vedic (PG) College, Chhatrapati Shahu Ji Maharaj University, Kanpur, 208 001, India
c
Chemical Research Laboratory, Department of Chemistry, Dayanand Anglo-Vedic (PG) College, Chhatrapati Shahu Ji Maharaj University, Kanpur, 208001, India

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

• Removal of toxic elements from waste­

water effluent is very important.
• Nanohybrid absorbent is useful in
improving quality of treated water.
• Nanohybrid absorbents are advanced
remediation technology for reuse of
wastewater.

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

Handling editor: Hafiz M.N. Iqbal Removal of toxic elements from wastewater effluent has got a lot of attention because of their severe negative
effects on human and environmental health. In the past few years, rapid urbanization and industrial activities in
Keywords: developing countries have exacerbated the destruction of the environment. Most of the wastewater effluents are
Detoxification discharged untreated or inadequately treated, which has become a major concern due to its impact on sus­
Nanotechnology
tainability and the environment. This is imperative to implement, innovative and resourceful wastewater
Wastewater treatment
treatment technologies requiring low investment. Among the various treatment technologies, cutting-edge
Kinetics
Water purification processes in nano-material sciences have recently piqued the interest of scientists. Nanohybrid absorbents
have the potential in improving wastewater treatment and increase water supply by utilizing unconventional
water resources. Carbon nanotubes, titanium oxide, manganese oxide, activated carbon (AC), magnesium oxide,
graphene, ferric oxides, and zinc oxide are examples of nano-adsorbents that are used to eliminate pollutants.
This also demonstrated the effective removal of contaminants along with the harmful effects of chemicals,
colorants, and metals found in wastewater. The present manuscript examines potential advances in nanotech­
nology in wastewater treatment for the prevention of water and soil pollution. This systematic review aims to
highlight the importance of nanohybrid absorbents treatment technology for wastewater treatment and to
explain how nanohybrid absorbents have the potential to revolutionize industrial pollution. There are also other

* Corresponding author.
** Corresponding author.
*** Corresponding author.
E-mail addresses: sharmaspspooja@gmail.com (P. Sharma), s_kumar@neeri.res.in (S. Kumar), spsinghbiome@gmail.com (S.P. Singh).

