Journal of Environmental Management 232 (2019) 803–817

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Journal of Environmental Management

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

Review

Clay based nanocomposites for removal of heavy metals from water: A T

review
Vijay Bahadur Yadava, Ranu Gadia,∗, Sippy Kalrab
a
Indira Gandhi Delhi Technical University for Women, Delhi, India
b
Central Road Research Institute-CSIR, New Delhi, India

A R T I C LE I N FO A B S T R A C T

Keywords: The exponential increment in world population, recent industrialization, civilization, agricultural and household
Adsorption activities leads to greater levels of water pollution in terms of organic and inorganic contaminants. However,
Heavy metals numerous workers have done research for the removal of these pollutants and various types of clays and/or
Water pollution modified clays have been extensively used for this purpose. But all identified adsorbent materials are not able to
Carbon nanotube (CNT)
remove pollutants after certain concentration and sometimes these contaminants are left as such in environment
Bentonite
which may create other environmental issues.
Montmorillonite
Kaolinite This paper presents comprehensive information for the adsorption of heavy metal ions from water and waste
water using various nanostructured adsorbents such as different clay minerals (kaolinite, montmorillonite) and
clay (bentonite), carbon nanotube and nanocomposites. In addition to this, the efficiency of developed materials
for the removal of heavy metals is also discussed in details along with comparison of their adsorption effi-
ciencies, pH and change in specific surface area, initial metal ion concentration and contact time. This paper also
states the future directions which could be followed to challenge the situation of removal of traces of heavy
metals from water, hence protecting water bodies from high pollution load.

1. Introduction
In view of population outburst, the demand of freshwater for var-
ious uses would increase. It is projected that the gross per capita water
availability would go down by 2050 (Central Pollution Control Board
MINARS/36/2013-14) and total demand of fresh water would be rises
rapidly and created water stress. The quality of water resources has
degraded at a very fast pace due to various organic and inorganic
pollutants released from anthropogenic as well as natural sources.
Water contamination is a crucial concern as it affects living entities
from recreation, domestic, fishing, transportation and other commercial
activities (Franklin, 1991; John, 1990; Droste, 1997). The key chal-
lenges to manage water quality is potholed geographic distribution of
surface water resources, temporal variation and rainfall pattern, re-
lentless droughts, overuse of groundwater, ground water pollution due
to leaching, drainage and salinization. It is due to partially treated and
untreated wastewater from urbanized areas, industries and runoff from
irrigation as well as traffic sectors and mismanagement of municipal
solid waste. Animal excreta in rural areas also plays major role in
contaminating water system.
In water more than 700 chemical contaminants has been reported
(Ali, 2010). Among these pollutants, heavy metal is one of the most
hazardous species, due to their toxic nature (Järup, 2003). Heavy me-
tals are added in water from various industries like metal plating in-
dustries, mining, tanneries, painting, batteries, fertilizer etc. Heavy
metals such as arsenic, lead, cadmium, nickel, chromium, zinc, copper,
mercury and cobalt etc. directly or indirectly entered into the water
bodies (Mahmud et al., 2016; Javadian, 2014; Samiey et al., 2014; Yao
et al., 2011; Jiang et al., 2010; Jiang et al., 2009). These metals are
highly toxic, non biodegradable and reside in various oxidation states
for long period in the environment. All urban pollution contains heavy
metals emanating from road dust, sediment and polluted air. They can
travel long distances in the environment in biological and non biolo-
gical form. Moreover biological form is more pronounced to affect the
humans and ecosystem. Hence, it is essential to remove heavy metal
ions from contaminated wastewater prior to its discharge to the water
bodies.
Various waste water remediation technologies such as membrane
filtration, flocculation, adsorption, precipitation, electrolytic removal,
ion exchange, reduction and reverse osmosis have been reported.
However these technologies have various limitations i.e., costly
equipment, high operational cost, high maintenance cost, partial metal

∗
Corresponding author.
E-mail addresses: vijaybhuenv@gmail.com (V.B. Yadav), ranugadi@igduw.ac.in (R. Gadi), sippykalra2002@gmail.com (S. Kalra).

https://doi.org/10.1016/j.jenvman.2018.11.120
Received 31 July 2018; Received in revised form 25 October 2018; Accepted 25 November 2018
Available online 06 December 2018
0301-4797/ © 2018 Elsevier Ltd. All rights reserved.
V.B. Yadav et al.
ions removal, high energy requirement and creation of lethal residual
metal sludge. Dumping of contaminated sludge is another foremost
limitation in most methodologies. Adsorption method for traces re-
moval suggested high efficiency, cost-effectiveness and easy handling.
Recovery of the metals and other adsorbed variety of pollutants is also
possible (Sharma et al., 2009).
Recently, nanostructured materials are being implemented for
water treatment. It shows exceptional properties due to their small di-
mension as they hold a high specific surface area and ‘surface area to
volume’ ratio (Mamalis, 2007). These characteristics advance the re-
moval efficiency of the nanostructured materials. In addition to high
specific surface area, these materials display distinctive features, like as
catalytic potential and high reactivity, which make them superior ad-
sorbing materials than common materials. Nanostructured materials
have a great number of active sites for contact with various chemical
species due to their large surface area (Hristovski et al., 2007; Li et al.,
2006; Khaleel et al., 1999). To get improved outcome for removal of
metallic species from water, nanostructured materials are appropriate
new alternatives for the treatment of wastewater (Li et al., 2014;
Vaseashta et al., 2007; Li et al., 2006; Tratnyek and Johnson, 2006;
Zhang, 2003; Ngomsik et al., 2005).
Various nanostructured carbon materials [carbon nanotube (CNT),
graphene, carbon fibers etc.] are well known for their extraordinary
adsorption properties (Liu et al., 2017; Parlayici and Pehlivan, 2017;
Abbas et al., 2016; Tofighy and Mohammadi, 2011; Kadirvelu et al.,
2001; Ricordel et al., 2001). Among these carbon materials, CNT are
one of the favorable material as they have a specific surface area of
952 m2g-1 (Pillay et al., 2013) and high aspect ratio, which varies from
500–100,000 (Zhu et al., 2002). Aliyu et al. (2017) reported aspect
ratio 878.57 for MWCNT at 750 °C. Manganese oxide-coated carbon
nanotube (MnO2/CNT) were prepared and used to treat Pb (II) from
water. The adsorption capacity of Pb (II) on MnO2/CNT decreased with
the declining pH of the solution (Tehrani et al., 2013).
Similarly, clay mineral is also used as an adsorbent since, it has good
adsorption capacity towards various metal ions, like arsenate (Shukla
et al., 2011; Arai et al., 2005) and lead (Tang et al., 2012). Kaolinite
and montmorillonite clay minerals were modified with H2SO4 for
copper removal (Bhattacharyya and Gupta, 2011); kaolin-supported
bacterial biofilm of bacillus species for chromium adsorption (Fathima
et al., 2012); kaolinite was pillared using MnO2 for cadmium (Sari and
Tuzen, 2014) etc. The removal efficiency of the metal ions increased
with the increase of temperature (Hernandez- Rivera and Green-Ruiz,
2014; Sandy et al., 2012; Nathaniel et al., 2011; Unuabonah and
Adebowale, 2009; Dal Bosco et al., 2006). In contrast, the removal
capacity increased with decrease in temperature in case of Ti-pillared
montmorillonite (Na et al., 2010).
Recently, nanocomposite synthesized by incorporating nanos-
tructured materials inside the interlayer space of clay mineral have
drawn increasing interest due to their special physicochemical prop-
erties and potential application in diverse fields (Dos Santos et al.,
2015; Ruiz- Hitzky et al., 2011; Gómez- Avies et al., 2010; Kyotani,
2006). This paper presents complete information for adsorption of
heavy metals from water using different nanostructured adsorbents
such as clay, clay minerals, CNT and nanocomposites. In addition to
this, the adsorption efficiency of developed materials for the remedia-
tion of heavy metals is also mentioned giving comparison of their ef-
ficiencies. This paper also expresses the future perspectives for removal
of traces from polluted water hence protecting water bodies from re-
ceiving more contamination.
2. Adsorption studies
Adsorption technique is phase transfer process, which involve two
essential constituents namely adsorbent and adsorbate. The surface
where adsorption occurs is provided by adsorbent and the species
which is adsorbed on the surface is adsorbate. Variation in temperature,
804
Journal of Environmental Management 232 (2019) 803–817
pH value and concentration of the liquid phase is responsible for the
reverse process known as desorption. In this process, adsorbed species
detached from the adsorbent surface to the liquid phase. The removal
capacity of adsorbents depends on adsorption properties (porosity,
specific surface area, pore volume, cation exchange capacity, interac-
tion time and adsorbent dose etc.) of adsorbents.
Adsorption is widely accepted for waste water remediation methods
due to its simplicity and the availability of broad range of adsorbents.
Further, adsorption technique can also be applied for the removal of
soluble and insoluble inorganic, organic and biological contaminants.
Furthermore, it can be used for reclamation and source reduction of
industrial, potable and other water purposes. Adsorption procedure has
certain limitations, such as, the lack of appropriate adsorbents of high
removal efficiency for very low metal concentration and non-avail-
ability of columns and batches on commercial level. Besides this, a
particular adsorbent cannot be used for all kinds of pollutants.
Adsorption technique is effective for the most part of natural phy-
sical, biological, and chemical systems and is commonly used in in-
dustrial applications as well as in potable water decontamination.
Among these treatment methods, adsorption is currently considered to
be appropriate for water and wastewater treatment because of its un-
complicated operation, cost effectiveness and easy handling (Kwon
et al., 2010; Yadanaparthi et al., 2009). In adsorption technique the
recovery of metals and other adsorbed species is also possible. Ad-
sorption technique is a widely used technique for the sorption of traces
from different industrial effluent water (Gottipati and Mishra, 2012).
Some extensively used adsorbents for adsorption of metal ions in-
clude clay minerals (Wilson et al., 2006), montmorillonite
(Bhattacharyya and Gupta, 2007), kaolinite (Yavuz et al., 2003), CNT
(Ma et al., 2013; Karanfil et al., 2011; Upadhyayula et al., 2009).
Usually, these adsorbents are locally and easily available in large
quantities and hence they are inexpensive except CNT (Mohan and
Pittman, 2007). The removal of heavy metal ions from water and
wastewater using adsorbents are affected by numerous factors such as
pH, temperature, the presence of other compounds, contact time, ad-
sorbent dose, initial pollutants concentration, etc. Fig. 1 summarizes the
complete adsorption procedure widely being followed.
2.1. Adsorption studies using CNT
The application of CNT and modified CNT as adsorbent for treat-
ment of heavy metal ions from water have been studied immensely
from the past few years. This review article covers the literature con-
sidering the different reaction conditions for adsorption including in-
itial concentration of metal ion, interaction time, adsorbent dose,
Fig. 1. Schematic representation of heavy metal removal practice.
V.B. Yadav et al. Journal of Environmental Management 232 (2019) 803–817

