Ecotoxicology and Environmental Safety 148 (2018) 702–712

Contents lists available at ScienceDirect

Ecotoxicology and Environmental Safety

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

Review

Adsorption of heavy metals on conventional and nanostructured materials T

for wastewater treatment purposes: A review
⁎
Alexander E. Burakova, Evgeny V. Galunina, Irina V. Burakovaa, , Anastassia E. Kucherovaa,
Shilpi Agarwalb, Alexey G. Tkacheva, Vinod K. Guptab
a
Tambov State Technical University, 106, Sovetskaya Str., Tambov 392000, Russia
b
University of Johannesburg, Corner Beit and Nind Street, John Orr Building, P.O Box 17011, Doornfontein 2028, South Africa

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

Keywords: The problem of water pollution is of a great concern. Adsorption is one of the most efficient techniques for
Wastewater treatment removing noxious heavy metals from the solvent phase. This paper presents a detailed information and review
Adsorbents on the adsorption of noxious heavy metal ions from wastewater effluents using various adsorbents – i.e., con-
Heavy metals ventional (activated carbons, zeolites, clays, biosorbents, and industrial by-products) and nanostructured (full-
Nanostructured materials
erenes, carbon nanotubes, graphenes). In addition to this, the efficiency of developed materials for adsorption of
the heavy metals is discussed in detail along with the comparison of their maximum adsorption capacity in
tabular form. A special focus is made on the perspectives of further wider applications of nanostructured ad-
sorbents (especially, carbon nanotubes and graphenes) in wastewater treatment.

1. Introduction bodies (Akpor et al., 2014).

Rational use of water resources appears to be one of the world's
urgent environmental problems, the solution to which largely lies in
treating wastewater that comes from human activities in various fields:
industries (such as metallurgical, mining, chemical, tannery, battery
and nuclear), agriculture, shipping and others. It is especially important
to control contents of heavy metals (Roccaro et al., 2013; Ariffin et al.,
2017) which are one of the most biologically dangerous and toxic
components of wastewater effluents. Heavy metals are the group of
trace elements i.e. metals and metalloids with an atomic density greater
than 4 ± 1 g/cm3, e.g., Cu, Zn, Hg, Cd, Pb, Sn, Fe, Mn, Ag, Cr, Co, Ni,
As, Al etc. These metal ions are generally considered as the most
widespread toxic mineral contaminants of soil and water systems
(Salem et al., 2000; Mohammed et al., 2011).
There are two main sources of heavy metals in wastewater effluents
viz. natural and anthropogenic. The former includes soil erosion, vol-
canic activities, weathering of rocks and minerals, whereas the later
comprises mineral processing, fuel combustion, street run-offs, landfills,
agricultural activities, and industrial activities (mining, printed board
manufacturing, metal finishing and plating, semiconductor manu-
facturing, textile dyes, etc). Due to stability, high solubility and mi-
gration activity of heavy metals in aqueous media, untreated or in-
adequately treated metal-contaminated wastewater effluents cause a
variety of health and environmental impacts when released into water
Heavy metals are absorbed by plants, thereby entering the animal
and human bodies through food chains and negatively affecting their
health and vital activity (Baldwin and Marshall, 1999; Barakat, 2011;
Akpor et al., 2014; Harvey et al., 2015). Table 1 demonstrates the ne-
gative effects on human health caused by the most hazardous heavy
metals (As, Cd, Cr, Cu, Hg, Ni, Pb, and Zn) and the maximum con-
taminant level (MCL) standards in drinking water set by the US En-
vironmental Protection Agency (US EPA) for these contaminants. The
structure of atom electron shells of these contaminants determines their
high reactivity, tendency to form complexes and, consequently, high
biochemical and physiological activity, thereby leading to several en-
vironmental and health impacts. Therefore, it is necessary to treat
heavy metal-contaminated wastewater prior to its discharge to the
environment in order to avoid negative consequences such as getting
into drinking water.
Heavy metals can be removed from aqueous media using various
conventional methods such as chemical precipitation, solvent extrac-
tion, membrane filtration, ion exchange, electrochemical removal,
coagulation etc. However, these techniques have some disadvantages
such as incomplete removal, high-energy requirements and availability
of toxic sludge, low efficiency, sensitive operating conditions and costly
disposal (Eccles, 1999; Barakat, 2011).
To overcome these drawbacks, many approaches aimed at devel-
oping cheaper and more efficient methods to improve the quality of

⁎
Corresponding author.
E-mail address: iris_tamb68@mail.ru (I.V. Burakova).