https://doi.org/10.1016/j.chemosphere.2021.133380
Received 28 September 2021; Received in revised form 13 December 2021; Accepted 18 December 2021
Available online 22 December 2021
0045-6535/© 2021 Elsevier Ltd. All rights reserved.
P. Sharma et al.
published review articles on this topic but the present review covers an in-depth information on nano-adsorbents
and their targeted contaminants.
1. Introduction
Water scarcity and pollution are considered undeniable global
problems and a significant challenge that must be addressed (Jain et al.,
2020). Pollutions in water are generally associated with a huge quantity
of discharged wastewater into the environment through industrial, and
sewage sources. Furthermore, due to the wide range of pollution sour­
ces, such as hospitals, dwellings, veterinary services, industries, agri­
culture, and their various application methods, the composition and
characterization of wastewater are entirely different and complex
(Shahedi et al., 2020; Lambropoulou and Nollet, 2014; Sharma et al.,
2021a, b, c). New advances in nanotechnology have revealed that
combustion, sonochemical, solgel, chemical, microwave, mechanical,
and other methods can be used to generate nanomaterials (Rangari
et al., 2017; Biswas et al., 2017, 2019). Researchers created nano ad­
sorbents for the treatment of wastewater to solve the limitations of
conventional adsorbents (Aguilar-Pérez et al., 2020 & 2021; Ali et al.,
2012). Nano adsorbents have several physico-chemical characteristics,
such as conductivity, strong chemical reactivity, high surface area,
catalytic, selectivity, magnetic, and optical properties (Kalfa et al., 2009;
Hurt et al., 2006; Ilisz et al., 2003; Li et al., 2003; Donlan et al., 2009).
Persistent organic pollutants (POPs) are among the substances that
may exist in wastewater that are hard to eliminate (Bilcke, 2002). Pol­
lutants are organic molecules that are resistant to chemical, photolytic,
and microbiological breakdowns (El-Shahawi et al., 2010; Sharma,
2021). They are characterized by semi-volatility, bioaccumulation, hy­
drophobicity, and toxicity as well as their extended persistence in the
environment according to the Stockholm Convention (Betianu and
Gavrilescu, 2006). Solvents, such as pesticides, coloring agents, and
industrial chemical by-products with a variety of elemental composi­
tions, such as perfluorinated compounds, dioxins, and polycyclic aro­
matic hydrocarbons (PAHs), are emerging pollutants (El-Shahawi et al.,
2010; Betianu and Gavrilescu, 2006; Trojanowicz, 2020). Protecting
water systems, humans, wildlife, and vegetation from these pollutants is
very critical (Atrous et al., 2019). Traditional wastewater treatment
methods, such as adsorption, electrocoagulation, membrane filtration,
flocculation, and coagulation have been extensively improved in the
recent decades to address the ineffectiveness.
The significant amount of these contaminants together with their less
degradation indicated environmental risk (Lofrano et al., 2013; Sharma
and Kumar, 2021a b; Sharma and Singh, 2021a, b; Sharma and Rath,
2021). Many studies, including precipitation, membrane filtration,
advanced oxidation, flocculation-coagulation, ozonation, ion exchange,
and oxidation have been conducted in the last decade to treat these
compounds from wastewater (Salleh et al., 2011). These technologies
have several drawbacks, including high energy expenditures,
by-product development, material regeneration, and disposal needs
(Salleh et al., 2011). The adsorption method is often used due to its ef­
ficiency, ease of application, and simple design. This has piqued the
interest of experts to reduce hazardous contaminants (Pathania et al.,
2017; Ahsaine et al., 2018a,b). The cost, removal efficiency, and its
engineering suitability influence the efficiency of an adsorption process
(Anfar et al., 2018). Researchers have experimented with various ad­
sorbents to boost the adsorption capacity of the adsorbent (Sabarinathan
et al., 2019). Furthermore, AC adsorption is one of the most investigated
processes. Many researchers have long known that AC composites are
effective adsorbents for removing a variety of contaminants (Zbair et al.,
2018a). Several researchers from around the world have examined the
adsorption mechanism and the reactions (Tran et al., 2017). The goal of
this review is to discuss the effectiveness of nanohybrids for eliminating
organic and inorganic pollutants from polluted industrial wastewater.
2
Chemosphere 292 (2022) 133380
The application, and prospects of nanohybrids for wastewater detoxifi­
cation are also covered in this review.
2. Wastewater and their composition
Wastewater contains a variety of toxic and deadly components
coming from a variety of sources, including industrial, sewage, and
agricultural waste, etc. (Sharma et al., 2021d, e, f, g; Tripathi et al.,
2021). It can be differentiated by its chemical composition, physical
appearance, and microbial masses (Ritter et al., 2002). In general,
wastewater is produced by normal living processes (Rajasekhar et al.,
2018; Rodriguez-Proteau and Grant, 2005). One of the most serious
threats to the world’s sustainable growth is the water supply and
pollution management issue (Vörösmarty et al., 2010; United Nations
Educational, 2018). One of the 17 Sustainable Development Goals
(SDGs) recommended by the United Nations (UN) in 2015 is clean water
and sanitation (United Nations Development Programme, 2015). The
consumption of water globally is now predicted to be around 4600
km3/year with a projected growth of “20–30% to 5500–6000 km3/year
by 2050” (Burek et al., 2016). Contaminants, such as fertilizers, anti­
biotics, heavy metals, and organic chemicals have become much more
prevalent in the aquatic system as a result of urbanization and indus­
trialization (Wen et al., 2017; Penuelas et al., 2013; Tong et al., 2017).
Although wastewater has several environmental and health concerns, it
provides a low-cost supply of nutrients, such as phosphorus and nitro­
gen, which are beneficial to crop productivity (IWMI and RUAF, 2002;
Scott et al., 2004; Sharma et al., 2020a,b). Inorganic pollutants like
metals, that have a high tendency to be absorbed by soil colloids and
change the soil and microbial properties (Bruins et al., 2000). Drinking