Table 1
Applications of CNT for the Removal of heavy metals.
Adsorbent Modifying agent Heavy Max. Adsorption Initial metal conc. (mg Cont- Adsorbent dose SA SA Final pH References
Metals capacity (mg g−1) L−1) act (g) Initial m2 g−1
time m2 g−1
(Min)

MWCNT - Raw Cr(VI) 3.115 1 240 75 mg 156 170 3 Ihsanullah et al.

- acid 1.314 (2016)
MWCNT - raw Cr(VI) 13.2 20 40 0.15 65.2 87.4 2.5–4 Kumar et al.
- Ionic liquid 85.83 (2015)
CNT - acid Cd (II) 4.35 1 120 0.5 156 170 7 Ihsanullah et al.
(2015)
CNT - acid Cd(II) 4.35 1 120 0.5 156 170 7 Al-Khaldi et al.
- Raw 1.661 (2015)
MWCNT - Functionalized Cd(II) 19.84 1 240 0.5 115.66 109.82 7 Liang et al.
- Alumina 27.21 74.21 (2015)
MWCNT - C6H5-OH Hg(II) 32.4 4 25 h 0.1 > 233 > 233 4.3 Chen et al. (2014)
- Hydroxyl 120.1 > 233
- COOH 127.6
MWCNT Sulphur Hg(II) 72.8 μg g−1 100 ppb 60 0.1 – 952 12.15 Pillay et al.
(2013)
MWCNT - amino & thiolated Hg(II) 84.66 100 60 60mg 110 – 6 Hadavifar et al.
(2014)
SWCNT - Raw Hg(II) 40.16 40 60 0.25 mg ml−1 – – 5 Bandaru et al.
- Thiol 131.58 (2013)
MWCNT - Raw Hg(II) 5.479 100–500 120 0.02 85.1 – 6 Gupta et al.
- Oxidised 27.32 152.5 (2014)
- Iodide 123.45 153
- Sulphur 151.51 155.3
MWCNT - Purified Cu(II) 36.82 20 360 0.025 169.7 28.7 5 Ge et al. (2014)
- sulfonated 43.16
CNT Activated Zn(II) 1.05 1.1 120 0.09 – 250 10 Mubarak et al.
(2013)
MWCNT Nitric acid Ni(II) 17.86 20 120 0.8 – 102 6.5 Mobasherpour
et al. (2012)
MWCNT - Raw Co(II) 3.4 × 10−5 mol/g 1.69 × 10−4 mol L−1 30 1 – – 6.8 Chen et al. (2012)
- Polyacrylic acid 1.66 × 10−4 mol g−1
MWCNT Hydroxyl apatite Co(II) 3.55 × 10−4 mol g−1 1.69 × 10−4 300 0.6 – – 6 Liu et al. (2013)
Mol L−1

solution pH etc. Table-1 summarizes the sorption capacities and the
reaction conditions of carbon nanotube for various heavy metals re-
moval from wastewater. Some important heavy metals adsorption from
waste water using CNT would be discussed in the following section.
Ihsanullah et al. (2016) used raw and modified MWCNT for sorption
of Cr (VI) from water. The maximum removal efficiency of raw MWCNT
and acid modified MWCNT was 3.115 mg g−1 and 1.314 mg g−1 at pH
3.0, initial metals ion concentration 1 mg L−1, adsorbent dose 75 mg,
and contact time was 240 min. Active surface area increased from
156 m2 g−1 to 170 m2 g−1 for raw to acid activated MWCNT. Cd (II)
removal from water using acid activated CNT was also studied and
maximum sorption capacity was 4.35 mg g−1 at 1 mg L−1 of solution
concentration; adsorbent dose 0.50 mg at contact time 120 min
(Ihsanullah et al., 2015).
Kumar et al. (2015) used raw and modified MWCNT for sorption of
Cr (VI)/Cr(III) from water. The maximum removal capacity of raw
MWCNT and modified MWCNT are 13.20 mg g−1 and 85.83 mg g−1,
respectively, using inductively coupled plasma mass spectrometry (ICP-
MS) the pH range was 2.5–4; initial metals ion concentration in solution
was 20 mg L−1, adsorbent dose: 0.15 mg and contact time, 40 min.
Surface area increased on addition of ionic liquid onto MWCNT from
65.2 to 87.4 m2 g−1. The maximum removal capacity of Cd(II) by using
acid activated CNT was reported as 4.35 mg g−1 (Al Khaldi et al., 2015;
Ihsanullah et al., 2015) whereas, metal ion removal capacity of
1.661 mg g−1 was obtained when raw CNT were used under same re-
action conditions (Al Khaldi et al., 2015). Adsorption capacity for
functionalized MWCNT and alumina decorated MWCNT was
19.84 mg g−1 and 27.21 mg g−1, respectively, under same reaction
conditions as Ihsanullah et al. (2015) the only difference was in contact
time (Liang et al., 2015). Adsorption capacity for Hg (II) ions removal
was reported on MWCNT modified with various modifying agents such
as Phenol, hydroxyl, carboxylic acid (Chen et al., 2014); sulphur (Pillay
et al., 2013); amino and thiolated (Hadavifar et al., 2014); raw
MWCNT, oxidised, Iodide and sulphur (Gupta et al., 2014). Adsorption
capacity for Hg (II) was observed to be 40.16 mg g−1 by using raw
SWCNT and 131.58 mg g−1 by using thiol modified SWCNT (Bandaru
et al., 2013).
Adsorption capacity for Cu(II) removal using purified MWCNT was
36.82 mg g−1 and sulfonated MWCNT was 43.16 mg g−1 (Ge et al.,
2014). For the adsorption of Zn (II) ion in aqueous solution, the removal
efficiency was found to be 1.05 mg g−1 (Mubarak et al., 2013). The
maximum removal capacity of Ni (II) ions was reported to be
17.86 mg g−1 when MWCNT treated with nitric acid (Mobasherpour
et al., 2012). For Co (II) the adsorption capacity of raw MWCNT was
3.40 × 10-5 mol/g; MWCNT modified with poly acrylic acid was
1.66 × 10−4 mol g−1 (Chen et al., 2012) and with hydroxyl apatite
modified MWCNT was 3.55 × 10−4 mol g−1 (Liu et al., 2013).
2.2. Adsorption studies using clay and clay minerals for removal of heavy
metals from water
Recently researchers have used clay minerals by modifying with
different procedure to get improved adsorption properties like as spe-
cific surface area, surface functional group, pore volume, CEC value,
pore size etc. for adsorption application by pre-treatment with chemical
or collective treatment with chemical in addition to other materials
(Adeyemo et al., 2017; Gao et al., 2015; Yavuz and Saka, 2013; Auta
and Hameed, 2012; Ijagbemi et al., 2010). Heavy metal removals by
using kaolinite, montmorillonite and bentonite in their raw and mod-
ified forms have been presented in the following section.

