Journal of Molecular Liquids 241 (2017) 1091–1113

Contents lists available at ScienceDirect

Journal of Molecular Liquids

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

Review

A comprehensive review on recent developments in bentonite-based

materials used as adsorbents for wastewater treatment
Sadanand Pandey ⁎
Department of Applied Chemistry, University of Johannesburg, P.O. Box 17011, Doornfontien, Johannesburg 2028, South Africa
Centre for Nanomaterials Science Research, University of Johannesburg, Johannesburg, South Africa

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

Article history: The chemical contamination of water from an extensive variety of toxic derivatives, specifically heavy metals, ar-
Received 24 April 2017 omatic molecules and dyes, is a genuine ecological issue attributable to their potential human lethality. In this
Received in revised form 15 June 2017 way, there is an earnest need to create advances that can remove harmful toxins found in wastewaters.
Accepted 25 June 2017
Among all the reported treatment techniques, adsorption is one of the more prevalent systems for the removal
Available online 28 June 2017
of contaminations from the water. Adsorption is a standout among the most simple and effective strategy for
Keywords:
treating industrial effluents, and a valuable device for ensuring nature. The increasing number of publications
Bentonite composite on adsorption of toxic compounds by modified bentonites demonstrates that there is a recent increasing interest
Nanotechnology in the synthesis of new low-cost adsorbents used in water treatment. The present review demonstrates the late
Adsorption advancements of nanotechnology in the synthesis of nanoadsorbents containing bentonite and its composites.
Heavy metals The primary target of this review is to depict the adaptable way of bentonite and its composite and their capacity
Inorganic contaminants to absorb variety of inorganic contaminants, which are available in the water. It is evident from the review that
modified bentonite composites (low-cost adsorbents) have demonstrated high removal capabilities for certain
inorganic contaminants from water.
© 2017 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1092
1.1. Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1092
2. Nanotechnology in water research . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1092
2.1. Nanoadsorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1093
3. Preparation and characterization of bentonite and its composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1093
4. Adsorption technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1093
5. Bentonite and its composites for water/wastewater treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1093
5.1. Bentonite and its composites for removal of inorganic contaminants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1094
5.1.1. Zinc (Zn2 +) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1094
5.1.2. Cadmium (Cd2 +) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1095
5.1.3. Lead (Pb2 +) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1097
5.1.4. Copper (Cu2 +) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1098
5.1.5. Cobalt (Co2 +) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1098
5.1.6. Nickel (Ni2 +) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1099
5.1.7. Silver (Ag+) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1100
5.1.8. Chromium (Cr6 +; Cr3 +) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1100
5.1.9. Mercury (Hg2 +) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1101
5.1.10. Indium (In3 +) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1101
5.1.11. Selenite (Se4 +) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1102
5.1.12. Arsenic (As3 +) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1103
5.1.13. Iron (Fe3 +, Fe2 +) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1103

⁎ Department of Applied Chemistry, University of Johannesburg, P.O. Box 17011, Doornfontien, Johannesburg 2028, South Africa
E-mail addresses: spandey@uj.ac.za, sadanand.au@gmail.com.

http://dx.doi.org/10.1016/j.molliq.2017.06.115
0167-7322/© 2017 Elsevier B.V. All rights reserved.
1092 S. Pandey / Journal of Molecular Liquids 241 (2017) 1091–1113

5.1.14. Thorium (Th4 +) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1103

5.1.15. Cesium (Cs+) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1103
5.1.16. Uranium (U6 +) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1104
5.1.17. Miscellaneous metal ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1105
5.1.18. Anions contaminant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1108
6. Regeneration of bentonite and its nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1109
7. Summary and outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1110
Notes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1110
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1110
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1110

1. Introduction Heavy metals such as mercury (Hg2+), arsenic (As3+), chromium

(Cr ), cadmium (Cd2+) and lead (Pb2+) are the various harmful inor-
6+

1.1. Background
Water is known to sustain all class of existence on our planet. The
possibility of pure and clean water is the supreme value to human
being. As world population increases, the consumption of water will
also be increased. According to the surveyor on water, in the year
2025, half the population of this planet will be going to face the
water-based infirmity or a water crisis [1]. This water crisis will also
have a great impact on the biodiversity including life of flora and fauna.
Water pollution is the major problem in the global surrounding. And
it is major causes of illness and mortality worldwide [2]. Now the
awareness for the disposal of industrial wastewater, pretreatment and
proper purification of water is the prime responsibility of all the people
around the globe. Many laws, policies and a lot of technological ad-
vancement have been made related to recycling of industrial water
and/or its treatment before it is discharged into the environment.
People are responsible for causing the water pollution on this earth.
This water pollution is the results of using different types of chemicals
used in agricultural sector (such as herbicides, pesticides, fertilizers),
use of detergents and soaps by human being in daily life, and major pol-
lution is cause by industrial sectors (such as textiles, electroplating,
mining and other chemical industries) which released highly toxic
chemicals (Scheme 1).
ganic contaminants that are establish in the surrounding. Out of which
cadmium (Cd2+) and lead (Pb2+) are very common one. These enter
water through industries such as metal plating, smelting, mining, phos-
phate fertilizers, cadmium-nickel and lead batteries, textiles and alloy
industries, paint industries, leather tanning, pigments, as well as from
sewage [3–5]. These pollutants are very dangerous for all of us, aquatic
conditions, and the ecosystem of the earth as a whole.
Besides nitrate (NO− 2− 3−
3 ), sulfate (SO4 ), phosphate (PO4 ), fluoride
(F−), chloride (Cl−), and oxalate (C2O2−4 ) have also some hazardous ef-
fects. High concentrations of NO− 3 result into blue babies disease
(methaemoglobinemia) in children. On the other hand, it is well-
known that fluorosis is due to high levels of F− in water. By 2030, the
global population is expected to reach up to 8.5 billion, and because of
this the world may be under great water scarcity. Therefore, the remov-
al of these pollutants from contaminated water is an urgent need for
providing disease-free health to our society.
2. Nanotechnology in water research
Nanotechnology is defined as technology for engineering and ma-
nipulating matter at the nanoscale (1–100 nm) in order to enhance its
properties. Nanotechnology has been extensively use in areas such as
drug research, material chemistry and the environment, information

Scheme 1. Different causes of water pollution in the environment.

 S. Pandey / Journal of Molecular Liquids 241 (2017) 1091–1113
and communication, heavy industry, textiles and cosmetics and energy
[6–23]. Nanotechnology-based methods are used for treatment of
wastewater containing organic, inorganic and pathogenic contami-
nants, are an area that is now being widely explored.
2.1. Nanoadsorbents
Nanoadsorbents find an extensive variety of applications in engi-
neering field as they are productive biocompatible adsorbents having
large specific surface area, more active sites and low intra-particle resis-
tances [24–29]. Nanoadsorbents have nanoscale pores, high selectivity,
high surface area, high permeability, good mechanical stability and
good thermal stability [30]. Nanomaterials could be basically divided
into four types [30]. (a) The first type of nanomaterials is carbon based
materials which consist predominantly of carbon and they are accessi-
ble in the form of hollow spheres, ellipsoids, or tubes. Spherical and el-
lipsoidal carbon nanomaterials are mention to as fullerenes, while
cylindrical ones are called nanotubes. It was clearly observed from liter-
ature that CNTs have capability to remove organic-inorganic contami-
nants from waste water because they can establish π-π electrostatic
interactions [31]. (b) The second type is called metal based
nanomaterials include quantum dots (QDs), nanogold (NG), nanosilver,
and metal oxides (MO), such as titanium dioxide. (c) The third type is
dendrimers which are nanosized polymers built from branched units.
The surface of a dendrimer has numerous chain ends, which can be
adapted to perform specific chemical functions. Such type of property
makes it useful for the application of catalysis. (d) The fourth type is
composites which are nanoparticles combined with other nanoparti-
cles. Nanoparticles, such as nanosized clays, are added to enhance me-
chanical, thermal, barrier, and flame-retardant properties.
In the present review, focus is on fourth type of nanoadsorbent i.e.
bentonite clay composite as adsorbent. Clay is one of the most abundant
natural and inexpensive inorganic filler materials. Clay was introduced
in the nanotechnology field as a new type of filler to produce poly-
mer-clay nanocomposites (PCNs) [32–36].The development of polymer
clay nanocomposites demand a superior affinity between clay surface
and the polymers/monomers [32,34,36]. The swellable clays like mont-
morillonite (MMT) are known as hydrophilic and therefore opposed
with hydrophobic polymers/monomers [37]. In order to change the
clay hydrophilicity surface modification are performed [32,37]. It can
be accomplish by ion exchange of surface inorganic cations (e.g. Na+,
K+, Ca2+) by organic cationic surfactants. Polymer and oligomers with
quaternary ammonium have been also used to modify the clay surface
to obtain polymer-modified clay [32,34,38]. The range from the funda-
mental structures (including textures) and properties of clays and clay
minerals, their analysis and characterization by modern instrumental
techniques are the general topics and are not examined in this, as they
are out of the space of this article. However, interested readers can con-
sult several Handbook of Clay Science [39,40].
Here in the present review article, we are focusing on the bentonite
and bentonite based composite adsorbents. Bentonite is absorbent alu-
minum phyllosilicate clay consisting mostly of montmorillonite. Ben-
tonite is broadly utilized as a part of different modern items and
procedures, for example, pharmaceuticals, beauty care products and
boring liquids to alter the rheology and control the steadiness of frame-
works [41]. The wide range of application of bentonite can be credited to
its physical and synthetic properties, for example, small particle size,
high porosity, vast surface area and high cation exchange capacity [42,
43]. The bentonite has phenomenal adsorption capacity and its adsorp-
tion capacity is control by the compound nature and pore structure [44].
The wide range of application of bentonite is also attributed to the
possession of natural mesopores in its structure. Bentonites are plastic,
impermeable and highly viscous when suspended in water [45]. In ad-
dition, it is available in abundance in almost all parts of world [46].
The present review demonstrates the late advancements of nano-
technology in the synthesis of nanoadsorbents containing bentonite
1093
and its composites. The primary target of this review is to depict the
adaptable way of bentonite and its composite and their capacity to ab-
sorb variety of inorganic contaminants, which are available in the
water. In view of the importance of water quality and emerging utilities
of nanotechnology, attempts have also been made to discuss various as-
pects of water treatment by adsorption using bentonite composite
based adsorbents.
3. Preparation and characterization of bentonite and its composites
The preparation and characterization of modify bentonites are the,
as a matter of first importance ventures in water treatment by nano-
technology. The most essential methods for the preparation of modify
bentonite including heat treatment [47], acid activation [48], treating
the cationic surfactants [49], and polymer alteration [50]. The composi-
tion and molecular structure of the altered bentonite can be modeled
through these techniques. The modify bentonite are described by Fouri-
er transform infrared spectroscopy (FTIR), thermogravimetric analysis
(TGA), X-ray diffraction (XRD examination, scanning electron microsco-
py (SEM), transmission electron microscopy (TEM) and Brunauer-
Emmet-Teller (BET) surface area analysis. Essentially, the reported
methods are used for the preparation of distinctive types of modified
clay for different applications, for example, biomedical, electronics, op-
tical, mechanical, environmental science etc.
4. Adsorption technology
In perspective of the significance of water quality and rising utilities
of nanotechnology, endeavors have been made to discuss different
types of water treatment by adsorption using nanoadsorbents [16,17,
26,27,51–61]. Adsorption is a procedure in which pollutants are
adsorbed on the solid surface. Essentially, it is a surface phenomenon
and adsorption takes place by physical strengths at the same time, in
some cases, weak chemical bondings additionally take an interest in ad-
sorption process. A molecule (contamination/pollutant) held fast to the
solid surface is called an adsorbate, and the strong surface as an adsor-
bent. Adsorption is controlled by different parameters, for example,
temperature, nature of the adsorbate and adsorbent, and the presence
of other pollutants along with the experimental conditions (pH, concen-
tration of pollutants, contact time, particle size, and temperature). Equi-
librium is built up when the concentrations of pollutant adsorbed and in
water become constant. The relationship between measures of pollut-
ant adsorbed and in water; at equilibrium, is called an adsorption iso-
therm. The adsorption technology is developed by batch process
followed by the column studies. The developed adsorption technology
is applied first at pilot and later on industrial scales by using large size
columns.
5. Bentonite and its composites for water/wastewater treatment
Adsorption is currently perceived as an effective and economic
method for contaminated water treatment. Among all the different
type of methods, removal of toxins by adsorbents is observed to be
straightforward (as far as operation), financially savvy and productive
systems for the removal of both organic and inorganic pollutants from
contaminated waters [62]. In the most recent couple of decades, there
are different types of adsorbents had been utilized for the removal of
contaminations from water [10,18,63]. In the present parts, we are
reviewing Bentonite and polymer-bentonite nanocomposites for metal
ion adsorption. Consideration is offered to natural clay (Bentonite) for
polymer clay nanocomposites synthesis and its application in metal
ion adsorption. As we have discuss earlier that the polymer clay nano-
composites demonstrates a portion of the significant properties. Due
to enhancing these properties, different types of polymer are being uti-
lized by distinctive specialists. Some recent polymer clay
1094 S. Pandey / Journal of Molecular Liquids 241 (2017) 1091–1113
nanocomposites for improving the mechanical, thermal, chemical and
opticals are reviewed here.
Choi et al. [64] reported the impact of silane functionalization of
montmorillonite on epoxy/montmorillonite nanocomposites which
brings about enhance mechanical and dynamic mechanical properties.
Zehetmeyer et al. [65] explored the change in morphological, optical,
and barrier properties of PP/MMT nanocomposites. Pascual et al. [66]
considered the Impact of the compatibilizer/nanoclay proportion on
last properties of polypropylene matrix altered with MMT-based
organoclay. Xu et al. [67] enhanced the UV-resistant property of lacquer
film essentially by solution intercalation method raw lacquer/
multihydroxyl polyacrylate/organophilic MMT nanocomposites. Li et
al. [68] studied and explored exfoliated epoxy/clay nanocomposites
for tensile modulus and tensile strength which was increased by 64.2
and 52.3%, respectively. Flexural modulus upgraded by 7.1%, flexural
strength by 14.6% and notch impact strength by 37.7%. Indeed, even
the glass transition temperature and thermal decomposition tempera-
ture moved to higher temperatures by 10.1 and 5.7 °C respectively.
Azhar et al. [69] explored the enhanced thermal stability of polymer–
MMT nanocomposites taking into account common natural polymers
(chitosan, alginate, gelatin and starch) and MMT prepared by using so-
lution intercalation method. Fu et al. [70] demonstrates a feasible syn-
thetic route to prepare a methyl acrylic acid-modified bentonite
(MAABT)/sodium polyacrylate (SPA) superabsorbent nanocomposite,
in which the MAABT serves as a reinforcing agent for SPA, as well as a
cross-linking joint to enhance the network of the nanocomposite.
With the fine dispersion of MAABT and strong interfacial interaction,
the MAABT/SPA nanocomposite achieved a water absorbency that was
as high as 1287 g/g. There are three types of contaminants; inorganic,
organic and pathogenic. It is not possible to cover all the three types of
contaminants under one article. So in the present review we have
targeted to cover the first types of contaminants under section “benton-
ite and its composites for removal of inorganic contaminants”.
5.1. Bentonite and its composites for removal of inorganic contaminants
Heavy metals, for example, mercury (Hg2+), arsenic (As3+), chro-
mium (Cr6 +), Cadmium (Cd2 +) and lead (Pb2 +) are probably the
most dangerous inorganic contaminants found in nature. These con-
taminants in water cause serious effects on the health of human beings,
creatures, and plants. There are numerous researchers and specialists
are working for removal of heavy metal ions from water. In this section,
a brief and recent review of the adsorption of inorganic contaminants by
bentonite and its composites is described. This review, which is not ex-
haustive, shows some selected examples of adsorbents used in waste-
water treatment. Reported adsorption capacities are noted when
possible to give an idea of the adsorbent effectiveness. In liquid-phase
adsorption, it is commonly known that adsorption capacities of an ad-
sorbent is attributed to many factors and the adsorbate–adsorbent in-
teraction play an important role as well as that between adsorbate
and water. The control sorption performances of a sorbent depend on
the following physicochemical factors: firstly, the nature of the adsor-
bent such as its physical structure (porosity, surface area, particle
size), its chemical structure (ionic charge) and functional groups (vari-
ety, density); secondly, the chemistry and accessibility of the adsorbate
(e.g. its pKa, polarity, functionality, molecular weight and size); and fi-
nally, the solution conditions, referring to its pH, ionic strength, temper-
ature and the adsorbate concentration. Consequently, the reader is
encouraged to refer to the original papers for information on experi-
mental conditions. Application and efficiency of different types of char-
acteristic clay: Bentonite and their composites in removing different
metal ions are evaluated in the accompanying segments and adsorption
capacity, kinetics, adsorption isotherm and other parameter for metal
ion removal by using different bentonite based adsorbents are present-
ed and some of them are tabulated in Table 1 and Table 2 shows differ-
ent sources of contaminations, potential toxic effects of heavy metals
along with their US EPA maximum contamination level (MCL) in drink-
ing water.
5.1.1. Zinc (Zn2+)
Zinc is a trace element that is essential for human health. However,
too much zinc can cause eminent health problems, such as stomach
cramps, skin irritations, vomiting, nausea and anemia [71,72]. Maxi-
mum contaminant levels (MCLs) are standards that are set by the Unit-
ed States Environmental Protection Agency (EPA) for drinking water
quality. A MCL is the legal threshold limit on the amount of a substance
that is allowed in public water systems under the Safe Drinking Water
Act. US EPA has established a maximum contaminant level (MCL) for
zinc of 5 mg per liter (mg/L) in drinking water [73] (Table 2).
Ding et al. [74] used Ca-bentonite and Na-exchanged bentonite for
Zn2+ ion removal. Various factors such as the initial concentration of
Zn2 +, the liquid-to-solid ratio, pH, adsorption time, stirring speed,
coexisting ions, temperature and bentonite particle size were varied in
order to optimize the Zn2+ adsorption. The results confirm the adsorp-
tion process of bentonite fit better with Freundlich isotherm model, the
removal of Zn2+ by Ca-bentonite and Na-exchanged bentonite reached
equilibrium in 2 h, and adsorption of Na- bentonite was superior to Ca-
bentonite. The adsorption rate of Zn2+ increased with increasing pH,
temperature, stirring speed, time span and with decreasing bentonite
particle, the initial concentration of Zn2+ and the liquid-to-solid ratio.
Araujo et al. [75] evaluated the adsorption capacity of Zn2+ by bole
bentonite clay. Bofe clay was subjected to a thermal treatment for opti-
mizing its adsorption capacity. The Langmuir and Freundlich models
were used for the analysis of adsorption equilibrium. The calcined
Bofe clay is able to remove Zn2+ from synthetic wastewater. Langmuir
model provided the best fit for sorption isotherms with a maximum
amount of metal adsorbed of 4.95 mg/g of calcined clay. The adsorption
was strongly influenced by the initial conditions and modifies the phys-
icochemical characteristics of the clay. Lin and Juang [76] reported re-
moval of Zn2 + on sodium dodecylsulfate-MMT nanocomposite. The
clay was modified by anionic surfactant SDS, which penetrated into in-
terlamellar region of the clay by the expansion of clay sheets in the c-
axis. The author reported that the adsorption depend on solution pH
and by increasing pH, the number of negatively charged sites increases,
which supports adsorption of Zn2 +. The Qmax was 202.9 mmol kg−1.
Adsorption of Zn2 + on sodium dodecylsulfate-MMT was quick amid
the initial 10 min and the equilibrium reaches within 120 min. A pseu-
do-first-order mechanism was proposed with a rate coefficient of 6.64
× 10−4 min−1 at 298 K.
Kaya and Oren [77], revealed natural bentonite and Na-enriched
bentonite as an adsorbent for Zn2+ removal at diverse pH values, initial
metal ion concentrations and slurry concentrations. Results acquired
from the effect of pH on the Qmax of the bentonite showed that the
major factor which influenced this parameter are competition of the
H+ ions with Zn2+ ions (under pH 4), ion exchange (pH 4–7), and par-
ticipation of the heavy metal species to the adsorption and precipitation
of some onto the bentonites (pH 8). The cation exchange capacity (CEC)
(meq/100 g) and specific surface area (m2/g) of natural bentonite are
393.44 & 132.33 respectively; and for Na-enriched bentonite are
441.96 & 67.11 respectively.
Sen and Khoo [78], showed the removal of Zn2+ from wastewater by
using bentonite as adsorbent. Kinetic experiments clearly indicate that
adsorption of Zn2+ on bentonite are two-step processes: a very rapid
adsorption of Zn2+ to the external surface is followed by possible slow
decreasing intraparticle diffusion in the interior of the adsorbent. This
has also been confirmed by an intraparticle diffusion model. The most
extreme Qmax (mg/g) of bentonite was found to 62.5 with the Zn2+ con-
centration of 30–90 mg/L range. The correlation coefficient (R2) was ob-
served to be 0.994 in bentonite. The values demonstrate Langmuir
isotherm model was favorable. Generally the kinetic studies revealed
that adsorption procedure follows the pseudo-second-order kinetics
model and R2 = 0.99 in both the cases. Thermodynamics study was
 S. Pandey / Journal of Molecular Liquids 241 (2017) 1091–1113 1095