water contains complex pollutants, which contribute to soil deteriora­
tion and harm the environment and ecosystem worldwide (Chen et al.,
2016; Li et al., 2013).
In developing countries, wastewater is the main source of irrigation
for agriculture. This wastewater is used to irrigate more than 20 million
hectares around the world (Drechsel et al., 2002). Untreated wastewater
is currently being thrown in vast quantities into the natural environment
and farmers are using this for irrigation purpose (UNESCO, 2003). A
major pollutant in aquatic environment is municipal wastewater (Chen
et al., 2017; Du et al., 2020). The chemical composition of the influent
wastewater as well as the treatment techniques used has a significant
impact on the sewage sludge quality, which is the primary by-product of
wastewater treatment (Zhang et al., 2017; Turek et al., 2019; Tytła,
2019). Various pollutants in wastewater are in sewage sludge (80–90%),
and therefore dumping the sludge into water bodies can significantly
increase the organic load, resulting in a reduction in dissolved oxygen
(DO) levels and nutrient cycling (Okoh et al., 2007; McCasland et al.,
2008). Standard wastewater treatment techniques do not ensure the
calculable elimination of pollutants, which can result in the second
round of pollution after being discharged (Cantinho et al., 2016). Bio­
logical or chemical pollutants can be present in the discharged effluent.
Microbial pollution can come from human or animal faeces, which can
carry a variety of viruses, protozoa, and bacteria that can cause disease
in humans (Ohoro et al., 2019; Akpor, 2011). Waste is a heterogeneous
mixture composed of 99.9% water and remaining 0.1% of suspended
solids (350–1200 mg/L), organic compounds, such as faeces, toilet
paper, food waste, dissolved biodegradable organics, such as proteins,
carbohydrates, and lipids, inorganic solids, such as sediment soil, salts,
metals, and particulate stuff with a chemical oxygen demand (COD) of
250–1000 mg/L, and several microorganisms (up to 109 number/L)
(Warwick et al., 2013). In wastewater, approximately 63% of phosphate
compounds have been identified as a soluble fraction (Warwick et al.,
P. Sharma et al.
2013). The composition of different organic and inorganic pollution
loads has been shown in Fig. 1.
2.1. Organic pollutants
The globe has evolved enormously in the recent years in all the
sectors, including mankind, society, science, and technology. As a
consequence, a growing number of dangerous pollutants are found in
aquatic habitats (Srivastava and Majumder, 2008). High colors are
found in wastewater from industrial processes, such as food, dying,
plastics, leather, rubber, and cosmetics (Pathania et al., 2017). The
annual dye output is over 7–105 tons, with about 10,000 different va­
rieties of dyes (Perkins, 1991). The issue is that during manufacture and
processing, more than 15% of these colors are present in industrial
wastes (Anfar et al., 2018). For example, these chemicals are extremely
hazardous. Rhodamine B (RhB) has the potential to harm humans and is
suspected of being cancer-causing (Anfar et al., 2018). Acridine orange
has been the subject of extensive research due to its potentially harmful
biotic consequences (Zbair et al., 2018b). Methylene blue can cause
cyanosis, eye burns, elevated heart rate, and diarrhoea in humans
(Ahsaine et al., 2018a,b). Humans are at risk from crystal violet, which
causes cancer (Ahsaine et al., 2018a,b). Furthermore, benzene groups
can be used to detect hazardous compounds that are difficult to break
down or eliminate and cause significant water pollution (Tatarchuk
et al., 2019). For example, 2,4,6-chlorophenol, a phenolic chemical that
was widely employed as an antiseptic, pulp bleacher, and insecticide for
leather and woods are identified as a priority persistent pollutant (Yang
et al., 2019). Diuron (3-(3,4-dichlorophenyl)-1,1-dimethyl urea) is one
of the most persistent and hazardous herbicides with a half-life of 370
days in ecological habitats. It has major pollution concern (Meephon
et al., 2019).
Fig. 1. Composition of wastewater effluent in environment. (Percentage of organic and inorganic waste was taken from Jain et al., 2021).
3
Chemosphere 292 (2022) 133380
2.2. Inorganic pollutants
Inorganic pollutants, such as heavy metals (Fe, Ni, Cu, As, Zn, Cr, Cd)
are the most common pollutant which is present in wastewater (Sharma,
2021). Toxic metals are most commonly released by industries, such as
pulp paper, plating, mining, battery, ceramics, and glass manufacturing
(Khraisheh et al., 2004; Sharma). Metals on the surface of microbiota
and within cells can disrupt living organisms’ metabolic cycles (Sri­
vastava and Majumder, 2008). These pollutants are extremely toxic and
typically non-biodegradable, allowing them to bioaccumulate via the
food chain (Inyang et al., 2016). The Comprehensive Environmental
Response Compensation and Liability Act (CERCLA, 2011) has classified
heavy metals in order of toxicity Pb (2) Hg (3) > Cd (7) > Cr (17) > Co
(52) > Ni (57) > Zn (75%), U (97), Cu (125) > Mn (140) (Inyang et al.,
2016). The maximum contaminant level (MCL) values as per EPA was
defined as Hg (0.002 mg/L), Cu (1.3 mg/L), Pb (0.015 mg/L), Cr (0.1
mg/L), Cd (0.005 mg/L), Zn (5 mg/L), and Mn (0.05 mg/L)” (Srivastava
and Majumder, 2008). The high concentrations of these pollutants and
less biodegradability pose a severe risk to the environment (Lofrano
et al., 2013). Many studies like advanced oxidation, membrane filtra­
tion, flocculation-coagulation, oxidation, ozonation, precipitation, and
ion exchange have been conducted in the last decade to treat these
compounds from wastewater (Salleh et al., 2011). Because of its effec­
tiveness, ease of implementation, and design, the adsorption method is
frequently employed. This has piqued the interest of scientists to reduce
hazardous contaminants (Pathania et al., 2017; Ahsaine et al., 2018a,b;
Mullick and Neogi, 2018).
3. Wastewater: risk assessment
Ecological risk assessment (ERA) is a process that collects, organizes,
and analyse the environmental data to evaluate the risk or probability of
negative effects on life forms, populations, or biosphere induced by
multiple stressors associated with human activities (Ashraf et al., 2014).
P. Sharma et al. Chemosphere 292 (2022) 133380