805
 Table 2
Application of clay based nanomaterials for the removal of heavy metals.
Modifying agent Heavy Metals Max. Adsorption capacity (mg g−1) Initial metal conc. (mg Contact Time Adsorbent dose (g) SA Initial m2 g−1 SA Final m2 pH References
L−1) (Min) g−1
V.B. Yadav et al.

kaolinite and its modified form as adsorbents

Unmodified Cu (II) 10.8 50 1440 1 10.7 16.09 5 Danková et al., 2015
Mn-Kaolin 39.8
– Ni(II) 166.67 100–300 180 0.1 13.41 – 5 Dawodu and Akpomie (2014)
Mn(II) 111.11
Untreated Fe 7.35 0.25–1.25 120 0.1–1 – – 6–8 Hassouna and Shaban (2014)
H2SO4 Mn 0.43
Acetic Acid Fe 10.43
Mn 2.70
Fe 7.01
Mn 2.04
– Pb(II) 7.75 50–2000 120 >1 12.76 – 4.5 Shahmohammadi- Kalalagh
Zn(II) 4.95 (2011)
Cu(II) 4.42
– Cr(VI) 0.571 0.1–0.5 1440 0.2 – – 2–4 Ajouyed et al. (2011)
– Pb(II) 3.36 50–130 60 0.5 15 – 4.9 Mbadcam et al., 2011
4.73 50
HNO3, Pb 2.35 12.5–20 30 0.5 3.8 – 5.5–7.0 Jiang et al. (2010)
NaNO3 Cd 0.88
Ni 0.90
Cu 1.22
– Pb(II) 54.35 50–400 1440 0.5 g 100 ml−1 16.9 25.5 5 Al-Harahsheh et al. (2009)
Kaolinite-TBA Fe (II) 9.3 50 40 0.1 3.8 14.2 3–5.8 Bhattacharyya and Gupta
Co(II) 9 (2009)

806
Ni(II) 8.4
Unmodified Pb 4.5 150–400 0–300 15 g L−1 5.5 Unuabonah et al. (2008)
PVA Cd 36.23 5 g L−1
Pb 4.38
Cd 29.85
Kaolinite Fe 11.2 50 300 2 3.8 – 1–10 Bhattacharyya and Gupta
Co 11 240 (2008)
Ni 10.4 180
K1 –Kaolinite Cr (VI) 11.6 10–250 240 2 3.8 15.6 4.6 Bhattacharyya and Gupta
K2 -Acid activated Cr (VI) 13.9 13.4 (2006)
K3 -ZrO Cr (VI) 10.9 14
K4 -(TBA) Cr (VI) 10.6
Unmodified Cu(II) 4.4 50 360 2 3.8 – 5.7 Bhattacharyya and Gupta
ZrO 28.8 13.4 (2006)
TBA 3 14
Montmorillonite (Mt) and its modified form as adsorbents
Sodium Pb(II) 3.71 5–20 60 0.25 42 – 2–7 Taha et al. (2017)
Cd(II) 2.45
Ni(II) 1.76
- Raw Cu(II) 4.1 mol/g 10 – 1 64.4 – 2–10 Yang et al. (2015)
Ni(II) 4.0
- Raw Ni(II) 117.45 100–500 20–30 0.1–0.5 23.2 30.7 2–8 Akpomie and Dawodu
- NaOH Mn(II) 102.76 (2014)
Ni(II) 125.95
Mn(II) 111.95
(continued on next page)
Journal of Environmental Management 232 (2019) 803–817
 Table 2 (continued)

Modifying agent Heavy Metals Max. Adsorption capacity (mg g−1) Initial metal conc. (mg Contact Time Adsorbent dose (g) SA Initial m2 g−1 SA Final m2 pH References
L−1) (Min) g−1
V.B. Yadav et al.

- Raw Hg 15.29 ppb 200 ppb 120 0.02 241.41 154.54 – Varadwaj et al., 2014
- Sulphonic and Amin (APTES) Cd 44 ppb
Pb 30 ppb
Hg 6.19 ppb
Cd 18 ppb
Pb 15 ppb
- Raw Cr(II) 30.4 0.005–2 1440 1–2.5 220–270 5–8 Dos Anjos et al. (2014)
Cu(II) 4.3
Pb(II) 6
Zn(II) 15
Co(II) 0.6
Ni(II) 2.9
Cd(II) 12
Mn(II) 17
Sr(II) 10
Ba(II) 8.3
As(III) 6.7
V (III) 10.2
- Raw Cu (II) 18.69 12.5–400 120–240 1 73.92 – 3–9 Çoruh and Geyikci (2012).
- Raw (Ca-Mt) Cu 12.4 32 60 0.5 120 – 5.0 Wu et al. (2011)
- Humic Acid Cd 12.63
Cr 11.86
Cu 15.6
Cd 15.25
Cr 14.14

807
- Raw Pb(II) 28 0.1–0.001 N 600 0.2 – – 4–4.8 De Pablo et al. (2011)
- Ca Cu(II) 4.3
Cr(III) 0.8
Zn(II) 34.7
Ba(II) 6.98
Hg(II) 36.81
Ni(II) 4.8
Mn(II) 3.8
Cd(II) 6.97
Pb(II) 25
Cu(II) 4.3
Cr(III) 2.1
Zn(II) 35.23
Ba(II) 10.7
Hg(II) –
Ni(II) 5.96
Mn(II) –
Cd(II) –
- Cellulose and Sodium Cr (VI) 22.2 20 40 0.5 – 87.09 3.8–5.5 Kumar et al. (2011)
- Ca Hg(II) 0.0003 mol/g. 0.00003–0.00086 mol per dm3 60 2.5 × 104 mg per dm3 93.5 660 2.76–7.4 Kónya and Nagy, 2011
- Acetic acid Cu 27.39 10–100 60 1 17.84 71.94 6 Sdiri et al. (2011)
Cd 6.784
Pb 131.579
Zn 22.72
- H2 SO4 Cu (II) 0.4(Multilayer) 280.32 180 – 156 251 2.4 Oubagaranadin et al.
Zn (II) 0.58(Mono) 282.72 (2010)
- TBA Fe (II) 22.6 50 40 0.1 19.8 42.2 3–5.8 Bhattacharyya and Gupta
Co(II) 22.3 (2009)
Ni(II) 19.7
(continued on next page)
Journal of Environmental Management 232 (2019) 803–817
 Table 2 (continued)

Modifying agent Heavy Metals Max. Adsorption capacity (mg g−1) Initial metal conc. (mg Contact Time Adsorbent dose (g) SA Initial m2 g−1 SA Final m2 pH References
L−1) (Min) g−1
V.B. Yadav et al.