Table 1
Reported maximum adsorption capacities (Qmax), adsorption isotherm and adsorption kinetics in the literature for some inorganic pollutants obtained on bentonite and bentonite based
composite adsorbents.

Inorganic contaminants

Pollutant Adsorbent Applicable Applicable kinetic Adsorption capacity Ref.

isotherm models models

Zinc (Zn2+) Ca-bentonite and Na-exchanged bentonite Freundlich NS – [74]

Bole bentonite clay Langmuir NS 4.95 mg/g [75]
Bentonite Langmuir Pseudo-second-order 62.5 mg/g [78]
Cadmium GMZ bentonite Langmuir Pseudo-second-order 3.16 mg/g [84]
(Cd2+) Natural bentonite (B) and modified bentonite samples (NaB), (Mn-B) Langmuir Pseudo-second-order 63.29, 72.99, 103.09 & 108.69 [86]
and (Mn-NaB). mg/g respectively
Lead (Pb2+) Bentonite Langmuir & NS 52.6 mg/g [88]
Freundlich
Xanthated bentonite composite (XBent) Freundlich 99.9%. [89]
Organo-bentonite by microwave irradiation Sips model Pseudo-second-order 0.193 mmol/g [90]
Natural Brazilian bentonite (BBT) and modify natural BBT Langmuir Pseudo-second-order 20.6, 27.6, & 29.5 mg/g [95]
(BBTAPS,BBTAEAPS)
Poly acrylic acid–organobentonite (PAA–Bent) nanocomposite Langmuir NS 93.0 mg/g [97]
Chitosan/bentonite (PMAA-g-CS/B) nanocomposite Langmuir Pseudo-second-order 126.6 mg/g [98]
Bentonite clay based hydroxyapatite nanocomposites (BT–HAp) Langmuir Pseudo-second-order 346 mg/g [100]
Copper 1:10 phenanthroline-grafted Brazilian bentonite Langmuir 110 mg/g [105]
2+
(Cu ) Non-crosslinked (CCB) Langmuir Pseudo-second-order 12.21 mg/g [106]
Crosslinked chitosan-coated (CCB-ECH) bentonite beads Freundlich 9.43 mg/g
Activated raw bentonite (BA) obtained from Maghnia (Western Langmuir & Pseudo-second-order 0.18 mmol/g [108]
Algerian) Freundlich
Crosslinked chitosan immobilized on bentonite (CIB). Langmuir Pseudo-second-order 9.85 mg/g [109]
Epichlorohydrin crosslinker (CIB-ECH) Langmuir 1.75 mg/g
Glutaraldehyde crosslinker (CIB-GLA) Freundlich model 4.17 mg/g
Ethylene glycoldiglycidyl ether crosslinker (CIB-EDGE) Langmuir 10.52 mg/g
Alginate immobilized bentonite Langmuir Pseudo-second-order 131.6 mg/g [112]
5%Bentonite/chitosan (5%Bt/CS) nanocomposite Langmuir Pseudo-second-order 337 mg/g [113]
Cobalt (Co2+) Saudi activated clay (bentonite) Langmuir & Pseudo-second-order 7.3 mg/g [118]
Freundlich
Fe3O4/bentonite nanocomposite Langmuir Pseudo-second-order 18.76 mg/g [119]
Modified bentonite clay with 8-hydroxy quinolone (8HQ-Bent) NS Pseudo-second-order 4.42 mmol/g [120],
2+
Nickel (Ni ) Bentonite/iron oxide composite Langmuir – 12 mg/g [125],
Bentonite from Milos island North Greece Langmuir & Pseudo-second-order 26.32 mg/g [126]
Freundlich
Saudi natural bentonite Langmuir & Pseudo-second-order 47.62 mg/g [128]
Freundlich
Sodium pyrophosphate modified bentonite (NPP-bentonite). Langmuir & – 30.3 mg/g [129]
Freundlich
+
Silver (Ag ) Natural bentonite Langmuir Pseudo-second-order 69 mg/g [132]
Chromium Biopolymer chitin/bentonite nanocomposite Freundlich – 1.81 dm3/g [139]
(Cr6+) Modified bentonite Langmuir Pseudo-second-order 4.21 mg/g [141]
Mercury KI modified bentonite supported by starch sorbent (B–S–I) – – 604.3 μg/g [145]
(Hg0, KI modified bentonite sorbent (B–I) 450.2 μg/g
Hg2+) CTS–PVA/(BT-30%) nanocomposites – – 392.19 mg/g [146]
Indium Chitosan-coated bentonite (CCB). Langmuir Pseudo-second-order 17.89 mg/g [148]
(In3+)
Selenite Organic-pillared bentonite (OPBent) Langmuir & Pseudo-second-order 0.113 mmol/g [151],
(Se4+) Freundlich
Arsenic Organobentonites prepared by modification of bentonite with various Langmuir Pseudo-second-order 46.7 × 10−3 g mg−1 h−1 [155]
(As5+) cationic surfactants,
Arsenic 3.1 × 10–3 g mg−1 h−1
(As3+)
Thorium Magnetic organo-bentonite-Fe3O4 poly(sodium acrylate) (OB-Fe3O4 PSA Langmuir Pseudo-second-order 6.55 mmol/g [160]
(Th4+) 3.6) superabsorbent nanocomposites.
Sodium bentonite composite. Langmuir Pseudo-second-order 41.24 mg/g [162]
Magnetic bentonite composite 31.34 mg/g
Cesium (Cs+) Chitosan-grafted magnetic bentonite (CS-g-MB) Langmuir – 1.21 mmol/g [164].
Uranium Bentonite from Huangshan county Langmuir – 9.19 × 10−5 mol/g [168]
(U6+)

performed at three distinctive temperatures. Enthalpy ΔH0 (kJ/mol) and
entropyΔS0 (J/mol·K) was observed to be −0.268 & −0.0011 in ben-
tonite. Shima and Gholamreza [79], study the improve adsorption
mechanism. In order to increase adsorption capability for Na-bentonite
rather than Ca-bentonite origin, nano-bentonite sample with Na activa-
tion was used by the author. Also for investigation of environmental ef-
fect, some parameters such as pH, adsorbent concentration, metal ion
concentration and stirrer speed on the adsorption rate of Zn2 + used
Experimental Design software (EDS) and Central Composite Design
(CCD) model. Finally, the authors have optimized each parameter for ef-
fective adsorption process determination and possible conditions for ac-
cess to adsorption recovery up to 99% were investigated.
5.1.2. Cadmium (Cd2+)
The various sources for Cd2+ are from welding, fertilizers, nuclear
emission plants, steel and plastics industries, cooling tower blow down,
1096 S. Pandey / Journal of Molecular Liquids 241 (2017) 1091–1113

Table 2
Shows different sources of contaminations, potential toxic effects of heavy metals along with their US EPA maximum contamination level (MCL) in drinking water.

Heavy Sources of contaminations Harmful effects to human being US EPA maximum References
metal ions contamination level (MCL) in
drinking water

Zinc Refineries; plumbing; brass platting; wood pulp Vomiting, and anemia; stomach nausea; skin irritations; 5 mg/L [72,73]
production; ground and newsprint paper production; cramps
steel works with galvanizing
lines; zinc and brass metal works
Cadmium Welding; fertilizers; nuclear emission plants; steel and Bronchiolitis, emphysema, fibrosis; skeletal damage; 0.005 mg/L [73,80]
plastics industries; cooling tower blow down; damage to kidney; cancers
electroplating, metal plating; nickel–cadmium
batteries; galvanized pipe corrosion; natural deposits;
batteries, paints
Lead Natural/industrial deposits; plumbing; solder; brass Kidneys, nervous system damage; mental retardation; 0.015 mg/L [73,87]
alloy faucets anemia; cancer
Copper Natural/industrial deposits; wood preservatives; Gastrointestinal irritation, damaged in kidney and liver; 1.3 mg/L [73,103]
plumbing; chemical industry; pesticides industry; convulsions, cramps, vomiting, or even death; increased
mining blood pressure and respiratory rates
Cobalt Natural sources include wind-blown dust, seawater Respiratory irritation, wheezing, asthma, decreased lung 2 μg/L but values up to 107 μg/L [115]
spray, volcanoes, forest fires, and continental and function, pneumonia, and fibrosis; Gastrointestinal have been reported.
marine biogenic emissions. Anthropogenic sources effects (nausea, vomiting, and diarrhea), effects on the
include the burning of fossil fuels, sewage sludge, blood, liver injury, and allergic dermatitis
phosphate fertilizers, mining and smelting of cobalt
ores, processing of cobalt alloys, and industries that use
or process cobalt compounds.
Nickel Zinc base casting; printing; electroplating; silver Cyanosis, rapid respiration; shortness of breath; 0.05 mg/L [73,122]
refineries; battery manufacturing; production of some tightness of the chest, chest; pain; nausea and vomiting;
alloys dry cough; bone nose, and lung cancer; dizziness and
headache
Silver Weathering of rocks and the erosion of soils; processing Liver and kidney damage, irritation in eyes, skin, 0.10 mg/L [131]
of ores, steel refining, cement manufacture, fossil fuel respiratory, and intestinal tract, and changes in blood
combustion, municipal waste incineration, and cloud cells
seeding.
Chromium Cooling tower blowdown; electroplating; industrial Severe diarrhea; vomiting; pulmonary congestions liver 0.1 mg/L [73,133]
wastewater discharge to environment and kidney damage
Mercury Pesticides; batteries; paper industry; mineral deposits; Damage to kidneys, reproductive systems and immune 0.002 mg/L [73,144]
fossil fuel or ores system
Indium Cultivated soils; in industry as by-product of smelting Irritation of the eyes, nose, throat and lungs causing – [147]
zinc and lead sulfide ores coughing; damage lungs, liver and kidney.
Selenium Natural deposits; mining, smelting, coal/oil combustion bad teeth, yellowish discoloration of the skin, skin 0.05 mg/L [149]
eruptions, chronic arthritis, diseased nails, and
subcutaneous edema
Arsenic Natural deposits; smelters, glass, electronics wastes; Skin; nervous system toxicity; hematologic disorders; 0.010 mg/L [73,84]
orchards developmental abnormalities and neurobehavioural
disorders; lungs, bladder and kidney, cancer and other
internal tumors; vascular diseases and diabetes; infant
mortality; hearing loss; reproductive toxicity
Iron Staining of laundry and plumbing; constructional Haemorrhagic necrosis and sloughing of areas of mucosa 0.3 mg/L [156]
material; paints and plastics in the stomach; genetic disorder (haemochromatosis)
Thorium Found in soil, rock, and water. It is formed by the Bone cancer, liver diseases 15 picocuries per liter (15 [158]
radioactive decay of uranium pCi/L)
Cesium Erosion and weathering of rocks and minerals; mining Acute radiation syndrome, which includes such effects as Average annual drinking water [163]
and milling nausea, vomiting, diarrhea, bleeding, coma, and even limit of 80 picocuries per liter
death; damage cells and might also cause cancer; in child (pCi/L) for 134Cs or 200 pCi/L for
137
causes changes in behaviour or decreased mental Cs
abilities
Uranium Uranium mining, processing, reclamation, and waste Renal toxicity; toxic effects on the cardiovascular system, 30 μg/L [166,167]
handling, exposure pathways to living organisms, liver, muscle, and nervous system; birth defects
including people, may exist for chemical and
radiological materials via inhalation, ingestion,
absorption through the skin, and gamma radiation