https://doi.org/10.1016/j.ecoenv.2017.11.034
Received 22 August 2017; Received in revised form 7 November 2017; Accepted 13 November 2017
Available online 22 November 2017
0147-6513/ © 2017 Elsevier Inc. All rights reserved.
A.E. Burakov et al.
Table 1
MCL standards and ill effects of hazardous heavy metals (Babel and Kurniawan, 2003).
Heavy metal Ill effects
As Skin and vascular diseases, visceral cancer
Cd Renal disorders and damage, Carcinogenic
Cr Headache, Diarrhea, Nausea, Carcinogenic
Cu Liver damage, Wilson's disease, Insomnia
Hg Rheumatoid arthritis, Circulatory & Nervous
disorders
Ni Dermatitis, Chronic Asthma, Carcinogenic
Pb Cerebral disorders, Renal, Circulatory & Nervous
disorders
Zn Depression, lethargy, neurological signs, increased
thirst
treated effluents have been proposed. The majority of them are based
on using adsorption processes, since adsorption appears to have the
greatest impact on transport, toxicity and biological availability of
heavy metals (especially, at their trace amounts) in aqueous media
besides, it is easy to operate and cost effective (Leung et al., 2000;
Coelho et al., 2014; Santhosh et al., 2016).
Adsorption is often accompanied with the inverse process – deso-
rption, which represents the transfer of adsorbate ions from the ad-
sorbent surface to the solution. Depending on the adsorbate amount
desorbed from the adsorbent, one can judge on the reversibility of ad-
sorption: the more adsorbate is desorbed, the more reversible the ad-
sorption process is (Mishra, 2014).
There are two types of adsorption – physical, in which the increase
in the adsorbate concentration at the interface is due to non-specific
(i.e., not dependent on the substance nature) van der Waals forces, and
chemical (chemisorption) caused by chemical reactions between the
adsorbate and the adsorbent which create covalent or ionic bonds.
Physical adsorption is weakly specific, reversible, its thermal effect is
small (units of kJ/mol), whereas chemisorption is selective, usually
irreversible, its heat ranges from tens to hundreds of kJ/mol (Gupta
et al., 2015; Tripathi and Ranjan, 2015; Singh and Gupta, 2016).
Nowadays, adsorption is considered as an efficient and low-cost
technique for removing noxious heavy metal ions from wastewater ef-
fluents. This process is flexible in design and operation and allows for
producing high-quality treated effluents. Furthermore, since the ad-
sorption is reversible in some cases, adsorbents can be regenerated
through desorption (Fu and Wang, 2011).
There are many factors which affect the efficiency of adsorbents for
heavy metal removal from wastewater: e.g., initial concentration,
temperature, adsorbent dose, pH, contact time, and stirring speed. The
percentage (rate) of heavy metal adsorption usually increases with in-
crease in the above-mentioned factors (Sahu et al., 2009; Bisht et al.,
2016).
The adsorption of heavy metals can be described by the commonly
used Langmuir or Freundlich isotherm models. The Freundlich equation
is often useful for modeling sorption of metals onto solids with het-
erogeneous surfaces and has frequently proved superior to the
Langmuir equation for the adsorption of cations such as heavy metals.
Although there is a disagreement regarding the effectiveness of the
Langmuir and Freundlich models in interpreting the metal adsorption,
some parameters of these models, such as the Langmuir maximum
adsorption capacity (qmax) and the Freundlich constant related to the
distribution coefficient (KF), are widely acceptable in characterizing the
metal sorption capacity of various materials (Shaheen at al, 2012).
Materials used as adsorbents should have a high adsorption inter-
action towards the target contaminants in order to effectively remove
them from wastewater effluents. The adsorbents may be of mineral,
organic or biological origin – e.g., activated carbons, zeolites, clay
minerals, industrial by-products, agricultural waste, biomass, and
polymeric materials (Kurniawan et al., 2005; Barakat, 2011; Gautam
et al., 2014).
Ecotoxicology and Environmental Safety 148 (2018) 702–712
Over the past twenty years, nanotechnology has been applied in
almost all branches of science and technology. As a matter of fact,
different materials based on carbon nanostructures such as fullerenes,
MCL, mg/L
carbon nanotubes, graphene and graphene oxide have been synthesized
0.05 and used to remove the contaminants considered herein from aquatic
0.01 (Rao et al., 2007; Gupta and Saleh, 2013; Gautam and Chattopadhyaya,
0.05
2016; Santhosh et al., 2016). Taking into account the importance of
0.25
3.0 × 10-5 water quality and emerging benefits of nanotechnology, attempts have
been made to discuss various issues of water treatment using na-
0.20 noadsorbents. In this regard, such nanomaterials may present oppor-
6.0× 10-3 tunities for elaborating perspective solutions to the water pollution
problem.
0.80
Considering the aforementioned, the present paper contains a re-
view on the use of various types of materials i.e. conventional and
nanostructured as adsorbents for removing heavy metals from waste-
water effluents. Besides, a comparison of these materials regarding the
adsorption capacity for the considered contaminants is provided, with a
conclusion on perspectives of employing nanomodified adsorbents.
2. Adsorption removal of heavy metals from wastewater
Adsorption (in the case considered in the present review) is the
process taking place when a liquid solute (adsorbate) accumulates on
the surface of a solid (adsorbent) and forms a molecular or atomic film.
2.1. Adsorption on conventional materials
There exist numerous adsorbents of different nature and they can be
employed in initial or modified forms for removing noxious heavy
metals ions from wastewater effluents. The most frequently used ones
are activated carbons, zeolites, clay minerals, industrial solid waste,
and biomaterials (Singh and Gupta, 2016). Some of them are described
below.
2.1.1. Activated carbons and agricultural waste on the basis thereof
Adsorbents based on activated carbons (ACs) are widely used to
remove heavy metal contaminants due to their well-developed porous
structure (large mesopores and micropore volumes) and a high specific
surface area, as well as different surface functional groups (including
carboxyl, carbonyl, phenol, quinone, lactone, and others) bound to the
edges of the graphite-like layers. The most widely used carbonaceous
materials for the AC industrial production are coal, wood and coconut
shell (Jusoh et al., 2007; Kang et al., 2008; Fu and Wang, 2011;
Deliyanni et al., 2015).
Since coal-based ACs are expensive, their use has been limited
nowadays, and further efforts have been made to convert cheap and
abundant sources into ACs (Anirudhan and Sreekumari, 2011). In this
regard, ACs can be prepared from various agricultural waste.
Kongsuwan et al. (2009) explored the use of AC from eucalyptus
bark in the binary component sorption of Cu2+ and Pb2+. The max-
imum adsorption capacity for Cu2+ and Pb2+ was 0.45 and 0.53 mmol/
g, respectively, and adsorption was found to be the major mechanism
for the uptake of both heavy metals. Poultry litter to manufacture AC
for treating heavy metal-contaminated water was investigated by Guo
et al. (2010). They revealed that poultry litter-based AC possesses a
significantly higher adsorption affinity and capacity for heavy metals
than commercial AC derived from bituminous coal and coconut shell.
Karthikeyan et al. (2005) removed Cr6+ from wastewater using AC
derived from rubber wood saw dust. They achieved the maximum ad-
sorption capacity of 44 mg/g at the optimum pH 2.0, which was higher
as compared to the other adsorbents such as coconut tree saw dust
(Selvi et al., 2001), coconut shell carbon (Babel and Kurniawan, 2004),
sugarcane bagasse (Sharma and Forster, 1994), and treated saw dust of
Indian rose wood (Garg et al., 2004), where the Cr6+ maximum ad-
sorption capacity was found to be only 3.60, 10.88, 13.40, and 10 mg/
g, respectively. Lo et al. (2012)derived AC from Moso and Ma bamboo
703
A.E. Burakov et al.
and reached 100-% removal using once activated Ma bamboo and