- Raw Ni 5.68 50–300 50–100 1 699 – 2.45–9.6 Ijagbemi et al. (2009)

Cu 4.42
- Citric acid Ni 1.92 50 432 0.05 29.7 – 4–7.5 Marcussen et al. (2009)
- RLs Cu (II) 37.6 600 20 0.2 65.6 610 4.7–4.8 Özdemir and Yapar
- RLs(low) 48.3 (2009)
- RLs(High) 30.1
- Cu-RL 31.5
- Activated C 43.7
- Raw Fe 28.9 50 300 2 19.8 – 1–10 Bhattacharyya and Gupta
Co 28.6 240 (2008)
Ni 28.4 180
- Raw Cu(II) 7.1 50 360 2 19.8 – 5.7 Bhattacharyya and Gupta
- ZrO 3.2 35.8 (2006)
- TBA 27.3 42.2
K-10 Cd 6.3 50 60 0.1 232 – 1–6 Dal Bosco et al., 2006
Mn 4.8
Bentonite and its modified form as adsorbents
- Raw Zn(II) 14.92 100 1–180 0.2–10 g per 200ml 56.44 – 7.42 Mohellebi and Lakel
(2016)
- Raw Pb(II) 51.19 50–800 30 1 62.567 – – Al-Jlil, 2015
Cr (III) 13.79
- Cross link Chitosan Cr(VI) 89.13 10–200 240 0.05–0.25 37.67 11.54 2.0 Liu et al. (2015)
- Raw Cd 31.25 50 120 1 87 – 5.0 Anna et al. (2015)
Cu 32.26
Ni 26.32

808
Pb Multimetal 84.47
Cd, Cu, Ni, Pb 7.69
Cu, Cd, Ni, Pb 9.01
Ni, Cd, Cu, Pb 7.63
Pb, Cd, Cu, Ni 19.61
- Sodium Cu(II) 56.89 10–220 30 0.1 42 754.4 5.5 Musso et al. (2014)
Zn(II) 103.83 1–210
- Raw Cr (III) 4.68 100 120 1.0 – 570 7.0 Chen et al. (2012)
- Raw Zn(II) 6.137 1.92–88 150 1 – – 4.5 Araujo et al. (2013)
- Raw Pb(II) 20.68 2 mol per dm3 180 2.25 mmol g−1 34.1 597.3 8 Guerra et al. (2013)
- APS 27.65 612.3
- AEAPS 29.54
- Raw Zn(II) 1.75 1–60 180 1 – – 8 Bellir et al. (2013)
- Organo Cu(II) 0.285 mmol g−1 400 80 0.1–1 – – 5 Sandy et al. (2012)
- Raw Pb 59.7 100 300 0.1 48 – 6 Anirudhan et al. (2012)
- Amin Hg 52.4 27.1 6
- COOH Cu 29 25.5 5.5
Pb 110 5.5
Hg 102.7 5.5
Cu 45.8 5
Pb 123.3
Hg 113.6
Cu 53.1
− Cr 38.8 1 μg ml−1 30 30 mg 34 24.9 4 Wang et al. (2011)
4 Amino antypyrene Hg 52.9
Pb 55.5
- Raw Zn(II) 73.5 100 150 0.2–2 40.7 62.4 4–7 Zhang et al., 2012
- Alkaline-Ca 149
- Calcined Ni 1.91 2.66–177 250 1–4 78.89 92.589 5.3 Vieira et al. (2010)
(continued on next page)
Journal of Environmental Management 232 (2019) 803–817
V.B. Yadav et al. Journal of Environmental Management 232 (2019) 803–817

2.2.1. Kaolinite

Leyva-Ramos et al. (2008)

Shawabkeh et al. (2007)

Mekhemer et al. (2008)
Various researchers have used raw kaolinite and modified kaolinite

Dal Bosco et al., 2006

Veli and Alyüz, 2007
Arfaoui et al. (2008)
to evaluate removal efficiency of different heavy metal species from

Hu et al. (2007)
water solutions and their results are tabulated in Table 2. The adsorp-
tion capacities of Cr (VI) on interaction with raw kaolinite and kaolinite
activated by acid, ZrO and TBA were 11.6, 13.9, 10.9 and 10.6 mg g−1,
References

respectively. The adsorption was strongly reliant on the pH of the so-

lution with Cr (VI) removal increasing from pH 1 to 7, after which the
uptake decreased (Bhattacharyya and Gupta, 2006). Ajouyed et al.
(2011) reported lower removal capacity of 0.571 mg g−1 for Cr (VI) for

7, 8
2–6

5–6

1–6
lower adsorbent dose and higher contact time.
5.0

6.0
pH

The adsorption of Fe (III) ions from water onto the kaolinite and its
SA Final m2

modified forms was evaluated by Hassouna and Shaban (2014),

Bhattacharyya and Gupta (2009) and Bhattacharyya and Gupta (2008).
g−1

The removal of Fe (III) on kaolinite and modified kaolinite increased on

–

–
–

–
–

–
increasing initial concentration and interaction time. The maximum
removal capacity of 11.2 mg g−1 was reported by Bhattacharyya and
105.8

153.8
113.2
354.3
236.2
93.5

45.9

Gupta (2008). The higher adsorption capacity of 28.8 mg g−1 was ob-
SA Initial m2 g−1

135

139
2

–
–

tained for modified kaolin as compared to 10.8 mg g−1 for unmodified

kaolin with 50 mg L−1 as initial metal ion concentration of Cu (II) ion
(Danková et al., 2015). The sorption of Cu (II) ions onto the kaolinite
(Shahmohammadi-Kalalagh, 2011), kaolinite-ZrO, kaolinite-TBA
(Bhattacharyya and Gupta, 2006) were also studied and have been ta-
bulated in Table 2. Dawodu and Akpomie (2014) reported maximum
Adsorbent dose (g)

adsorption capacity as 166.67 mg g−1 for Ni (II) ion with unmodified

0.5
0.1

0.1

0.5

0.1

kaolinite with initial metal ion concentration 100–300 mg L−1, ad-

2

sorbent dose 0.1 g and pH 5. The adsorption capacity, 11 mg g−1 for Co

(II) ion and 10.4 mg g−1 for Ni (II) ion was obtained on using kaolinite
(Bhattacharyya and Gupta, 2008). Although, the surface area increased
due to modification of kaolinite by TBA, but lower removal efficiency of
Contact Time

9 mg g−1 for Co(II) and 8.4 mg g−1 for Ni (II) was observed due to
lower adsorbent dose used for less contact time (Bhattacharyya and
(Min)

120 h

1440

Gupta, 2009).
60

30

10
05
60
–

Adsorption capacities of Pb (II) ions in water are also reported onto

Initial metal conc. (mg

kaolinite (Shahmohammadi-Kalalagh, 2011), kaolinite- TBA (Jiang

et al., 2010) and kaolinite-PVA (Unuabonah et al., 2008). Al-
Harahsheh et al. (2009) used Jordanian kaolinite, washed with sulfuric
acid solution followed by surface modification using 3-chloropropyl-
triethoxysilane and sodium hydroxide, for removal of Pb (II) ion with
L−1)

utmost adsorption capacity of 54.35 mg g−1. Removal of Cd (II) ion

500–1000
0.5–3.0 M

from water using kaolinite and its modified form has been studied by
50&600
10–150

25–27

Unuabonah et al. (2008) and only for kaolinite by Jiang et al. (2010). A
160
Max. Adsorption capacity (mg g−1)

50

detailed description of the reaction conditions of all the above studies

including other heavy metal ions such as Zn (II) ion and Mn (II) ions
onto kaolinite and its modified forms are represented in Table-2.