electroplating, metal plating, nickel–cadmium batteries, galvanized pipe
corrosion, natural deposits, batteries, paints. Cadmium exposure also
causes prostate and renal cancer Bronchiolitis, emphysema, fibrosis; skel-
etal damage, damage to kidney [80–82]. US EPA has established a maxi-
mum contaminant level (MCL) for cadmium of 0.005 mg/L in drinking
water cadmium metal ion has been removed from water by using adsorp-
tion technology (Table 2). Jobstmann and Singh [83], examined the Cd2+
adsorption by hydroxy-aluminum-pillared montmorillonite nanoclay
and additionally unpillared montmorillonite. The Adsorption isotherm ex-
perimental data follows the Freundlich isotherm model with (R2 = 0.98 to
0.99) with Qmax of 3775.5 and 507.0 μM1 − n kg−1 Ln for unpillared and
pillared clays, respectively.
Chen et al. [84,85] researched the removal of Cd2+ by Gaomiaozi
(GMZ) bentonite. The authors discovered Qmax (mg/g) of 3.16 for
Cd2+ adsorption onto the bentonite. The adsorption mechanism was
concluded to be complexation, electrostatic interaction and ion-ex-
change. Schütz et al. [86], study the removal of Cd2+ from aqueous so-
lution by utilizing natrified bentonite (NaB) prepared from the slurry,
which contained the activating agent (Na2CO3) and distilled water to
which the bentonite was included. The stabilization took 24 h at ambi-
ent temperature. The final product was dried at 60 °C and after that it
was squashed physically. In this way, the manganese oxide-bentonite
composite (Mn-B), manganese oxide-natrified bentonite composite
(Mn-NaB) and pure manganese oxides were prepared through
 S. Pandey / Journal of Molecular Liquids 241 (2017) 1091–1113
precipitation process. Results shows Qmax (mg/g) of B, NaB, Mn-B and
Mn-NaB was observed to be 63.29, 72.99, 103.69 and 108.69 separately.
Thus adsorbents follow the order: B b NaB b Mn-B b Mn-NaB.
5.1.3. Lead (Pb2+)
Lead (Pb2+) is found to be very hazardous heavy metal ion for the
human being. The sources of Pb2+ are through natural/industrial de-
posits, plumbing, solder, brass alloy faucets. The accumulation of Pb2+
in the body disturbs processes such as haemoglobin synthesis, renal
function and cause neurological and behavioural disturbances in chil-
dren [3,87]. The permissible capacity of Pb2+ in drinking water set by
the WHO is 10 μg/L. US EPA has established a maximum contaminant
level (MCL) for Pb2 + of 0.015 mg/L in drinking water [73] (Table 2).
Naseem and Tahir [88], reported adsorption of Pb2 + by bentonite
from aqueous solution (20 mg of Pb2+ per 1 g of clay at pH 3.4). The ad-
sorption increases from 30 to 94.5% with an increment in pH of the so-
lution from 1.4 to 3.4 and declines to 40% at pH 5.0. The Qmax (mg/g) for
Pb2+-bentonite interactions has been demonstrated to be 52.6. He et al.
[89] reported that successful grafting of bentonite onto Xanthate by
simple solution reaction. The synthesized xanthated bentonite compos-
ite (XBent) was characterized by FT-IR, TGA, XRD, SEM and BET. XBent is
environmentally friendly adsorbent was applied to remove Pb2+ from
aqueous solutions. The optimum conditions were as follows: Pb2+ con-
centration (500 mg/L), bentonite concentration(2 g/L), pH 5.0, contact
time (60 min) under 200 rpm at 25 °C. The removal rate of Pb2+ was
up to 99.9%. It was found that the Pb2 +-XBent adsorption isotherm
model fitted well to the Freundlich isotherm. XBent appears to have po-
tential to be used later in water treatment as a type of inorganic polymer
reagent.
Nathaniel et al. [90] explore the synthesis of organo-bentonite by
microwave irradiation for Pb2+ ion removal. Synthesis by using micro-
wave irradiation is the advance technology [91–93]. The Qmax (mmol/g)
ascertained from Langmuir adsorption isotherm of natural and modi-
fied- bentonite was observed to be 0.047 and 0.193 respectively. The
temperature dependent forms of the Langmuir, Freundlich, and Toth
models were utilized to correlate equilibrium data. The pseudo-second
order kinetic corresponds to the experimental data decently. It demon-
strates that organo-bentonite had higher adsorption capacity than the
natural one. Babu et al. [94] reported biosorption removal of bentonite
for the removal of Pb2+ from aqueous solutions. Results exhibited that
higher pH (5.0) favored metal ion removal. It is observed that the 88%
removal of Pb2+ by adsorbent bentonite can be better performed at a
size of 75 μm of bentonite, at a concentration of 100 mg/L, at a pH of 5
and at optimum time of contact 3 h.
Guerra et al. [95] considered the Pb2+ adsorption investigation of
characteristic Brazilian bentonite (BBT) and modify BBT. Modification
was performed by functionalization of 3-aminopropyltrietoxisilane
(APS) and 3, 2-aminoethylaminopropyltrimetoxisilane (AEAPS) on the
surface of component minerals of BBT and assigned as BBTAPS and
BBTAEAPS respectively. The most extreme Pb2+ Qmax (mg/g) of bentonite
types were 20.6843, 27.6524, and 29.5413 for BBT, BBTAPS, BBTAEAPS sep-
arately by utilizing a Perkin Elmer Flame Atomic Absorption (AA) Spec-
trometer. The favorable optimized condition for Pb2 + binding was at
pH 6 and adsorption time is 180 m in all the three cases. The most ex-
treme binding was seen in BBTAEAPS. Experimental results reveal the ad-
sorption is Langmuir adsorption Isotherm. With KL (dm3 mmol−1)
values 0.4222, 0.5671, & 0.6156, for BBT, BBTAPS, BBTAEAPS separately;
and R2 values 0.9856, 0.9876, 0.9987, for BBT, BBTAPS, and BBTAEAPS re-
spectively. Experimental data was accomplished by the pseudo-second
order model, demonstrating that the chemisorption rate is by all ac-
counts the controlling step in the methodology with ks (g mmol− 1-
min− 1) values 0.7761, 0.8145, and 0.919, for BBT, BBTAPS, and
BBTAEAPS respectively. The R2 of the pseudo-second-order rate equation
value 0.9999, 0.9998, 0.9997, for BBT, BBTAPS, and BBTAEAPS respectively.
The thermodynamic study was additionally indicated in this article. It
demonstrates the increment in the temperature result in upgrading
1097
Pb2 + removal efficiency by 15.40%, 13.37% and 11.22% for BBTAPS,
BBTAEAPS, and BBT, separately, in 4 h, at 413 K. The activation energy
(Ea) kJ/mol was observed to be 25.51, 30.16 and 31.76 for BBT, BBTAPS
and BBTAEAPS separately. Guerra et al. have given the clarification for
most extreme adsorption on the bases of surface area. The BET investi-
gation reveals that the surface area of BBTAEAPS is 612.3 m2/g has an es-
sentially higher surface area than the BBTAPS (597.3) and BBT (34.1). It
was likewise observed that BBTAEAPS has pores b2 nm in diameter (mi-
cropore) notwithstanding some mesopores (44 nm diameter). The nat-
ural bentonite has small N2 BET surface areas and mesopores in light of
the fact that N2, instead of H2O, OH−, and H3O+, is unable to penetrate
into the octahedral position in structure of interstratified smectite–illite
may have in the center a vacancy.
Haiyan et al. [96] reported removal of Pb2+ ion by using sodium base
bentonite compounds polypropylene amine superabsorbent arranged
by aqueous solution synthetic method. The authors affirms that the
measure of bentonite was 15 g, the absorbent's mesh was between 80
and 100 mesh, the absorbency of resin was observed to be 248 g/g in
water. The most elevated adsorption effectiveness of 99.4% was accom-
plished. The experimental information for adsorption isotherm was
study by the Langmuir and Freundlich. Rafiei et al. [97] reported Pb2+
removal by using novel poly acrylic acid–organobentonite (PAA–Bent)
nanocomposite by successive intercalation of cetyltrimethylammonium
(CTA) surfactant and polyacrylic acid (PAA) into the bentonite (Bent)
interlayer spaces. Maximum Pb2 + sorption capacity of the Bent and
PAA–Bent predicted by Langmuir model were 52.3 and 93.0 mg/g, re-
spectively, showing that the synthesized nanocomposite superiorly
adsorbed Pb2+ from the solution as compared to the Bent. The maxi-
mum Pb2+ removal efficiency of 99.6% was achieved by the nanocom-
posite at 25 °C with b 30 min contact time for a 7.5 g/L solid-to-liquid
ratio and an initial metal concentration of 400 mg/L.
Rijith et al. [98] study the removal of Pb2+ from water and simulated
battery manufacturing wastewater by using novel composite matrix
polymethacrylic acid-grafted chitosan/bentonite (PMAA-g-CS/B)
which was prepared through graft copolymerization reaction of
methacrylic acid and chitosan in the presence of bentonite and N,N′-
methylene-bisacrylamide as cross linker. The Qmax (mg/g) increases
with increase in temperature. It has increased from 99.9 to 126.6 for
Pb2+ adsorption with rise in temperature from 20 to 50 °C. The adsorp-
tion of Pb2 + on PMAA-g-CS/B follow Langmuir adsorption isotherm.
Perelomov et al. [99] investigated the uptake of Pb2+ by Na-rich ben-
tonite (Na-bentonite) and Al-pillared bentonite (Al-bentonite) in the
presence or absence of organic acids containing different functional
groups. Na-bentonite adsorbed more of Pb2+ than Al- bentonite in the
presence of citric acid and lysine. Choudhury et al. [100] synthesis the
bentonite clay based hydroxyapatite nanocomposites cross-linked by
glutaraldehyde for Pb2+ ion removal from aqueous solution. A novel
nanocomposite (BT–HAp) was developed by chemical synthesis using
hydroxyapatite nanoparticles and bentonite clay with the addition of
glutaraldehyde as a cross-linking agent. The nanocomposites were syn-
thesis at three differents pH 3, 7 and 10. The nanocomposite synthesized
at pH 7 showed a higher sorption capacity of Pb2+. The Langmuir iso-
therm model best represented the phenomenon having a Qmax (mg/g)
of 346 at 30 °C. The sorption mechanism was well described by the
pseudo-second order kinetic model indicating the coexistence of both
physisorption and chemisorption.
Luo et al. [101] investigated the Pb2 + removal by using reusable
magnetic cellulose nanocomposite beads entrapping activated benton-
ite (MCNB). The fabrication of composite material was performed by
optimal extrusion dropping technology by blending cellulose with the
carboxyl-functionalized magnetite nanoparticles and acid-activated
bentonite in NaOH/urea aqueous solution. Kinetics data could be best
fitted into the pseudo-second-order rate model indicates a chemisorp-
tion. The adsorption data were fitted with Langmuir and Freundlich iso-
therm models. The maximum monolayer adsorption capacity of MCNB
was found to be 2.86 mg/g for Pb2+ at 298 K. Since MCNB shows high
1098 S. Pandey / Journal of Molecular Liquids 241 (2017) 1091–1113
hydrophilicity and rich porous structure, the dissolved lead ionic species
easily penetrate into the bead and interact with the inorganic fillers to
form a complex and facilitate the lead adsorption. The thermodynamic
parameters (ΔG, ΔH and ΔS) indicated that the adsorption processes
were feasible, spontaneous, endothermic and mainly controlled by
chemical mechanisms. The regeneration study of MCNB reveals the sim-
ilar adsorption capacity for Pb2 + (98%) after fifth cycles reveals that
MCNB has excellent stability.
5.1.4. Copper (Cu2+)
The sources of Cu2+ in the environment are through natural/indus-
trial deposits, wood preservatives, plumbing, chemical industry, pesti-
cides industry and mining. Excessive ingestion of copper brings about
serious toxicological concerns, such as gastrointestinal irritation, dam-
aged in kidney and liver, convulsions, cramps, vomiting, or even
death. It also increased blood pressure and respiratory rates [102,103]
(Table 2). US EPA has established a maximum contaminant level
(MCL) for Cu2+ of 1.3 mg/L in drinking water [73]. Alvarez-Ayuso and
Garcia-Sanchez [104], likewise reported the adsorption of Zn2 + on
same adsorbent. The interactions were trailed by Langmuir isotherm
with greatest monolayer adsorption capacities Qmax (mg/g) of 23.1 for
Na-bentonite while just 5.8 for Ca-bentonite. De Leon et al. [105] report-
ed the adsorption of Cu2 + on 1:10 phenanthroline-grafted Brazilian
bentonite. Langmuir monolayer adsorption capacity Qmax (mg/g) was
observed to be 110.0. Dalida et al. [106] reported the removal of Cu2+
from aqueous solutions by utilizing non-crosslinked (CCB) and
crosslinked chitosan-coated (CCB-ECH) bentonite beads. The equilibri-
um information of CCB concurred well with the Langmuir model
while CCB-ECH beads demonstrated a superior Fit with the Freundlich
model. In light of the isotherm study, CCB is a homogenous adsorbent,
while CCB-ECH is a heterogeneous adsorbent. The Qmax (mg/g) of CCB
and CCB-ECH at pH 4 are 12.21 and 9.43, respectively. The kinetic data
correlated well with the pseudo-second order equation, which suggests
that chemisorption is the rate-limiting step.
Sandy et al. [107] investigated the adsorption of Cu2+ ions from an
aqueous solution utilizing direct alkylbenzene sulfonate modified ben-
tonite (organo-bentonite). Modification of bentonite was performed
by microwave heating with a concentration of linear alkylbenzene sul-
fonate surfactant equal to 1.5 times that of the cation-exchange capacity
(CEC) of the crude bentonite. A few adsorption comparisons (Langmuir,
Freundlich, Sips and Toth) with temperature dependency were utilized
to correlate the equilibrium data. The Sips model had the best fit for the
adsorption of Cu2+ ions onto organo-bentonite. Kinetic data takes after
the pseudo-second order model. Thermodynamically, the adsorption of
Cu2+ ions take place through chemisorption and the procedure is endo-
thermic (ΔH0 N 0), irreversible (ΔS0 N 0) and non-spontaneous (ΔG0 N
0). Abdelhamid et al. [108] reported the utilization of activated benton-
ite (BA), got from Maghnia (Western Algerian) for removal of Cu2+ ions
to 30% from natural bentonite (BN). The interface phenomenon of ben-
tonite-Cu2 + aqueous solution explains to Langmuir and Freundlich
models. The adsorption data gave better fits with Langmuir R2 = 0.98
and 0.99; and Freundlich R2 N 0,995 and 0.98 for BN and BA respectively.
The yielded Langmuir monolayer capacities were observed to be 0.12
and 0.18 mmol/g for BN and BA respectively and Freundlich adsorption
capacities of 0.321 and 0.043 for the BN and BA, separately. The adsorp-
tion energy was figured by utilizing Dubinin-Radushkevich equation.
Grisdanurak et al. [109] reported the Cu2 + removal by utilizing
noncrosslinked and crosslinked chitosan immobilized on bentonite
(CIB). Grisdanurak et al. [109] have utilized three unique types of
Crosslinking agents, for example, epichlorohydrin (ECH), glutaralde-
hyde (GLA), and ethylene glycoldiglycidyl ether (EDGE) to enhance
the chemical and mechanical properties of the adsorbent. The surface
area and average pore diameter (nm) of bentonite, chitosan, CIB, CIB-
ECH, CIB-EGDE & CIB-GLA are 94.2 (5.84), 3.40 (6.41), 39.17 (5.02),
38.96 (6.21), 20.18 (7.33) & 13.45 (8.33) respectively. It is observed
that the surface area decreases with a decrease of pore volume. The
sub-par properties of CIB and its crosslinked structures in examination
to bentonite were because of the hydroxylated edge–edge interaction
of the silicate layers forming hydrogen bonds with another silicate hy-
droxylated group. The Qmax of the adsorbents are arranged in the fol-
lowing order: CIB-ECH N CIB-EDGE N CIB N N CIB-GLA and the values
are 1.75, 10.52, 9. 85 & 4.17 respectively. Langmuir and Freundlich equa-
tion were utilized to examine the isotherm information. Equilibrium
studies demonstrated that CIB, CIB-EDGE, and CIB-ECH associated well
with the Langmuir model while CIB-GLA fits well with the Freundlich
model. Kinetics of Cu2+ adsorption was best portrayed by the pseudo-
second-order mathematical equation, which shows that chemisorption
is the rate limiting step. The rate law kinetic constant K2 (g/mg min) at
500 ppm is 0.0152, 0.0558, 0.0205, & 0.0930 for CIB, CIB-EGDE, CIB-ECH
& CIB-GLA respectively. The R2 is observed to be 0.99 in all the 4 cases. In
the desorption study, N92 and 75% of Cu2+ could be recouped from CIB-
EDGE and CIB-ECH beads utilizing HCl solution (pH 1) agitated for
120 min. This study decides the likelihood of crosslinked CIB beads as
a conceivable material for permeable reactive barriers (PRBs) for the
treatment of polluted groundwater.
Gongren [110], utilized acidity modified bentonite for removing
Cu2 +. The author reported that the removal rate of 99% Cu2 + ion,
under the initial concentration of Cu2 + 13.6 mg/L, adsorbent dose
8 g/L, pH 7, the vibration speed is 150–160 rpm, the adsorption time is
30 min. Nourmohamadi et al. [111] investigated the adsorption of
Cu2+ onto synthesized magnetite bentonite nano – absorbent by CCD
design of experiments. Synthesized magnetite-bentonite nanoparticles
(20–40 nm) were produced by co-precipitation method. The experi-
ments were designed by design of experiment (DOE) software. The op-
timization results shows 89% of Cu2+ were absorbed from wastewater.
Tan and Ting [112], evaluated the use of alginate-immobilized bentonite
to remove Cu2+ as an alternative to mitigate clogging problems. The ad-
sorption efficacy (under the influence of time, pH and initial Cu2+ con-
centration) and reusability of immobilized-bentonite (1% w/v
bentonite) was tested against plain alginate beads. The Qmax (mg/g) of
alginate and alginate immobilized bentonite for Cu2+ was found to be
107.5 and 131.6 respectively. Both adsorbents demonstrated compli-
ance to the pseudo-second order kinetic model. Moussout et al. [113]
reported the removal of Cu2 + from aqueous solution using chitosan
(CS) and 5%bentonite/chitosan (5%Bt/CS) nanocomposite. It was found
that the experimental data fitted well to Langmuir isotherm over the
whole temperature and concentration ranges. The Qmax (mg/g) for the
Cu2+ was 404–422 for CS and 282–337 for 5%Bt/CS at 25–45 °C. The
thermodynamic study showed that the adsorption process was sponta-
neous and endothermic. It was observed that the complexation of Cu2+
with NH2 and C_O groups as active sites was found to be the main
mechanism in the adsorption processes.
Jin et al. [114] reported sorbent for simultaneous removal of Cu2+
and 2,4-dichlorophenol (2,4-DCP) from aqueous solution by using mod-
ification of bentonite with humic acid (HAB). Results clearly shows that
amount of sorption was 22.40 mg/g and 14.23 mg/g for Cu2+ and 2,4-
DCP, respectively at 30 °C. Fourier-transform infrared (FTIR) spectra re-
sults confirmed that new bonds and band intensity emerged after the
sorption of Cu2+ and 2, 4-DCP onto the HAB. These suggest that simul-
taneous sorption of 2, 4-DCP and Cu (II) onto HAB could occur through:
firstly, a mechanism that partitions between 2, 4-DCP and HA; and sec-
ondly, the ion-exchange mechanism between Cu2+ and bentonite.
5.1.5. Cobalt (Co2+)
The major sources of cobalt contamination are electroplating, alloys,
metallurgical, petrochemical paints, and coal industries. Excessive expo-
sure to Co2+ causes toxic impact to human being such as respiratory ir-
ritation, wheezing, asthma, decreased lung function, pneumonia, and
fibrosis, gastrointestinal effects (nausea, vomiting, and diarrhea), and
effects on the blood, liver injury, and allergic dermatitis. US EPA has
established a maximum contaminant level (MCL) for Co2+ of 1.3 μg/L
in drinking water but values up to 107 μg/L have also been reported
 S. Pandey / Journal of Molecular Liquids 241 (2017) 1091–1113
[115] (Table 2). Core–shell iron nanoparticles where synthesized in the
presence of K10 bentonite for the Co2+ removal by Shahwan et al. [116].
The amount of adsorbed Co2+ ions increased due to deprotonation of
oxyhydroxyl groups on the external surface of the core–shell iron nano-
particles. The rate of adsorption was evaluated using first and second
order rate equations. The adsorption was described by the Freundlich
model. The adsorbent effectively removed Co2+ ions from aqueous so-
lution even after 8 successive uses. When the Co2+ concentration was
increased to 100.0 mg/L, N90% of Co2+ was adsorbed after three uses.
Assameur and Boufatit [117], reported the removal of Co2+ by acid
activated bentonite. The outcome demonstrates that most extreme
binding of 98% can be achieved when adsorption take place at pH 5, ini-
tial concn 10 ppm, contact time 60 min. It demonstrates the adsorption
model kinetics best fitted to pseudo second order with R2 = 0.99. Re-
sults demonstrate that the request fit is Freundlich N Langmuir. Al-
Shahrani [118], studies the removal of Co2+ from wastewater utilizing
Saudi activated clay (bentonite). It was found that adsorption of Co2+
ions on Saudi activated bentonite was generally quick and the equilibri-
um was achieved after 30 min. Adsorption was additionally dependent
on solution pH where cobalt removal rate was observed to be 99% at
pH 8. Besides, around 100% cobalt removal was observed when solution
