Water Purification by Using Adsorbents - A Review (2018)

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Environmental Technology & Innovation 11 (2018) 187–240

Contents lists available at ScienceDirect

Environmental Technology & Innovation


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

Water purification by using Adsorbents: A Review


N.B. Singh a, *, Garima Nagpal b , Sonal Agrawal a , Rachna a
a
Research and Technology Development Centre, Sharda University, Greater Noida, India
b
Department of Applied Science, SRM University, Modi Nagar, India

article info a b s t r a c t
Article history: There are number of water purification techniques but the adsorption is one of the most
Received 10 August 2017 simplest, effective and economical method for wastewater purification. In this article
Received in revised form 30 April 2018 a large number of solid adsorbents such as Natural adsorbents, Agricultural Wastes,
Accepted 25 May 2018
Industrial wastes, Biomass, Nanoadsorbents: Carbon based nanomaterials, Nobel metal
Available online 2 June 2018
based nanomaterials, Metal oxide based nanomaterials, Spinel ferrite based nanomaterials,
Nanocomposites, Dendritic polymers; Geopolymer cement have been discussed for the
Keywords:
Adsorbents removal of different pollutants from waste water. Removal of Fluoride, Phosphate, Nitrate
Metal ions and Radionuclides from wastewater has also been reviewed in this article. Adsorption
Dyes isotherm models, kinetic models, thermodynamic parameters and adsorption mechanism
Phosphates have also been discussed. The present article lists different type of adsorbents and reviews
Nitrates state-of-the-art of the removal of different pollutants from water. The efforts have been
Fluorides made to discuss the sources of contamination and toxicities of pollutants. Adsorption
Nanomaterials mechanisms responsible for pollutants removal by different adsorbents have been re-
viewed. Attempts have also been made to point out the advantages and drawbacks of
adsorbents and the future research needs in the area of water purification by adsorbents.
© 2018 Elsevier B.V. All rights reserved.

Contents

1. Introduction............................................................................................................................................................................................. 188
2. Sources of water pollution ..................................................................................................................................................................... 189
3. Toxic elements and health risk .............................................................................................................................................................. 189
4. Water purification methods ................................................................................................................................................................... 189
5. Adsorption ............................................................................................................................................................................................... 189
5.1. Adsorption process..................................................................................................................................................................... 189
5.2. Adsorption isotherm models ..................................................................................................................................................... 191
5.3. Kinetic models ............................................................................................................................................................................ 194
5.4. Thermodynamics of adsorption ................................................................................................................................................ 196
5.5. Adsorption and DFT calculations ............................................................................................................................... 196
6. Adsorbents and water purification ....................................................................................................................................................... 197
6.1. Lowcost adsorbents.................................................................................................................................................................... 197
6.2. Natural adsorbents ..................................................................................................................................................................... 199
6.3. Agricultural wastes .................................................................................................................................................................... 200
6.4. Industrial wastes ........................................................................................................................................................................ 203
6.5. Biomass ....................................................................................................................................................................................... 206
6.6. Nanoadsorbents.......................................................................................................................................................................... 208

* Corresponding author.
E-mail address: n.b.singh@sharda.ac.in (N.B. Singh).

https://doi.org/10.1016/j.eti.2018.05.006
2352-1864/© 2018 Elsevier B.V. All rights reserved.
188 N.B. Singh et al. / Environmental Technology & Innovation 11 (2018) 187–240

6.6.1. Carbon based nanomaterials...................................................................................................................................... 209


6.6.2. Boron nitride materials .............................................................................................................................................. 213
6.6.3. Nobel metal based nanomaterials ............................................................................................................................. 215
6.6.4. Nanoscale zerovalent iron (NZVI).............................................................................................................................. 215
6.6.5. Metal oxide based nanomaterials.............................................................................................................................. 215
6.6.6. Spinel ferrite based nanomaterials............................................................................................................................ 217
6.6.7. Nanocomposites ......................................................................................................................................................... 218
6.6.8. Dendritic polymers based adsorbents....................................................................................................................... 224
6.7. Geopolymer cement as adsorbent ............................................................................................................................................ 224
7. Fluoride removal ..................................................................................................................................................................................... 225
8. Phosphate removal ................................................................................................................................................................................. 225
9. Nitrate removal ....................................................................................................................................................................................... 227
10. Removal of radionuclide’s ...................................................................................................................................................................... 229
11. Adsorption mechanism .......................................................................................................................................................................... 230
12. Future prospects ..................................................................................................................................................................................... 230
13. Conclusions.............................................................................................................................................................................................. 230
References ............................................................................................................................................................................................... 232

1. Introduction

Water is the most important compound for life on earth and it is a major global challenge for the 21st century to have
drinkable water. Pure and uncontaminated water is the basic requirement for all living organisms. More than 71% of the earth
surface is covered with water, but only less than 1% water is drinkable as per international standards because of different
contaminations. The main sources of water contamination include waste water discharge from industries, agricultural
activities, municipal wastewater, environmental and global changes. The presence of heavy metals, dyes and microorganisms
even in trace amounts, are very dangerous to human health, aquatic systems and the environment.
Even a trace amount of heavy metal ions and dyes is a risk for human beings and can be a cause for various diseases (Jamil
et al., 2010; Khan et al., 2008; Singh et al., 2010; Peng et al., 2004). The removal of such toxic elements and compounds which
are present in low concentrations is a difficult and challenging task. Various remediation technologies have been developed
for the removal of pollutants including toxic heavy metals, dyes, pesticides, fertilizers, organic acids, and halogenated
and phenolic compounds, among others. Techniques such as precipitation, incineration, flocculation, coagulation, ion
exchange, reverse osmosis, membrane filtration, electrochemistry, photo electrochemistry, advanced oxidation processes,
and biological methods have demonstrated different degrees of remediation efficiency (Zhu et al., 2016). Some drawbacks of
the methods are: low removal efficiency, high production of sewage sludge, non-cost-and-energy efficiency, generation of
toxic by-products, as well as the addition of more potentially toxic chemicals into the environment. Adsorption method has
been found to be the most effective and economical process. During the recent years, a lot of research on use of various
adsorbents for purification of wastewater has been carried out. The most common adsorbents for removal of different
pollutants from aqueous solution are listed by Scheme 1 (Raval et al., 2016).
Number of adsorbents has been used for the removal of pollutants from water and their mechanisms have been discussed
in number of research and review papers. Agricultural waste peels, biomass based activated carbon and industrial byproducts
have been used as low cost adsorbents for the removal of pollutants from water and wastewater (Bhatnagar et al., 2015;
Yagub et al., 2014; Ahmad and Danish, 2018; Olu-Owolabi et al., 2017; Georgieva et al., 2015). The effectiveness of various
adsorbents has been compared with commercial activated carbon. Chitosan is found to be one of the most important
materials in adsorption applications. Amino and hydroxyl groups present in the molecules contribute to many possible
adsorption interactions between chitosan and pollutants (dyes, metals, ions, phenols, pharmaceuticals/drugs, pesticides,
herbicides, etc.) (Vakili et al., 2014; Kyzas and Bikiaris, 2015). Low cost and high porosity of natural clay made them good
candidate for water purification. Bentonite and its composites were also used as nanoadsorbents by use of nanotechnology
(Bialczyk et al., 2017; Pandey, 2017). Nanomaterials possess a series of unique physical and chemical properties and are
being used as nanoadsorbents. Nanomaterials, nanocomposites, hydrogel nanocomposites and boron nitride nanomaterials
were used as emerging approaches for water purification (Masoumi et al., 2016; Mittala et al., 2016; Lin et al., 2017; Yu et al.,
2018). They were also compared with traditional adsorbents and their potential use for environmental applications (Adeleye
et al., 2016; Dubey et al., 2017; Luo et al., 2017; Tan et al., 2015). Carbon based materials like graphene, graphene oxide,
reduced graphene oxide as well as nanocomposites of graphene were reviewed as promising group of materials for removal
of organic and inorganic pollutants from water (Sharma et al., 2015; Chowdhury and Balasubramanian, 2014; Bharath et
al., 2017; Wang et al., 2016; Kyzas et al., 2015). Nano zerovalent iron materials were used for removal of contaminant
from water. Carbon nanotubes, carbon dots and carbon nanofibers were used as adsorbents, sensors and catalysts due to
their unique physicochemical, electrical and mechanical properties (Sarkar et al., 2017; Shi et al., 2018; Zhang et al., 2018).
However, there are lot of advantages and drawbacks of nanomaterials (Kyzas and Matis, 2015). Metal organic frameworks
were used as adsorbents for purification of contaminated water (Hasan and Jhung, 2015). Interaction mechanisms were
studied to understand the adsorption procedure. Spinel ferrite magnetic materials are emerging composite metal oxides for
the removal of aqueous pollutants due to their size, shape and high surface area (Reddy and Yun, 2016). Hierarchal porous
N.B. Singh et al. / Environmental Technology & Innovation 11 (2018) 187–240 189

Scheme 1. Different type of adsorbents for removal of pollutants from aqueous solution (Raval et al., 2016).

composites prepared by hydrothermal routes have also been used as promising adsorbents for pollutant removal (He et al.,
2017; Lei et al., 2017a, b, c, d; Hea et al., 2017). Possible interaction mechanism and environmental applications were studied
with the help of DFT calculations (Zou et al., 2016a, b, c).
This review article summarizes different type of pollutants and their removal from aqueous solution using different type
of adsorbents.