2.2.2. Montmorillonite
138.17
202.63

Many studies have been reported in literature on removal of various

34.7
53.4
25.4
8.45

11.2
113
109
112

103

6.0

metal ions using raw and modified montmorillonite in the last decade
74
50
83

40
75

(Table 2). Adsorption of Pb (II) has been studied using raw montmor-
illonite by various researchers (Dos Anjos et al., 2014; Varadwaj et al.,
2014; De Pablo et al., 2011) and the maximum sorption capacity was
found to be 28 mg g−1 (De Pablo et al., 2011). After modification of
Cu (II)
Co (II)
Zn (II)

Zn (II)
Cr(VI)

Cr(VI)

Cd(II)
Co(II)
Heavy Metals

clay, removal capacity of Pb (II) increased up to 131.579 mg g−1 (Sdiri

Mn
Cd

et al., 2011) due to presence of more active sites onto the surface of clay
HCl, Nitric, Phosphoric and NaOH

after treatment with acetic acid.

Removal of Cu (II) by using raw montmorillonite by various re-
search groups (Yang et al., 2015; Dos Anjos et al., 2014; Çoruh and
Acid activated pillared

Acid activated pillared

Acid activated (0.5 M)

Geyikci, 2012; De Pablo et al., 2011; Wu et al., 2011; Ijagbemi et al.,

Acid activated (3 M)

2009; Özdemir and Yapar, 2009; Bhattacharyya and Gupta, 2006) re-
Table 2 (continued)

vealed that maximum adsorption capacity was found to be

Org-Bentonite
Clay purified
Modifying agent

Pillared clay

18.69 mg g−1 due to optimum reaction conditions (Çoruh and Geyikci,

Untreated

2012). Studies with modified montmorillonite (Çoruh and Geyikci,

Raw

Raw

Raw

- Raw

2012; De Pablo et al., 2011; Sdiri et al., 2011; Wu et al., 2011;