Numerous papers describe the fundamental principles of ecological risk Table 1

assessment (Caeiro et al., 2005). Heavy metal-induced soil contamina­ Source of pollutants and their adverse effects.
tion has deleterious consequences for the macrofauna of soil (Nahmani Source Pollutants Effects References
et al., 2005; Tessaro et al., 2016). Pollutants contamination reduces
Nutrients Fertilizer Effect on Ma et al. (2018)
biomass activity, resulting in denaturation of protein, disruption of pollutants eutrophication
functional activity, and soil degradation. For instance, soil pollutants process
influence the reproduction, population survival, and functioning of Domestic Sewage and Waterborne diseases Rajasulochana
earthworms, a critical bio-monitor organism for soil contaminants wastewater contaminated water and Preethy
(2016)
(Peijnenburg, 2002; Hirano and Tamae, 2011). Pb can be permanently Marine debris Macroscopic Plastic pollution Hlongwane et al.
retained in earthworm waste nodules (Mostafaii et al., 2016). Beetles pollutants (2019)
responded to organic and chemical fertilizer to improve soil quality and Different Radioactive Bones, teeth, skin Bayoumi and
yield according to Tessaro et al. (2016). Beetles are an important group Isotopes pollutants and can cause Saleh (2018)
Municipal Industrial Water Caused water Liu et al. (2018)
of soil organisms as soil bioindicators (Brown et al., 1999). Arsenic has
pollutant pollutants and air pollution.
carcinogenic effects, such as epigenetic changes, damaged dynamic DNA Inorganic Metals compounds, Aquatic flora and Sizmur et al.
maintenance system, and the production of reactive oxygen species pollutants trace elements, fauna, public health (2017)
(ROS), such as superoxide (O2), hydrogen peroxide (H2O2), nitric oxide inorganic salts, problems
(NO), and singlet oxygen (1O2) (Martinez et al., 2011). The heart, brain, heavy metals, and
mineral acids
and blood arteries as well as gastrointestinal tissue are all affected by Detergents, Organic pollutants Aquatic life Wang et al.
chronic As contamination. Chronic As toxicity results in irreversible insecticides, problems, cacogenic (2019)
alterations in the organs, such as skin cancer, bladder cancer, and liver herbicides.
cancer, as well as increased mortality rate (Reasoner and Geldreich, Agricultural Agricultural Directly affect the Tang et al.
chemicals pollutants freshwater (2016)
1985). Cd and its conglomerates cause a variety of health problems in
resources
people, which are exacerbated by humans’ inability it through the Pathogens Viruses and bacteria Water borne Khalid et al.
kidney (Satarug, 2018). Exceeding this limit causes illness, such as lung diseases (2019)
damage and respiratory discomfort (Mudgal et al., 2010). Stomach Land Sediments and Damaging fish Richter and
discomfort, vomiting, and diarrhoea, proximal tubular cells, and bone cultivation, suspended solids spawning, affecting Ayers (2018)
demolition, aquatic
demineralization are all caused by Cd (Jaishankar et al., 2014. Cr has a
mining environment of
proclivity for corroding and causing allergic reactions in humans. Cr operations insects and fishes
tends to corrode and cause allergic reactions in the body. Above a
certain dose, serious respiratory, cardiovascular, neurological, and
haematological consequences as well as death (Shekhawat et al., 2015). and biological contaminants must be monitored; however, most
Hg often known as quicksilver is a natural chemical element that can be measuring projects focus on a limited number of specific contaminants
found in the environment in the form of organic, and inorganic. (USEPA, 2004a; USEPA, 2004b). Because of the significant increase in
Water-soluble forms of Hg, ingestion of any kind, or inhalation of Hg antibiotic resistance in both the clinic and the environment, ARBs,
vapor can all induce toxicity (Zahir et al., 2005). Hg intake during pharmaceuticals, and antibiotic resistance genes (ARGs) as well as in­
pregnancy harms the foetus, transmitting its toxicity via food and fections are now being detected and removed from industrial water
breastfeeding to babies (Berlin and Ullberg, 1963). Hg vapor inhaled as a (Luddeke et al., 2015; Jäger et al., 2018; Ventola, 2015; Al-Gheethi
red blood cell attached penetrates the brain (Eggleston and Nylander, et al., 2018; Weinberg and SingerMeyer,). Different treatment technol­
1987). Higher amounts of mercuric vapor exposure may cause anorexia, ogy for the wastewater has been shown in Fig. 4. Some treatment stra­
neurological dysfunction, and DNA repairs disruption gastrointestinal tegies are described in this section (see Fig. 5).
disturbances (Crespo-López et al., 2009). Hg exposure causes hyper­
tension, rage, carotid atherosclerosis, anxiety, and sometimes even 4.1. Absorbents and nano-absorbent
sadness (Siblerud et al., 1994). The effect of Pb in the human body with
regular physiological functions can result in irreparable health problems The literature covers biotechnology, membrane processes, radiation
(Kalia and Flora, 2005). Excessive amounts of Pb in the blood harm the processes, catalytic processes, ionizing and magnetically assisted pro­
neurological system (Goyer, 1993). Chronic Pb poisoning causes recur­ cesses wastewater treatment methods (Saleh and Gupta, 2012; Ngo and
rent vomiting, seizures, and death. The erythrocyte’s life span is reduced Guo, 2009; Ambashta and Sillanpää, 2010). One of the most studied
when the cell membrane becomes more fragile (Lockitch, 1993). Renal approaches for removing pollutants from the aqueous mixture is
impairment is caused by high levels of Pb exposure (>60). The biggest adsorption (Jiuhui, 2008). Adsorption is popular because of its excellent
place for lead build-up in the body is the bone (Flora et al., 2012; effectiveness and ease of use (Han et al., 2008). It is low cost, flexibility,
Renner, 2010). Table 1 and Fig. 2 show the risk assessment of waste­ ease of operation, and performance against a variety of pollutants.
water effluent on human health. Nano-adsorbents are nanoparticles (NPs) having a high adsorption af­
finity produced from organic or inorganic sources. They are extremely
4. Treatment technologies effective at isolating a wide range of pollutants of various molecular
sizes due to their large specific surface area, porosity, and active surface
The primary sources of pollution like industrial, medicinal, and (Santhosh et al., 2016; Pacheco et al., 2006). Regeneration is another
wastewater treatment can damage surface waters (USEPA, 2004a; important feature of nano-adsorbents. Yang et al. investigated the
USEPA, 2004b). Heavy metals, detergents, pathogens, and desorption of hydrocarbons from carbon nanoparticles in water in 2007
antibiotic-resistant bacteria (ARB) are among the chemical and biolog­ (Yang and Xing, 2007). The adsorption capacities of nano-metal oxides
ical pollutants that enter wastewater treatment plants (Anjali and at different pH have been provided in Table 1.
Shanthakumar, 2019; USEPA, 2004a; USEPA, 2004b). Inadequate For wastewater treatment, a vast number of nano-adsorbents are
wastewater pollution elimination harms both the environment and the used. They have been discovered to be extremely efficient at eliminating
economy (Wakelin et al., 2008; Naidoo and Olaniran, 2014). Waste­ contaminants from water. Therefore, it is impossible to do a direct ca­
water treatment plants effluent intermixes with sources of drinking pacity comparison because it is dependent on some factors, like the
water in places like the United States’ Great Lakes region (Sedmak et al., shape and size of the NPs as well as operating variables, such as tem­
2005; Blair et al., 2013; Kim and Aga, 2007). In these locations, chemical perature, pH, reaction duration, and experiment design. Removal of