pH was increase to N 8. The adsorption data gave better fits with Lang-
muir (R2 = 0.975) and Freundlich (R2 = 0.936) isotherms and yielded
Langmuir monolayer capacity of 7.3 and Freundlich adsorption capacity
of 2.33 for acid activated bentonite. Moreover, the estimation of the
mean free energy (Ea = 91.3 kJ/mol) determined by D–R equation dem-
onstrated that adsorption procedure is chemisorptions. Co2 + ion ad-
sorption into Saudi activated bentonite was well represented to by the
pseudo-second-order kinetic model with R2 was ~1.0.
Hashemian et al. [119] reported the removal of Co2+ from aqueous
solution using Fe3O4/bentonite nanocomposite synthesis by chemical
co-precipitation method. The characterization results indicated that
the metal oxides mainly occurred in the form of spinel structure of
Fe3O4 and the presence of Fe3O4 significantly affect the surface area
and pore structure of the bentonite. The specific surface area of benton-
ite, Fe3O4, and Fe3O4/bentonite were determined to be 34.44, 98.44, and
140.5 m2/g, respectively. TEM image of Fe3O4/bentonite shows the par-
ticle diameter at 10 nm. The Qmax (mg/g) of Co2+ by Fe3O4/bentonite
nanocomposite was determined to be 18.76. The adsorption process fol-
lows pseudo-second-order kinetics. The equilibrium data was analyzed
by Langmuir model showing high correlation coefficient.
Cobalt has many radioisotopes, the most important of which are
60
Co, 57Co and 58Co which are γ-emitters, 60Co has the longest half-life
among the cobalt radioisotopes, and it is widely used in medical and in-
dustrial applications. Metwally and Ayoub [120], studied the chemi-
sorption of 60Co radionuclide from aqueous solution using modified
bentonite clay with 8-hydroxy quinoline, as a chelating agent. The sorp-
tion capacity of 60Co radionuclide onto both natural bentonite and 8HQ-
Bent were determined and found to be 2.6 mmol/g and 4.42 mmol/g, re-
spectively. This result indicated that the modification of bentonite by 8-
hydroxy quinoline enhances the sorption capacity. The results indicated
that the sorption process well fit pseudo-second-order model, the sorp-
tion is controlled by intra-particle diffusion mechanism, and the process
is chemisorption since the value of diffusion coefficient is in the order
10–15 m2/s.
5.1.6. Nickel (Ni2+)
Excessive intake of nickel may cause serious lung and kidney prob-
lems aside from gastrointestinal distress, pulmonary fibrosis and skin
dermatitis [121]. Sources of Ni2 + are zinc base casting, printing,
electroplating, silver refineries, battery manufacturing, and production
of some alloys [122]. US EPA has established a maximum contaminant
level (MCL) for Ni2+ of 0.05 mg/L in drinking water [73] (Table 2).
Xu et al. [123] reported Ni2 + removal by consolidating bentonite
with PAM. On the base of these tests, the orthogonal examinations are
made with pH, amount of bentonite and amount of PAM and 3 levels
1099
to figure out the best treatment process in wastewater treatment com-
bining so as to contain Ni2+ bentonite with PAM (pH = 8.5,concentra-
tion of bentonite is 5.0 g/L, concentration of PAM is 1.0 mg/L). Cui-na
and Shu-li [124], reported the removal of Ni2+ cations from counterfeit
wastewater by Ca-bentonite and Na-bentonite of Handan was studied.
The outcomes demonstrated that the equilibrium time of adsorbing
Ni2+ cations were 15 min. The removal rate of Ni2+ cations increased
with the increment of pH, amount of bentonite and time of adsorption.
Na-bentonite sorbed more Ni2+ than Ca-bentonite; the removal rate of
Ni2+ came to up to 96%. The concentration of wastewater treated by Na-
bentonite was 0.825 mg/L, which is lower than the national emission
standards. Vereš and Orolínová [125], examined the removal of Ni2+
ion by utilizing incorporated bentonite/iron oxide nanocomposite by
the method for coprecipitation from the solution of ferric and ferrous
salts. The study demonstrated that the bentonite/iron oxide composite
and treated bentonite were viable in removing Ni2+ ions from aqueous
solution contrasted with the commercial bentonite from the region
Stará Kremnička. The Qmax on chose sorbents in low concentration
range shows following order: composite bentonite/iron oxide compos-
ite N treated bentonite N natural bentonite. The Qmax (mg/g) at 5 ppm is
12, 6, and 4 in composite bentonite/iron oxide nanocomposite, treated
bentonite, natural bentonite respectively. Vieira et al. [126] reported re-
moval of Ni2 + by utilizing Bofe-sort bentonite clay from BoaVista,
Paraíba, situated in the northeastern locale of Brazil. Bourliva et al.
[127] reported two common Greek clays, bentonite from Milos Island
and vermiculite from Askos region, North Greece were utilized for
Ni2 + removal from aqueous solutions. The adsorption takes place at
pH 5. General the kinetic studies demonstrated that the Ni2+ adsorption
procedure follow pseudo-second-order kinetics. The pseudo first-order
plots of log (qe-qt) versus t had great linearity R2 is 0.998 and the rate
constant, K2 was 0.58 × 10−2 g/mg min for bentonite and 0.52 × 10–
2 g/mg min for vermiculite. The adsorption fits better with Langmuir
(R2 N 0,95) and Freundlich (R2 N 0,93) isotherms and yielded Langmuir
Qmax (mg/g) of 26.32 to 38.46 and Freundlich adsorption capacity of
2.95 to 3.05 mg(1 – 1 / n) L1/n/g for the bentonite and vermiculite,
respectively.
Al-Shahrani [128], researched the activated Saudi characteristic ben-
tonite tests, which were obtained from khulays stores for removal of
Ni2+ ions. It was observed that increment in pH from 2 to 9 results in
adsorption of Ni2+ from 70 to 100% in 40 min. The adsorption isotherm
data were very much fitted with both Langmuir and Freundlich adsorp-
tion isotherm. The Qmax (mg/g) was observed to be 47.62 and R2 =
0.9318 in Langmuir. The R2 for the second order kinetic model is
0.999. In this way it is clear from the S. S. Al-Shahrani [128] study that
Saudi activated bentonite can be considered as a promising adsorbent
for the removal of Ni2+ from wastewater.
Sandeep and Suresha [129], study the removal of Ni2 + ions from
aqueous solution and electroplating wastewater by using sodium pyro-
phosphate modified bentonite composite (NPP-bentonite). Maximum
Ni2+ ion adsorption of 87.30% was accomplished at pH 6.0 with adsor-
bent dose of 2 g/L with contact time of 120 min and initial metal ion con-
centration of 50 mg/L. The equilibrium adsorption information fitted
well to Langmuir and Freundlich isotherm models with Langmuir ad-
sorption capacity (mg/g) of 30.3 and Freundlich adsorption capacity of
3.98 (mg/g)/(mg/L)1/n.
Li et al. [130] was used to prepared the negatively charged Na-satu-
rated bentonite (Na-bent) with high adsorption capacity to Ni2+ was
used to support NZVI for improving the removal and reduction of
Ni2 +, and the functions of Na-bent. NZVI/Na-bent not only showed
much higher removal efficiency of Ni2+ (98.5%) than the sum (48.8%)
of those by bare NZVI removal (41.9%) and by Na-bent adsorption
(6.9%), but also greatly enhanced the reduction efficiency of Ni2+ into
Ni0 by facilitating the electron transfer from Fe0 core to the surface-
adsorbed Ni2+. and improved the reduction of toxic Ni2+ into lower-
toxic Ni0. Furthermore, the efficient reduction of Ni2+ by NZVI/Na-bent
will contribute to the formation of bimetallic Fe/Ni/Na-bent composite
1100 S. Pandey / Journal of Molecular Liquids 241 (2017) 1091–1113
that will be more reactive for degradation of other refractory contami-
nant. The regeneration study on NZVI, NZVI/Al-bent and NZVI/Nabent
was also performed. It was observed that Ni2+ removal by NZVI de-
creased from 41.8% to 27.1% after four cycles; however, Ni2+ removal
only decreased from 45.5% to 40.6% by NZVI/Al-bent and from 98.5% to
93.7% by NZVI/Na-bent, respectively. The results indicated that the repet-
itive usability of NZVI was distinctly improved by support on Na-bent and
Al-bent.
5.1.7. Silver (Ag+)
Sources of Silver are through weathering of rocks and the erosion of
soils, processing of ores, steel refining, cement manufacture, fossil fuel
combustion, municipal waste incineration, and cloud seeding. Excessive
intake of Ag may causes liver and kidney damage, irritation in eyes, skin,
respiratory, and intestinal tract, and changes in blood cells [131]. US EPA
has established a maximum contaminant level (MCL) for Ag+ of
0.1 mg/L in drinking water (Table 2). Hefne et al. [132] depicted Ag+
could be adsorbed and in this way higher critical amounts removed by
bentonite from aqueous solutions. The removal % of Ag+ increased
with the increment of contact time, amount of adsorbent and pH. Lang-
muir model preferred spoke to the sorption process over the Freundlich
model. The Qmax (mg/g) was observed to be 53 and 69 at 293 K & 333 K
respectively. The R2 of Langmuir model equation value 0.989. Kinetic
modeling results demonstrated that the pseudo second-order equation
with K2 (g/mg·min) is 0.05 and (R2) worth is 1. An outcome demon-
strates the high Qmax of washed bentonite (WB) contrasted with natural
bentonite (NB) and calcined bentonite (CB). Depending upon the nega-
tive value of ΔG, the adsorption of Ag+ on NB surfaces was spontaneous
and the adsorption was endothermic process. The values of ΔH (kJ/mol)
and ΔS (kJ mol K−1) is 4.15 and 0.05 respectively.
5.1.8. Chromium (Cr6+; Cr3+)
The most common sources of chromium pollution are electroplating,
leather tanning, dye, photographic, and cement industries. Respiration
in Cr6+ for a short period of time causes irritation of the nasal, cough
and chest pain whereas swallowing results in abdominal pain, diarrhea,
heart failure, damaging the gut, liver and kidneys. Contact of Cr6 +
causes dermatitis or skin ulcers [133]. US EPA has established a maxi-
mum contaminant level (MCL) for Cr of 0.1 mg/L in drinking water
[73] (Table 2). Tahir and Naseem [134], reported removal of Cr3 + by
bentonite nanoclay from tannery wastewater. Most extreme of 93% ad-
sorption has been achieved on pre-treated (with sludge) wastewater
specimens with a shaking time of 15 min, while 76% is achieved if
there should be an occurrence of untreated examples with a shaking
time of 45 min at a pH of 2.5. The procedure of uptake takes after both
the Langmuir and Freundlich isotherm models. Zhou et al. [135], report-
ed the modify nanoclay such as pillared montmorillonites; Fe/Zr
pillared montmorillonites (Fe/Zr4:1-Mts), Fe/Zr pillared montmorillon-
ites (Fe/Zr1:1-Mts), Fe pillared montmorillonite (Fe Mt) and Zr pillared
montmorillonite (Zr-Mt) for adsorption of Cr6+ from aqueous solution.
The Langmuir adsorption isotherm gave the best relationship of the
equilibrium data, and the evaluated most extreme equilibrium uptake
of Cr6+ of Fe/Zr4:1-Mt, Fe/Zr1:1-Mts, Zr-Mt & Fe Mt was 22.35, 21.11,
19.23 & 16.21 mg/g separately at pH 3.0, 25 °C. It takes after pseudo sec-
ond order kinetics with K2 [g/(mg·min)] 0.073 and R2 = 0.999 if there
should arise an occurrence of Fe/Zr4:1-Mt. It shows maximum binding
of Cr6+ take place by Fe/Zr4:1-Mt. Pandey and Mishra [54], reported ad-
sorption of Cr6+ by utilizing organic-inorganic nanocomposite of chito-
san and nanoclay (Cloisite 10A) with joined properties of hydrophilicity
of an organic polycation and adsorption capacity of inorganic polyanion.
It is well known that Clay has lamellar structure with (− ve) charged
surface that allows the polycationic chitosan to probably have polar in-
teractions. The possibilities of these clay chitosan nanocomposites as a
hybrid material are shown in the proposed Scheme 2. The information
fitted better to Langmuir isotherms, the R2 value being 0.998 and
0.999 at 15 °C & 35 °C respectively demonstrating unilayer adsorption.
In view of Langmuir model, Qmax was ascertained to be 357.14 mg/g.
The adsorption indicated pseudo second order kinetics with a rate con-
stant of 8.0763 × 10−4 g mg−1 min−1 at 100 ppm Cr6+ concentration.
The complex structures of Cr6 + with (+ ve) charged outer surface
would be probably get adsorbed at the (− ve) charged silica surface.
Based on these possibilities of interaction between the polymer and fill-
er, hydrated Cr6+ probably can get chelated or can have charged inter-
action with chitosan. Also it has the possibility to interact on the
negatively charged clay surface. The interaction of chitosan and clay sur-
face with the Cr6+ was proposed in Scheme 3. The adsorption ability
was almost completely resumed after the regeneration of acid-treated
sorbent. The removal decreased nominally per cycle up to 4th cycle sug-
gesting very high efficiency of the adsorbent. In the last cycle 78.47% ad-
sorption was feasible.
Rashmi et al. [137] reported the maximum binding of Cr3+ by zirconi-
um modified montmorillonite (ZrO-M) and ZrO-Bent clay compound
(ZrO-M) occurs at pH 6. The clays were modified by treating them with in-
tercalating solution zirconium oxychloride solution (ZrOCl2·8H2O). The
surface area of these intercalated clay compounds was determined to be
126 g/m2 of ZrO-B and 145 g/m2 of ZrO-M. The modified clays are micro-
porous and shows large number of small flakes with severely crumpled
structures. It was observed that the ZrO-M shows better capacity of
87.8% for chromium at pH 6, interaction time of 15 min contrasted with
that of ZrO-Bent clay compound (ZrO-M) 83.7%. The aftereffects of the
present examination demonstrate that clay minerals intercalated with zir-
conium oxychloride are powerful adsorbents for the removal of chromium
metal from aqueous solutions.
Kumar et al. [138] reported the removal of Cr6+ by utilizing cellulose-
montmorillonite nanocomposite material as the adsorbent. The XRD pat-
tern of the composite material shows sharp and pointed diffraction
peaks (Fig. 1a) at 2θ values corresponding to 6.25°, 8.8°, 18.14°, 20.73°,
and 22.79°, which indicates the crystalline nature of the polymeric
composite with certain degree of exfoliation. It was also observed that
after adsorption of Cr6+, crystalline nature of the composite is not
disturbed and the new sharp peaks obtained at 2θ values corresponding
to 39° and 42.47°are attributed to the adsorption of Cr6+ (Fig. 1b). The
material showed a most extreme adsorption capacity of 22.2 mg/g as per
the Langmuir isotherm model. The spontaneity of the adsorption
procedure could be affirmed from the investigation of the adsorption
thermodynamics. In the regeneration study, ascorbic acid was quite
effective in reducing Cr6+ to the less toxic Cr3+. The adsorbent could be
reused for 10 adsorption-desorption cycles with good efficiency. After
10th cycles, the adsorption of Cr6+ decreases. This reason for decrease is
attributed to the decrease in the effective interaction between the
adsorbent and the adsorbate due to the nonavailability of active sites for
adsorption. Saravanan et al. [139] reported the adsorption of Cr6+ ion by
utilizing a characteristic biopolymer chitin/bentonite nanocomposite
from aqueous solution. The authors' studies incorporate batch adsorption
equilibrium to study the impact of a few parameters, for example, pH,
contact time, adsorbent dosage and metal ion concentration. The ideal
uptake of free ionic Cr6+ happens at pH 4. The monolayer adsorption
capacity Qmax (dm3/g) was observed to be 1.810. As indicated by
regression coefficient, the Freundlich adsorption isotherm (R2 = 0.9576)
was more fitted for Cr6+ than Langmuir (R2 = 0.8716). Ming-ping and
Yong-jian [140], study the organically modify bentonite (nanoclay) by uti-
lizing hexadecyltri-methylammonium bromide (CTMAB) for the removal
of Cr6+ ions from wastewater. The ideal condition for most extreme ad-
sorption was recommended as pH 3.0 to 5.0, stirring time around
30 min, and organobentonite dose 10 g/L. It was seen that 35 mg/L of
Cr6+ ion in wastewater can remove N98.0%, utilizing the above enhanced
conditions. Thus the most extreme adsorption proficiency confirm the
modify organobentonite as a successful adsorbent for Cr6+ removal from
wastewater. Moradi et al. [141] reported the application of modified ben-
tonite for removal of Cr6+ from aqueous solution. The Qmax (mg/g) of Cr6+
according to Langmuir model was obtained at 4.21. The experimental data
properly obeyed the Langmuir and pseudo-second-order models.
 S. Pandey / Journal of Molecular Liquids 241 (2017) 1091–1113
Scheme 2. Organic–inorganic hybrid of chitosan and clay.
[Reprinted with permission from Ref. [54] [Pandey, S., Mishra, S.B. Organic-inorganic hybrid of chitosan/organoclay bionanocomposites for hexavalent chromium uptake. J. Colloid
Interface Sci. 361, 2011, 509–520.]. Copyright 2011 Elsevier].
Hu et al. [142] investigated simultaneous removal of Cr6 + and
Amido Black 10B (AB10B) dye using quaternized chitosan coated ben-
tonite. The results showed that the antagonism effect existed between
Cr6+ and AB10B in binary systems. The equilibrium time for Cr6+ ad-
sorption was less than the one for AB10B adsorption. The maximum ad-
sorption capacities of the modified bentonite, according to the Langmuir
isotherm model were 847.5 mg/g for AB10B and 66.6 mg/g for Cr6+ at
298 K. The experimental results demonstrated that both Cr6 + and
AB10B were well described by the pseudo-second-order model. Ther-
modynamic study depicted that the adsorption of Cr6 + and AB10B
onto the modified bentonite was both spontaneous. The adsorption
for Cr6+ was exothermic while the one for AB10B was endothermic in
nature.
Soliemanzadeh and Fekri, [143] reported the removal of Cr6 + by
using Bentonite-supported “green” nanoscale zero-valent iron (B-
NZVI), prepared using green tea extracts. The adsorption of Cr6+ onto
natural bentonite was lower (Qmax = 1.34 g/g) than B-NZVI
(45.06 g/g). The adsorption capacity on Cr6+ was determined at about
45, 60.50 and 66 mg/g at pH 5, for 0.001, 0.01 and 0.05 M ionic strength,
respectively. The adsorption isotherm and kinetic data for B-NZVI was
fitted well with the Langmuir and pseudo-second order model, respec-
tively, which implied that the adsorption process was chemisorptions.
5.1.9. Mercury (Hg2+)
Mercury in coal-fired flue gas exists in three forms: oxidized mercu-
ry (Hg2+), particulate bounded mercury (Hgp) and elemental mercury
(Hg0). Out of which first to is easy to remove by air pollution control de-
vices (APCDs). But Hg0 is difficult to capture due to its volatility, chem-
ical inertness, and water-insolubility. Sources of Hg are pesticides,
batteries, paper industry, mineral deposits, fossil fuel or ores etc. Exces-
sive intake of Hg causes damage to kidneys, reproductive systems and
immune system [144]. US EPA has established a maximum contaminant
1101
level (MCL) for Hg2+ of 0.002 mg/L in drinking water [73] (Table 2).
Keeping this point in mind Shao et al. [145] reported the synthesis of
novel KI modified bentonite supported by starch sorbent (B–S–I) and
the comparison between B–S–I and the traditional KI modified benton-
ite sorbent (B–I) in Hg0 removal was performed under simulated flue
gas. The results showed that B–S–I exhibited more remarkable Hg0 re-
moval ability than B–I. The starch loaded on B–S–I was considered to
greatly promote the surface reactivity and more sulfur groups could
be formed, which favored the chemisorption of Hg0. Increasing temper-
ature in the range of 80–140 °C caused a rise in Hg0 removal. The ad-
sorption capacity (μg/g) of B–S–I and B–I (12.5% I) in each case was
found to be 604.3 and 450.2 respectively. Bentonite serving as support
showed a good reusability to resynthesize B–S–I for Hg0 removal.
Wang et al. [146] reported the removal of Hg2+ by using CTS–PVA/BT
nanocomposites. The surface of CTS–PVA/BT nanocomposites contain-
ing 1%, 3%, 5% and 7% BT contents seems to be loose and porous com-
pared to that of CTS-g-PVA, and no obvious protuberance was
observed. While the BT content above 7%, many protuberances appear
on the surface. Further enhancement in % BT content in the nanocom-
posite, the protuberances becomes more results in aggregation of clay
tactoids in the polymeric matrix (Fig. 2). The adsorption capacities for
Hg2 ions with a BT content of 0%, 10%, 30% and 50% are 460.18, 455.12,
392.19 and 360.73 mg/g, respectively, which are much higher than
that for Cu2+, Cd2+ and Pb2+ ions. This shows CTS–PVA/BT nanocom-
posites have special adsorption selectivity for Hg2 ions.
5.1.10. Indium (In3+)
The source of indium is cultivated soils, in industry as by-product of
smelting zinc and lead sulfide ores. Excessive intake of Indium can
causes irritation of the eyes, nose, throat and lungs causing coughing,
damage lungs, liver and kidney in human being [147] (Table 2). Calagui
et al. [148] explored the removal of In3+ ions from aqueous solution by
1102 S. Pandey / Journal of Molecular Liquids 241 (2017) 1091–1113