91.7% removal using twice activated Ma bamboo. The removal effi-
ciency decreased for once activated Moso bamboo and twice activated
Moso bamboo by 20–77%, since their average pore diameter was less
than 2 nm, and the adsorbent is mesoporous in nature. Kobya (2004)
prepared AC using hazelnut shell, and the maximum adsorption capa-
city of 170 mg/g was reached at the optimum pH 1.0, which is higher
than the adsorption capacity of other adsorbents such as wood AC,
coconut shell AC (Selomulya et al., 1999) and tyre AC (Hamadi et al.,
2001), which was found to be only 87.6, 58.5, and 107.1 mg/g, re-
spectively.
Rice husk-based AC was prepared by Nasehir et al. (2010) through
chemical activation using ZnCl2 as chemical agent. The effects of acti-
vation temperature, activation time, and ZnCl2: char impregnation ratio
on the Cu2+ removal from aqueous solutions was studied. The optimum
material was obtained under the following conditions: activation tem-
perature of 500 °C, activation time of 1.71 h, and impregnation ratio of
1.04, which resulted in the Cu2+ removal rate of 33.92%. The removal
of Cu2+ from aqueous media via AC prepared from chestnut shells and
grape seeds as the adsorbent material was investigated by Özçimen and
Ersoy-Meriçboyu (2009). Adsorption experiments were performed with
variations in the initial metal ion concentration, temperature, and pH.
The authors found that the adsorption capacity of adsorbents increases
with an increase in temperature, pH, and surface area. Issabayeva et al.
(2010) obtained the same result for palm shell AC used to remove Cu2+
from aqueous solutions. Their results revealed that these ions are better
removed at high pH.
The ability of AC prepared from apricot stones for removing Ni2+,
Co2+, Cd2+, Cu2+, Pb2+, Cr2+and Cr6+ from aqueous solutions by
adsorption was investigated by Kobya et al. (2005). Apricot stones were
carbonized and activated after treatment with H2SO4 (1:1) at 200 °C for
24 h. The respective metal adsorption was found to be highly depen-
dent on pH. The optimum pH for removal (99.99%) was 1.0 for Cr6+,
whereas that for the other metal ions it varied from 3.0 to 6.0 for re-
moval efficiency ranging from 97.48% to 99.68%. The adsorption ca-
pacity for the metal ions decreased in the following sequence
Cr6+ > Cd2+ > Co2+ > Cr3+ > Ni2+ > Cu2+ > Pb2+. Almost the
same tendency was revealed by Fiol et al. (2006) for AC prepared from
olive stone waste generated in olive oil production as a metal biosor-
bent for Pb2+, Ni2+, Cu2+, and Cd2+ from aqueous solutions. The ef-
fects of contact time, solution pH, ionic medium, and initial metal
concentration were studied in batch experiments at room temperature.
The maximum metal sorption (85%) was found to take place at an in-
itial pH of approximately 5.5 to 6.0. The highest value of the Langmuir
maximum adsorption capacity (qmax) was found to be 6.88 10−5 mol/g
for Cd2+, followed by Pb2+ (4.47 10−5 mol/g), Ni2+ (3.63 10−5 mol/
g), and Cu2+ (3.19 10−5 mol/g). The results obtained illustrate that
olive stone waste, which has very low economic value, can be used for
the treatment of contaminated wastewater. AC prepared from olive
stone under the activation temperature of 650 °C, activation time of 2 h
and 20-% ZnCl2 was employed to adsorb Cd2+ from aqueous solutions
(Kula et al., 2008). The authors reported the maximum adsorption ca-
pacity of 1.85 mg/g achieved at the equilibrium time of 60 min, op-
timum pH of > 6.0, and adsorbent dosage of 1.0 g/50 mL. The same
precursor was studied by Uğurlu et al. (2009) to remove Ni2+ from
aqueous solutions by adsorption. They found that the maximum ad-
sorption capacity is 0.67 mg/g under the similar conditions. Another
study was reported by Alslaibi et al. (2013) for olive stone AC prepared
via microwave to remove a group of metals from synthetic wastewater:
Fe2+, Pb2+, Cu2+, Zn2+, Ni2+ and Cd2+. The optimum conditions
obtained were as follows: radiation power of 565 W, irradiation time of
7 min, and KOH:char impregnation ratio of 1.87. The removal effi-
ciency was found to be 98.55% for Cu2+, 95.32% for Cd2+, 98.19% for
Ni2+, 98.83% for Pb2+, 99.32% for Fe2+, and 98.36% for Zn2+ at pH
5.0, contact time of 3 h, initial metal concentration of 20 mg/L, and
agitation speed of 200 rpm.
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Ecotoxicology and Environmental Safety 148 (2018) 702–712
The adsorption of heavy metal ions from synthetic solutions was
performed with the use of sawdust from beech, linden, and poplar trees
by Božić et al. (2009). The results reveal that the maximum adsorption
capacity (7–8 mg/g of sawdust) for all the studied sawdust types was
achieved at pH 3.5–5.0. The acidification of the aqueous phase led to a
decrease in the adsorption capacity of the sawdust due to an increased
proton concentration occupying active sites in the adsorbent structure.
The degree of adsorption higher than 80% can be achieved for Cu2+;
however, this value is very low for Fe2+, which does not exceed 10%.
The removal of Pb2+ and Cu2+ from aqueous solutions was studied by
El-Ashtoukhy et al. (2008) using pomegranate peel AC. The material
was carbonized and activated in a muffle furnace at 500 °C for 1 h, then
soaked for 24 h in nitric acid. Batch adsorption experiments were per-
formed as a function of pH, contact time, and adsorbent dose. It was
found that the optimum pH required for maximum adsorption is 5.6
and 5.8, for Pb2+ and Cu2+ respectively. The removal of Pb2+ and
Cu2+ increased with time and reached saturation in about 120 min. By
increasing the initial concentrations, the percent metal removal de-
creased, whereas the percent removal of metal ions increases with in-
creasing weight of the adsorbents due to the greater availability of the
exchangeable sites or surface area at higher concentration of the ad-
sorbent. The similar phenomenon was reported by Acharya et al. (2009)
after studying the Pb2+ removal using AC prepared from Tamarind
wood at the ZnCl2: precursor impregnation ratio of 3:1, activation
temperature of 439 °C, and activation time of 40 min. The maximum
Pb2+ removal of 97.74% was achieved at the adsorbent dosage of 5 g/
L, pH 6.5, and initial Pb2+ concentration of 20 mg/L.
Apart from the above-mentioned materials, ACs modified with al-
ginate (Park et al., 2007), tannic acid (Üçer et al., 2006), magnesium
(Yanagisawa et al., 2010) and surfactants (Ahn et al., 2009)could be an
effective option for removing heavy metals.
2.1.2. Zeolites
Zeolites are crystalline alumino silicates that can occur naturally or
can be produced industrially on a large scale. They are among the best
adsorbents for the removal of heavy metal ions, since they are com-
posed of hydrated aluminosilicate minerals made from the interlinked
tetrahedral of alumina (AlO4) and silica (SiO4) moieties (Choi et al.,
2016). Zeolites have good ion exchange properties, a high surface area
and a hydrophilic character, which make them suitable for extracting
heavy metals from wastewater effluents.
Clinoptilolite is the most abundant natural zeolite, and it was found
to effectively remove heavy metals owing to its ion exchange capability,
followed by pretreatment (Babel and Kurniawan, 2003; Bose et al.,
2002; Shaheen et al., 2012). The selectivity series of clinoptilolite in the
sodium form for various heavy metal ions was determined to be follows:
Pb2+ > Cd2+ > Cu2+ > Co2+ > Cr6+ > Zn2+ > Ni2+ > Hg2+
(Zamzow et al., 1990).
Modified zeolites provide a higher adsorption capacity compared to
natural ones. There exist various methods for zeolite modification. For
instance, nanosized zeolite has more accessible pores which make it
more suitable for heavy metal removal. Among nanosized zeolite ad-
sorbents, NaX zeolite (Ansari et al., 2014) has been widely used to re-
move heavy metals (in particular, Cd2+) from wastewater (Erdem et al.,
2004; Ibrahim et al., 2010; Aliabadi et al., 2013; Rad et al., 2014). Rad
et al. (2014) synthesized NaX nanozeolite according to a microwave
heating method, and then polyvinylacetate polymer/NaX nanocompo-
site nanofibers were prepared using an electrospinning method. The
potential of these composite nanofibers was studied regarding Cd2+.