2. Sources of water pollution

Sources that contribute to water pollution can be categorized into two groups

(i) Point sources: Factories, Sewage system, Power plants, Underground coalmines, Oil wells, etc. Every year about 300–
400 MT of heavy metals, toxic sludge, solvents, and other harmful materials go into water due to industrial activity.
(ii) Non-point sources: Non-point sources are diffused across a broad area and their contamination cannot be traced to
a single discharge point. (See Table 5.)

3. Toxic elements and health risk

Effects of Toxic metal ions and pollutants on human health are continuously being analyzed by international organizations
such as WHO, USEPA, and EU. High concentrations of these toxic elements cause several adverse effect on human health.
Some of the toxic elements, their permissible limits in water and effect on human health are summarized in Table 1.

4. Water purification methods

Several treatment technologies are employed to remove pollutants from water/wastewater which include flocculation,
coagulation, biological oxidation, sedimentation, photo-Fenton treatment, advanced oxidation processes (AOPs), oxidation
with chemical oxidants (ozone or hydrogen peroxide, etc.), photocatalytic oxidation/degradation, membrane processes,
electrochemical oxidation/degradation, adsorption and combined methods (Fu and Wang, 2011; Wang et al., 2003; Connell
et al., 2008; Kurniawan et al., 2006; Galil and Rebhun, 1990). Different methods used in purification of water are given in
Fig. 1.
Due to huge discharge in water, number of techniques for wastewater treatment have been developed (Quist-Jensen et
al., 2015). However, the most of these technologies are not capable of fixing water pollutants in an effective way. Major
threats and drawbacks to common water purification systems are given in Fig. 2 (Das et al., 2014).

5. Adsorption

5.1. Adsorption process

During the process of adsorption, following terms need to be clarified.


190 N.B. Singh et al. / Environmental Technology & Innovation 11 (2018) 187–240

Table 1
Toxic Elements in drinking water and their impact on human health.
Toxic elements Permissible Effect of toxic elements on human health References
limits (ppm)
Arsenic 0.01 Arsenic toxicity causes different diseases IPCS (2001), WHO (2003a)

Antimony 0.02 Antimony trioxide is carcinogenic only to lungs. WHO (2003b)

Barium 0.7 Low concentration of barium causes hypertension, WHO (2003b)


heart problem, damage of blood vessels and nerves.

Benzene 0.01 High concentrations affect the central nervous system, WHO (2003d)
lower concentration affect the haematopoietic system.

Cadmium 0.003 High concentration of cadmium causes kidney and JECFA (2000)
liver damage, anemia, carcinogenic in inhalation,
retard growth and also causes renal arterial
hypertension.

Chlorine 5 Causes heart disease and dementia. WHO (2003e)

Chromium 0.05 Chromium is carcinogenic via inhalation route, causes WHO (2003f)
lung cancer and genotoxic in nature.

Copper 2 Moderate concentration Causes gastrointestinal WHO (2003g)


effects, elevated concentration of copper causes
Wilson disease and other disorders in the body. High
concentration of Copper can also cause taste problems
and liver damage.

Cyanide 0.07 Cyanide is very toxic in nature and affects thyroid and WHO (2003h)
nervous system.

Fluoride 1.5 High concentration of fluoride affects skeletal tissue, WHO (2003i)
bones, teeth and causes dental fluorosis and much
higher concentration causes skeletal fluorosis.

Lead 0.01 Affects peripheral nervous system and central nervous WHO (2003j)
system and also affect calcium and vitamin D
metabolism. High concentration of lead is
carcinogenic.

Manganese 0.40 High concentration of manganese causes neurological WHO (2003k)


problems through drinking water

Mercury 0.006 Inorganic Mercury compounds affect kidney and WHO (2005a)
nervous system disorders, oral poisoning causes
haemorrhagic gastritis and colitis.

Molybdenum 0.07 Toxic for bottle-fed infants. WHO (2003l)

Nickel 0.07 Toxicity of nickel compounds are dermatitis and WHO (2005b)
carcinogenic to human.

Selenium 0.01 High concentration of selenium is toxic for nails, hair WHO (2003m)
and liver.

Tetrachloroethene 0.04 High concentration of tetrachloroethene causes WHO (2003n)


central nervous system depression and at lesser
concentrations causes liver and kidney damage.

Tetrachloro methane 0.005 Highly toxic to liver and kidney and carcinogenic WHO (2003n)

Toluene 0.7 Toluene affects gastrointestinal tract, harmful for WHO (2003o)
central nervous system and irritation of
mucousmembranes.

1,1,1-Trichloro ethane 2 High concentrations cause hepatic steatosis (fatty WHO (2003p)
liver), also affect lungs and gastrointestinal tract.

Uranium 0.015 Causes Nephritis, less information is available on the WHO (2003q)
chronic health affect and also on carcinogenic nature.

Vinyl chloride 0.0003 High concentration is carcinogenic, genotoxic, also WHO (2003r)
causes chromosomal aberrations.
(continued on next page)

Adsorption: Adsorption is a process that occurs when a gas or liquid solute accumulates on the surface of a solid or a liquid
(adsorbent), forming a molecular or atomic film (adsorbate) . Depending on the type of attractions between adsorbate and
N.B. Singh et al. / Environmental Technology & Innovation 11 (2018) 187–240 191

Table 1 (continued)
Toxic elements Permissible Effect of toxic elements on human health References
limits (ppm)
Nitrate 50 Elevated concentration of nitrate is toxic to infants, WHO (2005c)
pregnant women and children and also affects the
thyroid gland.
Nitrite 3 Methaemoglobinaemia forms of nitrite react with WHO (2005c)
hemoglobin to form methemoglobin which block the
oxygen transport. Elevated level of methemoglobin
causes cyanosis, blue-baby syndrome.

Rhodamine B RB is very toxic and causes skin irritation, eye Rochat and Rerat (1978)
irritation, respiratory tract irritation. This is also
carcinogenic, toxic for nervous, reproductive and
developmental system.

Acid yellow 17 dye Even at low concentration, this dye affect Karthikeyan and
gastrointestinal tract, skin, lungs, hemoglobin adducts Jothivenkatachalam
and disturbance of blood formation. (2014)

Phenolic compounds High concentration of phenolic compounds is very Abdelwahab and Amin
toxic and mutagenic and absorbed through theskin. (2013)

Congo red Causes irritation in eye and skin, induces somnolence Mittal et al. (2009);
and respiratory problems and carcinogenic in nature. Chatterjee et al. (2009)

Methylene Blue Causes discoloration of skin, etc. Anirudhan and


Ramachandran (2015)

Crystal violet Causes bladder cancer, nausea, vomiting and central Rammel et al. (2011)
nervous system depression at high concentration.

Azo dyes Causes chromosomal damage and also reductive Vajnhandl and
cleavage of azo groups form carcinogenic aromatic Le Marechal (2007)
amine.

Basic fuchsin (BF) Causes eye burn and irritation to skin. Khan et al. (2015)

DDT 0.001 Causes endocrine and reproductive disorders, Chronic USEPA (1989); Wauchope
liver damage, immuno-suppression, cytogenic affects. et al. (1992)

Endosulfan Affects kidney, fetus, liver, reproductive system and Howard (1991)
Mutagenic in nature.

Malathion Carcinogenic, Mutagenic,etc. Wauchope et al. (1992)

Chlorpyrifos Causes neurobehavioral disorders like persistent Wauchope et al. (1992);


headache, blurred vision, memory, concentration Howard (1991)

Carbaryl Affects kidney, nervous system, mutagenic. Howard (1991)

Carbofuran 0.04 Affect function of nervous system. Howard (1991)

Simazine 0.004 Causes cancer of testes Wauchope et al. (1992);


Ahrens (1994)

adsorbent, the adsorption can be divided into two types—Physical and chemical adsorption also known as physisorption and
chemisorptions.
Adsorbate: The substance that concentrates at the surface is called adsorbate.
Adsorbent: The material upon whose surface the adsorption takes place is called an adsorbent.
The above terms can be shown diagrametically (Fig. 3) (Worch, 2012).
Adsorption isotherm: Plot of the amount of adsorbate on the adsorbent as a function of its pressure (if gas) or concentration
(if solution) at constant temperature is known as adsorption isotherm. There are variety of adsorption isotherms discussed
later in this article.
In water treatment, molecules or ions are removed from the liquid phase by adsorption onto solid phase and has been
proved as an efficient removal process for contaminants (Foo and Hameed, 2009; Nouri et al., 2007). Adsorption processes
proceed via different steps (Fig. 4) (Lata and Samadder, 2016).
The adsorbents used in water purification can be broadly divided into following categories (Fig. 5).