Scheme 3. Possible interaction mechanism of Cr (VI) with chitosan and organoclay.

[Reprinted with permission from Ref. [54] [Pandey, S., Mishra, S.B. Organic-inorganic hybrid of chitosan/organoclay bionanocomposites for hexavalent chromium uptake. J. Colloid
Interface Sci. 361, 2011, 509–520.]. Copyright 2011 Elsevier].

utilizing chitosan-covered bentonite nanocomposite (CCB). The equilib-
rium data was best depicted by Langmuir isotherm. The Qmax (mg/g) is
17.890. The R2 is 0.970. The mean energy (E) was found in the scope of
1–8 kJ/mol, showing that the governing sort of adsorption of In3+ ions
onto CCB is basically physical. The adsorption energy of In3+ particles
best fits the pseudo-second order (R2 N 0.99), which confirm that chem-
ical sorption as the rate-limiting step. Thermodynamic parameters, in-
cluding Gibbs free energy, enthalpy, and entropy showed that the
In3 + particles adsorption onto CCB was feasible, spontaneous and
endothermic in the temperature scope of 278–318 K. The values of ΔS
(kJ/mol·K) and ΔH (kJ/mol) was found to be 0.0293 and 7.310.
5.1.11. Selenite (Se4+)
Selenium (Se) pollution in groundwater has become a worldwide
issue caused by industrial, agricultural, petrochemical and mining
activities. It causes liver damage in human being. US EPA has established
a maximum contaminant level (MCL) for Selenium of 0.05 mg/L in
drinking water [149] (Table 2). Keliang et al. [150] reported sorption

Fig. 1. XRD pattern (a) cellulose-clay composite adsorbent and (b) after chromium (VI) adsorption on the adsorbent.
[Reprinted with permission from Ref. [138] [Kumar, A.S.K., Kalidhasan, S., Rajesh, V., Rajesh, N. Application of cellulose-clay composite biosorbent towards the effective adsorption and
removal of chromium from industrial wastewater. Ind. Eng. Chem. Res. 51 (1), 2012, 58–69.]. Copyright 2012 American Chemical Society].
 S. Pandey / Journal of Molecular Liquids 241 (2017) 1091–1113
of Se4+ particle on filtered GMZ bentonite under surrounding tempera-
ture as functions of contact time, pH, Se4 + ion concentration and co-
existing ion Eu3+ utilizing batch techniques. Sorption kinetics of Se4+
ions was effectively depicted by the pseudo-second-order rate mathe-
matical equation. In this manner from the experimental results, one
can clearly confirm that GMZ bentonite may have great possibilities
for immobilizing selenium in nuclear wastes.
Orucoglu and Haciyakupoglu [151], reported that Organic-pillared
bentonite (OPBent) was produced by modification of sodium bentonite
with aluminum polyoxy and hexadecylpyridinium cations. Variation in
structure after modification was demonstrated by using different char-
acterization techniques. Se removal efficiency of OPBent is investigated
by using 75Se. The maximum adsorption capacity (Qmax) of Se4+ on the
OPBent composite was found to be (0.113 mmol/g). The zero-valent
iron permeable reactive barrier (ZVI-PRB) is a promising technology
for in-situ groundwater remediation. Dong et al. [152] describe the
role of pillared bentonite (Al-bent) when homogeneously mixed with
ZVI result in removal of selenate (Se6+) from simulated groundwater
in column experiments. The Se6+ removal was increased because first
Al-bent could facilitate the mass transfer of Se6+ from solution to iron
surface and accelerate Se6+ reduction. Al-bent to the ZVI system could
promote the reduction of Se6+ to Se0 and Se2− of less toxicity and sol-
ubility. Therefore the enhancement on the removal of Se6+ in the ZVI/
Al-bent system was mainly due to the synergetic effect between adsorp-
tion by Al-bent and reduction by ZVI.
5.1.12. Arsenic (As3+)
Water contamination by arsenic salt is one of the big environmental
pollution. The sources of arsenic are from natural deposits, smelters,
glass, electronics wastes, orchards etc. It causes life time diseases such
as cancer, neurological disorder, nausea, hyperkeratosis, muscular
weakness, and many others [84,85,153]. US EPA has established a max-
imum contaminant level (MCL) for arsenic of 0.010 mg/L in drinking
water [73] (Table 2). Zahra et al. [154] reported the Bentonite contains
montmorillonite has the quality to adsorb inorganic and organic mate-
rials. Rate adsorption was resolved for bentonite-arsenic solution sys-
tem as a function of; contact time, pH, and temperature, mesh size
and adsorbate dose. Most extreme arsenic adsorption was seen at 20
°C at pH 2 and 8. Least particle size favors greatest arsenic adsorption.
The time taken to keep up equilibrium was 30 min. Bentonite is suitable
for removal of arsenic from wastewater. 95% arsenic evacuation is con-
ceivable by batch adsorption process utilizing bentonite. Sua et al. [155]
study, the removal of As5+ and As3+ by utilizing organobentonites ar-
ranged by modification of bentonite with different cationic surfactants,
from aqueous solution. The experimental information demonstrated
that the adsorption capacity of bentonite modify with octadecyl benzyl
dimethyl ammonium (SMB3) were 0.288 mg/g for As5+ and 0.102 mg/g
for As3 +, which were much higher contrasted with 0.043 and
0.036 mg/g of unmodified bentonite (UB). Sorption kinetics was effec-
tively portrayed by the pseudo-second-order model with rate constants
of 46.7 × 10−3 g/mg h for As5+ and 3.1 × 10−3 g/mg h for As3+, respec-
tively. The most extreme adsorption capacity Qmax (mg/g) of As5+ and
As3 + determined from the Langmuir comparison is 1.48 mg/g and
0.82 respectively.
5.1.13. Iron (Fe3+, Fe2+)
Iron poisoning is a leading cause of poisoning deaths in children.
Symptoms begin with acute gastroenteritis, followed by a quiescent pe-
riod, then shock and liver failure. Excess of iron also causes
haemorrhagic necrosis and sloughing of areas of mucosa in the stomach,
genetic disorder (haemochromatosis) etc. US EPA has established a
maximum contaminant level (MCL) for Iron of 0.3 mg/L in drinking
water [156] (Table 2). Tahir and Rauf [157], reported the adsorption of
Fe2 + particle utilizing bentonite nanoclay from aqueous solutions in
the scope of 80–200 mg/L, time of 1–60 min, dosage from 0.02 to 2 g
and pH of 3. The procedure of uptake takes after both the Langmuir
1103
and Freundlich isotherm models furthermore the first-order kinetics.
The most extreme removal (N98%) was seen at pH of 3 with initial con-
centration of 100 mg/L and 0.5 g of bentonite. The productivity of Fe2+
removal was additionally tried utilizing wastewater from galvanized
pipe manufacturing industry. N90% of Fe2+ can be successfully removed
from the wastewater by utilizing 2.0 g of the bentonite. The impact of
cations (i.e. zinc, manganese, lead, cadmium, nickel, cobalt, chromium
and copper) on the removal of Fe2+ was studied over in the concentra-
tion range of 10–500 mg/L. All the included cations lessened the adsorp-
tion of Fe2+ at high concentrations except Zn.
5.1.14. Thorium (Th4+)
Thorium, the most abundant heavy metal, has been widely used in
nuclear fuel industry, catalysis, high temperature ceramic, and high
quality lenses. It is found in soil, rock, and water. It is formed by the ra-
dioactive decay of uranium. US EPA has established a maximum con-
taminant level (MCL) for Thorium of 15 picocuries per liter (15 pCi/L)
in drinking water [158,159]. The accidental release of thorium from in-
dustries may increase its amount in the environment. Longterm expo-
sures to thorium enhance the chances of developing lung diseases and
lung, pancreas, and bone cancers. Thorium solubility is high at pH 2.0,
with Th4+ as the soluble species. Wu et al. [160] reported the adsorption
of Th4+ from aqueous solution by using novel magnetic organo-benton-
ite-Fe3O4 poly(sodium acrylate) (OB-Fe3O4 PSA) superabsorbent nano-
composites. The positive ferrous and ferric ions were loaded on the OB
surface by coordination reactions between ferrous/ferric ions and
silanol/aluminol groups (Si/Al–OH) using the wet impregnation process
[161]. The OB/Fe3O4 magnetic nanoparticles (OB-Fe3O4) were prepared
by co-precipitation technique in the aqueous dispersion of OB pre-mod-
ified with FeCl3 [161]. The nanocomposite was synthesized by copoly-
merization of partially neutralized acrylic acid (SA) on OB-Fe3O4
nanoparticle by using N,N′-methylenebisacrylamide as crosslinker and
ammonium persulfate as initiator. The maximum Qmax (mmol/g) of
Th4 + on OB-Fe3O4 PSA 3.6 superabsorbent at pH 3.0 and T = 298 K
was about 6.55. Thermodynamics study confirms, that Th4+ adsorption
on OB-Fe3O4 PSA superabsorbent was an endothermic and spontaneous
process. Regeneration study of OB-Fe3O4 PSA superabsorbent can be
perform by desorption of Th4 + using 0.1 mol/L HCl solution and the
Qmax was found to be higher than 3.6 mmol/g even after 5th consecutive
adsorption–desorption processes [160]. Miraoui and Didi [162], report-
ed the sorption of Th4+ by sodium bentonite and magnetic bentonite
composite. Various parameters have been studied to assess the perfor-
mance of maghemite nanocomposite clay for the removal of Th4 +.
The time needed for magnetic bentonite to adsorb the maximum of
Th4+ is 45 min and 60 min for sodium bentonite. The Qmax (mg/g) of so-
dium bentonite and magnetic bentonite are 41.24 and 31.34 respective-
ly. It was found that the sorption of Th4 + on sodium and magnetic
bentonite was better suited to the Langmuir adsorption model.
5.1.15. Cesium (Cs+)
137
Cs have come to the forefront as the most significant concern be-
cause of the harmful health effects of this isotope and its potential to
persist for decades. It causes acute radiation syndrome, which includes
such effects as nausea, vomiting, diarrhea, bleeding, coma, and even
death, damage cells and might also cause cancer. In children it causes
changes in behaviour or decreased mental abilities. It comes from envi-
ronments caused by erosion and weathering of rocks and minerals;
mining and milling. US EPA has established a maximum contaminant
level (MCL) for average annual drinking water limit of 80 picocurie
per liter (pCi/L) for 134Cs or 200 pCi/L for 137Cs [163] (Table 2). A chito-
san-grafted magnetic bentonite (CS-g-MB) was successfully synthe-
sized via a plasma-induced method by Yang et al. [164]. The CS-g-MB
composite shows good magnetic properties, low turbidity, and high sta-
bility in aqueous solution and exhibits significant adsorption capacity
for Cs+ ions. In the presence of Mg2+, K+, Li+, and Na+ ions, the Cs+ ex-
change is constrained in the order of Li+ ≈ Mg2+ b Na+. The maximum
1104 S. Pandey / Journal of Molecular Liquids 241 (2017) 1091–1113

Fig. 2 SEM images of CTS–PVA/BT nanocomposites with various BT contents.