The reported maximum adsorption capacity was found to be 838.7 mg/
g with 80-% removal at the optimum pH 5.0. Choi et al. (2016) mod-
ified zeolite by replacing Si4+and Al3+ sites in the lattice with ex-
changeable cations such as Na+, Mg2+, K+, or Ca2+, leading to a net
negative charge. Mg-modified zeolite demonstrated some advantages
(non-toxicity, low cost, abundance, and availability) and large pore size
of 40–50 nm compared to the non-modified adsorbent. This modified
A.E. Burakov et al.
adsorbent showed the Ca+ removal of more than 98% at the optimum
pH 7.0. Besides, its adsorption capacity was found to be 1.5 times
higher than that of the K- and Na-modified zeolites, and up to 2.0 times
higher than that of the natural zeolite.
Furthermore, due to its low cost, fly ash – a coal combustion by-
product – can be used for zeolite formation based on the hydrothermal
process (Hui et al., 2005). Javadian et al. (2014) converted fly ash into
amorphous zeolite and achieved the maximum Cd2+ adsorption capa-
city of 26.246 mg/g with 84-% removal at the optimum pH 5. Similarly,
Visa (2016)hydrothermally transformed fly ash into zeolite using NaOH
to remove Cd2+, and reported that this product possesses a high specific
surface area, has many micropores, and is able to remove more than
80% of Cd2+ at the pH 7.0–8.0.
2.1.3. Clay minerals
There are three main groups of clays: kaolinite, smectites (bento-
nites), and mica. Among them, bentonites (in particular, montmor-
illonite) possess the greatest cation exchange capacity, it is highly se-
lective and regenerable, and it was found to be 20 times cheaper as
compared to ACs (Tripathi and Ranjan, 2015; Bisht et al., 2016).
The heavy metal removal capacity of clay minerals is less as com-
pared to zeolites. However, they are used for removing different heavy
metal species from wastewater due to a number of advantages over
other adsorbents such as high surface area, excellent physical (plasti-
city, bonding strength, shrinkage), chemical (large zeta potential, ca-
tion exchange property, shows monobasicity) and structural/surface
(load bearing strength, resistance to wear, resistance to chemical at-
tack) properties (Singh et al., 2001; Krikorian and Martin, 2005; Asçı
et al., 2007).
Bertagnolli et al. (2011) employed a bentonite clay after calcination
at 400–500 °C. After calcination, the chemical morphology and com-
position of the clay was found not to change, although the resulting
structural alterations affect its behavior toward water and enable to use
infixed bed columns with no expansion. This material presented the
Cu2+ maximum adsorption capacity of 11.89 mg/g. De Almeida Neto
et al. (2014) described the Cu2+ adsorption in a fixed bed using the
Bofe bentonite calcinated clay, and reported the Cu2+ maximum ad-
sorption capacity of 19.0638 mg/g. The equilibrium time increased
from 120 to 400 min, which is much less compared to the equilibrium
time obtained in the case of removing Cu2+ with chitosan immobilized
on bentonite (Futalan et al., 2011). Furthermore, the bed was re-
generated using NaCl/HCl solution at pH 5.0, thereby yielding 50-%
elution efficiency. It increased the removal capacity, since the bed be-
comes free from the heavy metals after contact with the eluent. Vengris
et al. (2001) modified the clay using HCl followed by neutralization of
the resultant solution with NaOH for the Cu2+ removal from waste-
water. This procedure resulted in the increased metal adsorption ca-
pacity by the modified clay compared with the unmodified one. The
acidic treatment led to the decomposition of the montmorillonite
structure. The maximum adsorption capacity obtained for the single
component solutions was 0.75 mg/g, whereas for the ternary compo-
nent solutions it was 0.80 mg/g. The experimental data fitted well the
Langmuir isotherm. In the same manner, Oubagaranadin et al. (2010)
modified a montmorillonite-illite clay using H2SO4 for the Cu2+ and
Zn2+ removal from wastewater. The BET model fitted well the ex-
perimental data, and the shape of the isotherm indicated that the metal
adsorption is multilayer.
Jiang et al. (2010) investigated a kaolinite clay to remove Pb2+,
Cd2+, Ni2+ and Cu2+ from wastewater. The metal uptake was rapid,
the maximum adsorption was observed within 30 min. This clay was
used for removing metal ions from real wastewater containing Pb2+,
where its concentration was reduced from 160.00 to 8.00 mg/L
2.1.4. Biomaterials
Biosorption of heavy metals from aquatic media is a relatively new
and promising process in the removal of heavy metal contaminants. The
705
Ecotoxicology and Environmental Safety 148 (2018) 702–712
major advantages of biosorption are its high effectiveness in adsorbing
heavy metal ions and the use of in expensive materials. This process is
particularly suitable for treating dilute wastewater. Typical biosorbents
can be derived from three sources: 1) non-living biomass such as bark,
lignin, shrimp, krill, squid, crab shell, etc.; 2) algal biomass; and 3)
microbial biomass such as bacteria, fungi and yeast (Apiratikul and
Pavasant, 2008).
Different forms of inexpensive, non-living plant material such as
potato peels (Aman et al., 2008), sawdust (Kaczala et al., 2009), black
gram husk (Saeed et al., 2005), eggshell (Jai et al., 2007), seed shells
(Amudaa et al., 2009), coffee husks (L. Oliveira et al., 2008; W.E.
Oliveira et al., 2008), sugar-beet pectin gels (Mata et al., 2009), citrus
peels (Schiewer and Patil, 2008), sugarcane bagasse (Dos Santos et al.,
2010), cashew nut shell (Coelho et al., 2014), among others, have been
widely studied as potential adsorbents for heavy metals.
Algae, a renewable natural biomass proliferating ubiquitously and
abundantly in the littoral zones of world, has attracted the attention of
many researchers as organisms to be tested and used as new adsorbents
to remove metal ions. Several advantages in applying algae include
their wide availability, low cost, high metal adsorption capacity and
reasonably regular quality (Apiratikul and Pavasant, 2008; Sharma and
Garg, 2014).
Studies on algae as heavy metal adsorbents include the biosorption
of Cu2+ and Zn2+ using dried marine green macroalgae
Chaetomorphalinum (Ajjabi and Chouba, 2009), biosorption of Cu2+,
Cd2+, Pb2+, and Zn2+ using dried marine green macroalgae Caulerpa
lentillifera (Pavasant et al., 2006), the biosorption of chromium from
wastewater using green algae Ulvalactuca (El-Sikaily et al., 2007), and
the biosorption of Pb2+ from wastewater by green algae Cladophor-
afascicularis (Deng et al., 2007). The biosorption of Cu2+ and Zn2+ by
dried marine green macroalgae (C.linum) was investigated by Ajjabi and
Chouba (2009). At the optimum particle size of 100–315 mm, biosor-
bent dosage of 20 g/L and pH 5.0, the dried alga produced the max-
imum Cu2+ and Zn2+ uptake values of 1.46 and 1.97 mmol/g, re-
spectively.
Microbial removal of metal ions from wastewater has been con-
sidered as being highly efficient. The biosorption of heavy metals in
aqueous solutions by bacteria includes Bacillus cereus (Pan et al., 2007),
Escherichiacoli (Souiri et al., 2009; Quintelas et al., 2009), Pseudomo-
nasaeruginosa (Gabr et al., 2008; Tuzen et al., 2008), etc. has been
studied. In these works, the maximum adsorption capacity was found to
be about 70–123 mg/g (e.g., in the case of Pb2+ and Ni2+), and the
adsorption process was successfully described by the Langmuir and
Freundlich isotherm models. Moreover, bacteria species such as Ba-
cillus sp., Micrococcusluteus,Pseudomonascepacia,Bacillussubtilise and
Streptomycescoelicolor have been effectively used for the Cu2+, Cd2+
and Ni2+ removal from wastewater (Nakajima, 2002; Öztürk et al.,
2004; Hassan et al., 2009). Veneu et al. (2013) employed Streptomyces
lumalinharesii for the Cu2+ removal from wastewater, and the adsorp-
tion rate of 81% was achieved at the optimum pH 5.0 with the best fit to
the Freundlich isotherm model.
Fungi are easy to grow, produce high yields of biomass and at the
same time can be manipulated genetically and morphologically. Fungi
biosorbents include Aspergillusniger (Amini et al., 2009; Tsekova et al.,