4
P. Sharma et al. Chemosphere 292 (2022) 133380

Fig. 2. Risk assessment of wastewater effluent on the human health.

heavy metals from wastewater by adsorption using nano-adsorbents has 4.1.2. Graphene
been provided in Table 2 & Fig. 3. The nano-adsorbents are divided into Despite their effectiveness against a wide range of water toxins,
different categories which are also presented in this section. graphene family adsorbents have not been studied as thoroughly as
CNTs and activated carbon. Graphene-based adsorbents, such as gra­
4.1.1. Activated carbon phene oxide and reduced graphene oxide can adsorb a wide variety of
The common carbon-based adsorbent is AC. Despite having a similar chemicals, such as synthetic organic and inorganic pollutants (Huang
surface area to carbon nanotubes (CNTs), activated carbon is not suit­ et al., 2011; Li et al., 2013). Graphene Oxide (GO) was used as a carbon
able for big organic compounds. These large organic compounds, such as nanotube alternative and as a treating wastewater solution (Zhao et al.,
most antibiotics and medicines, are frequently inaccessible to its mi­ 2014). CNTs’ inner walls are not accessible for adsorption of aqueous
cropores (Chowdhury, and Balasubramanian, 2014). CNTs are best media (Huang et al., 2011). Furthermore, the adsorption properties of
suited for adsorption of such compounds due to larger holes in the organic contaminants in aqueous environment have been studied but at
bundles formed in aqueous media and more accessible adsorption sites. a much lower level than the carbon allotropes (Sitko et al., 2013). The
In 2010, Yang and Xing used Carbon NPs for organic chemical adsorp­ structure and absorption sites of graphene sheets have been shown in
tion in an aqueous medium (Yang and Xing, 2010). It was revealed that Fig. 3.
organic compounds with low molecular weight had a poor adsorption
affinity for AC. Because of their various pollutant-CNT interactions, 5. Factors affecting adsorption processes
CNTs absorb a considerable amount of these organic compounds (Qu
et al., 2013a,b). Notwithstanding its limitations, activated carbon is a Temperature, pH, adsorbent dose, and incubation/contact time are
popular and effective adsorbent (Saleh and Gupta, 2014). all the factors that influence heavy metals adsorption from wastewater
using nano-adsorbents. According to Srivastava et al. (2015), pH has a
significant impact on adsorption of heavy metals from wastewater. At
pH 5.5, the maximum adsorption of Zn (II) on magnetic nano-adsorbent
was observed. Maximum adsorption of Pb (II) and Cr (III) are 93% (pH
Table 2 6.0) and 99.6% (4.0), respectively (Lingamdinne et al., 2016).
Adsorption capacities of nano metal oxides at different pH for various pollutants.
Furthermore, increasing contact time also increases the heavy metal’s
S. Adsorbate Absorbent pH References adsorption from an aqueous solution. Adsorption of heavy metals is
No.
initially high due to the high concentration of metals but begins to
1. Ni (II) γ-Al2O3 – Tarasevich and Klimova, decline due to active site blockage (Shirsath and Shirivastava, 2015).
2001 According to Lingamdinne et al., 2016, the equilibrium time for adsor­
2. Reactive MgO 8 Moussavi and Mahmoudi,
bent dosage of Pb (II) and Cr (III) from wastewater is 120 min. Hydro­
Blue 2009
3. Reactive MgO 8 Moussavi and Mahmoudi, phobicity, surface charge, and the new functional groups influence
Red 2009 heavy metals adsorption. Such techniques improve the adsorption ca­
4. Cu (II) Goethite 6 Grossl et al. (1994) pacity of nano-adsorbents (Tarigh and Shemirani, 2013; Wang et al.,
(α-FeOOH)
2015). Several studies reporting the efficacy of various nano-adsorbents
5. Pb (II) ZnO 6.7 Ma et al. (2010)
6. Cr (IV) 17) ү-Fe2O3 2.5 Hu et al. (2006) for removal of heavy metals are provided in Table 3.
7. Cu (II – 6.5 Hu et al. (2006)
8. Ni (II) – 9.5 Hu et al. (2006) 6. Pollutants removal efficiency of nano-adsorbents
9. Cu (II) Hematite 5.2 ± Chen and Li, 2010
(α-Fe2O3) 0.1
Nanotechnology has successfully developed nano-adsorbents for

5
P. Sharma et al. Chemosphere 292 (2022) 133380

Fig. 3. Wastewater effluent treatment approaches using different absorbent strategy.