[Reprinted with permission from Ref. [146] [Wang, X., Yang, Li., Zhang, J., Wang, C., Li, Q. Preparation and characterization of chitosan–poly(vinyl alcohol)/bentonite nanocomposites for
adsorption of Hg2+ ions. Chemical Engineering Journal. 251, 2014, 404–412.]. Copyright 2014 Elsevier].

adsorption capacity (Qmax) of Cs+ on the CS-g-MB composite in the con- surfaces, whereas inner-sphere surface complexation and co-precipita-
taminated simulated groundwater (1.21 mmol/g). tion were the main sorption mechanism at high pH values.
Liu et al. [170] synthesized Polyaniline (PANI) modified bentonite
5.1.16. Uranium (U6+) (PANI/bentonite) synthesized by plasma induced polymerization of an-
Uranium (U6+) a radioactive and hazardous heavy metal, originates iline on bentonite surface, and applied to uptake of uranium (VI) ions
from nuclear industry and other anthropogenic activities such as lignite from aqueous solution. The confirmation of modified bentonite was
burning in power stations, ore processing, and the use of fertilizers. Ura- perform by XRD, where natural bentonite and PANI/bentonite are fairly
nium in the aqueous solutions is poisonous to a series of aquatic organ- similar between 10° and 65°, which clearly depict there is no structural
isms owing to using of uranium-containing phosphate fertilizers, change in bentonite after plasma treatment process. The confirmation
discharging from nuclear power plant wastewater and releasing from of incorporation of PANI onto bentonite are known by appearance of
geological repository of high-level radioactive waste [165]. Uranium in- new diffraction peak at 2θ = 9.06 (Fig. 3). Further confirmation was
directly or directly cause detrimental health influences such as liver
damage, shortness of breath, serious kidney disease, birth defects and
even death [166] (Table 2). US EPA has established a maximum contam-
inant level (MCL) for uranium of 30 μg/L in drinking water [167]. Xiao et
al. [168] reported local bentonite from Huangshan county (Anhui prov-
ince, China) used as an adsorbent to remove U6+ ions from aqueous so-
lutions as a function of various environmental parameters such as
contact time, pH, ionic strength, foreign ions, humic acid and tempera-
ture under ambient conditions. At pH b 6.5, the sorption of U6+ on the
bentonite increased with increasing pH, whereas the sorption of U6+
on bentonite decreased with increasing pH at pH N 6.5. The cations
and anions influence the sorption of U6+ on bentonite obviously at pH
b 7.0, and no influence is found at pH N 7.0. The sorption isotherms of
U6+ on bentonite can be well described by the Langmuir model. The
Qmax (mol/g) was found to be 9.19 × 10−5.
Zong et al. [169] reported removal of U6+ ion by using Na-bentonite.
The adsorption equilibrium obtained in 10 h. The sorption of U6+ ion
was influenced by ionic strength at pH 7.5. The presence of fulvic acid
(FA) or humic acid (HA) promoted the sorption behaviour of U6+ ion
onto Na-bentonite at low pH values while decline the sorption perfor-
mance at high pH values. Thermodynamics studies reveal that Na-ben- Fig. 3. XRD patterns of bentonite and PANI/bentonite.
Ref. [170] [Reprinted with permission from Ref. [Liu, X., Cheng, C., Xiao, C., Shao, D., Xu, Z.,
tonite was spontaneous and endothermic. At low pH values, the Wang, J., Hu, S., Li, X., Wang, W. Polyaniline (PANI) modified bentonite by plasma
sorption performance of U6+ ion was dominated by outer-sphere sur- technique for U (VI) removal from aqueous solution. Applied Surface Science, 411, 2017,
face complexation and ion exchange with Na+/H+ on Na-bentonite 331–337]. Copyright 2017 Elsevier].
 S. Pandey / Journal of Molecular Liquids 241 (2017) 1091–1113
performed by Liu et al. [170] by using the technique of XPS spectroscopy
in order to study the functional groups on bentonite and PANI/bentonite
surfaces. It was found that C 1s spectra of bentonite can be deconvoluted
into five components at 284.5 ± 0.2, 285.2 ± 0.2, 286.2 ± 0.2, 287.2 ±
0.2 and 289.1 ± 0.2 eV, which are attributed to the sp2-hybridized
graphite-like C atoms (C_C), sp3-hybridized C atoms (C\\C), \\C\\O
(i.e. alcohol and ether),\\C_O (i.e. ketone and aldehyde), and\\COOH
(i.e. carboxylic and ester) species, respectively (Fig. 4a). The quantita-
tive analysis results of XPS C 1s spectra of bentonite and PANI/bentonite
reveal that the peak fractions of C_C and\\COOH are increase and de-
crease after PANI modification, respectively. This result clearly confirms
that PANI was modified on the surface of bentonite successfully, and
parts of \\COOH were reduced by PANI in the synthesis process. Fur-
ther, the XPS O 1s spectra of bentonite and PANI/bentonite can be
deconvoluted into three peak components with binding energy at
531.8 ± 0.1, 532.6 ± 0.1 and 533.9 ± 0.1 eV, which are also assigned
to \\COO\\, \\C_O and \\C\\OH groups, respectively (Fig. 4b). The
quantitative analysis results of XPS O1s spectra of bentonite and PANI/
bentonite reveal that the peak fraction of\\COOH decreases, indicates
the reduction of\\COOH in synthesis process.
It was found that adsorption of U6+ (10 mg/L) on PANI/bentonite
surface is fairly depend on solution pH, ionic strength, and temperature
in solution. The modified PANI on PANI/bentonite surface significantly
enhances its adsorption capability for U6+. The presence of humic acid
(HA) can sound enhance U6 + adsorption on PANI/bentonite at pH
b 6.5 because of the strong complexation, and inhibits U6+ adsorption
at pH N 6.5. The data fitted well to pseudo-second-order confirming
chemisorption as the rate limiting the reaction. The adsorption data
fitted well to Langmuir adsorption isotherm hence implying monolayer
adsorption. The Qmax of U6+ on PANI/bentonite surface calculated from
the Langmuir model is 14.1 mg/g at 293 K.
According to the thermodynamic parameters, the adsorption of U6+
on PANI/bentonite surface is a spontaneous and endothermic process.
The results highlight the application of PANI/bentonite composites as
candidate material for the uptake of trace U6+ from aqueous solution.
The regeneration study of PANI/bentonite reveals the similar adsorption
capacity for U6+ as compared with raw PANI/bentonite, which reveals
that PANI/bentonite has excellent stability.
5.1.17. Miscellaneous metal ions
In the above subsections, the removal of a particular metal ion was
examined on a particular bentonite and its composite, however few pa-
pers depicted the removal of more than one metal ion on a solitary ben-
tonite and its composite, which are discussed herein.
Lin and Juang (2002) [76] depicted the evacuation of Cu2+ and Zn2+
by utilizing sodium dodecylsulfate-modified montmorillonite nano-
composite from aqueous solution. The researchers reported that more
Cu2 + was adsorbed as contrasted and Zn2 +. Dubinin-Kaganer-
Radushkevich model was received to depict the single-solute sorption
isotherms. The kinetic parameters of the models firmly fitted a pseu-
do-second-order. Yun et al. [171] examined the adsorption of heavy
metal ions i.e. Cu2 + and Pb2 + onto bentonite clay modified with 4′-
methylbenzo-15-crown-5 (MB15C5-bentonite). For bentonite modified
with (MB15C5-bentonite) composite and N-Bentonite, the equilibrium
information firmly fitted the Langmuir display and demonstrated the
following affinity order: Pb2+ N Cu2+. The modified bentonite compos-
ite gave a higher Qmax than the unmodified sodium bentonite for both
Cu2 + and Pb2 +. The Qmax (mg/g) of 0.403 and 0.488 for Cu2 + and
Pb2 + were acquired for the modified bentonite contrasted and
0.287and 0.396 for Cu2+ and Pb2+ if there should be an occurrence of
unmodified bentonite. The kinetic parameters of the models firmly
fitted a pseudo-second-order model in all cases. Peng and Li [172] re-
ported the adsorption capacity and mechanism of acid-modified ben-
tonite to heavy metal ions. The outcomes demonstrated that the acid
modify bentonite had great adsorbing capacity for Ni2 + and Cd2 +
ions. The ideal conditions for the removal of the titled metallic ions
1105
were proposed as pH estimation of 5.0 to 7.0, concentration of Ni2 +
and Cd2+ in wastewater beneath 45 mg/L, and blending time around
60 min. The Ni2+ and Cd2+ ions in the wastewater, with substance un-
derneath 45 mg/L, were removed at a rate over 98.5%, indicating great
adsorption-removal efficiency. Ayari et al. [173] reported utilization of
sanitized and modified bentonite clay by HCl (3 M) for the removal of
some heavy metals ions (Pb2 +, Zn2+, Ni2 +) from aqueous solutions.
These are the absolute most critical polluting influences of industrials
effluents. The clay portion utilized as a part of this work was an inter-
stratified illite-smectite with 89 meq/100 g CEC of calcined clay and
504 m2/g specific surface areas, which is utilized as a part of the purified
and modified form, to test its legitimacies of sorption for the removal of
these above dangerous metals from aqueous solutions. The sorption
procedure is reflected by Langmuir and Freundlich-sort isotherm. The
removal capacity follows the order: Pb2+ N Zn2+ N Ni2+ for both natural
and treated sorbents. Equilibrium modeling of the adsorption demon-
strated that the adsorption of these three metals ions was fitted to a
Freundlich isotherm in all cases.
Faghihian and Nejati-Yazdinejad [174], modify sorbent (Cys–Ben)
demonstrated affinity for soft and moderately soft heavy metal ions
(HMI), for example, Cd2 + and Pb2 +, likely as a consequence of the
soft fundamental character of the thiol ligand side chains. The subse-
quent modified system was successful for metal binding with capacities
of 0.503 and 0.525 mmol/g for Pb2+ and Cd2+, respectively. The sorp-
tion parameters were determined from a Langmuir fit to the sorption
isotherms of the contemplated ions. The study demonstrated that the
sorption capacity of Cys–Ben was higher than that of N-Ben for these
particles. Bedelean et al. [175] reported bentonite test from the Petreşti
store, Cluj County (Romania), was utilized to uproot heavy metal ions
(Cd2+, Pb2+, Cr3+) from wastewaters. The bentonite test was utilized
as a part of powdered structure (d b 0.2 mm) with no concoction treat-
ment. The bentonite test turned out to be effective for the removal of
these metal ions; removal efficiencies up to 100% (Pb2 + removal)
were accomplished. Pan and Lu [176], study the effect on absorb Pb2+,
Ni2 +, Cd2 + from wastewater with Ca-bentonite from Weifang-
Yongquan of Sandong territory. Experiments results demonstrate that
normal Ca-bentonite and altered Ca-bentonite can assimilate the
Pb2+, Ni2+, Cd2+ adequately. Olu-Owolabi et al. [177], modify the ben-
tonite clay with goethite, humic acid, and a binary mixture of goethite
and humic acid reagents, which expanded its CEC from 95 to 105.32,
120.4, and 125.8 meq/100 g of bentonite clay, separately. The successful
pre-change of bentonite clay with goethite, humic acid, and goethite–
humic acid reagents was affirmed from their FTIR which proposed
that alteration was viable on the AlAlOH and Si\\O sites for goethite
and humic acid modification and AlAlOH for goethite–humic acid alter-
ation. The goethite–humic acid-modified bentonite gave the best ad-
sorption capacity of ≈10 and 16 mg/g at 30 and 50 °C, separately, for
both Cu2+ and Cd2+ ions.
Shi et al. [178] reported Bentonite-supported nanoscale zerovalent
iron (B-nZVI) was prepared using liquid-phase reduction. Electroplating
wastewater was treated with B-nZVI which exhibited higher potential
to remove Cr, Pb, and Cu N 90%. Talaat et al. [179] reported the crude
and treated Egyptian kaolin and additionally Ca and Na-bentonites
(Ca-B and Na-B) for heavy metals removal. The treatment was per-
formed using acid washing and calcination. The XRD design for Na-ben-
tonite uncovers that it contains 20.3%, 15.5% kaolin, 33.9% quartz and
30.5% K-feldspar (as microcline) when contrasted with Egyptian ben-
tonite of El-Fayoum region which contains 40–60% montmorillonite
and 20–30% kaolinite, while bentonite of Abu Tartour contains 5% kao-
linite, 56% montmorillonite, 9% illite and 11% free quartz. Adsorption
of Cr3+, Ni2+, Cd2+, Cu2+, Zn2+ and Pb2+ salts at low concentrations
were examined in batch mode. The clay dose was 0.5 g/L with metal
concentrations from 0.3 mg/L to 10.3 mg/L. The most extreme accom-
plished Cr3 + adsorption capacity Qmax (mg/g) for the tested clay are
9.2, 14.7 and 15.7 for Kr, Ca-B and Na-B, respectively. With respect to
Ni2 + adsorption, Ca-B shows best results coming to 11.6 mg/g
1106 S. Pandey / Journal of Molecular Liquids 241 (2017) 1091–1113
Fig. 4. XPS C1s (a) and O1s (b) spectra of bentonite and PANI/bentonite.
Ref. [170] [Reprinted with permission from Ref. [Liu, X., Cheng, C., Xiao, C., Shao, D., Xu, Z., Wang, J., Hu, S., Li, X., Wang, W. Polyaniline (PANI) modified bentonite by plasma technique for U
(VI) removal from aqueous solution. Applied Surface Science, 411, 2017, 331–337.]. Copyright 2017 Elsevier].
adsorption capacity. It is reasoned that Ca-B had the most elevated ad-
sorption capacity for Cu, Cd, Pb, Zn and Ni. It is likewise watched that
the selectivity of metals adsorbed is in the request of Pb N Cr N Cd N Cu
N Zn N Ni. This may be attributed to the affinity of combination of each
metal on the clay. The adsorption of Cd2 +, Cu2 + and Ni2 + were all
around spoke to utilizing Freundlich isotherm, while that of Pb2+ and
Zn2+ fitted well with Langmuir isotherm. The outcomes demonstrate
that the utilization of bentonite could give a cheap and in fact reason-
able choice for heavy metals removal from contaminated water.
Futalan et al. [180] study the comparative and competitive adsorp-
tion of Cu2+, Ni2+ and Pb2+ from aqueous solution utilizing chitosan
immobilized on bentonite composite (CHB) was explored. BET surface
area (m2/g) was found to be 2.12, 84.28, & 33.17 for chitosan, bentonite
& CHB respectively. The Total pore volume (cm3/g) was reported to be
0.032, 0.085, and 0.048 for chitosan, bentonite & CHB respectively. The
adsorption data of single and binary systems demonstrated that Cu2+
and Pb2+ best fits Freundlich isotherm while Ni2+ fitted best to Lang-
muir. In binary systems, a decrease in adsorption capacities and iso-
therm constants was observed, demonstrating inclination of
adsorption in the request of Pb2+ N Cu2+ N Ni2+. In single and binary
metal systems, Pb2+ has the most impressive adsorption capacity over
Cu2+ and Ni2+. This is affected by the electronegativity estimation of
a metal ion, where the values are organized in the request: Pb2 +
(2.33) N Cu2+ (1.95) N Ni2+ (1.91). The Qmax (mg/g) of Pb, Cu & Ni is
36.01, 23.11 & 17.51 respectively at 25 °C. Kinetic investigations of sin-
gle system demonstrated that the pseudo-second order is the best fit
with high correlation coefficients (R2 N 0.99).
Okoye and Obi [181], explored the Aluminum-Pillared and
Unpillared Bentonite Clays for adsorption of Cu2 +, Cd2 +, Hg2 +, and
Pb2+. The transformation of natural clay mineral (unpillared bentonite
clays) into pillared clay was accomplished using aluminum (0.1 M Al
(NO3)3·9H2O) by adding slowly a basic solution of 0.2 M NaOH on the
aluminum solution under constant stirring. The subtle element tech-
nique is as indicated by Okoye and Obi [181]. The surface area and po-
rosity demonstrates the BET surface area (m2/g), micro pore volume
(cm3/g), micro pore area (m2/g) and total pore volume (cm3/g) values
as 29.99, 0.0011, 2.70, and 0.0010 respectively in characteristic benton-
ite; and 49.86, 0.0014, 3.30, and 0.013 separately in aluminum-pillared
bentonite. The outcomes demonstrated pseudo-second order model ki-
netic to fit the sorption process. Rate law constant K2 (g·mg−1·min−1)
for unpillared bentonite was observed to be 0.18, 0.14, 0.12, and 0.11 in