2010), Rhizopusarrhizus (Aksu and Balibek, 2007; Bahadir et al., 2007),
Saccharomycescerevisiae (Chen and Wang, 2008; Cojocaru et al., 2009),
Lentinusedodes (Bayramoglu and Arıca, 2008), etc. There are a number
of works dedicated to the removal of heavy metals using Rhizopus
biomass. Bhainsa and D'Souza (2008) studied the Cu2+ removal using
NaOH-treated Rhizopusoryzae biomass in a batch reactor. The maximum
Cu2+ capacity of the viable and pretreated biomass was found to be
19.4 and 43.7 mg/g, respectively. Biosorbents were characteristic of
broad sources, low-cost and rapid adsorption. However, the separation
of biosorbents would be difficult after process.
Yeast is a fungi that has a larger size than bacteria and, like other
eukaryotic organisms, has a nucleus and associated cytoplasmic
A.E. Burakov et al.
organelles. The cytoplasm present in living cells is important for the
living cells because it interacts with metal ions and after entering into
the cells, the heavy metal ions are separated into compartments for
removal (Wang and Chen, 2009). Waste beer yeast is a by-product of
the brewing industry that is a cheap and promising adsorbent for
copper removal from wastewater (Han et al., 2006). These researchers
reported the Cu2+ maximum uptake of 1.45 mg/g with a preferred fit to
the Langmuir and Freundlich isotherms; the process reached equili-
brium within 30 min.
2.1.5. Industrial solid waste
Industrial solid waste also possesses an adsorption capacity and can
be used for adsorbing heavy metals from wastewater. It is produced as a
by-product and is rarely used for any other purposes. The by-product
nature renders it to be easily available and very economical as well. The
heavy metal adsorption capacity of the industrial waste could be in-
creased followed by slight physical and chemical modification. By-
products such as fly ash (Bayat, 2002; H.J. Wang et al., 2007; S.B. Wang
et al., 2007; S.-G. Wang et al., 2007; Al Zboon et al., 2011), blast fur-
nace sludge (Dimitrova, 1996; Srivastava et al., 1997), waste slurry,
lignin (Srivastava et al., 1994; Demirbas, 2004; Suhas Carrott and
Ribeiro Carrott, 2007), Fe(OH)3 (Namasivayam and Ranganathan,
1993, 1998) and red mud (Altundogan et al., 2000; Gupta and Ali,
2002) have been used as effective adsorbents during the past for their
technical feasibility to remove toxic heavy metals from contaminated
water. Other industrial waste such as coffee husks (L. Oliveira et al.,
2008; W.E. Oliveira et al., 2008), Areca waste (Zheng et al., 2008), tea
factory waste (Malkoc and Nuhoglu, 2007), sugar beet pulp (Pehlivan
et al., 2006), waste pomace of olive oil factory waste (Malkoc et al.,
2006), battery industry waste, waste biogas residual slurry
(Namasivayam and Yamuna, 1995), sea nodule residue (Agrawal et al.,
2004) and grape stalk waste (Villaescusa et al., 2004) have been uti-
lized as low-cost adsorbents for the removal of toxic heavy metals from
wastewater.
Several adsorbents have been used for the adsorption of Zn2+ from
wastewater. The Zn2+ maximum adsorption capacity was found to be
168 mg/g for powdered waste sludge, 73.2 mg/g for lignin, 55.82 mg/g
for cassava waste, which is higher compared with the adsorption ca-
pacity of 52.91 mg/g achieved for the bentonite clay, and in most cases
lower (except for the powdered waste sludge) compared with the ad-
sorption capacity of 128.8 mg/g achieved the dried marine green
macroalgae biomaterial (Zwain et al., 2014).
Among the industrial by-products, red mud has the advantage of
being cheap and available and possesses a high metal adsorption ca-
pacity. However, it also has some disadvantages, such as the difficulty
of dealing with the wastewater produced during its activation before
application, and its regenerating/recovering after application (Zhu
et al., 2007). Nevertheless, Zhu et al. (2007) have succeeded in devel-
oping red mud as a novel adsorbent to remove Cd2+ from wastewater.
In this regard, the adsorption process onto this granular material was
found to be spontaneous and endothermic in nature. The authors
achieved the Cd2+ maximum adsorption capacity of 52.1 mg/g at the
pH 3.0- 6.0. In the same manner, Gupta and Sharma (2002) also used
red mud to remove Cd2+ from wastewater, and complete removal was
obtained at lower concentrations (1.78 10-5 − 1.78 10-4 M), whereas
60–65-% removal was achieved at higher concentrations (1.78 10-4 –
1.78 10-3 M) at the optimum pH 4.0–5.0. Ma et al. (2009) used red mud
containing substantial amounts of CaCO3 to remove several heavy
metal ions (Cu2+, Zn2+, and Cd2+) from wastewater. With an increase
in saturation degree of binding sites on red mud particles by the heavy
metals, the proportion of HCH3COO-extractable Cu fraction (acetic
acid-extractable Cu fraction) increased accordingly. Cu2+, Zn2+ and
Cd2+ were found to increasingly bind with HCH3COO-extractable
forms until the adsorption capacity of red mud was depleted. Ju et al.
(2012) mixed 2–8% w/w granular red mud with cement and reported
the Cd2+ adsorption capacity of 9 mg/g. It was also found that an
706
Ecotoxicology and Environmental Safety 148 (2018) 702–712
increase in temperature increases the adsorption equilibrium adsorp-
tion, thereby assuming that the adsorption process is endothermic in
nature.
2.2. Adsorption on nanostructured materials
Conventional materials, some of which are described above, usually
suffer from low metal adsorption capacity and cannot provide the de-
sired removal efficiency for the majority of heavy metals in wastewater
treatment (Rao et al., 2007). In this regard, scientists perform studies on
developing novel adsorbents with improved characteristics.
Nowadays, there is an increasing tendency to employ nanos-
tructured materials, such as fullerenes (Darwish, 2013), and especially,
carbon nanotubes (Burakov et al., 2014) and graphene (Melezhyk et al.,
2016), in many fields, including the removal of heavy metals from
wastewater effluents, due to their unique physical, chemical and me-
chanical properties. They have very high strength, resistance, electrical
conductivity, and thermal stability. Besides, their high specific surface
of these nanomaterials is combined with the manifestation of various
types of intermolecular interactions, thereby allowing them to be ef-
fectively used in various adsorption systems.
2.2.1. Fullerenes
Fullerenes were discovered in 1985 through spectrometric mea-
surements on the interstellar dust (Kroto et al., 1985). They represent
closed-cage carbon molecules containing pentagonal and hexagonal
rings. Their formula is C20+m, where m is an integer number. Fullerenes
comprise a wide range of isomers and homologous series - from the
most studied C60and C70 to the so-called higher fullerenes like C240,
C540 and C720. The relatively high electron affinity, hydrophobic surface
and high surface/volume ratio of these materials allows for employing
them for extraction of different species from aqueous media (B.T. Zhang
et al., 2013; M. Zhang et al., 2013).
The adsorption capacity of fullerenes is usually related to surface
defects (Valcarcel et al., 2008). It is assumed that the adsorption of
species on fullerenes occurs as a result of penetration of a sorbate into
the lattice. In the fullerene C60, the space between carbon nanoclusters,
where adsorbate ions come to through defects, acts as micropores
(Kaneko et al., 1993).
The low tendency of fullerenes for aggregation and their large
specific surface area make it possible to use them as adsorbents for
purifying industrial wastewater from heavy metals (Lucena et al., 2011;
Scida et al., 2011). Alekseeva et al. (2016) used fullerenes either alone
or as part of a polystyrene-based composite film material. They estab-
lished that the Cu2+ removal efficiency is higher in the first case, and
the equilibrium isotherm of the Cu2+ adsorption on the fullerene fits to
the Langmuir model. The adsorption capacity of a monomolecular layer
with reference to Cu2+ was found to be 14.6 mmol/g.
However, their direct use is unprofitable due to high price.
Therefore, studies on the modification of conventional sorbents (ACs,
zeolites, lignin, etc.) by small amounts of fullerenes with the purpose of