5.2. Adsorption isotherm models

An adsorption isotherm is a curve describing the phenomenon governing the retention (or release) of a substance from
the aquatic environments to a solid surface at a constant temperature and pH (Limousin et al., 2007; Allen et al., 2004).
192 N.B. Singh et al. / Environmental Technology & Innovation 11 (2018) 187–240

Table 2
Adsorption isotherm models Foo and Hameed (2010)a .
Isotherms Nonlinear form Linear form Plot
Ce 1 Ce Ce
= + v sCe
qe bQ0 Q0 qe
1 1 1 1 1
= + vs
q0 bCe qe Q0 bQ0 Ce qe Ce
Langmuir qe = 1+bCe
qe qe
q e = Q0 − qe v s
bCe bCe
qe qe
= bQ0 − bqe v sqe
Ce Ce
1/n
Freundlich qe = KF Ce log qe = log Kf + 1
n
log Ce log qe v s log Ce

Dubinin–Radushkevich qe = (qs ) exp(−kad ε 2 ) ln qe = ln(qs ) − kad ε 2 ln qe v sε 2

Tempkin qe = RT
bT
ln AT Ce qe = RT
bT
ln AT + RT
bT
ln Ce qe v s ln Ce
θ θ θ
Flory–Huggins C0
= KFH (1 − θ ) nFH
log = log KFH + nFH log(1 − θ )
C0
log v s log(1 − θ )
C0

qsH Cen H
( ) ( )
Hill qe = KD +Cen H
log qs −
qe
= nH log(Ce ) − log KD log qs −
qe
v s log(Ce )
H qe H qe
( ) ( )
ln KR QCe − 1 v s ln(Ce )
KR Ce
Redlich–Peterson qe = g ln KR QCe − 1 = g ln(Ce ) + ln(ag )
1+aR Ce e e

βS ( ) ( )
Ks Ce
Sips qe = βS βs ln Ce = − ln KS
qe
+ ln (as ) ln
KS
qe
v s ln (Ce )
1+aS Ce
( ) ( )
Toth qe =
KT Ce
(aT +Ce )1/t
ln
qe
KT
= ln (Ce ) − 1t ln(ar + Ce ) ln
qe
KT
v s ln(Ce )
ACen 1 1 B
Koble–Corrigan qe = 1+BCen qe
= ACen
+ A

q b C
Khan qe (1+sb kC e)a – –
k e k

βR
aRP rR Ce
Radke–Prausnitz qe = β −1 – –
aRP +rR Ce R
( ) ( )r
Ce ∝ qs
Frenkel–Halsey–Hill ln Cs
= − RT qe d
– –
( )1/3
k
MacMilla–Teller qe = qs ln(Cs /Ce )
– –

a
qe amount of absorbate in the absorbent at equilibrium (mg/g), q0 maximum monolayer coverage capacity (mg/g), Ce equilibrium concentration (mg/L),
b Langmuir isotherm constant (dm3 /mg), n adsorption intensity, T temperature (K), KF Freundlich isotherm constant (mg/g), R universal gas constant
(8.314 J/mol K), bT Temkin isotherm constant, AT Temkin isotherm equilibrium binding constant (L/g), ε Dubinin–Radushkevich isotherm constant, qs
theoretical isotherm saturation capacity (mg/g), β Dubinin–Radushkevich isotherm constant (mol2 /kJ2 ), C0 adsorbate initial concentration (mg/L), θ degree
of surface coverage, nFH Flory–Huggins isotherm model exponent, KFH Flory–Huggins isotherm equilibrium constant (L/g), KD Hill constant, qsH Hill isotherm
maximum uptake saturation (mg/L), nH Hill cooperativity coefficient of the binding interaction, KR Redlich–Peterson isotherm constant (L/g), Redlich–
Peterson isotherm constant (1/mg), g Redlich–Peterson isotherm exponent, Sips isotherm model constant (L/mg), KS Slips isotherm model constant (L/g),
βS Sips isotherm model exponent, T Toth isotherm constant (L/mg), KT Toth isotherm constant (mg/g), t Toth isotherm constant, A Koble–Corrigan isotherm
constant (Ln mg1−n /g), B Koble–Corrigan isotherm constant (L/mg)n , α k Khan isotherm model exponent, bk Khan isotherm model constant, α RP Radke–
Prausnitz isotherm model constant, γ R Radke–Prausnitz isotherm model constant, β R Radke–Prausnitz isotherm model exponent, α Frenkel–Halsey–Hill
isotherm constant (Jmr/mole) with r is the sign of inverse power of distance from the surface, d Interlayer spacing (m), k MacMillan–Teller (MET) isotherm
constant.

Table 3
Kinetic models for adsorption.
Order Equations Straight line plot References
( )
k1
pseudo-first-order log (qe − qt ) = log qe − 2.303
t log (qe − qt ) VS t Çiftçi and Henden (2015)
t 1 t t
pseudo-second-order = + VS t Çiftçi and Henden (2015)
qt k2 q2e qe qt

Elovich qt = β ln(αβ ) − ln t qt VS ln t Chien and Clayton (1980)


Intra particle diffusion qt = Kp t 1/2 + C qt VS t 1/2 Weber and Morris (1963)
Bt = −0.4977 − ln(1 −
qt
Boyd kinetic model q0
) Bt VSt Okewale et al. (2013)
( ) ( )
Ct Ct
Bangham’s model log log C0
− qt m = log k0 + qt log t log log C0
− qt m VS log t Malana et al. (2011)

Adsorption equilibrium is established when an adsorbate phase is in contact with the adsorbent for long time (Ghiaci
et al., 2004). Typically, the isotherm is depicted graphically expressing the adsorbent concentration against its residual
concentration. It provides a perception about mechanism of adsorption, degree of harmony of the adsorbents and surface
N.B. Singh et al. / Environmental Technology & Innovation 11 (2018) 187–240 193

Fig. 1. Different methods for purification of water.

Fig. 2. Some major threats to conventional water purification systems.

properties (Bulut et al., 2008). A large number of equilibrium isotherm models have been used and given in Table 2 (Foo and
Hameed, 2010).
194 N.B. Singh et al. / Environmental Technology & Innovation 11 (2018) 187–240

Fig. 3. Basic terms of adsorption (Worch, 2012).

Fig. 4. Pathways of adsorption process.

Fig. 5. Adsorbents for water remediation.

Different models given in Table 2 are based on different assumptions. Langmuir isotherm assumes monolayer adsorption
on homogeneous surface with definite number of adsorption sites. Freundlich model is suitable for heterogeneous surface
and can be applied to multilayer adsorption. Both are most commonly used isotherm models to determine performance
of adsorbents. D–R isotherm is mainly used to determine adsorption mechanism (physical or chemical adsorption) with
mean free energy on a heterogeneous surface. Temkin isotherm assumes that there is a linear decrease in heat of adsorption.
Flory–Huggins isotherm indicates spontaneous nature and feasibility of adsorption process. Hill isotherm model follows
the hypothesis that ligand binding sites of a macromolecule can affect other binding sites of the same macromolecule. R–P
isotherm is the most commonly used three parameter isotherms. It is a combination of Langmuir and Freundlich models.
It can be used over a vast range of concentrations and can be used in both homogeneous and heterogeneous systems. Sip
isotherm is used for predicting heterogeneous adsorption system at wide range of adsorbate concentration. It approaches
Freundlich isotherm at low concentration and Langmuir isotherm at high concentration (Shahbeig et al., 2013; Kumar and
Kirthika, 2009). Application of these isotherm models for removal of pollutants using activated carbon, natural materials,
agricultural waste, industrial waste and other adsorbents have been studied by numerous researchers.