Fig. 4. Structure and absorption sites of graphene sheets.

treating wastewater which is rapidly increasing and fascinating (For­
stner and Wittmann, 1985). Nanotechnology is the study of materials,
their processing, characterization, production, and applications in a
wide range of industries (Ragurajan et al., 2018; Golieskardi et al., 2019;
Padmanabhan et al., 2019; Nuge et al., 2020). Nanomaterials have
unique features that are not present in their bulk counterparts. Some of
these qualities include selectivity, conductivity, catalytic, magnetic,
surface area to mass ratio, and optical capabilities (Lu et al., 2019).
Nanomaterials have a huge surface area and a large number of active
surface sites, making them chemically active. Some of the prominent
nanomaterials utilized in wastewater treatment include carbon nano­
fibers, graphene, titania nanotubes, ordered mesoporous carbon (OMC),
and carbon nanotubes. Because of the wide surface area, there is a
higher concentration of surface flaws, which increases interaction with
contaminants. To improve their adsorption capabilities, nanoparticles
are sometimes coated with additional coating agents. The composite

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P. Sharma et al. Chemosphere 292 (2022) 133380

Fig. 5. Wastewater effluent treatment approaches using electrostatic interaction (a), magnetic nanocomposite (b), and conjugation (c).

Table 3
Removal heavy metals by nano-adsorbents from wastewater effluent at different pH and adsorbent dose.
Heavy metals Nano-adsorbents pH Time (min) Adsorbent dose (g/L) Removal efficiency (%) Reference

V Magnetic zeolite-polymer composite 4–5 1440 0.15 73 Mthombeni et al., 2015

Zn (II) Magnetic nano-adsorbent 5.5 90 2.5 95 Shirsath and Shirivastava (2015)
Pb2+ Zeolite materials obtained from fly ash 6–7.5 90 6 >80 Visa, 2016
Cu2+ Nanocomposite 6.5 15 0.19 99 Neyaz and Siddiqui, 2015
As ZIF-8 nanoparticles 7 240–420 0.20, 0.05 60.03 Jian et al., 2015
Hg (II) ZnS nanocrystals 1–6 5 10 99.99 Qu et al., 2013
Pb2+ Magnetic nano-adsorbent 6 10 20 80 Khani et al., 2016

possessed a larger surface area and a higher removal efficiency when
TiO2 was coated with CNTs than the precursor in its natural state (Ilisz
et al., 2003; Hurt et al., 2006). Non-toxic end products are produced
when toxins are photo-catalytically degraded using TiO2-based nano­
materials (Mahmoodi et al., 2007). Such nanoparticles have excellent
absorption properties as well as chemical constancy (Chen et al., 2005).
Synthesis technique and operating circumstances influence structural
features, such as surface area, chemical content, pore volume, pore size,
porosity, and thermal stability of NPs. The common methods used for
nanoparticle synthesis include spray pyrolysis solgel, chemical vapor
deposition (CVD), ion sputtering, thermal spraying, impregnation,
electrodeposition, catalytic growth, laser ablation, and thermal plasma
synthesis (Liu and Zhang, 2007; Sharma et al., 2009). Because of its
small rate, high purity, homogeneous product production, and envi­
ronmental approachability, the solgel method is getting a lot of interest
for nanoparticle synthesis (Zeng et al., 1998). Alumina, TiO2, Al2O3,
Fe3O4, MnFe2O4, CNTs, nano-zerovalent iron, mesoporous carbon,
magnetite, and graphene are produced and employed as adsorbents for
pollution removal (Sharma et al., 2009). The role of nano adsorbents in
removal of pollutants is discussed in the following section as well as with
recent publication data. Heavy metals elimination using
nano-adsorbents have been provided in Table 4.
7. Pollutants removal using activated carbons
Activated carbon is a wide term for a variety of carbonized materials
with high porous surface area. In the environment and industry, acti­
vated carbon is used to eliminate, extract, segregate, and change a va­
riety of chemicals in liquid and gas phases (Heidarinejad et al., 2020).
Because of its great qualities, activated carbon is increasingly used in
water treatment, purification, and air filtration (Samsuri et al., 2014a,b;
Kosheleva et al., 2019; Yousefi et al., 2019). Activated carbon is a porous
adsorbent material with a large surface area and porosity that can
contain up to 90% carbon (Morin-Crini et al., 2019; Samsuri et al.,
2014a,b; Gopinath and Kadirvelu, 2018). Structures of carbon also
contain the primary functional groups and important adsorbing pollut­
ants, such as carbonyl, quinone, carboxyl, phenol, and lactone. The
activated carbon structure also contains functional groups or chemical
atoms of sulphur, nitrogen, hydrogen, and oxygen. The different
adsorption properties of activated carbon are due to the current