Cu2+, Cd2+, Hg2+, and Pb2+ respectively. While Rate law constant K2
(g·mg− 1·min− 1) for Aluminum pillared bentonite was observed to
be 0.41, 0.32, 0.18, and 0.15 in Cu2+, Cd2+, Hg2+, and Pb2+ respectively.
The estimation of R2 is observed to be 0.8 in every one of the cases.
Aluminum pillared bentonite indicated higher adsorption rate and
also high capacity for the entire metal ion reported in this study, and
the request of selectivity are given accordingly: Cu2+ N Cd2+ N Hg2+
N Pb2+. Positive entropy (ΔS°) found in all cases demonstrates a fast re-
versible adsorption – desorption phenomena, showing physisorption of
the metal ions on the adsorbent surfaces. The thermodynamic parame-
ter ΔG° (kJ/mol), ΔH° (J/mol), ΔS° (J/mol·K) values − 2.65, + 33.10,
+13.42 for Cu2+; −2.54, +34.15, +14.12, for Cd2+; −2.46, +36.10,
+12.82 for Hg2+ and −2.39, +37.03, +13.27 for Pb2+ in unpillar ben-
tonite at (298 K). While if there should arise an occurrence of Aluminum
pillared bentonite ΔG° (kJ/mol), ΔH° (J/mol), ΔS° (J/mol·K) qualities are
−2.80, +31.80, +12.30 for Cu2+; −2.70, +32.60, +13.10 for Cd2+;
− 2.55, + 29.20, + 10.00 for Hg2 + and − 2.50, + 28.03, + 10.77 for
Pb2+. The estimations of ΔH° and Ea were both positive and lie in the
scope of physisorption. The outcomes obviously recommend that the
adsorption of all the metal ions contemplated in this work is controlled
by both surface adsorption and ion exchange phenomena.
Futalan et al. [182] researched the competitive removal of Cu2+, Ni2+
and Pb2+ from aqueous solution by utilizing chitosan immobilized on
bentonite (ChB). The vicinity of Na+ ions was seen to stifle the adsorption
capacity in the request of: Ni2+ N Cu2+ N Pb2+. To determine the kinetic
rate four kinetic models, for example, pseudo-first order or Lagergren,
pseudo-second order, intraparticle diffusion and film diffusion equation
were connected to the experimental data. Kinetics study reveal that ad-
sorption of Cu2+, Ni2+ and Pb2+ in a multi-metal system onto ChB
takes after the pseudo-second order mathematical equation. This implies
that the rate-deciding step is chemisorption, which implies that covalent
bonds are framed through sharing of electrons between ChB and metal
ions. The isotherm study demonstrates that Pb2+ and Cu2+ take after
Freundlich isotherm while Ni2+ is best depicted with the Langmuir
model. Furthermore, adsorption capacity Qmax (mg/g) for Cu2+, Ni2+
and Pb2+ are 12.6, 6.1 and 15.0, respectively. The particular adsorption
of Pb2+ over Cu2+, and Ni2+ onto ChB is because of properties, for exam-
ple, electronegativity, hydrolysis constant and softness value. Zhu et al.
[183] readied a novel superabsorbent composite by intercalation poly-
merization of acrylic corrosive (AA) and 2-acrylamido-2-methyl-1-pro-
pane sulfonic corrosive (AMPS) in the vicinity of montmorillonite
(MMT), utilizing ammonium persulfate (APS) as an initiator and N, N′-
methylenebisacrylamide (MBA) as a cross linker. Greatest receptiveness
of the composite in distilled water and 0.9% sodium chloride solution
was 722 and 108 g/g, respectively. The composite was utilized for removal
of heavy metal ions from aqueous solutions. Greatest measure of adsorp-
tion for Ni2+, Cu2+ and Pb2+ was 211.0, 159.6 and 1646.0 mg/g, separate-
ly, and the adsorption was as per both Langmuir and Freundlich model.
The % desorption of Ni2+, Cu2+ and Pb2+ was 90.3%, 95.6% and 84.5%,
 S. Pandey / Journal of Molecular Liquids 241 (2017) 1091–1113
separately. After desorption, the relating dry composites could in any case
adsorb metal ions. The most extreme of adsorption for Ni2+, Cu2+ and
Pb2+ was 201.7, 148.6 and 1440.3 mg/g, separately, after desorption
once. These outcomes demonstrated that MMT/P (AA-co-AMPS) super-
absorbent composite could be recovered and reused in wastewater treat-
ment. Urbano and Rivas [184], reported removal of Cu2+,Cd2+ and Al3+
ions by utilizing poly(2-acrylamido-2-methyl-1-propane sulfonic corro-
sive)-montmorillonite composites incorporated through in situ polymer-
ization. Retention experiments were carried out in batch procedures for
Cu2+, Cd2+, and Al3+ ions. At pH estimations of 3.0 and 5.0, the retention
were higher when the sulfonic acid group were completely separated.
Mohammed-Azizi et al. [185] recorded Algerian clay, a bentonite of Mos-
taganem (N.W. Algeria), has been acid-activated (HCl). The acid-activated
clay was utilized as adsorbent for the removal of Zn2+, Pb2+, Cu2+, and
Ni2+ ions from aqueous solution utilizing adsorption method. The opti-
mum parameters of our study acquired were pH value extend (4–6),
acid-activated clay (1 g), shaking time (1 h), and initial concentration of
metal ions (10 mg/L). The outcomes have demonstrated that Algerian
bentonite clay had critical potential for removing Zn2+, Pb2+, Cu2+, and
Ni2+ ions from contaminated water.
Aljli and Fares [186] reported removal of Cu2+ and Ni2+ ions from
wastewater by utilizing bentonite clay from Jeddah, Saudi Arabia. The
BET investigation of Bentonite Clay shows surface area of
62.5671 m2/g and pore volume 0.098005 cm3/g. It was found that the
adsorption capacity of bentonite clay expanded with an increment in
the test temperature. Isotherm study was performed in the concn
scope of 50–1000 ppm, and thermodynamic study in the scope of 20
°C–80 °C. The greatest adsorption capacity Qmax (mg/g) was 13.22 for
Cu2 + at 20 °C. For Ni2 + ions, the most extreme capacity was
9.29 mg/g at 20 °C. ΔH (kJ/mol) and ΔS (kJ/mol·K) is 4.8 and
0.005849 in Ni2+ and 3.3 and 0.007071 in Cu2+ at 293 K. It was found
that, all the three isotherm models (Langmuir, Freundlich and Lang-
muir-Freundlich) corresponds the experimental data well.
Hebbar et al. [187] reported the removal of heavy metal ion i.e. Cu2+,
Ni2 + and Cd2 + by using polyetherimide/porous activated bentonite
clay nanocomposite membrane. It was observed that the nanocompos-
ite membrane shows an increment in porosity, hydrophilicity and a re-
duction in hydraulic resistance. Elemental mapping studies confirmed
the intercalation of activated bentonite clay within the polymer matrix.
The membranes showed maximum rejection of 69.3%, 76.2% and 82.5%
for 250 ppm of Cu2+, Ni2+ and Cd2+ solutions, respectively. Glatstein et
al. [188] reported the adsorption of cadmium, copper and lead by natu-
ral Na-bentonite. Rifai and El Safa [189], reported bentonitic clay (south-
east El-Hammam City, Egypt) was subjected to pillaring using hydroxyl-
aluminum solution. It was observed that XRD patterns of the aluminum
pillared nano-bentonite (APNB) showed severe alteration of the crystal
structure after pillaring. Poly metal solutions with different metal con-
centrations of Cu, Co, Ni, Zn, Cd and Pb (0.001, 0.005 and 0.01 mol),
and pH (1, 2.5, 5 and 6) were subjected to treatment by the APNB. The
removal process was found to be very rapid and spontaneous and the
contact time may be short (several minutes) for most adsorption to
occur. The rate of Cu2 +, Zn2 +, Co2 +, Cd2 +, Ni2 + and Pb2 + sorption
remained higher or equal to the CEC. For each metal ion, the most
effective immobilization occurs over a particular pH around 5. The
preference of the APNB adsorption for heavy metal ions that are through
the cation exchange processes decreases in the order: Cu2 + N Zn2 +
N Co2+ N Cd2+ N Ni2+ N Pb2+. Ahmad and Mirza [190], evaluated the re-
moval of Pb2+ and Cd2+ by using methionine modified bentonite/algi-
nate (Meth-bent/Alg) nanocomposite. The equilibrium was attained in
120 min and the optimum pH for adsorption was found 5 and 4 for
Pb2+ and Cd2+ respectively. The experimental data is better fitted to
pseudo second order kinetics and Freundlich isotherm model. The
adsorption capacities for Pb2 + and Cd2 + obtained from Langmuir
isotherm was 30.86 and 217.39 mg/g at 303 K. The thermodynamic
parameter shows the process to be exothermic, spontaneous with
increased randomness of the adsorbent.
1107
Olekhnovich et al. [191], reported the heavy metal ion such as Co2+,
Cu2+, Ni2+ removal by using poly(acrylic acid)-co-acrylamide/benton-
ite composite. Studies and the analysis of absorption processes confirm
that the bentonite-containing polymer composite has high degree of af-
finity with of heavy metal ions. The maximum removal capacity of the
polymer hydrogel materials for Co2+, Cu2+, Ni2+ were 0,45, 0,65, 0,5
respectively. Ahmad and Hasan [192], perform the experiment on re-
moval of metal ion i.e. Cu2+, Pb2+, and Cd2+ ions from aqueous solution
by using L-cysteine modified bentonite-cellulose nanocomposite (cellu/
cys-bent). The initial concentrations range used for adsorption experi-
ment was 20–100 mg/L and the adsorbent affinity for metal ions was
found to be in order of Cu2 + N Pb2 + N Cd2 +. Based on the Langmuir
model, Qmax (mg/g) of Cu2+, Pb2+, and Cd2+ at 50 °C was found to be
32.36, 18.52, and 16.12, respectively. The Langmuir isotherm and pseu-
do-second order model were found to be better fitted than the other
isotherms and kinetic models. The thermodynamic parameters con-
firmed the process to be endothermic and spontaneous in nature.
Masindi and Gitari [193] and Gitari [194], fabricated the cryptocrys-
talline magnesite and bentonite clay composite for the removal of Co2+,
Cu2+, Ni2+, Pb2+ and Zn2 +. Optimization experiments revealed that
15 min of equilibration, 1 g of dosage, 500 mg/L of concentration and
1 g: 100 mL S/L ratios were the optimum conditions for removal of
metal ions. Removal of Co2 +, Cu2 +, Ni2 +, Pb2 + and Zn2 + was 100%.
The data fitted well to pseudo-second-order confirming chemisorption
as the rate limiting the reaction. The adsorption data fitted well to Lang-
muir adsorption isotherm. Al-Farhan [195], used bentonite modified by
magnetic hematite nanoparticles to clean post-production water con-
taminated by Cd2+ and Pb2+ ions. The colloidal solutions of iron (III)
hydroxide and iron (II) oxide were used to cover the surface of benton-
ite clay. The magnetic hematite nanoparticles XRD results shows hema-
tite nanoparticles of size 22.76 nm were covered the clay surface. The
clay loaded with nanoparticles was used as active agent in the removal
of Cd2+ and Pb2+ ions in their aqueous solutions. The removal efficien-
cy towards Pb2+ ions was relatively higher than Cd2+ ions.
Olu-Owolabi et al. [196] investigated; bentonite (BEN) clay was cal-
cined after modification with Carica papaya seeds or pine cone to obtain
C. papaya-modified bentonite (CPB) and pine cone-modified bentonite
(PCB). The efficiencies of these adsorbents for the removal of Pb2 +,
Cu2+ and Cd2+ ions from aqueous solutions were studied as a function
of pH, time, sorbate concentration and temperature. The sorption capac-
ity values for the BEN, CPB and PCB for Pb2+ are (19.6, 10.2 and 10.5),
Cu2+ (17.8, 32.8 and 13.61) and Cd2+ (23.2, 20 and 16.45) respectively.
The adsorption fitted pseudo-second order (R2 = 0.966) and intra-par-
ticle diffusion models and indicated mainly surface phenomena involv-
ing sharing of electrons between the adsorbent surfaces and the metal
ion species.
Taha et al. [197] for the first time investigated the adsorption poten-
tial of the Egyptian Na-activated bentonite (Na-AB) to remove Pb2+,
Cd2+, and Ni2+ from synthetic ternary-ion solutions and contaminated
seawater. The isotherm equations due to Langmuir and Freundlich iso-
therm models showed good fits with the experimental data. Na-AB
has a Langmuir monolayer capacity in a decreasing order of; Pb2 +
(5.43 mg/g) N Cd2+ (3.14 mg/g) N Ni2+ (2.77 mg/g), these are consid-
ered high capacity values relative to the initial concentration (10 mg/L
of each metal). The multi-component adsorption kinetics was more ac-
curately described by pseudo-second-order model. Activation energy
was calculated as 17.54, 13.73, and 28.66 kJ/mol for Pb2+, Cd2 +, and
Ni2 + respectively, suggesting physical adsorption. Application study
on polluted seawater, showed removal efficiency within range of 92–
100% not only for Pb2+, Cd2+, and Ni2+ but also for other co-existing
metals like Cu2+, Mn2+, Cr3+, and Zn2+.
El-Korashy et al. [198] reported the fabrication of bentonite/thio-
urea-formaldehyde composite material by in situ polymerization of
thiourea and formaldehyde in the presence bentonite microgranules
as a support for Pb2 +, Mn7 + and Cr6 + sorption. The optimum pH is
being close to 4 for Mn7 + and Pb2 + sorption, while maximum Cr6 +
1108 S. Pandey / Journal of Molecular Liquids 241 (2017) 1091–1113
sorption was at pH 2. The data fitted well to pseudo-second-order
confirming chemisorption as the rate limiting the reaction. The adsorp-
tion data fitted well to Langmuir adsorption isotherm hence implying
monolayer adsorption. The Qmax are 13.38, 14.81 and 4.20 mg/g for
Pb2+, Mn7+, and Cr6+, respectively. The regeneration study shows the
removal efficiency and a metal recovery over 90% for four successive
sorption/desorption cycles. The thermodynamics parameter reveals en-
dothermic nature of the sorption process.
Kumararaja et al. [199] investigated the remediation of a metal
spiked soil; Cu2+, Zn2+ and Ni2+ by using an aluminum-pillared ben-
tonite as the immobilizing agent. The adsorption data were fitted with
Langmuir and Freundlich isotherm models. The maximum monolayer
adsorption capacity of pillared bentonite was found to be 61.4, 32.3
and 50.3 mg/g for Cu2+, Zn2+ and Ni2+, respectively.
Putro et al. [200] prepared the waste paper as raw material for the
synthesis of nanocrystalline cellulose (NCC), and combining this NCC
with bentonite to produce a nanocomposite material for removing
Pb2+ and Hg2+ in single and binary systems. The adsorption isotherm
shows that Langmuir equation can represent the experimental data bet-
ter than Freundlich, the adsorption capacity (Qmax) for Pb2+ is higher
than Hg2 + in both systems (single system Qm (0.44 mmol/g) for Pb
and 0.23 mmol/g for Hg for composite). Apart from this all systems ex-
hibit endothermic process, except for bentonite which shows the exo-
thermic process.
Masindi and Gitari [193,194] investigated the fabrication of crypto-
crystalline magnesite and bentonite clay composite for simultaneous re-
moval of Co2+, Cu2+, Ni2+, Pb2+ and Zn2+ from wastewater in a single
step process. Optimization results clearly exhibit that 15 min of equili-
bration, 1 g of dosage, 500 mg/L of concentration and 1 g:100 mL S/L ra-
tios were the optimum conditions for removal of metal ions from
wastewater. The Removal of Co2 +, Cu2 +, Ni2 +, Pb2 + and Zn2 + was
found to be 100%. The data fitted well to pseudo-second-order
confirming chemisorption as the rate limiting the reaction. The adsorp-
tion data fitted well to Langmuir adsorption isotherm hence implying
monolayer adsorption.
5.1.18. Anions contaminant
5.1.18.1. Fluoride (F−). Inorganic contamination of drinking water and
its sources is brought on by natural and anthropogenic components. A
percentage of the inorganic contaminant, for example, Fluoride and ni-
trate are exceptionally lethal for individual. Fluorosis is endemic and has
influenced a huge number of individuals Toyoda and Taira [201]. The al-
lowable furthest capacity of Fluoride in drinking water is 1.5 mg/L in
drinking water Ayoob and Gupta [202]. US EPA has established a maxi-
mum contaminant level (MCL) for Fluoride of 4 mg/L in drinking water.
Likewise, abundance of nitrates in drinking water causes
methaemoglobinemia or blue child sickness. Hence, removal of these
abundance inorganic contaminants from water is of prime significance.
Karthikeyan et al. [203] reported removal of Fluoride by nanoclay.
Fluoride uptake was discovered greatest at pH 2, and it diminished
with expansion in pH. The material with particle size of 75 μm displayed
most extreme rate of fluoride adsorption contrasted with the other par-