5.3. Kinetic models

Various kinetic models for adsorption have been suggested for rate of adsorption of toxic elements or pollutants on
adsorbents and are given in Table 3.
N.B. Singh et al. / Environmental Technology & Innovation 11 (2018) 187–240 195

Table 4
Thermodynamic parameters for adsorption of heavy metal ions on various low cost adsorbents (Saha and Chowdhury, 2011).
Adsorbent Adsorbate T (K) ∆G◦ (KJmol−1 ) ∆H◦ (KJmol−1 ) ∆S◦ (Jmol−1 )
Rubber (Hevea brasiliensis) leaf powder Cu(II) 300 −3.38 −31.96 −95.94
310 −2.17
320 −1.48
Modified oak sawdust Cu(II) 293 −2.840 4.331 240
303 −3.064
313 −3.330
Mimosa tannin resin Cu(II) 298 −2.47 42.09 153
303 −4.83
318 −8.51
338 −9.38
353 −11.45
Hazelnut shell activated carbon Cu(II) 293 −6.83 18.77 40.4
303 −6.66
313 −6.03
323 −5.71
Penicillium simplicissimum Cd(II) 293 −18.27 20.03 130.90
303 −19.81
313 −20.88
Red algae (Ceramium virgatum) Cd(II) 293 −19.5 −31.8 −42.4
303 −19.0
313 −18.7
323 −18.2
Coconut copra meal Cd(II) 299 −7.41 −13.70 21.20
311 −7.15
323 −6.97
333 −6.66
Fennel biomass Cd(II) 303 −5.017 10.34 51
313 −5.470
323 −6.016
Chitosan Cr(VI) 303.15 −2.409 −50.782 159
313.15 −1.306
323.15 0.178
333.15 2.429
Walnut Hull Cr(VI) 303 −23.03 64.14 287.4
313 −25.63
323 −28.77
Acacia leucocephala bark Ni(II) 303 −6.147 10.389 55
313 −6.945
323 −7.847
Baker’s Yeast Ni(II) 300 −23.519 −30.702 −23.658
313 −23.408
323 −23.149
333 −22.708
Oyster shell powder Ni(II) 303 −20.0 44.90 127.7
318 −22.9
333 −26.4
Lichen (Cladonia furcata) biomass Ni(II) 293 −18.3 −37.5 −71.5
303 −14.4
313 −14.3
323 −14.4
Acacia leucocephala bark powder Pb(II) 303 −3.876 −21.147 57
313 −4.379
323 −4.997
Penicillium simplicissimum Pb(II) 293 −20.04 39.13 202.52
303 −22.60
313 −24.06

(continued on next page)


196 N.B. Singh et al. / Environmental Technology & Innovation 11 (2018) 187–240

Table 4 (continued)
Adsorbent Adsorbate T (K) ∆G◦ (KJmol−1 ) ∆H◦ (KJmol−1 ) ∆S◦ (Jmol−1 )
Lichen (Cladonia furcata) biomass Pb(II) 293 −21.2 −35.4 −57.6
303 −17.4
313 −17.2
323 −17.1
Pine bark (Pinus brutia Ten.) Pb(II) 273 −2.74 1.97 17.21
283 −2.89
293 −3.08
303 −3.25
313 −3.42

5.4. Thermodynamics of adsorption

During the process of adsorption, thermodynamic functions such as entropy, enthalpy and free energy changes can be
calculated with the help of Van’t Hoff equation Eq. (1) (Moussavi and Khosravi, 2011; Tsai et al., 2005; Sprynskyy et al., 2006).
d(lnKeq ) ∆H
= (1)
dT RT 2
Where
qe
Keq =
Ce
Keq− equilibrium constant.
The change in free energy could be evaluated with the help of Eq. (2)

∆G0 = ∆H 0 − T ∆S 0 (2)
Gibbs free energy change is related to equilibrium constant (Eq. (3)).

∆G0 = −RTlnKeq (3)


By combining Eqs. (2) and (3), Eq. (4) is obtained.
∆H0 ∆ S0
ln Keq = − + (4)
RT R
The change in enthalpy and entropy of the adsorption process could be evaluated from the slope and intercept of line
obtained by plotting ln Keq vs 1/T .
If ∆H ◦ is positive, reaction is endothermic in nature (Teng and Hsieh, 1998) meaning thereby that as temperature
increases, adsorption efficiency also increases. However, if ∆S0 is positive the randomness increases at the time of the
adsorption and if ∆G0̂ is negative, adsorption is spontaneous or favorable (Crini, 2008). Spontaneous and non spontaneous
processes of adsorption are given as.

spontaneous ∆H◦ <0 ∆S0 >0 ∆G◦ <0


reactions
Non-spontaneous ∆H◦ >0 ∆S◦ <0 ∆G◦ >0
reactions

Gibb’s free energy, enthalpy and entropy changes are critical design variables in estimating the performance and predict-
ing the mechanism of an adsorption separation process and are also one of the basic requirements for the characterization
and optimization of an adsorption process. The typical value of the thermodynamic parameters for adsorption of heavy
metal ions and synthetic dye molecules onto various low cost adsorbent are given in Tables 4 and 5, respectively (Saha and
Chowdhury, 2011).

5.5. Adsorption and DFT calculations


A novel β -cyclodextrin (CD) modified, multifunctional, layer-by-layer graphitic carbon nitride (g–C3 N4 /β -CD) was used as
an effective adsorbent for the removal of methyl orange (MO) and Pb(II) from aqueous solutions under various environmental
conditions (e.g., solution pH, solid content, contact time and temperature). The kinetic results indicated that the adsorption
was dominated by chemisorptions. Further the adsorption of MO or Pb(II) on the g- C3 N4 or g- C3 N4 /β -CD was explored by
plane wave-based DFT calculations using the Vienna Ab initio Simulation Package (VASP) code (Zou et al., 2016a, b, c).
The optimized complexes of the (g–C3 N4 )–MO and (g–C3 N4 /β -CD)–MO are depicted in Fig. 6(a) and (b). From Fig. 6(a)
and (b), one can see that the MO molecules lay down on the g–C3 N4 plane and formed better π –π interactions with the XX
rings of the g–C3 N4 plane. As shown in Fig. 6, the MO forms hydrogen bonds of 2.555 Å, 2.943 Å or 3.265 Å with the N atoms
N.B. Singh et al. / Environmental Technology & Innovation 11 (2018) 187–240 197

Fig. 6. Optimized complexes for the g–C3 N4 or g- C3 N4 /β -CD monolayer with MO or Pb(II). (a) (g- C3 N4 )–MO, (b) (g- C3 N4/ β -CD)–MO, (c) (g- C3 N4 )–Pb and
(d) (g- C3 N4 /β -CD)–Pb (Zou et al., 2016a, b, c).

in the g–C3 N4 surface. In the (g–C3 N4 /β -CD)–MO structure, there is an even stronger hydrogen bond of 1.841 Å between the
β -CD and MO, and other hydrogen bond distances in the g–C3 N4 /β -CD –MO system (e.g., 2.363 Å, 2.506 Å, 2.803 Å, 3.166
Å and 3.378 Å) are similar to those in the g- C3 N4 –MO system. The adsorption energy (Ead ) was calculated as Ead = Eg
-C3 N4 +EA + EB − E(g−C3N4)−A−B (A: β - CD and B: MO or Pb(II)) (Zou et al., 2016a, b, c).
According to the results from the spectroscopy analysis and DFT theoretical calculations, the adsorption of Pb(II) on
the g- C3 N4 and g- C3 N4 /β -CD was mainly dominated by surface complexation and electrostatic interactions, whereas the
interaction of MO with the g- C3 N4 and g- C3 N4 /β -CD was mainly attributed to hydrogen bonds and π –π interactions (Zou
et al., 2016a, b, c).
Adsorption of benzene, aniline and naphthylamine on rGOs was studied by batch experiments and DFT calculations in
order to understand their interaction modes with rGOs. The DFTcalculations indicated that (1) the adsorption energy (Ead )
followed the order of Ead (benzene) < Ead (aniline) < Ead (naphthylamine) ; (2) the binding energy (Ebd ) values of aromatic mixtures
indicate that the intramolecular interactions between the aromatic compounds themselves have an important influence on
the adsorption on rGOs. The DFT calculations are in good agreement with the batch adsorption results. These findings are
very important and useful to understand the mechanisms of adsorption of aromatic compounds on rGOs as well as assessing
the effect of the benzene-ring number and polar functional groups on the adsorption of coexisting aromatic compounds on
rGOs (Yu et al., 2016). Thus DFT gives useful informations.

6. Adsorbents and water purification

Because of simplicity and cost effectiveness, adsorption technique is considered to be suitable for wastewater treatment.
The adsorbent selection for removal of water contaminants depends on concentration and type of pollutant present in the
water, efficiency and adsorption capacity for pollutant. Additionally the adsorbents should be non-toxic, cost effective, easily
available and can easily be regenerated. A large number of adsorbents such as natural materials, agricultural wastes and
residues, industrial byproducts and biomass materials have been used for purification of water and wastewater (Bhatnagar
et al., 2015; Gupta et al., 2009).

6.1. Lowcost adsorbents

Low cost adsorbents can be categorized as shown in Fig. 7 (Worch, 2012).