NT-25

Oubagaranadin et al., 2010; Özdemir and Yapar, 2009; Bhattacharyya

-
-
-
-
-
-
-
-
-
-
-
-

and Gupta, 2006) showed maximum sorption capacity to be

809
V.B. Yadav et al.
48.3 mg g−1 (Özdemir and Yapar, 2009).
Adsorption studies of Cd (II) on raw montmorillonite was carried
out by Dos Anjos et al. (2014); De Pablo et al. (2011); Wu et al. (2011);
Dal Bosco et al. (2006) and maximum sorption capacity was found to be
12.63 mg g−1 (Wu et al., 2011). Modification of montmorillonite by
Humic acid increased its capacity significantly (15.25 mg g−1) due to
change in the surface characteristics (Wu et al., 2011).
Cr (III) removal on raw montmorillonite was considered by various
researchers (Dos Anjos et al., 2014; Wu et al., 2011; De Pablo et al.,
2011) in their studies and maximum sorption capacity was found to be
11.86 mg g−1 (Wu et al., 2011). With modified montmorillonite (De
Pablo et al., 2011; Kumar et al., 2011; Wu et al., 2011) the maximum
removal was 22.2 mg g−1 and no significant changes were observed on
material after adsorption (Kumar et al., 2011). Modified montmor-
illonite was nearly three times more efficient as compared to raw
montmorillonite for Cr (III) removal (De Pablo et al., 2011).
The maximum sorption capacity of Ni (II) on virgin montmorillonite
(Yang et al., 2015; Akpomie and Dawodu, 2014; Dos Anjos et al., 2014;
De Pablo et al., 2011; Ijagbemi et al., 2009; Bhattacharyya and Gupta,
2008) and its modified form (Taha et al., 2017; Akpomie and Dawodu,
2014; Dos Anjos et al., 2014; De Pablo et al., 2011; Bhattacharyya and
Gupta, 2009) was 117.45 mg g−1 and 125.95 mg g−1, respectively due
to increased porosity of material (Akpomie and Dawodu, 2014).
Removal of Mn (II) on the raw and modified montmorillonite
showed maximum capacity to be 102.76 and 111.95 mg g−1, respec-
tively (Akpomie and Dawodu, 2014). Sorption capacity of Zn (II) on
raw montmorillonite and modified montmorillonite was 34.7 mg g−1
and 35.23 mg g−1, respectively. It was observed that maximum ad-
sorption capacity of Zn (II) depended on cations that precipitated at
greater pH (De Pablo et al., 2011). Hg (II) removal using montmor-
illonite showed maximum capacity to be 36.18 mg g−1 (De Pablo et al.,
2011). The adsorption on modified montmorillonite was studied by
Varadwaj et al. (2014) and Kónya and Negy (2011). Few adsorption
studies of other heavy metals like Iron (Bhattacharyya and Gupta, 2009,
2008); Ba (II) (Dos Anjos et al., 2014; De Pablo et al., 2011); Co (II)
(Dos Anjos et al., 2014), As, Sr and Va (Dos Anjos et al., 2014) are also
reported.
2.2.3. Bentonite
The application of bentonite clay and modified bentonite clay as
adsorbent for removal of Co (II) Pb (II), Cu (II), Cr (III), Cr (VI), Ni (II),
Hg (II), Cd (II), and Zn (II) metal ions from water have been considered
immensely in last ten years. The different reaction conditions for ad-
sorption including initial concentration of metal ion, interaction time,
adsorbent quantity, pH of the solution etc. are critical for the adsorption
studies, as they describe sorption processes. Table 2 summarizes the
adsorption capacities and reaction conditions of bentonite and its
modified forms for various heavy metals removal from wastewater.
Some important studies on heavy metal sorption from waste water
using bentonite clay and its modified form have been discussed in the
following section.
The highest sorption capacity of Pb (II) using unmodified bentonite
from water solution was 59.7 mg g−1 and with modified bentonite was
123.3 mg g−1 (Anirudhan et al., 2012). For Cr (III) (Al- Jlil, 2015; Chen
et al., 2012) removal with raw bentonite, maximum efficiency was
found to be 13.79 mg g−1 (Al- Jlil, 2015) and with bentonite modified
using 4-Aminoantypyrene was 38.8 mg g−1 (Wang et al., 2011). For Cr
(VI) removal (Arfaoui et al., 2008; Leyva-Ramos et al., 2008) maximum
removal capacity was found to be 113 mg g−1 (Arfaoui et al., 2008) and
with modified bentonite (Liu et al., 2015; Arfaoui et al., 2008; Leyva-
Ramos et al., 2008) the maximum capacity was 112 mg g−1 (Liu et al.,
2015).
Maximum removal capacity of Cd (II) onto raw bentonite clay was
found to be 8.45 mg g−1 (Hu et al., 2007) and on modified form the
capacity was 31.25 mg g−1 (Anna et al., 2015) due to change in surface
adsorption properties after modification. Zn (II) removal on raw
810
Journal of Environmental Management 232 (2019) 803–817
bentonite clay was studied by various researchers (Mohellebi and Lakel,
2016; Araujo et al., 2013; Bellir et al., 2013; Veli and Alyüz, 2007) and
maximum removal capacity was found to be 75 mg g−1 (Veli and Alyüz,
2007). On using modified bentonite, the adsorption capacity increased
to 202.63 mg g−1 (Shawabkeh et al., 2007).
Copper removal with raw bentonite was studied by various re-
searchers (Anna et al., 2015; Anirudhan et al., 2012; Veli and Alyüz,
2007) and the maximum removal capacity was 40 mg g−1 (Veli and
Alyüz, 2007); with modified bentonite, maximum capacity was
56.89 mg g−1 (Musso et al., 2014).
The sorption capacity of mercury was found to be 52.4 mg g−1 for
raw bentonite and 113.6 mg g−1 for modified form (Anirudhan et al.,
2012). For removal of Co (II) on raw bentonite, the capacity was
34.7 mg g−1 (Mekhemer et al., 2008) and on modified bentonite, the
capacity was 138.17 mg g−1 (Shawabkeh et al., 2007). Adsorption
studies of Ni (II) (Anna et al., 2015; Vieira et al., 2010) showed max-
imum removal capacity to be 26.32 mg g−1 (Anna et al., 2015). The
adsorption capacities of mono and multi metal system (Cd (II), Cu (II),
Ni (II), Pb (II)) by different combination of multi-metals was studied by
Anna et al. (2015). For mono metal sorption capacity was
31.25 mg g−1, 32.26 mg g−1, 26.32 mg g−1 and 84.47 mg g−1 for Cd
(II), Cu (II), Ni (II) and Pb (II), respectively. For different multi metal
combinations the adsorption capacities varied [7.69 mg g−1 for Cd (II),
Cu (II), Ni (II) and Pb (II); 9.01 mg g−1 for Cu (II), Cd (II), Ni (II) and Pb
(II); 7.63 mg g−1 for Ni (II), Cd (II), Cu (II) and Pb(II) and 19.61 mg g−1
for Pb (II), Cd (II), Cu(II) and Ni(II)]. In case of different combination of
multi metal system, the adsorption capacities were found to be different
and less than that of mono metal due to antagonistic effects. From these
studies it was observed that bentonite clay showed a high selectivity
toward single metal as compared to multi-metal system due to the re-
ciprocal competitive effect between heavy metals in multi-component
systems (Anna et al., 2015). Shawabkeh et al. (2007) reported that
adsorption properties of bentonite clay increased almost thrice after
treatment with nitric and phosphoric acid followed by sodium hydro-
xide; showing increase in -sorption capacity from 73.50 mg g−1 to
202.6 mg g−1.
2.3. Nanocomposites materials for removal of heavy metals from water
Nanocomposite materials comprise of number of phases in which at
least one of the phase has size in nanoscale range (Roy et al., 1986).
Nanocomposite materials are classified on the basis of their matrix type
into three different classes: Ceramic Matrix, metal matrix and polymer
matrix. Ceramic-matrix nanocomposites preferably constitutes, metal
or ceramic as finely dispersed phase to obtain specific nano-scopic
properties. The metal matrix nanocomposites have irregular reinforced
materials as dispersed phase. In polymer matrix nanocomposites, na-
nosized particles are appropriately added to a polymer matrix and these
materials are also known as nanofilled polymer composites (Manias,
2007).
The nanocomposite materials contain high porosity and enormous
surface area to make it a potential contender for wastewater treatment.
Various sorption properties (active surface area, porosity, pore volume
and CEC etc.) of nanocomposite materials are increased by functiona-
lisation of one or more components of nanocomposites (Anirudhan
et al., 2012; Guerra et al., 2013; Danková et al., 2015). It has been used
for removal of water pollutants especially metal ions (Sharma et al.,
2009).
In general various nanocomposite materials (Zare and Lakouraj,
2014; Zare et al., 2015, 2016, 2018a,b; Lakouraj et al., 2014a,b;
Hasanzadeh et al., 2016) have been used as adsorbents for the sorption
of heavy metals from water. Adsorbents based on clay and polymer
nanocomposites such as kaolinite-PVA (Unuabonah et al., 2008);
polyaniline- Mt (Chen et al., 2014); Cellulose-Mt (Kumar et al., 2012)
PMEA-clay (Solenera et al., 2008) poly (acrylic acid)/organo-mon-
tmorillonite (Ma et al., 2017) β-cyclodextrin in the presence of
V.B. Yadav et al.
bentonite (Heydari et al., 2017) have also been reported in literature for
efficient adsorption of heavy metals from water.
Lakouraj et al. (2014a,b) stated that nanocomposite material (so-
dium alginate tetra sodium tiocalyx [4] arene tetra sulphonate) based
nanogels have super paramagnetic properties. They have fabricated
nanogels for heavy metal removal such as copper, cadmium, lead, co-
balt, nickel and chromium at aqueous condition at pH 7. The removal
efficiency of lead was found to be 99.8%, which was maximum among
all the heavy metals ions. In another study nanocomposite based on
poly pyrrole and modified –alt-maleic PSMA-g-4 ABSA anhydride was
synthesised to study antioxidant and heavy metal sorption activity at
pH 6. The maximum capacity of nanocomposite was found for copper
(Zare et al., 2015). Zare and Lakouraj (2014) studied removal efficiency
of Cu (II), Pb(II) and Cd(II) from water onto the biodegradable poly-
aniline/dextrin conductive nanocomposite and the maximum efficiency
was found for Cu(II). Zare et al., (2018a,b) has extensively reviewed
PANI and its derivatives based on conductive nanoadsorbents for re-
moval of heavy metals ion/dye from wastewater. The synthesis of na-
nogel and super-paramagnetic nanocomposite thiacalix[4] arene func-
tionalized Chitosan (Lakouraj et al., 2014a,b) was used as adsorbent for
removal of heavy metals. They used initial metal ion concentration as
50 mg L−1, with contact time of 120 min at pH 7 for the adsorption
studies. Adsorption trends for both nanocomposite and nanogel for
removal of heavy metals were found as Pb(II) > Cd(II) > Co(II) > Ni
(II) > Cu(II) > Cr (III) and Pb(II) > Cd(II) > Cu(II) > Ni(II) > Co
(II) > Cr (III) from water. They also studied desorption and reusability
of nanocomposites.
Pb(II) removal from aqueous solution on to poly aniline-co-3-ami-
nobenzoic acid based magnetic core shell nanocomposite was studied
by Zare et al. (2016). The adsorption capacity of Pb (II) was
138.31 mg g−1 at pH 6, interaction time 50 min, Initial concentration
50 mg L−1 and adsorbent dose 50 mg (Zare et al., 2016). Sulphonated
magnetic nanocomposite based on reactive PGMA-MAn copolymer@
Fe3O4 nanoparticle was used for removal of copper from water showing
adsorption capacity of 49.51 mg g−1 at equilibrium (Hasanzadeh et al.,
2016). Based on the results of BET surface area, Hasanzadeh et al.
(2016) reported the size enlargement of Fe3O4 particles during coating
process due to decrease in specific surface area from 86.711 to
8.23 m2 g−1 in the modified copolymer nanocomposites.
Zare and Lakouraj (2014) used super-paramagnetic poly (aniline-co-
m-phenylene diamine) @Fe3O4 nanocomposite for removal of Pb (II),
Cd(II) and Co (II), adsorption capacity was maximum 116.27 mg g−1
for Co (II) removal was found. Zare et al. (2018a) also studied the
synthesis, characterization and application of Poly (N-vinylpyrrolidone-
co-maleic anhydride@eggshell/Fe3O4 for removal of Cd(II) and Pb(II)
with maximum adsorption capacity as 312.5 and 32.75 mg g−1, re-
spectively. Same research group also synthesized and used poly m-
phenylenediamine grafted dextrin for removal of Pb(II) and Methylene
Blue dye (Zare et al., 2018b). Some carbon based nanocomposites such
as biochar supported hydrated manganese oxide (HMO) was used for
removal of Pb(II) and Cd (II) by using fix bed and batch techniques
(Wan et al., 2018a) and manganese oxide impregnated graphene oxide
was used for sorption of Cd(II) and Cu (II) with 93% adsorption effi-
ciency (Wan et al., 2018b).
2.3.1. Clay based nanocomposite for removal of heavy metals from water
Various adsorption studies on nanocomposites specially, clay based
for the removal of different noxious heavy metals from water has been
reported in Table 3 and described in the following section. The removal
of Pb (II) from aqueous solution on the nanocomposites was studied by
different research groups (El Adraa et al., 2017; Dukic et al., 2015; Irani
et al., 2015; Futalan et al., 2011; Unuabonah et al., 2008) and the
maximum removal capacity was found to be 430 mg g−1 onto Mt-hy-
drogel (Irani et al., 2015). The maximum sorption capacity for Cd (II)
was 72.31 mg g−1 on chitosan-clay nanocomposite (Tirtom et al., 2012)
and 0.25 mg g−1 for Cr (III) on chitosan-clay nanocomposite (Cittan
811
Journal of Environmental Management 232 (2019) 803–817
et al., 2014). For Cr (VI) removal the maximum capacity was found to
be 296 mg g−1 on Mt-SPC and 66.10 mg g−1 on bentonite-nZVI nano-
composite (Soliemanzadeh and Fekri, 2017).
The sorption studies of Cu (II) on various clay based nanocomposites
(El Adraa et al., 2017; Dukic et al., 2015; Kalantari et al., 2015; Futalan
et al., 2011; Anirudhan and Suchithra, 2010; Zhao et al., 2010) showed
maximum removal efficiency to be 106.2 mg g−1 on Humic acid-im-
mobilized-amine modified polyacrylamide-bentonite (HA-Am-PAA-B)
nanocomposite (Anirudhan and Suchithra, 2010). The capacity in-
creased by multiple of two (11 mg g−1 -20 mg g−1) on bentonite-PAA
due to change in pH from 6.2 to 5 (Zhao et al., 2010). The maximum
adsorption capacity of Zn (II) and Co (II) on HA-AmPAA-bentonite
nanocomposite was found to be 96.1 mg g−1 and 52.9 mg g−1 respec-
tively, at room temperature. The efficiency of HA-Am PAA-B in re-
moving metal ions from different industry wastewaters was also re-
ported (Anirudhan and Suchithra, 2010).
The removal efficiency of Ni (II) on different nanocomposites in
aqueous solution was investigated by various researchers (El Adraa
et al., 2017; Kalantari et al., 2015; Tirtom et al., 2012; Futalan et al.,
2011; Quintelas et al., 2009) and the maximum removal capacity was
found to be 73.81 mg g−1 (Kalantari et al., 2015). The adsorption ca-
pacity of E-coli-kaolinite nanocomposite for removal of Iron was found
to be 16.5 mg g−1 (Quintelas et al., 2009) from water. Chitosan–poly
(vinyl alcohol)/bentonite (CTS–PVA/BT) nanocomposites showed
maximum adsorption capacity for Hg(II) as 460 mg g−1 (Wang et al.,
2014). Their removal depends on the solution pH, metal concentration,
adsorbent dose and temperature.
2.3.2. Characterizing mechanisms and amount of heavy metal ions
adsorption
The characterizing mechanisms and amount of heavy metals ad-
sorption on to the various clay based nanocomposite are summarized in
Table 4. Mt/cystene nanocomposite was synthesized by chemical route
and used for removal of various heavy metals (Co (II), Ni (II), Cu (II), Zn
(II), Cd (II), Hg (II) and Pb (II)), the maximum amount of heavy metal
adsorption efficiency was found to be in range of 0.219 m mol g−1 to
0.242 m mol g−1 (El Adraa et al., 2017). Bentonite/NZVI nanocompo-
site was fabricated by chemical and physical process for removal of Cr
(VI), which has adsorption capacity of 66.10 mg g−1 for Cr (VI) removal
from water (Soliemanzadeh and Fekri, 2017). The amount of Co (II)
adsorption was 18.76 mg g−1 onto Fe3O4/bentonite nanocomposites,
which was synthesized using chemical co-precipitation (Hashemian
et al., 2015). Irani et al. (2015) fabricated Mt/Hydrogel nanocomposite
through emulsion polymerization reaction and lead adsorption was
found to be 460 mg g−1.
Mt/SPC nanocomposite was prepared by physico-chemical tech-
nique for sorption of Cr (VI), showing removal capacity of 296 mg g−1
(Mao et al., 2014). An Mt/algi/PA nanocomposite, fabricated by che-
mical oxidative polymerization technique was used for removal of Cr
(VI) from water with heavy metal uptake of 29.89 mg g−1 (Olad and
Farshi Azhar, 2014).
Some other nanocomposites such as bentonite/NZVI
(Soliemanzadeh and Fekri, 2017); Kaolinite/ZrO and Kaolinite/TBA
(Bhattacharyya and Gupta, 2006); Mt/cellulose/sodium (Kumar et al.,
2011); Bentonite/cross link chitosan (Liu et al., 2015); bentonite/Al13
pillared (Arfaoui et al., 2008) etc. have also been reported for removal
of Cr (VI) from water (Table 4). Free radical co-polymerization method
was adopted for fabrication of bentonite/PAA nanocomposite for re-
mediation of copper from water, having metal uptake capacity as
29–33 mg g−1 (Zhao et al., 2010). Other researchers also reported Cu
(II) removal using various clay based nanocomposites such as kaolinite/
ZrO and TBA, Mt/ZrO and TBA (Bhattacharyya and Gupta, 2006); Mt/
humic acid (Wu et al., 2011); Sodium/bentonite (Musso et al., 2014).
Pb (II) adsorption reported by various researchers (Guerra et al.,
2013; Anirudhan et al., 2012; Wang et al., 2011; Varadwaj et al., 2014;
Unuabonah et al., 2008) by applying different clay based
V.B. Yadav et al. Journal of Environmental Management 232 (2019) 803–817