ticle sizes. The Langmuir most extreme sorption capacity for fluoride
was observed to be 1.485–1.910 mg/g at distinctive temperatures. Fluo-
ride removal was observed to be antagonistically influenced just in the
vicinity of HCO− 3 . Adsorption happened on the surface and in addition
through intraparticle diffusion pattern of the adsorbent material. Ma
et al. [204] synthesized granular Zr-stacked bentonite (GZLB) arranged
with polyvinyl Liquor (PVA) trying to remove fluoride from aqueous so-
lutions. Recovery by alum displayed to expand the defluoridation capac-
ity of prepared sorbent. An adsorption capacity of 755 mg/kg was
achieved at pH 6.97 and inlet fluoride concentration of 6.34 mg/L. Tor
[205], examined defluoridation of aqueous solution using clay. The
greatest removal of fluoride was achieved at pH 6. Beneath pH 5, ad-
sorption was not favorable because of the development of weakly
ionized hydrofluoric acid in acidic conditions. At higher pH, above pH
pzc (6.5), the fluoride sorp-tion diminished because of the negative
charge of the MMT surface. The fluoride saturation capacity of clay
was accounted for 0.263 mg/g at room temperature. The interaction be-
tween the metal oxides at the surface of montmorillonite and fluoride
ions was represented the uptake of fluoride by the sorbent. The
adsorbed fluoride was found to desorb by washing the adsorbent with
a solution pH of 12. Kamble et al. [206] modify the bentonite clay with
an electropositive molecule (utilizing lanthanum, magnesium and man-
ganese), so as to improve its adsorption capacity for fluoride ions from
drinking water. Thakre et al. [207] examined the chemically modified
bentonite clay utilizing magnesium chloride as a part of request to up-
grade its fluoride adsorption capacity. It was watched that the MB
lives up to expectations adequately over extensive variety of pH and
demonstrated a most extreme fluoride removal capacity of 2.26 mg/g
at an initial fluoride concentration of 5 mg/L, which is vastly improved
than the unmodified bentonite.
5.1.18.2. Nitrate (NO−3 ). Nitrate sources in groundwater may result from
point sources such as sewage disposal systems and livestock facilities,
non-point sources such as fertilized cropland, parks, golf courses,
lawns, and gardens. Nitrate toxicity causes common clinical signs seen
include rapid but weak pulse, muscle tremors, tachypnea, blue-grey
mucous membranes, ptyalism, depression, weakness, staggering gait,
disorientation, frequent urination and a subnormal body temperature.
If left untreated, the condition rapidly deteriorates to prostration,
coma and even death. US EPA has established a maximum contaminant
level (MCL) for nitrate of 10 mg/L in drinking water. Bekele et al. [208]
reported acid activated natural bentonite clay for nitrate removal.
NO− 3 removal capacity of acid activated Ethiopian bentonite clay from
aqueous solution was observed to be more noteworthy than 80% of
NO− 3 ions at ideal states of contact time (90 min), acid activated Ethiopi-
an bentonite clay (2.0 g), initial nitrate concentration (250 mg/L), pH
(5), and temperature (30 °C). The adsorption information great fits
with Langmuir (R2 = 0.9946) and Freundlich (R2 = 0.8874) isotherms
and yielded Langmuir monolayer capacity of 8.68 and Freundlich ad-
sorption capacity of 3.68 for acid activated bentonite. Mena-Duran et
al. [209] reported the removal of NO− 3 from aqueous solutions by
using calcium bentonite modified by acid thermo activation with HCl
(2 N) and H2SO4 (2 N and 4 N). The NO− 3 capacity was observed to be
22.28%. It was clarified that an ionic exchange occurred between chlo-
rine (because of the HCl treatment) and nitrate ions. The ionic exchange
was likewise affirmed by the vicinity of KCl in the clay deposit. Xi et al.
[210] arranged the surfactant hexadecyltrimethylammonium bromide
(HDTMA) modified clay minerals and assessed them for NO− 3 adsorp-
tion. It was found that untreated Queensland (QLD) bentonite did not
expel NO− 3 from the solution, and kaolinite likewise indicated compara-
tive conduct for NO− 3 removal. The clays modified with nonfunctional
surfactant (HDTMA) in 2 or 4 cation exchange capacity (CEC) enor-
mously upgrade the removal of NO− 3 . Among all these organoclays,
HDTMA modified QLD-bentonite demonstrated the best result. The ad-
sorption capacity (mg/g) of H-B-2CEC and H-B-4CEC were 12.83 mg/g
and 14.76 mg/g respectively for NO− 3 removal.
5.1.18.3. Phosphates (PO3−
4 ). The sources of phosphates include natural
decomposition of rocks and minerals, stormwater runoff, agricultural
runoff, erosion and sedimentation, atmospheric deposition, and direct
input by animals/wildlife. Excessive intake of phosphate result in dam-
age blood vessels, increased prevalence of cardiovascular diseases and
induce aging processes. Kuroki et al. [211] reported the removal of
PO3−
4 by using La (III)-modified bentonite composite. The composite
was prepared from the Northeast Brazilian region modified with lantha-
num (NT-25La) using an ion exchange process. The adsorption data
have shown that composite reaches equilibrium between modified
clay and PO3−4 solution within 60 min of contact. The PO3−
4 retention
at room temperature reached 95%, when initial phosphate
 S. Pandey / Journal of Molecular Liquids 241 (2017) 1091–1113
concentration in solution was 5 mg/L. Adsorption of PO3−4 was best de-
scribed by a Langmuir isotherm, with maximum PO3− 4 sorption capacity
of 14.0 mg/g. Masindia et al. [212] used the novel technology for the re-
moval of phosphate (PO3− 4 ) from municipal effluents by nanocomposite
of cryptocrystalline magnesite-bentonite clay. The synthesis of nano-
composite was performed by vibratory ball miller method. Optimiza-
tion experiments for PO3− 4 removal are: 30 mins of shaking time, 1 g
of composite, 100 mg/L of PO34 −, 1:100 S/L ratios, 250 rpm, pH 10 at
RT. The Langmuir sorption capacity of nanocomposite was accounted
for 82 mg/g. Adsorption data fitted well to the Langmuir adsorption iso-
therm than Freundlich adsorption isotherms, thus confirming monolay-
er adsorption. Adsorption kinetics data fitted well to pseudo second-
order kinetics than first-order kinetics, thus suggesting chemisorption.
Bouraie and Masoud [213] investigated PO3− 4 removal from aqueous
solutions by using modified bentonite (MB) with magnesium hydroxide
in batch system. Surface morphology of the raw bentonite shows more
smooth and spongy appearance with irregular structure as compare to
MB after the treatment with Mg ions, which lead to the formation of
Mg(OH)2 clusters between the interlayer spaces of bentonite. These
Mg(OH)2 clusters formed between the interlayers are rigid enough
not only to prevent the interlayer spacing from collapsing, but also to
generate pores. After adsorption, MB surfaces became swollen. This
swelling could be the result of PO3−
4 adsorption. Phosphate ion removal
by MB was pH dependent, and the optimum adsorption was observed at
pH 7. The adsorption process was relatively fast and equilibrium condi-
tions were established within 120 min at 45 °C. The results were ana-
lyzed according to the Langmuir and Freundlich isotherm equations.
The adsorption data is well interpreted by the Langmuir isotherm. Phos-
phate solution at a concentration of 25 mg/L was adsorbed by MB, and
the final adsorption efficiency was N 54%. The results showed that phos-
phate adsorption density of MB was high with the maximum adsorption
density of 14.33 mg/m2, which suggested that MB was an excellent ad-
sorbent for effective phosphate removal from water. Thermodynamical-
ly negative ΔG°, positive ΔH°, and positive ΔS° demonstrated the high
affinity, and endothermic adsorption process between MB and phos-
phate from aqueous solutions.
6. Regeneration of bentonite and its nanocomposites
Recovery of adsorbents in water treatment is one of the vital view-
points as it controls the economy of water treatment innovation. My ex-
ploratory experience and perception direct to me that pH subordinate
solvents assume urgent parts in recovery of adsorbents [214]. A few re-
searchers endeavored to recover bentonite and its nanocomposites for
reusing. In view of industrial developments of the various kinds of sor-
bents described in the literature, the stability of the materials and the re-
producibility of the sorption properties is also of utmost importance.
Unfortunately, in the area of recovery of pollutants from bentonite
and its nanocomposites, the regeneration of spent sorbents, the stability
and reproducibility of the sorbents, a literature survey produces very lit-
tle information except in recent publications.
Haiyan et al. [96] reported removal of Pb2+ ion by utilizing sodium
base bentonite compounds polypropylene amine superabsorbent pre-
pared by aqueous solution synthetic method. Recovery study was per-
formed by using 2 mol/L HCl as eluent of resin recovery, the recovered
tar adsorption productivity of Pb2+ of 86.92% was watched. Dalida et
al. [106] reported the removal of Cu2+ from aqueous solution by utiliz-
ing non-crosslinked (CCB) and crosslinked chitosan-coated (CCB-ECH)
bentonite beads. The desorption study was performed utilizing eluent
solutions, tap water (pH 7) and HCl solution (pH 1 and pH 3). The
best Cu2 + ion recuperation was gotten utilizing HCl solution (pH 1).
Tahir and Naseem [134], reported removal of Cr3 + by bentonite clay
from tannery wastewater. N 99% recuperation has been accomplished
by utilizing 5 g of the bentonite with 3 M sulfuric acid solution. Sua et
al. [155] study, the removal of As5 + and As3 + by utilizing
organobentonites arranged by modification of bentonite with different
1109
cationic surfactants, from aqueous solution. Recovery study was per-
formed which demonstrated desorbed rates were 74.61% and 30.32%
for As5+ and As3+ separately, after recovery of SMB3 in 0.1 M HCl solu-
tion. Tahir and Rauf [157], reported the adsorption of Fe2+ ion utilizing
Bentonite clay from aqueous solution. N99% recuperation has been ac-
complished by utilizing 5 g of the bentonite with 3 M nitric acid solu-
tion. Futalan et al. (2012) [182], examined the aggressive removal of
Cu2 +, Ni2 + and Pb2 + from aqueous solution by utilizing chitosan
immobilized on bentonite (ChB). In the recovery study, 0.1 M of HCl,
NaCl and NaOH was utilized. HCl gave the most astounding desorption
capacity however with most material harm to ChB. After three cycles
of adsorption-desorption, % desorption utilizing HCl was 79, 70 and
81% for Cu2+, Ni2+ and Pb2+, respectively. Zong et al. [169] reported
the recycling of U(VI) sorption onto Na-bentonite. It is very clear that
the recycling was available for 6th cycles at least as illustrated in Fig.
5, and demonstrated a satisfied sorption proportion even in the 6th
cycles.
Ahmad and Mirza [190], evaluated the removal of Pb2+ and Cd2+ by
using Methionine modified bentonite/Alginate (Meth-bent/Alg) nano-
composite. The desorption study shows that 99% of the adsorbed Pb2+
and Cd2+ can be desorbed by using 0.1 M oxalic acid as eluting agent
with regeneration capability up to fifth cycle successfully. Wu et al.
[160] reported the adsorption of Th4+ from aqueous solution by using
Novel magnetic organo-bentonite-Fe3O4 poly(sodium acrylate) (OB-
Fe3O4 PSA) superabsorbent nanocomposites. OB-Fe3O4 PSA superabsor-
bent could be regenerated through the desorption of Th4 + using
0.1 mol/L HCl solution and the adsorption capacity was still higher
than 3.6 mmol/g after five consecutive adsorption–desorption process-
es. Tan and Ting [112], reported that plain alginate and alginate-
immobilized bentonite beads have good reusability potential. Treat-
ment with 10 mM HCl successfully eluted 93.05% and 94.33% of the
Cu2+ ions loaded onto plain alginate and alginate-immobilized benton-
ite, respectively, after three cycles of sorption–desorption test. There
was no significant difference in the percentage of Cu2 + desorbed in
the three sorption–desorption cycles for both the plain alginate
(93.15%, 93.54% and 92.48%) and immobilized-bentonite (92.38%,
96.03% and 94.75%). This demonstrated high reusability of the devel-
oped immobilized-bentonite without observable losses in their Cu2+
removal capacities.
Fig. 5. Recycling of U (VI) sorption onto Na-bentonite. T = 298 K, CU(VI)initial = 2.0
× 10−5 mol/L, pH = 5.5 ± 0.1, I = 0.01 mol/L KNO3.
Ref. [169] [Reprinted with permission from Ref. [Zong, P., Wu, X., Gou, J., Lei, X., Liu, D.,
Deng, H. Immobilization and recovery of uranium (VI) using Na-bentonite from aqueous
medium: equilibrium, kinetics and thermodynamics studies. J. Mol. Liq. 209, 2015, 358–
366.]. Copyright 2015 Elsevier].
1110 S. Pandey / Journal of Molecular Liquids 241 (2017) 1091–1113
7. Summary and outlook
Critical evaluations of composite materials as adsorbent in this arti-
cle indicates that bentonite/bentonite composite have been used for
the removal of metal ions and anions from water successfully. Recently,
bentonite and modified bentonites as adsorbents are gaining wide at-
tention due to their higher potential for inorganic contaminants remov-
al from water. In most studies, pseudo-second-order kinetic model was
found to fit well with the experimental data. Furthermore, inorganic
contaminants sorption by various adsorbents has been found to fit
well by Freundlich and/or Langmuir isotherm models.
Results from the recent advances in using bentonites and its modi-
fied nanocomposites show the flexible nature of the clay and its
ecofriendly nature. They are capable of removing inorganic contami-
nants from drinking water with very high removal ratios of toxic trace
metals, nutrients, and organic matter. In most of the cases, they proved
to be better or comparable with the existing commercial filter materials,
adsorbents, and conventional methods used for decontamination of
drinking water. Being natural and their abundance presence makes
them a low-cost green, nontoxic adsorbent which can be used for re-
moval of different contaminants from water and making clean and
pure drinking water available for developed and developing nations.
From the past to the future, the nature of adsorbents used was signif-
icantly changed. Now we are looking for low cost adsorbent such as nat-
ural and modify bentonite. The key-factor of each organic/inorganic
adsorbent of the past was only adsorption capacity, but now many fac-
tors were introduced in order to study an effective organic/inorganic
contaminants adsorbent (pH, kinetic rate, ionic strength, adsorbent's
dosage, etc.). More attention was also given on the nature and especially
porosity and surface area of adsorbents, creating a new promising class
of nanomaterials. However, apart from all of the above, the main draw-
back of the already published organic/inorganic-adsorption studies is
that their use is still in the laboratory stage mostly without pilot studies
or commercialization. Limited attempts for detailed economic and mar-
ket analyses are available. The applications of natural and modify ben-
tonite in commercial water treatment plants are expected to be a
great breakthrough in future. It is relatively less difficult to demonstrate
it in a laboratory; it is a little more challenging to demonstrate it at a
pilot scale, but to really increase it to a large scale would call for a signif-
icant financial and technological effort.
Notes
The authors declare no competing financial interest.
Acknowledgements
The author is thankful to the National Research Foundation,
(Grant No: 91399) South Africa for financial support. This research
is supported by the following: Center for Nanomaterials Science
Research, University of Johannesburg; the Faculty of Science,
University of Johannesburg.
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