198 N.B. Singh et al. / Environmental Technology & Innovation 11 (2018) 187–240

Table 5
Thermodynamic parameters for adsorption of dyes on various low cost adsorbents.
Adsorbent Adsorbate T (K) ∆G◦ (KJmol−1 ) ∆H◦ (KJmol−1 ) ∆S◦ (Jmol−1 )
Treated ginger waste Malachite green 303 −1.515 47.491 167
313 −2.133
323 −3.016
Degreased coffee beans Malachite green 298 −8.19 27.2 33.3
308 −10.0
318 −10.6
Neem sawdust Malachite green 298 −4.02 −54.56 −169.57
308 −2.33
318 −1.73
Luffa cylindrical Malachite green 288 −6.1 32.1 132.2
298 −7.1
308 −8.7
Brazil nut shell Methylene blue 293 −2.27 −5.22 −112.23
303 −2.09
333 −1.97
Bentonite Methylene blue 283 −17.0 9.21 92.2
293 −17.7
303 −18.5
308 −19.4
Modified wheat straw Methylene blue 293 −9.96 21.92 108
303 −11.22
313 −12.14
Cattail root Congo red 293 −7.871 −54.116 157
303 −6.800
313 −4.702
Ca-bentonite Congo red 293 −6.4962 5.1376 37.2
303 −6.7567
313 −7.1991
323 −11.179
Non-living aerobic granular sludge Acid yellow 17 293 −5.14 −9.84 −15.79
308 −5.13
323 −4.65
P.vulgaris L. waste biomass Reactive red 198 293 −4.744 −9.74 −17.04
303 −4.573
313 −4.403
323 −4.302
Pinus sylvestris L. biomass Reactive red 195 293 −13.253 29.422 144.672
303 −14.022
313 −15.723
323 −17.555
Activated carbon from Brazilian-pine fruit shell Reactive Orange 16 298 −32.9 15.3 162
303 −33.7
308 −34.6
313 −35.3
318 −36.2
323 −36.9
Paulwnia Tomentosa Steud. leaf powder Acid orange 52 298 −0.85 −6.02 −17
308 −0.71
318 −0.51
Brazil nut shell Indigo carmine 293 −5.42 −3.20 −29.39
303 −5.71
333 −6.60
Activated carbon from bagasse pith Rhodamine B 293 −7.939 4.151 65.786
308 −9.902
323 −12.361
343 −26.729

(continued on next page)


N.B. Singh et al. / Environmental Technology & Innovation 11 (2018) 187–240 199

Table 5 (continued)
Adsorbent Adsorbate T (K) ∆G◦ (KJmol−1 ) ∆H◦ (KJmol−1 ) ∆S◦ (Jmol−1 )
Activated carbon from Euphorbia rigida Disperse orange 25 283 −24.084 44.308 242.17
288 −25.736
293 −26.495
Wheat bran Astrazon yellow 303 −14.472 46.81 175
7GL 313 −17.803
323 −22.552

Fig. 7. Low cost adsorbents.

6.2. Natural adsorbents

There are number of naturally occurring materials which have characteristics of an adsorbent and are present in large
quantities. Although there are number of naturally occurring adsorbents, but among them chitin, zeolite, clay, peatmoss,
wood and coal have successfully been utilised for the removal of heavy metal ions, dyes, and organic compounds from
water/wastewater (Bhatnagar and Minocha, 2006).
Chitin is one of the most promising natural biopolymer in adsorption application. It is main component of exoskeleton,
cuticle and cell wall of crustaceans, insects and microorganisms respectively. The deacetylation of chitin also results in the
formation of chitosan and its derivatives which are even more promising than chitin for adsorption (Kyzas and Bikiaris,
2015). Chlorophenols from aqueous solution were removed by chemically modified chitosan (Zhou et al., 2014). The removal
of 2,4-dichlorophenol and 2,4,6-trichlorophenol was maximum with adsorption capacity of 315.46 mg/g and 375.94 mg/g.
Acid blue 9 and food yellow 3 were removed from aqueous solution using chitosan powder from shrimp shells (Dotto and
Pinto, 2011). The effect of parameters such as pH, contact time and stirring rate were determined and optimum conditions
were found to be pH 3, 60 min and 150 rpm for acid blue 9 and pH 3, 60 min and 50 rpm for food yellow 3. Under these
conditions the adsorption capacities were 210 mg/g and 295 mg/g for acid blue 9 and food yellow 3 respectively.
Zeolites are microporous, crystalline aluminosilicates. Its common formula is sodium alumino ortho silicate
(Na2 O.Al2 O3 .xSiO2 .yH2 O) where silicon and aluminum atoms are tetrahedrally coordinated with each other through shared
oxygen atom (Fig. 8). In nature they are present in abundance and thus low cost resource. They have cation exchange ability
and molecular sieve properties thus widely used as adsorbent in water purification (Wang and Peng, 2010). Among various
natural zeolites clinoptilolite has been widely studied. These zeolites with their pretreatments have been employed for
removal of dyes, phenols and heavy metals from water/wastewater (Syafalni et al., 2014; Shaheen et al., 2012; Khalid et al.,
2004).
The capacity of natural zeolite for adsorption of Zn2+ , Cu2+ and Pb2+ from aqueous solution was studied (Perić et
al., 2004). The removal efficiency was higher for Pb and Cu than for Zn ions. Cr–bentonite was used for sorption of 4-
hydroxyphenol in aqueous solution (Zheng et al., 2008). Removal of Reactive Red 239 and Reactive Blue 250 has been
studied with hexamethylenediamine modified natural zeolite (Alver and Metin, 2012). Natural zeolite (NZ), anionic–cationic
surfactant-modified zeolite (ACSMZ) and cationic surfactant-modified zeolite (CSMZ) have been used for the removal of
color, turbidity, ammonia and chemical oxygen demand (COD) from wastewater (Syafalni et al., 2014). All three zeolites
were found to be highly efficient for color reduction.
Clay (Hydrated alumina silicate) is a natural adsorbent used for water decontamination. Clays are mainly montmorillonite,
bentonite and kaolinite. Clay has high sorption capacity, low permeability, high chemical and mechanical stability and large
2− 3−
surface area (Odom, 1984). A large number of cations (Ca2+ , Mg2+ , H+ , K+ , NH+ + −
4 , Na ) and anions (SO4 , Cl , PO4 and

NO3 ) are present on clay surface which can be easily replaced with ions present in adsorbate (Srinivasan, 2011). These clays
in their natural and modified form have been utilised for adsorption (Sahoo et al., 2014; Ozcan et al., 2007; Vengris et al.,
2001). Kaolinite, Montmorillonite and acid-activated forms of these clays were utilised for adsorption of Pb2+ and Cd2+ from
200 N.B. Singh et al. / Environmental Technology & Innovation 11 (2018) 187–240

Fig. 8. Zeolite structure.

aqueous solution (Sen Gupta and Bhattacharya, 2009). The adsorption was favoured by high pH. Lead, Zinc and Cadmium
adsorption on kaolinite clay modified with phosphate have also been reported (Amer et al., 2010). Removal of anionic red
dye (congo red) by bentonite clay blend with kaolinite have been investigated (Ogunmodede et al., 2015). pH, contact time,
temperature and initial concentration were found to have effect on adsorption capacity. Removal of safranin-o by natural
raw kaolinite has been reported (Adebowale et al., 2014) and was found to be 90%.
Peat is a naturally available porous material with large surface area. This natural material is present in abundance,
relatively inexpensive and has high adsorption capacity for a variety of pollutants (Poots et al., 1976a, b). The main
components of peat are lignin, cellulose and humic acid. They bear polar functional groups which make them effective
agents for purification of water/wastewater (Gupta and Suhas, 2009; Sharma and Forster, 1993). However, raw peat can be
directly used as adsorbent but chemical pretreatments result in development of more robust medium (Sun and Yang, 2003).
Methylene blue and Malachite green dyes were removed from their synthetic solutions using peat as adsorbent (Chieng et
al., 2014). The adsorption equilibrium data was best fitted into Sip and Redlich–Peterson isotherm model. The maximum
adsorption was 0.45 mmol/g and 0.31 mmol/g for Methylene blue and Malachite green respectively. p-nitrophenol was
removed from aqueous solution using fibrous peat (Jaerger et al., 2015). Parameters such as pH, adsorbent dose, contact time
and temperature have been optimized. The adsorption equilibrium data was best fitted with Langmuir adsorption isotherm
and maximum adsorption was 23.4 mg/g.
Wood is a natural adsorbent present in large amount with very low cost. More over, there is no need of regeneration after
its use as it can be discarded by burning (Poots et al., 1976a, b, 1978). A large number of plants with their wood and bark
were used for adsorption of pollutants from water and wastewater. Eucalyptus bark was used without any pretreatment for
the removal of remazol BB dye (Morais et al., 1999). Eucalyptus bark was also used for removal of Cr6+ from industrial waste.
The removal of Cr6+ was maximum at pH 2 and Cr6+ concentration 250 mg/L with adsorption capacity of 45 mg/g (Sarin
and Pant, 2006). Heavy metal ions like Cu2+ , Cd2+ and Zn2+ were removed by using Papaya wood as biosorbent (Saeed et al.,
2005). The percent removal was found to be 97.8, 94.9 and 66.8% for Cu2+ , Cd2+ and Zn2+ respectively at pH 5 and adsorbent
dose 5g/L.
Different conditions for the removal of heavy metals by natural materials are given in Table 6.
The efficiencies of natural materials for the removal of dyes are given in Table 7.
The efficiency of natural materials for removing organic compounds is given in Table 8.