enhancing their adsorption capacity have been performed (Samonin
et al., 2008, 2014). It was found that the introduction of fullerenes leads
to the development of the porous structure of the adsorbent, increases
hydrophobicity, and also improves the adsorption capacity of the ma-
terial in the adsorption of heavy metals from water. For instance, after
having introduced 0.001–0.004% of fullerenes into ACs, their adsorp-
tion capacity for Pb2+ and Cu2+ increased by 1.5–2.5 times (Samonin
et al., 2008).
As a separate application field for fullerenes, it is worth noting the
extraction of heavy metals (preconcentration) in the form of chelates
formed with various chelating reagents – e.g., with pyrrolidine-am-
monium dithiocarbamate or pyrrolidine-sodium diethylcarbamate
(Gallego et al., 1994). To regenerate and reuse fullerenes as adsorbents,
chelates are desorbed by appropriate solvents.
It should be noted that there are not so much publications regarding
A.E. Burakov et al.
the use of fullerenes for removing heavy metals from wastewater. At
present, they are mostly employed to extract organic compounds from
aquatic media (Gupta and Saleh, 2013).
2.2.2. Carbon nanotubes
Carbon nanotubes (CNTs) were discovered in 1991 (Iijima, 1991).
They represent single- or multi-walled long carbon cylinders in the form
of rolled graphite sheets (where carbon forms a continuous hexagonal
network) with a diameter from one to several tens of nanometers and a
length of up to several centimeters. CNTs have led research to new area
in many investigations due to their advantages: unique structural,
electronic, optoelectronic, semiconductor, mechanical, chemical and
physical properties (Haddon, 2002). These properties combined with
chemical stability, large specific surface area (150–1500 m2/g, which is
many times higher than for fullerenes) and availability of well-devel-
oped mesopores make CNTs efficient adsorbents for heavy metal re-
moval (Gupta et al., 2011a; Wang et al., 2012).
Since CNTs can be covalently or non-covalently modified (functio-
nalized) with various organic molecules, they are able to more selec-
tively interact with adsorbates and have greater maximum adsorption
capacity after modification (Rao et al., 2007; Chen et al., 2009; Bisht
et al., 2016; Gupta et al., 2016). There is a certain opinion that in the
processes of adsorption purification of wastewater effluents from heavy
metals CNTs can eventually replace ACs and other adsorbents (Hussain
and Mitra, 2011). In this regard, Table 2 compares the heavy metal
maximum adsorption capacity of CNTs and some conventional mate-
rials.
Stafiej and Pyrzynska (2007) elucidated that the pH and metal ion
concentrations in aqueous media could affect the adsorption char-
acteristics of CNTs. The sorption mechanisms were found to be gov-
erned by the surface features, ion exchange process and electrochemical
potential (Gao et al., 2009). The latter plays a significant role in multi-
component sorption where redox reactions are likely to take place not
only on the adsorbent surface, but also among different adsorbates (Li
et al., 2003a; Sadegh et al., 2017). Nevertheless, it is commonly be-
lieved that chemical interactions between heavy metal ions and CNT
surface functional groups appear to be the major sorption mechanism
(Lu et al., 2006; Rao et al., 2007; Santhosh et al., 2016).
Oxidized CNTs have also shown exceptionally high sorption capa-
city and efficiency for Pb2+, Cd2+ and Cr6+ from water (Li et al., 2002,
2003b; Robati, 2013). H.J. Wang et al. (2007) showed that the ad-
sorption capacity of multi-walled CNTs treated with concentrated
HNO3 can be significantly increased mainly due to oxygen functional
groups created on the surface of acidified nanotubes that can react with
Pb2 + to form complex or salt precipitates on the surface. The ad-
sorption equilibrium time for the acidified CNTs was found to be 20 min
at the pH 2.0, which is much less than for ACs (about 120 min).
Table 2
Metal maximum adsorption capacity (qm, mg/g, calculated from the Langmuir equation) for CNTs and some conventional adsorbents.
Heavy metal ion (adsorbate) Adsorbent qm, mg/g
2+
Cu As-produced CNTs 8.25
NaOCl-modified CNTs 47.39
AC 19.50
Sawdust 37.17
Zeolite 8.13
Ni2+ Multi-walled CNTs 3.72
NaClO-modified single-walled CNTs 47.86
NaClO-modified multi-walled CNTs 38.46
Granulated AC 2.88
Montmorillonite 12.89
Pb2+ Acidified multi-walled CNTs 49.71
Original bentonite 19.19
Cicer arientinum biomass 27.79
Pine wood char 4.13
AC F-400 30.11
Ecotoxicology and Environmental Safety 148 (2018) 702–712
CNTs can also be used to prepare composites with Fe2O3, ZrO2 and,
using a coprecipitation method, with Fe3O4, Al2O3 (Yang et al., 2009;
Gupta et al., 2011b; Ntim and Mitra, 2012; Tang et al., 2012) to remove
Cr, As, Ni, Pb and Cu ions. The adsorption of ions on these composites
was found to depend on the pH value, so desorption can be easily ac-
complished by changing the pH. In addition, the adsorption process was
well described by the Langmuir model. Depending on the pH and
temperature, the sorption capacity of the composites varied from 10 to
31 mg/g. Luo et al. (2013) prepared MnO2/Fe2O3/acid oxidized multi-
walled CNT nanocomposites to remove Cr6+. The maximum adsorption
capacity of this nanocomposite was found to be 186.9 mg/g with the
maximum removal capacity of 85% at the optimum pH 2.0. Yu et al.
(2011) suggested that instead of chemically oxidized multi-walled
CNTs, plasma-oxidized multi-walled CNTs be used as adsorbents for a
number of metals. Compared with chemically oxidized CNTs, plasma-
oxidized tubes showed an increased adsorption capacity, mainly due to
the addition of functional groups containing oxygen to the CNT surface.
The study of the regeneration process showed that the metal ions are
easily extracted (desorbed) from the plasma-oxidized CNTs.
Zhao et al. (2010) and S.G. Wang et al. (2007) developed CNT-based
hybrid adsorbents using TiO2 and MnO2, respectively, for extracting
Pb2+ was considered. The results showed that these hybrid systems can
be used as an effective sorbent for this metal (in the first case, the ad-
sorption capacity was 137 mg/g, and in the second case, it was
78.74 mg/g).
Burakov et al. (2014) proposed to modify ACs with CNTs synthe-
sized by chemical vapor deposition of carbon from the gas phase at
catalytic sites formed on the AC surface and in AC macropores from the
original components. These hybrid adsorbents showed an increased (by
10–30%) adsorption capacity for Ni2+ and Co2+. Romantsova et al.
(2016) made an attempt to consider the heterogeneity of the surface of
the above-mentioned nanomodified adsorbents, for which the dual-site
combined Langmuir-Freundlich equation was used to distinguish be-
tween two types of adsorption sites – with greater and lesser energy of
affinity for the adsorbate (Ni2+): the former are responsible for che-
mical reactions and surface complexation, whereas the latter char-
acterize electrostatic interactions and ion exchange. It was found that
the Ni2 + sorption is mainly controlled with the greater- energy sites,
and the nanomodification leads to a 20-% increase in the adsorption
capacity at small (up to 0.1 mol/L) equilibrium adsorbate concentra-
tions.
Table 3 summarizes the maximum adsorption capacity of previously
reported CNTs – original or modified with different functional groups.
2.2.3. Graphene and graphene-based materials
Graphene, discovered in 2004, is a two-dimensional, atomic-scale
hexagonal lattice made of carbon atoms. Like CNTs, it also has unique
Conditions Reference
pH6.0, 300 K Wu (2007)
pH6.0, 300 K Wu (2007)
303 K Rao et al. (2009)
pH 6.6, 303 K Ahmad et al. (2009)
pH 5.0, 298 K Sljivic et al. (2009)
pH 5.4, 293 K Yang et al. (2009)
298 K Lu et al. (2009)
298 K Lu et al. (2009)
pH4.5, 298 K Godino-Salido et al. (2009)
pH 6.0, 298 K Ijagbemi et al. (2009)
pH 5.0, 298 K H.J. Wang et al. (2007), S.B. Wang et al. (2007), S.-G. Wang et al. (2007)
303 K Kul and Koyuncu (2010)
pH 4.0, 303 K Nadeem et al. (2009)
pH 5.0, 298 K Mohan et al. (2007)
pH 5.0, 298 K Mohan et al. (2007)
707
A.E. Burakov et al. Ecotoxicology and Environmental Safety 148 (2018) 702–712