7
P. Sharma et al. Chemosphere 292 (2022) 133380

Table 4 Huang and Zhao, 2016; Khadhri et al., 2019). Presently, significant
Heavy metals removal from wastewater effluent by adsorption using nano- effort is being put into using garbage as a raw material in the
adsorbents. NPs-Nanoparticle; MWCNTs- Multi Walled Carbon Nano-tubes. manufacturing of activated carbon (Crini et al., 2019). “Agricultural
S. Absorbent Metals Capacity Time References by-products including biomass, maize stalks, fruit stones, bagasse, rice
No rolls, and olive corn as well as cherry and hard shells grape seeds, apricot
1. γ-alumina NPs and Ni 99.41% and 30 min Agarwal stones, pistachio, almond, fruit pulp, pecan shells, bones, and coffee
MWCNTs 87.65%, et al. (2016) beans, can be used to make activated carbon” (Klasson et al., 2013; Jolly
2. Iron NPs modified As (V) cellulose 5–600 Hokkanen et al., 2006). The mineral content and biodegradability of this material
micro fibrillated 2.460 min (75 et al. (2015)
must be kept to a minimum during initial storage (Samsuri et al., 2014a,
mmol g− 1 min)
3. Ascorbic acid- Cd (II) 79.58% 60 min Savasari b; Prauchner et al., 2016; Zhu et al., 2010).
stabilized zero- et al. (2015)
valent iron 8. Challenges of conventional adsorbents
nanoparticles
4. Modified henna Cu (II) 99.11% 85 min Davarnejad
with Fe3O4 4 and Panahi,
One of the nanomaterials that have been reported for use in waste­
2016 water treatment is self-assembled monolayer on mesoporous supports
5. Magnetite Fe3O4/ Pb (II) 79.29 mg 12 h Fan et al. (SAMMS), polymeric nanoparticles (NPs), carbon-based nanomaterials,
Chitosan g− 1 (2017) zeolite, metal NPs, and biopolymers (Baruah et al., 2019). Adsorption,
nanoparticles
pathological control, nanofiltration, biosorption, disinfection, photo­
(Fe3O4/CSNPs)
6. Nano scale zero Pb (II), – 30 min Liu et al. catalysis, sensing, and monitoring are some of the
valent iron Cd (II), (Pb), 20 (2014) nanotechnology-based wastewater remediation processes. Some of the
particles (nZVI) 2- Cu (II), min (Cd, limitations of conventional adsorbents are presented in this section.
7 Ni (II) Cu, Ni)
7. Hematite As (III) 2899 ± 8h Dickson et al.
and As 71.09 μg (2017)
8.1. Cost of technology
(V) g− 1 and
4122 ± Activated carbons are extensively employed to remove a variety of
62.79 μg contaminants although their applications are sometimes limited due to
g− 1
the high cost of high-quality activated carbon (Babel and Kurniawan,
8. Nanoscale Cd (II) 425.72 mg 50 min Li et al.
zerovalent iron g− 1 (2016) 2003). Due to the limited adsorption capabilities of low-quality adsor­
particles bents and need to eliminate active substances, chemical activation de­
supported on mands extensive rinsing (Aksu and Kabasakal, 2004). Activated carbon
reduced graphene is treated with various complexing agents to improve removal effi­
oxide
ciency. Activated carbon is less appealing in small-scale industries due to
9. γ-Al2O3 NPs Cd (II) 17.22 mg 30 min Tabesh et al.
g− 1 (2018) its higher cost (Babel and Kurniawan, 2003). Physical and chemical
10. Graphene oxide- Cr (VI) 208.8 mg 12 h Al Nafiey activation have limitations, such as the need for a longer amount of time
Cobalt oxide g− 1 et al. (2017) and a high temperature for physical activation.
11. Aluminium Ni 94.52 mg 6h Hokkanen
substituted g− 1 et al. (2015)
goethite 8.2. Exhaustion
(Al–FeOOH)
12. Titanate Th (I) 709.2 mg 10 min Depault et al. The adsorbent (activated carbon) becomes depleted during waste­
nanotubes and Th g− 1 (2006) water treatment and loses its ability to absorb contaminants further.
(III)
13. Nanoscale Cd (II) 425.72 mg 50 min Li et al.
Many techniques, including chemical, thermal, electrochemical, and
zerovalent iron g− 1 (2016) oxidation, are used to regenerate exhausted adsorbent for reuse in
particles wastewater. In comparison to activated carbon, this regeneration pro­
supported on cess incurs additional costs and reduces adsorption effectiveness (Zhou
reduced graphene
and Lei, 2006; Taiwo and Adesina, 2005).
oxide

8.3. Surface adjustment

functional groups, which are generally formed through precursors,
thermal purification, and activation processes (Yousefi et al., 2019;
Bhatnagar et al., 2013). High quality wastewater treatment is based on
simple process design, simple process operation, resistance to corrosive
and toxic environments, and high adsorption potential in gas and liquid
purification. All the benefits of activated carbon for zeolites or
polymer-based adsorbents include supportive catalysts (Bhatnagar et al.,
2013; Belala et al., 2011; Rambabu et al., 2015). Carbonized materials,
in theory, are all carbon-rich organic molecules that can be utilized to
make activated carbon. Livestock, agricultural waste, and industrial
by-products can all be used to make activated carbon (Khadhri et al.,
2019; Huang and Zhao, 2016; Njoku et al., 2014). It is estimated that
global production of activated carbon is around 100,000 tonnes per year
(Samsuri et al., 2014a,b). The most common commercial sources of
activated carbon are anthracite, wood, peat shells, bituminous charcoal,
lignite, and coconut. Olive and almond shells are also utilized as alter­
native sources. These materials have a carbon content of 40–90% (wt.)
and a density of 0.4–1.45 g/m3 (Cui et al., 2011; Mishra et al., 2010;
Surface morphology has several drawbacks, such as procedure cost,
metals leaching, the regeneration of limitations in the column, surface-
modified activated carbon, surface water, pilot, and treatment of
groundwater (Bhatnagar et al., 2013). Adsorption capability of activated
carbon for specific contaminants is reduced when other metal ions are
present (Makeswari and Santhi, 2013). This technique just moves con­
taminants from the liquid to the solid phase, where they must be treated
further to be removed entirely (Homem and Santos, 2011).
8.4. Separation of adsorbent
Another challenge for potential adsorbents is the ease with which
they may be removed from treated wastewater. After treatment, con­
ventional adsorbents are difficult to remove and traditional separation
procedures, such as filtration, precipitation, chromatography, and
centrifugation result in adsorbent deformation and deactivation. Water
treatment will be more expensive and time-consuming as a result of this
process. As a result, separation processes that are both cost-effective and