6.3. Agricultural wastes

Agricultural residues, fruits and vegetable peels are the discarded waste materials and find no application anywhere. They
can be used as low cost adsorbent after little processing (Anastopoulos and Kyzas, 2014). Agricultural wastes are mainly
composed of lignin and cellulose and act as attractive alternative adsorbents due to their specific structure and chemical
properties. Specific functional groups such as alcohol, phenol, aldehyde, carboxyl and ketone are present in their polymer
chains which help in the removal of various pollutants from water (Bhatnagar et al., 2015). A large number of agricultural
wastes (Fig. 9) such as orange peel (Hassan, 2014), pomelo peel (Tasaso, 2014), lemon peel (Kannan and Veemaraj, 2010),
banana peel (Ponou et al., 2014) rice husk (Lakshmi et al., 2009), wheat bran (Singh et al., 2006), pulse seed coat (Ahalya et
al., 2005), coconut shells (Hameed et al., 2008), etc. have been reported for purification of wastewater.
Morphology and surface area of peels also play very important role during adsorption. The SEM pictures showing
morphologies of some agricultural wastes are give in Fig. 10.
N.B. Singh et al. / Environmental Technology & Innovation 11 (2018) 187–240 201

Table 6
Adsorption parameters of various natural materials for removal of heavy metals.
Adsorbents Type of Conditions Adsorption Adsorption Refrences
pollutants efficiency isotherm
(mg/g) model
Chitosan (modified) Cd2+ pH-6.5 217.4 Langmuir Arvand
and
Pakseresht
(2013)

Clay (Roasted) Cr6+ pH –3 14.18 Langmuir Ahmad et


adsorbent dose al. (2016)
– 0.5 g/50 ml

Bentonite Cu2+ pH-3 19.54 Freundlich Karapinar


Cd2+ 46.56 and Donat
(2009)

Chitosan coated Kaolinite Cu2+ pH-7 8.9 Langmuir Chen et al.


(2015a, b)

Natural clay Mn2+ pH-4, 10.0 Langmuir Eba et al.


adsorbent dose (2010)
– 0.25 mg/50
ml

Zeolite Pb2+ pH-5.7 65.75 Langmuir He et al.


Cu2+ pH-5.8 56.06 (2016)
Cd2+ pH-8.6 52.12
Ni2+ pH-7.7 34.40
Mn2+ pH-8.7 30.89

Zeolite (natural) Zn2+ adsorbent dose 5.89 Langmuir Perić et al.


Cu2+ –1.0 g/100 ml 3.08 – (2004)
Pb2+ 13.65 Freundlich

Clinoptilolite (raw) Cu2+ adsorbent dose 13.6 Langmuir Doula and


Modified –1.0 g/95 ml 37.5 Dimirkou
(2008)

Shrimp shell (chitin) Zn2+ pH-7 270.27 Langmuir Jaafarazadeh


As5+ pH-4 11.57 Langmuir et al.
(2014)
Jaa-
farazadeh
et al.
(2016)

Perlite Ni2+ pH-6, 2.24 Langmuir Torab-


Cd2+ adsorbent dose 1.79 Mostaedi
– 8.0 g/L et al.
(2010)

Oak sawdust Cr6+ pH-3 1.7 Langmuir Bartczak


Cu2+ pH-4 3.22 et al.
Ni2+ pH-8 3.29 (2015)

Poplar sawdust Cu2+ pH-5, 13.49 Langmuir Argun et


adsorbent dose al. (2007)
– 5.0 g/L

Pinus sawdust Cd2+ pH-5.5 95.0 Langmuir Raftari et


Pb2+ 98.0 al. (2011)

Banana peel was used as adsorbent for the removal of copper from water solution (Hossain et al., 2012). Carbofuran was
removed from aqueous solution using rice straw as adsorbent. (Chang et al., 2011). Increase in concentration of carbofuran
resulted in increase in adsorption whereas adsorption decreased when pH and temperature were increased. The maximum
adsorption capacity of carbofuran by rice straw was found to be 296.52 mg/g. Wheat, corn, sugarcane and bajra were also
utilised for copper removal from aqueous solution (Bandela et al., 2016). The maximum removal was 98% by bajra followed
by 74% by wheat, 71% by corn and 70% by bagasse at 5 ppm copper concentration. Orange peel was used as adsorbent for
Cr(VI) removal from aqueous solution (Mandina et al., 2013). The efficiency was increased by treating the adsorbent with
sodium hydroxide. Freundlich isotherm was found to be best fitted model with adsorption capacity 97.07 mg/g and 139.0
mg/g for raw and modified orange peel respectively. The adsorption of Cr(VI) was supported by presence of carboxyl and
hydroxyl groups in orange peel.
202 N.B. Singh et al. / Environmental Technology & Innovation 11 (2018) 187–240

Table 7
Adsorption parameters of various natural materials for removal of dyes.
Adsorbents Type of Conditions Adsorption Adsorption Refrences
pollutants efficiency isotherm
(mg/g) model
Chitosan Acid orange 12 pH-4 973.3 Langmuir Wong et
al. (2004)

Pine sawdust Acid blue 256 pH-3.5 280.3 Langmuir Ozacar


and Sengil
(2005)

Pinewood Acid blue 264 pH-6.4 1176 Langmuir Tseng et


(activated) Basic blue 9 pH-6.6 556 al. (2003)

Bentonite Supranol pH-6, 540 Langmuir Khenifi et


yellow 4 gL adsorbent dose al. (2007)
– 0.2 g/100 ml

Chitosan beads Direct red 81 pH-3 2383 Langmuir Chiou and


Reactive blue 2 2498 Li (2003)
Reactive red 2 2422
Reactive 2436
yellow 2

Chitasan Acid red 37 pH-6 128.21 Langmuir Kumari et


Acid blue 25 pH-4 263.15 al. (2009)

Zeolite Methylene pH-5, 1.28 Freundlich Fungaro et


blue adsorbent dose al. (2010)
– 1.0 g/100 ml

Kaolinite clay Safranin –O pH-12, 16.23 Langmuir Adebowale


adsorbate et al.
conc.–170 (2014)
mg/L

Table 8
Adsorption parameters of various natural materials for removal of organic compounds.
Adsorbents Type of Conditions Adsorption Adsorption Refrences
pollutants efficiency isotherm
(mg/g) model
Bentonite (organomodified) Phenol adsorbent 22.68 Langmuir Leili et al.
dose-20.0 g/L (2015)

Clay (modified) Phenol adsorbent 8.4 Langmuir Chen et al.


dose-20.0 g/L (2011a, b)
adsorbate conc
–100 mg/L

Clay Benzene pH-5.5 37.59 Langmuir Osagie and


Owabor
(2015)

Chitosan beads O –chloro pH-7 97.0 Langmuir Nadavala


phenol 108.6 et al.
Phenol (2009)

Pine wood (raw) Phenanthrene – 2.318 Langmuir Xi and


Napthalene 2.820 Chen
Acenaphthene 1.497 (2014)
Pyrene 0.417

Chitosan Ethoprophos Adsorbent 97.0 Langmuir Abdeen


dose –0.1 108.6 D–R and Mo-
g/100 ml hammad
(2014)

Pomelo peel was used for adsorption of methyl red from aqueous solution. It is mainly comprises of cellulose, pectin,
hemicelluloses and lignin etc. Variable factors such as pH, adsorbent dose and contact time were optimized for the removal
of methyl red. The adsorption process was best studied by Langmuir isotherm model. The removal efficiency was 94% at
pH 6.5 and adsorbent dose of 1 g/100 ml dye concentration (Tanzim and Abedin, 2015). The adsorption capacity was also
found to be comparable to other cellulose based adsorbents. Removal of Cd(II) from aqueous solution by using Sesame leaf
and stem waste with different pH, adsorbent dose, initial concentration and particle size was studied (Cheraghi et al., 2015).
N.B. Singh et al. / Environmental Technology & Innovation 11 (2018) 187–240 203

Fig. 9. Agricultural waste peels as low cost adsorbents.

Removal of Cd(II) increased with decrease in particle size. It was maximum at pH 6 with adsorption capacity of 84.74 mg/g.
The adsorption process was well described by both pseudo first order as well as pseudo second order.
Pb(II), Cu(II) and Ni(II) ions were removed from aqueous solution using garlic peel as adsorbent (Liang et al., 2013). To
increase the efficiency, the peel was mercerized. The FTIR and SEM studies indicated mercerized garlic peel has little pores
than native garlic peel as well as more accessible functional hydroxyl group which resulted in higher adsorption capacity.
The adsorption capacity using Langmuir isotherm model was 209 mg/g. Pineapple and plantain peel mixture was used to
remove 2,6-dichlorophenol from aqueous solution (Agarry and Ogunleye, 2015). Taguchi method was used to determine
the optimum value of parameters like pH, initial 2,6-dichlorophenol concentration, temperature and adsorbent dose ratio of
pineapple and plantain peel which resulted in maximum adsorption. Langmuir and Freundlich isotherm models were used
to study data. The Freundlich isotherm model provides the best fit with adsorption capacity 4.58 mg/g. The kinetic study of
adsorption process followed pseudo second order kinetic model.
The efficiencies of agricultural waste materials for the removal of heavy metals are given in Table 9.
The efficiencies of agricultural waste materials for the removal of dyes are given in Table 10.
The efficiencies of agricultural waste materials for the removal of organic compounds are given in Table 11.
Although the use of agricultural waste based adsorbents for removing various pollutants from water offers many
attractive features but still there are several gaps which need more attention. Agricultural waste adsorbents should be made
more efficient, reusable and applicable to multicomponent real industrial effluents.