Table 3 Ren et al. (2013) and B.T. Zhang et al. (2013) and M. Zhang et al.
Maximum adsorption capacity (qm, mg/g or mmol/g, calculated from the Langmuir (2013) studied the adsorption properties of GO, and they found that,
equation) of various types of CNTs or composites on the basis thereof for some heavy
like graphene, this material has a large sorption capacity for various
metal ions (Rao et al., 2007; Bisht et al., 2016; Santhosh et al., 2016).
pollutants, including heavy metals. However, due to the fact that GO is
Adsorbent Adsorbate qm Reference well dispersed in water, it is difficult to reuse it for metal adsorption
after reprocessing. To overcome this drawback, it was proposed to
CNTs Pb2+ 17.44 mg/g, Stafiej and Pyrzynska (2008)
combine GO with some magnetic materials, such as Fe3O4, MnFe2O4
pH7.0
CNTs (HNO3) Pb 2+
49.95 mg/g, Li et al. (2002) and CoFe2O4, which possess low toxicity and good biocompatibility
pH7.0 preferable in for purification of anthropogenic water (Li et al., 2012;
2+
Multi-walled Ni 7.53 mg/g, Lu and Liu (2006) Kumar et al., 2014; Zhang et al., 2014).
CNTs pH7.0 Hur et al. (2015) studied the adsorption of several metal ions (Cu2+,
Single-walled Ni2+ 9.22 mg/g, Lu and Liu (2006)
Pb , Cd2+) on magnetic GO synthesized in a simple way using ul-
2+
CNTs pH7.0
Multi-walled Pb2+ 97.08 mg/g, Li et al. (2003a) trasonic treatment of graphite oxide and Fe3O4. It was found that ir-
CNTs (HNO3) pH5.0 respective of the adsorbent, the metal adsorption depends mainly on pH
2+
CNTs Pb 1.406 mmol/g Anitha et al. (2015) and is controlled by the ion exchange between the positively charged
CNT-OH Pb2+ 2.07 mmol/g Anitha et al. (2015)
metal ions and the negatively charged adsorption sites on the adsorbent
CNT-CONH2 Pb2+ 1.907 mmol/g Anitha et al. (2015)
CNT-COO- Pb2+ 4.672 mmol/g Anitha et al. (2015) surface.
CNTs Cu2+ 1.219 mmol/g Anitha et al. (2015) Zhao et al. (2011b) synthesized few-layered GO from graphite via
CNT-OH Cu2+ 1.342 mmol/g Anitha et al. (2015) the modified Hammer method. This material was employed to remove
CNT-CONH2 Cu2+ 1.755 mmol/g Anitha et al. (2015) Pb2+ from aqueous solutions. It was found that the presence of the
CNT-COO- Cu2+ 3.565 mmol/g Anitha et al. (2015)
oxygen-containing groups on the surface of the adsorbent increases its
CNTs Cd2+ 1.291 mmol/g Anitha et al. (2015)
CNT-OH Cd2+ 1.513 mmol/g Anitha et al. (2015) maximum adsorption capacity (up to 1850 mg/g).
CNT-CONH2 Cd2+ 1.563 mmol/g Anitha et al. (2015) Lujaniene et al. (2016) reached a sufficiently high sorption capacity
CNT-COO- Cd2+ 3.325 mmol/g Anitha et al. (2015) (up to 574 mg/g) for a number of heavy metal ions (Co2+, Cu2+, Pb2+,
CNTs Hg2+ 1.068 mmol/g Anitha et al. (2015)
and Ni2+). Like in the other studies, here the adsorption process was
CNT-OH Hg2+ 1.284 mmol/g Anitha et al. (2015)
CNT-CONH2 Hg2+ 1.658 mmol/g Anitha et al. (2015)
also controlled by the initial and final pH of the solution.
CNT-COO- Hg2+ 3.300 mmol/g Anitha et al. (2015) Table 4 summarizes the information on the heavy metal adsorption
CNTs (HNO3) Cr6+ 0.5 mg/g, pH Atieh et al. (2010) capacity of some of the graphene-based materials previously used for
7.0 water treatment purposes.
CNTs/activated Cr6+ 264.5 mg/g, pH Sankararamakrishnan et al.
Al2O3 2.0 (2014)
N-CNTs Cr6+
638.56 mg/g, Shin et al. (2011) 3. Evaluation of present scenario & our insights
pH 8.0
Single-walled Zn2+ 43.66 mg/g, pH Lu and Chiu (2006) Several materials (namely, activated carbon, biomaterials, rubber
CNTs 7.0
waste, nanoparticles, CNTs – MWCNTs and SWCNTs, etc.) have been
(NaOCl)
Multi-walled Zn2+ 32.68, mg/g, pH Lu and Chiu (2006)
used as effective adsorbents for the removal of noxious impurities from
CNTs 7.0 wastewater. But there are certain limitations in terms of cost effec-
(NaOCl) tiveness and efficiency of the above-mentioned materials. Although, a
lot of work has been carried out in developing novel adsorbents for
wastewater treatment but countries like Russia and India is still short in
structural, mechanical, physical and chemical properties, which allow the cost effective technology transfers for effective wastewater treat-
for using it in many fields (Geim, 2009; Novoselov et al., 2012). Gra- ment because the developed material is not that much efficient and
phene is available in various forms such as pristine graphene, graphene economical. In the recent era, we are working on the aspects of the
oxide (GO) and reduced GO. adsorbent modification - i.e., activated carbon loaded on the nano-
From the past decade, there is a huge growth in the use of graphene particles for more effective and efficient removal of noxious impurities
and graphene based materials for environmental purposes, including from wastewater, in addition to this we are looking for the successful
wastewater treatment, due to their high specific surface area, enhanced technology transfer in the field of wastewater treatment using novel
active sites and the functional groups present on their surface, and good biomaterials as adsorbents.
chemical stability (Gopalakrishnan et al., 2015).
Graphene may be oxidized to add hydrophilic groups for heavy 4. Conclusion
metal removal (Bisht et al., 2016). Studies of many scientists confirm
that graphene-based materials have a strong sorption activity with re- A detailed compilation of the conventional and nanoparticles as
spect to heavy metals (e.g., Huang et al., 2011; Zhao et al., 2011a; Cong adsorbents is presented in the form of compact information in the
et al., 2012). present review. Keeping in view the nanotechnology interventions, we
Deng et al. (2010) considered functionalized graphene as an ad- are mainly focused on promising nanoadsorbents such as carbon na-
sorbent to remove Pb2 + from an aquepus medium. Its maximum ad- notubes, graphene and activated carbon loaded on nanoparticles etc.
sorption capacity was found to be 406.6 mg/g at the optimum pH 5.0. which have further perspectives of employing in the above-mentioned
The equilibrium of this process was achieved within 40 min. environmental field. In this regard, materials developed on the basis of
Li et al. (2016) developed an adsorbent representing graphene hy- nanotechnology and having unique physical, chemical and mechanical
drogel lignosulfonate-modified with various oxygen-containing groups. properties (especially, the nanomaterials mentioned above) can become
The researchers marked its large specific surface area, high porosity and a promising alternative to traditional adsorbents, both independently
activity of adsorption sites on the surface, as well as the great Pb2+ and as a part of hybrid materials for more efficient removal of heavy
maximum adsorption capacity of 1308 mg/g. The equilibrium of the metal pollutants from wastewater effluents.
process was reached in 40 min. In this work, the authors also note that
this sorbent is environmentally friendly and is subject to regeneration Acknowledgement
(processing), which makes it possible to employ it for wastewater
purification on a large scale. The work was supported by the Ministry of Education and Science of