8
P. Sharma et al.
successful are incredibly popular (Liu et al., 2011; Li et al., 2011).
8.5. Elimination proficiency
In general, AC cannot lower pollutant concentrations to ppb levels.
Furthermore, due to its nonpolar surface, AC has poor adsorption for
inorganic contaminants (Mohan and Pittman, 2006). Because of the
sluggish pore diffusion in activated carbon adsorption, the adsorption
equilibrium takes a long time to reach (Deng and Bai, 2004; Lu and Chiu,
2006). AC has a low adsorption capacity of <1%, while
non-functionalized multiwall carbon nanotubes have a high adsorption
capacity of 98%. It is possible that the reduced adsorption effectiveness
of AC is due to water filling the pores. Cr(VI) is unable to keep the solid
surface of AC (Nxumalo, 2006).
9. Future prospective
The efficiency and economic feasibility of any novel technique are
determined by two factors i.e., toxic probable assessment and cost cut­
ting. Market and costs prospects although nano-adsorbents have treat­
ment of water effectiveness in approximate circumstances, their
manufacture and use are expensive (Qu et al., 2013a; b). It thereby
provides various solutions to the cost problem. First, low-purity nano­
particles are used without sacrificing the efficiency of adsorption. “For
example, Lee et al. (2010) prepared amino fullerene photocatalysts from
fullerene soot instead of ultrapure C60 and saved an average of 90% on
production costs with only a 10% reduction in effectiveness (Lee et al.,
2010); second, long-term use of nano adsorbents may compromise their
cost-effectiveness; and (3) treatment costs will be reduced by renewal
and reprocessing nanomaterials” (Qu et al., 2013a,b). Due to increased
demand for clean water treatment, nano-adsorbent synthesis has
recently increased. Approximately € 2.28 million was spent on envi­
ronmental clean-up in 2003 (Li et al., 2006). Nanomaterials for clean-up
were worth €3.9 million in 2004 and €9.11 million in 2005 according to
a recent technical market assessment. The market is expected to nearly
double in size in 2009 (to €20 billion). Water purification will require
greater investment to meet the demands of this large population. The
market cost for nanomaterials used in remedy increased by 250% in
2015 (€ 1 trillion) and is predicted to reach €1.6 trillion by 2020
(German Federal Ministry of Education and Research, 2009; Li et al.,
2006). The increasing popularity of nanotechnologies could create a
potential market in the environmental sector on a national and world­
wide level as well as job opportunities for the growing population.
Nanotechnology for environmental applications has generated €227
billion in the European Union (EU) accounting for supporting 3.4
million employment and 2.2% of domestic materials (Roco, 2003;
Freeland et al., 2012; Schmidt-Ott et al., 2010).
10. Conclusions
Polluted water has emerged as a major global issue in the recent
decades due to manufacturing and agricultural operations to meet the
requirement for continuous worldwide population growth. Techno-
economic analysis of several water treatment procedures revealed that
nanohybrid adsorption is a useful strategy for effluent decontamination.
Furthermore, traditional adsorbents have some drawbacks, like high
adsorbent costs, poor separation effectiveness, depletion, and expensive
renewal, to name a few. Nano-adsorbents have recently received a lot of
interest in the wastewater effluent treatment process due to their unique
properties, such as selectivity, magnetic, and catalytic capabilities.
Nano-adsorbents’ exceptional qualities as well as their combination
with recent technology have contributed a new dimension to the
worldwide development. A wide spectrum of nano-adsorbents has been
effectively employed to remove pollutants. For assessing the total per­
formance of large-volume water treatment, more pilot and industrial-
scale studies are necessary. Research institutes and international
9
Chemosphere 292 (2022) 133380
research communities should develop appropriate guidelines to address
this issue in minimizing the risk to human health. Although the eco­
nomic benefits of nano-adsorbents for environmental remediation are
acceptable, safe and adequate ways to avoid adverse effects of nano-
adsorbents in the water treatment process are still required. Addition­
ally, there is an urgent need to develop modified nanomaterials that are
effective, efficient, easy to handle, and environment friendly. It’s also
important to consider the pricing issues and commercialization of these
wastewater treatment technologies.
Author’s statement
Pooja Sharma: Conceptualization, Writing-original draft prepara­
tion, and reviewing of the manuscript. Kavita Nanda: Writing-original
draft preparation. Mamta Yadav: Writing-original draft preparation.
Ashutosh Shukla: Writing-original draft preparation. Sudhir Kumar
Srivastava: Writing-original draft preparation. Sunil Kumar: Review­
ing and editing of the manuscript. Surendra Pratap Singh: Conceptu­
alization, Writing-original draft preparation, and reviewing of the
manuscript.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
The authors acknowledge the support extended by the Director,
CSIR-NEERI, Nagpur (India) while carrying out this review. Surendra
Pratap Singh is also grateful to the Science and Engineering Research
Board (SERB), a statutory body under the Department of Science and
Technology (DST), Government of India for the Start-up Research Grant
(SRG/2019/001940). The authors gratefully acknowledge all the
anonymous reviewers, Guest Editor, and Editor-in-Chief for their valu­
able comments and suggestion on the earlier version of this paper.
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