6.4. Industrial wastes

Industrial wastes are byproducts of industries and can be used as low cost adsorbents for the removal of heavy metals,
dyes and organic compounds from water and wastewater. They are locally available in large quantities and are inexpensive.
A large number of industrial wastes including palm oil ash (Zaini et al., 2014), red mud (Tor et al., 2006), tea factory waste
(Malkoc and Nuhoglu, 2007), Coffee waste (Anastopoulos et al., 2017), olive oil industry waste (Malkoc et al., 2006), fly ash
(Wang et al., 2007), bagasse ash (Gupta and Ali, 2004), blast furnace slag (Zhao et al., 2016) were explored for elimination of
toxic chemicals from water and wastewater. Morphologies of the waste products also affect the process of adsorption. SEM
pictures giving morphologies of some of the industrial wastes are given in Fig. 11.
Red mud was used for the adsorption of phenol from synthetic wastewater (Shirzad-Siboni et al., 2013). Sugarcane
bagasse treated with sulfuric acid was used as adsorbent to remove Cu(II) ions from synthetic wastewater (Rana et al.,
2014). Number of parameters like pH, initial metal ion concentration, adsorbent dose and contact time were optimized
for adsorption of Cu(II) ions. Coffee drinks being one of the most popular beverages worldwide, a significant quantity of by-
products is generated as well (6 Mt/yr). The main coffee industry by-products are the spent coffee grounds (SCG), the coffee
silverskin (CS) and the coffee husks (CH). The coffee companies, in an attempt to reduce their costs and avoid environmental
pollution, focus on alternative and profitable uses. Coffee residues are used as an adsorbent for water purification particularly
for pollutants like heavy metals and dyes (Anastopoulos et al., 2017).
Palm oil industry waste was used as adsorbent to remove disperse red and disperse blue dyes (Hasnain Isa et al., 2007).
The effects of various process parameters like pH, adsorbate concentration and agitation time were studied. The maximum
removal was 99% at pH 2 and agitation time 60 min. Both Langmuir and Freundlich isotherm models were used to describe
the adsorption of dyes. Langmuir isotherm model was found to be fitted well with adsorption capacity 49.50 mg/g and 61.35
mg/g for disperse blue and disperse red respectively. Kinetic study revealed that adsorption process followed pseudo-second
order rate equation. Steel making slag was used for adsorption of Cd(II) ions from acidic solution (Duana and Sua, 2014). It
204 N.B. Singh et al. / Environmental Technology & Innovation 11 (2018) 187–240

(a) SEM of banana peel. (b) SEM of orange peel.

(c) SEM of pomegranate peel. (d) SEM of pineapple peel.

(e) SEM of water melon peel. (f) SEM of garlic peel.

Fig. 10. SEM pictures of (a) SEM of Banana Peel [Reddy et al., 2015], (b) SEM of orange Peel (Mafra et al., 2013), (c) SEM of pomegranate Peel (Pathak et al.,
2016) (d) SEM of pineapple Peel (Pathak et al., 2016) (e) SEM of Water Melon Peel (Pathak et al., 2016) (f) SEM of Garlic Peel (Pathak et al., 2016) (g) SEM
of green pea Peel (Pathak et al., 2016) (h) SEM of pigeon Peel (Pathak et al., 2016) (i) SEM of Papaya peel (Abbaszadeh et al., 2015), (j) SEM of Jack fruit Peel
(Pathak et al., 2017), (k) SEM of Citrus Peel (Pathak et al., 2017), (l) SEM of Lemon Peel (Pathak et al., 2017).

was modified to have excellent acid neutralization capacity. Maximum removal of 99.1% was found at pH 4, adsorbent dose
10 g/L and Cd(II) concentration of 100 mg/L. Out of various isotherm studied the data was in good agreement with Langmuir
isotherm model with maximum adsorption capacity of 10.16 mg/g.
N.B. Singh et al. / Environmental Technology & Innovation 11 (2018) 187–240 205

(g) SEM of green pea peel. (h) SEM of pigeon peel.

(i) SEM of papya peel. (j) SEM of jack fruit peel.

(k) SEM of citrus peel. (l) SEM of lemon peel.

Fig. 10. (continued)

Fly ash was used as adsorbent for removing methyl orange from aqueous solution (Gao et al., 2015). It was modified with
Ca(OH)2 /Na2 Fe2 O4 . Number of process parameters was optimized to get best removal. The maximum removal of methyl
206 N.B. Singh et al. / Environmental Technology & Innovation 11 (2018) 187–240

Table 9
Adsorption capacities of various agricultural waste materials for removal of heavy metal ions.
Adsorbents Type of pollutants Conditions Adsorption Adsorption Refrences
efficiency isotherm
(mg/g) model
Rice Husk As3+ pH-7 0.139 Langmuir Ranjan et al. (2009)
(raw) As5+ pH-4 0.147

Sugarcane Bagasse Cu2+ pH-5 to 6 7.88 Langmuir Tchoumou et al. (2015)


Ni2+ adsorbent dose 14.31
– 20 g/L

Spruce sawdust As5+ Adsorbate 9.25 Langmuir Urik et al. (2009)


conc. –230µ
g/L

Mango peel Cu2+ pH-5 to 6 46.09 Langmuir Iqbal et al. (2009)


Ni2+ 39.75
Zn2+ 28.21

Peanut hull Cu2+ pH-5.5 21.25 Langmuir Zhu et al. (2009)


contact time –
2h

Banana peel Cu2+ pH-6.5 27.78 Langmuir Hossain et al. (2012)


adsorbent dose
– 0.5 g/100 ml

Tea waste Cu2+ pH-5 to 6 48.0 Langmuir Amarasinghe and Williams (2007)
Pb2+ adsorbent dose 65.0
– 1.5 g/200 ml

Spartina alternifora Cu2+ pH-6 48.49 Langmuir Li et al. (2013)


2+
Orange peel Cd – 13.7 Langmuir Lasheen et al. (2012)
Cu2+ 15.27
Pb2+ 73.53

Sunflower stalk Pb2+ pH-5 182.9 Langmuir Jalali and Aboulghazi (2013)
Cd2+ adsorbent dose 69.8
– 0.2 g/50 ml

Peanut husk Cr6+ pH-2 33.11 Langmuir Olguin et al. (2013)


2+
Bengal gram husk Cu pH-7 330 Langmuir Nagpal et al. (2016a)
adsorbate
conc. 20 mg/L

Neem leaves Zn2+ pH-4 147.08 Langmuir Arshad et al. (2008)


Cd2+ pH-9.5 158.0 Langmuir Sharma and Bhattacharya (2005)
Pb2+ pH-7 300.0 Langmuir Bhattacharyya and Sharma (2004)

orange was 99.2% at optimum pH 10, contact time 40 min and methyl orange concentration 50 mg/L. The experimental data
fitted Freundlich and pseudo-second order kinetic model. Sewage sludge based adsorbent activated with H2 SO4 was used
for phenol removal (Bausbaa and Menia, 2014). The adsorption capacity was maximum (26.16 mg/g) at adsorbent dose of
5 g/L and temperature 20 o C. The experiment data was fitted by Freundlich isotherm model showing multilayer adsorption
and pseudo-second order equation.
The efficiencies of industrial waste materials for the removal of heavy metals are given in Table 12.
The efficiencies of industrial waste materials for the removal of dyes are given in Table 13.
The efficiencies of industrial waste materials for the removal of organic compounds are given in Table 14.
There are many low cost industrial wastes used for the removal of pollutants from waste waters. However, the adsorption
capacities of the adsorbents vary depending on the characteristics of the adsorbents, the extent of chemical modification and
the concentration of adsorbates. These aspects require further exploration.