708
A.E. Burakov et al. Ecotoxicology and Environmental Safety 148 (2018) 702–712

Table 4
Maximum adsorption capacity (qm, mg/g, calculated from the Langmuir equation) of various graphene-based adsorbents for some heavy metal ions (Bisht et al., 2016; Santhosh et al.,
2016).

Adsorbent Adsorbate qm Reference

Graphene oxide (GO)/Fe3O4 Cu2+ 18.3 Wu (2007)

GO/SiO2/Fe3O4 Pb2+ and Cd2+ 333.3 and 166.7 Wang et al. (2013)
GO/Fe3O4/sulfanilic acid Cd2+ 55.4 Hu et al. (2014)
GO-MnFe2O4 Pb2+ 673 Kumar et al. (2014)
Reduced GO/COFe2O4 Pb2+ 299.4 Zhang et al. (2014)
GO/Mn-Fe2O3 Cd2+ and Cu2+ 87.2 and 129.7 Nandi et al. (2013)
GO/Fe3O4/sulfanilic acid Cu2+ 50.7, 56.8 Hu et al. (2013)
GO/Fe3O4 Cu2+, Pb2+, Cd2+ 23.1, 38.5, and 4.4 Hur et al. (2015)
GO Pb2+ 35.6 Lee and Yang (2012)
TiO2/GO Pb2+ 65.6 Madadrang et al. (2012)
GO-EDTA Pb2+ 479 Madadrang et al. (2012)
Graphene nanosheets (GNSs) Pb2+ 22.4 Huang et al. (2011)
GNSs-500 Pb2+ 35.2 Huang et al. (2011)
SiO2–GNSs Pb2+ 113.6 Hao et al. (2012)
MnO2/GNSs Hg2+ 10.8 Sreeprasad et al. (2011)
GO- based inverse spinel nickel ferrite composite Cr6+ 45, pH 4.0 Lingamdinne et al. (2015)
Fe(0) assembled on magnetic Fe3O4/grapheme nanocomposites Cr6+ 101, pH 3.0 Lv et al. (2014)
Copolymer of dimethylaminoethyl methacrylate with grapheme oxide Cr6+ 82.4, pH 1.1 Ma et al. (2015)
Graphene sand composite Cr6+ 2859.38, pH 1.5 Dubey et al. (2015)
GO Cr6+ 43.72, pH 5.0 Yang et al. (2014)
GNSs modified with cetyltrimethylammonium bromide Cr6+ 21,57, pH 2.0 Wu et al. (2013)

the Russian Federation under Grant No. 16.1384.2017/PCh.
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