Table 3
Applications of Nanocomposites for the Removal of heavy metals.
Adsorbents Heavy Adsorption capacity Initial metal conc. Contact Adsorbent dose SA Initial m2 SA Final m2 pH References
Metals (mg g−1) (mg L−1) Time (Min) (g) g−1 g−1

Cystene-Mt Co(II) 0.178–0.219 – – 0.5 – – 4.4 El Adraa et al. (2017)

- Ni(II) 0.176–0.228
Cu(II) 0.144–0.242
Zn(II) 0.211–0.235
Cd(II) 0.073–0.225
Hg(II) 0.147–0.229
Pb(II) 0.179–0.231
bentonite/NZVI Cr(VI) 1.34 5–100 1440 0.025 – – 5 Soliemanzadeh and Fekri
66.10 (2017)
bentonite Co(II) 9.74 800 – 0.1 34.44 – 9 Hashemian et al. (2015)
Fe3O4 15.22 98.44
Fe3O4-bentonite 18.76 140.5
Al-Pillared Mt Cd(II) 14.2 20–140 24 h 0.1 65.64 304.94 5 Ma et al. (2015)
Mt-Kaolinite/TiO2 Pb 71.1 25–800 60 0.05 – – 2–6.4 Dukic et al. (2015)
Cu 42.9
Zn 15.4
Cd 13.8
MT/Hydrogel Pb(II) 430 20–600 300 0.1 – – 2–6 Irani et al. (2015)
Mt Pb(II) 91.30 510.11 120 Sec 0.06 121.279 210.660 – Kalantari et al. (2015)
Fe3O4-Mt Cu(II) 93.37 182.94 0.08
Ni(II) 73.81 111.90 0.08
Chitosan/Clay Cr(III) 0.25 2.5 ml min−1 – 0.05 – – 7 Cittan et al. (2014)
Chitosan/PVA- Hg(II) 460 50 24 h 0.05 11.07 14.72 5.5 Wang et al. (2014)
bentonite
Mt- SPC Cr(VI) 296 50–500 120 0.02 987.2 863.4 5.5 Mao et al. (2014)
Mt-algi/PA Cr(VI) 29.89 50 5 -60 Sec 0.05 20–40 – 2–9 Olad and Farshi Azhar
(2014)
Chitosan/clay Ni(II) 32.36 100 0.5–24 h 0.1 – – 6 Tirtom et al. (2012)
Cd(II) 72.31 7
chitosan-bentonite Cu(II) 20.9 25–200 120–240 – 2.12 33.17 4 Futalan et al. (2011)
Pb(II) 28.77 84.28
Ni(II) 12.35
HA-AmPAA- Cu(II) 106.2 25–100 120 0.1 150.3 – 5 Anirudhan and
bentonite Zn(II) 96.1 203.5 9 Suchithra, 2010
Co(II) 52.9 336.3 8
bentonite-PAA Cu(II) 29–33 20 24 h 0.4 26.16 – 6.2 Zhao et al. (2010)
E.Coli/kaolinite Cd(II) 10.3 97 10 day 1 – – – Quintelas et al. (2009)
Cr(VI) 4.6 116
Fe(III) 16.5 110
Ni(II) 6.9 101
PVA -kaolinite Pb(II) 56.18 300 4.5 h 0.1–1 10.56 7.92 5.5 Unuabonah et al. (2008)
Cd(II) 41.67
AA/bentonite Pb(II) 1666.67 50–500 3h 0.025 g – – – Bulut et al., 2009
Ni(VI) 270.27
Cd(II) 416.67
Cu(II) 222.22

nanocomposites as adsorbent has also been discussed in Table 4.
Varadwaj et al. (2014) fabricated nanocomposite Mt/APTES by Che-
mical amidation method and applied it for almost complete removal of
very low initial lead concentration (200 ppb).
It is evident from the above review that more efficient materials are
required in actual pollution control processes. Therefore, it is required
to further enhance adsorption properties such as specific surface area,
micropore area, average pore diameter and total pore volume of clay by
using novel materials like CNT, since CNT are well known for their
extraordinary active surface area after modification (Gupta et al., 2014;
Zhao et al., 2010; Stafiej and Pyrzynska, 2007).
Recently, nanocomposites are synthesized by incorporating carbon
nano-fiber or CNT into the interlayer space of clay mineral have drawn
increasing attention due to their special physicochemical properties and
potential application for heavy metals removal (Yadav et al., 2018;
Chen et al., 2014; Sedaghat, 2013). This type of nanocomposites ob-
tained by directly intercalating carbon nanofiber or CNT within the
interlayer space of clay minerals or by in-situ transforming pre-inter-
calated materials. The main advantage of these nanocomposites are that
they minimize overall cost of raw material; have high thermal re-
sistance for easy regeneration by thermal treatment; hydrophobic
surface characteristics; controlled macroscopic shaping and high me-
chanical strength which facilitates manipulation and transport.
3. Future directions
Various materials like clay minerals, modified clay, activated/
modified carbon materials etc. have been used separately as well as in
combination as efficient materials for the removal of toxic con-
taminants from water and waste water. But there are certain limitations
in terms of removal of trace level of contaminants, cost effectiveness,
removal of multi-metal matrix through single adsorbent and efficiency
of above mentioned materials. Despite the fact, innumerable research
work has been carried out in developing innovative adsorbents for
water treatment but developed materials are not very efficient and cost
effective. In the recent times, researchers have focused on the adsorbent
material modification by various ways to achieve more effective and
efficient removal of heavy metal ions from water.
Therefore, more research is needed in the direction of enhancement
of active surface area, pore volume, pore size (Yadav et al., 2018), CEC
values, etc. It has been proposed to use modified clays to fill this gap as
this could be the most cost effective method for such treatment. There

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Table 4
Characterizing mechanism and amount of heavy metal ions adsorption.
Adsorbents Characterizing mechanism Heavy metals Adsorption capacity (mg g−1) References

−1
Mt/Cystene Chemical route Co (II) 0.219 m mol g El Adraa et al., 2017
Ni (II) 0.228 m mol g−1
Cu (II) 0.242 m mol g−1
Zn (II) 0.235 m mol g−1
Cd (II) 0.225 m mol g−1
Hg (II) 0.229 m mol g−1
Pb (II) 0.231 m mol g−1
Bentonite/NZVI Chemical & physical Cr (VI) 66.10 Soliemanzadeh & Fekri (2017)
Fe3O4/bentonite Chemical co-precipitation Co (II) 18.76 Hashemian et al. (2015)
AIPMtS Physical Cd (II) 14.2 Ma et al. (2015)
Mt/Kaolinite/Tio2 Mechano-Chemical Pb (II) 71.1 Dukic et al. (2015)
Cu (II) 42.9
Zn (II) 15.4
Cd (II) 13.8
Mt/Hydrogel Emulsion polymerization Pb (II) 430 Irani et al. (2015)
Mt/Fe3O4/Mt Chemical co-precipitation Pb (II) 91.3 Kalantari et al. (2015)
Cu (II) 93.37
Ni (II) 73.81
Chitosan/Clay Chemical Cr (III) 0.25 Cittan et al. (2014)
Chitosan/PVA-bentonite Interpenetration & cross linking Hg (II) 460 Wang et al. (2014)
Mt/SPC Physico-chemical Cr (VI) 296 Mao et al.
Mt-algi/PA Chemical oxidative polymerization Cr (VI) 29.84 Olad and Farshi Azhar (2014)
Chitosan/clay Chemical Ni (II) 32.36 Tirtom et al. (2012)
Cd (II) 72.31
Chitosan/bentonite Physico-chemical immobilization Cu (II) 20.9 Futalan et al. (2011)
Pb (II) 28.77
Ni (II) 12.35
HA-AmPAA-bentonite Chemical polymerization Cu (II) 106.2 Anirudhan and Suchithra, 2010
Zn (II) 96.1
Co (II) 52.9
bentonite-PAA Free-radical co-polymerization Cu (II) 29–33 Zhao et al. (2010)
E.Coli/kaolinite Bio-chemical Cd(II) 10.3 Quintelas et al. (2009)
Cr(VI) 4.6
Fe(III) 16.5
Ni(II) 6.9
PVA -kaolinite Physico-chemical Oxidation Pb(II) 56.18 Unuabonah et al. (2008)
Cd(II) 41.67
AA/bentonite Co-polymerization Pb(II) 1666.67 Bulut et al., 2009
Ni(VI) 270.27
Cd(II) 416.67
Cu(II) 222.22
Mn-Kaolin Surface coating Cu (II) 39.8 Danková et al., 2015
Kaolinite-TBA Chemical Fe (II) 9.3 Bhattacharyya and Gupta (2009)
Co(II) 9
Ni(II) 8.4
Kaolinite/PVA Chemical Pb 4.38 Unuabonah et al. (2008)
Cd 29.85
Kaolinite/ZrO Polynuclear ionic Cr (VI) 10.9 Bhattacharyya and Gupta (2006)
Kaolinite/TBA 10.6
Kaolinite/ZrO Polynuclear ionic Cu (II) 28.8 Bhattacharyya and Gupta (2006)
Kaolinite/TBA 3
Mt/APTES Chemical amidation Hg 6.19 ppb of 200 ppb Varadwaj et al., 2014
Cd 18 ppb
Pb 15 ppb
Mt/Humic Acid Covalent Cu 15.6 Wu et al. (2011)
Cd 15.25
Cr 14.14
Mt/Cellulose and Sodium Biopolymerisation Cr (VI) 22.2 Kumar et al. (2011)
Covalent
Mt/TBA Chemical Fe (II) 22.6 Bhattacharyya and Gupta (2009)
Co(II) 22.3
Ni(II) 19.7
Mt/Activated C Ionic Cu (II) 43.7 Özdemir and Yapar (2009)
Mt/ZrO Polynuclear ionic Cu (II) 3.2 Bhattacharyya and Gupta (2006)
Mt/TBA 27.3
Bentonite/chitosan Ionic Cr (VI) 89.13 Liu et al. (2015)
Bentonite/Na Covalent Cu (II) 56.89 Musso et al. (2014)
Zn (II) 103.83
Bentonite/AEAPS Chemical Pb (II) 29.54 Guerra et al. (2013)
Bentonite/Amin Chemical Pb 123.3 Anirudhan et al. (2012)
Bentonite/COOH Hg 113.6
Cu 53.1
(continued on next page)

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Table 4 (continued)

Adsorbents Characterizing mechanism Heavy metals Adsorption capacity (mg g−1) References

Bentonite/4 Amino antypyrene Chemical Cr 38.8 Wang et al. (2011)

Hg 52.9
Pb 55.5
Bentonite/Acid activated pillared Chemical & Pillaring Alumina Cr (VI) 103 Arfaoui et al. (2008)
Bentonite/NT-25 Chemical Cd (II) 111.2 Dal Bosco et al. (2006)
Mn (II) 6.0

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Acknowledgment
by activated carbon, carbon nanotubes, carbon nanofibers, and carbon fly ash: a
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IGDTUW, Delhi and Prof Satish Chandra, Director CSIR-Central Road
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