6.5. Biomass

Biosorption and bioaccumulation have been considered to possess great potential for removing toxic elements like heavy
metals, dyes and organic compounds from water (Aksu, 2005). Both living and dead microbial biomaterials such as algae
(Rubin et al., 2010), fungi (Fu and Viraraghavan, 2002), yeast (Das and Charumathi, 2012) and bacteria (Abbas et al., 2014)
etc have been reported to have significant uptake capacities for various toxic elements.
Algae are considered as one of the most promising types of biosorbents because they have high sorption capacity and
are readily available in large amount in seas and oceans (Flouty and Estephane, 2012; Trinelli et al., 2013). The biosorption
N.B. Singh et al. / Environmental Technology & Innovation 11 (2018) 187–240 207

Table 10
Adsorption capacities of various agricultural waste materials for removal of dyes.
Adsorbents Type of Conditions Adsorption Adsorption Refrences
pollutants efficiency isotherm
(mg/g) model
Rice Husk Crystal violet pH-10 37.83 Langmuir Chakraborty et al. (2011)
(modified)

Corn cobes Methylene pH-10 18.28 Freundlich Conrad et al. (2015)


blue adsorbate dose
–100 mg/L

Pineapple Methylene pH-10 119.05 Langmuir Hameed et al. (2009)


stem blue

Orange peel Acid violet 17 pH-2 19.88 Langmuir Shivaraj et al. (2001)
adsorbent dose
–600 mg/50 ml

Coir pith Congo red pH-2 6.7 Langmuir Namasivayam and Kavitha (2002)
adsorbent dose
– 900
mg/50 ml

Pine cone Methylene pH-7.2 109.89 Langmuir Sen et al. (2011)


blue pH-3.5 34.07 Freundlich Dawood et al. (2014)
Congo red 500.0 Langmuir

Casuarina Methyl violet pH-6.7 164.99 Langmuir Dahri et al. (2013)


equisetifolia 2B adsorbate
needle conc. – 100
mg/L

Pine tree Methylene pH-9.2 126.58 Langmuir Yagub et al. (2012)


leaves blue adsorbate dose
– 10 mg/L

Soy meal hull Direct red 80 pH-10 178.57 Langmuir Arami et al. (2006)
Direct red 81 120.48

Guava leaf Basic blue 9 295.0 Langmuir Ponnusami et al. (2008)

Peanut hull Reactive dye 35.5 Langmuir Tanyilizi (2011)

Fig. 11. SEM picture of (a) POFA (Ranjbar et al., 2014) (b) Coffee waste (Kua et al., 2016), (c) Fly ash (Kua et al., 2016), (d) Blast furnace slag (Kua et al., 2016)
(e) Red mud [Li et al., 2018] (f) Bagasse ash (Mangesh et al., 2014) (g) Waste Tea powder biomass [Gangadhar et al., 2016].

depends on the composition of the algal cell wall. Algal cell wall is made up of number of polysaccharides: mannan, xylan,
alginic acid, chitin, etc. These components, along with the proteins present, can provide acid binding sites such as amino,
208 N.B. Singh et al. / Environmental Technology & Innovation 11 (2018) 187–240

Table 11
Adsorption capacities of various agricultural waste materials for removal of organic compounds.
Adsorbents Type of Conditions Adsorption Adsorption Refrences
pollutants efficiency isotherm
(mg/g) model
Rice Husk 2,4- pH-6, 156.48 Langmuir Akhtar et al.
(modified) dichlorophenol adsorbent 407.5 Dubinin - (2006)
dose- Radushkevich
0.1 g/25 ml,

Tendu leaf Phenol pH-8, 7.69 Langmuir Nagda et al.


(raw and adsorbate conc 31.35 (2007)
modified) –10-25 mg/L

Banana peel 2,4- pH>7, 65.7 Langmuir Achak et al.


dichlorophenol adsorbent dose (2009)
–10 –30 g/L

Canola stalk P-Cresol pH-3, 41.6 Langmuir Balarak and


adsorbent Mahdavi
dose-4 g/L (2016)

Orange peel Naphthalene pH-7 7.40 Langmuir Agarry and


Aremu (2012)

Wheat bran Phenolic pH-10 487.3 Langmuir Achak et al.


compound (2013)

Hemidesmus Phenol pH-7, 370.37 Langmuir Srihari and Das


indicus adsorbent dose (2009)
– 30
mg/100 ml

Rice husk Benzene Adsorbent 365.0 Langmuir Yakout (2014)


(activated) dose –50
mg/100 ml

Sugarcane Oil-byproducts pH-7, 12.30 Langmuir Sarkheil et al.


Bagasse adsorbate (2014)
conc-200mg/L,
temp - 25o C

amine, hydroxyl, imidiazole, phosphate and sulfate groups (Oyedepo, 2011). The adsorption efficiency of algae in removing
heavy metals, dyes and organic compounds is given in Table 13.
Fungi and yeast are one of the industrial waste biomass and are excellent sorbent for toxic chemicals. The intracellular and
extracellular uptake of toxic elements by these dead and living cells depends upon cell wall. The cell wall of fungi and yeast
consist of number of polysaccharides, chitins, glucans and protein etc. The functional groups include phosphate, carboxylate,
sulfate, hydroxyl and amino groups. The interactions occur via ion-exchange, complexation and physical adsorption (Das et
al., 2008; Remacle, 1990). The efficiency of fungi and yeast for removing toxic elements like heavy metals, dyes and organic
compounds is given in Table 15.
Bacteria are also used as biosorbents for removal of toxic chemicals. Their small size, ubiquity, and capability to grow
under varying environmental conditions make them good adsorbents. Bacteria have polysaccharide slime layers and readily
provide amino, carboxyl, phosphate and sulfate group for metals biosorption. Bacterial biomass is generally produced as a
waste by-product of industrial operations or can be specifically propagated in large scale (Urrutia, 1997; Vasudevan et al.,
2001). There are number of bacteria species like Bacillus, Pseudomonas, Streptomyces, Escherichia, Micrococcus, etc., which
have been successfully used for uptake of dyes, metals or organics.

6.6. Nanoadsorbents

As discussed above adsorption is observed as one of the best promising techniques applied for the decontamination of
water/wastewaters from dyes, heavy metals and organic compounds and different type of adsorbents have been used. In
recent time a large number of research work has been done on removal of different pollutants from water/wastewater using
nanoadsorbents (nanoparticles) (Kurniawan et al., 2012; Deliyanni et al., 2009) (Table 16). In comparison to conventional
materials, the nanostructured adsorbents, mainly due to the exceptionally high surface area, show much higher efficiencies
and faster adsorption rates in water treatment (Sadegh et al., 2017). A variety of efficient, low-cost and eco-friendly
nanomaterials with unique functionalities have been proposed for potential applications in detoxification of industrial
effluents, groundwater, surface water and drinking water. An ideal adsorbent for wastewater treatment purposes should
satisfy the following criteria: (1) should be environmentally benign; (2) should demonstrate a high sorption capacity and
high selectivity especially to the pollutants occurring in water at low concentration; (3) the adsorbed pollutants can be easily
removed from its surface, and (4) should be recyclable (Sadegh et al., 2017).
N.B. Singh et al. / Environmental Technology & Innovation 11 (2018) 187–240 209

Table 12
Adsorption capacities of various industrial waste materials for removal of heavy metal ions.
Adsorbents Type of Conditions Adsorption Adsorption Refrences
pollutants efficiency isotherm
(mg/g) model
Paper mill Pb2+ pH-4.5, 14.1 Freundlich Suryan and
waste Cd2+ adsorbate conc 14.8 Ahluwalia
Ni2+ – 100 mg/L, 13.7 (2012)
Cu2+ contact time – 13.9
15 min

Red Mud Ni2+ pH-5, 13.69 Langmuir Hannachi et al.


adsorbent dose (2010)
– 10 g/L

Khangar Cr6+ pH-2, 200 Langmuir Nagpal et al.


adsorbent dose (2016b)
– 0.5 g/50 ml

Fly ash Zn2+ pH-6.4, 12.74 Freundlich Ashfaq and


Fe2+ adsorbate 15.88 Kaifiyan
conc. – (2016)
10-100mg/L

Paint industry Zn2+ – 82 Langmuir Kargi and Cikla


waste sludge (2006)

Red mud Pb2+ pH-4, 6.02 Langmuir Sahu et al.


adsorbate conc (2013)
– 10mg/L

Leather Cr6+ pH-3, contact 65.35 Langmuir Onenc et al.


industry waste time 24 h (2011)
sludge

Olive cake ash Cd2+ pH-6 8.38 Langmuir Elouear et al.


Ni2+ 7.32 (2008)

Table 13
Adsorption capacities of various industrial waste materials for removal of dyes.
Adsorbents Type of Conditions Adsorption Adsorption Refrences
pollutants efficiency isotherm
(mg/g) model
Rice straw fly Azorhodanine pH-3, 2.2 Freundlich El-Bindary et
ash dye adsoebent al. (2015)
dose 0.07 g/L

Red mud Congo red pH-7 7.08 Langmuir Tor and


(activated) Cengeloglu
(2006)

Modified blast Methyl orange pH-3-13, 167 Langmuir Gao et al.


furnace slag adsorbate conc (2016)
– 25 mg/L

Leather Basic red 18 pH-8 212.76 Langmuir Jain et al.


industry waste Acid red 111 pH-7 175.43 (2003)
sludge

Blast furnace Basic blue 6 pH-6.5, contact 67.34 Langmuir Santos et al.
slag time 120 min (2008)

Metal Remazol pH-7, temp 91.0 Langmuir Uçar et al.


hydroxide brilliant blue 25o C (2011)
waste

Aluminum Reactive red 2 pH-7, contact 14.92 Langmuir Jain et al.


hydroxide Reactive blue 4 time – 24 h 31.80 (2004)
sludge

6.6.1. Carbon based nanomaterials


Carbon-based materials such as activated carbon (AC), carbon fibers, aerogels, and nanostructures of carbon are well-
suited as adsorbents. AC has been mostly used as highly efficient adsorbent for removal of different pollutants. The term
activated carbon is basically referred as a carbonaceous material with high micropores volume, well developed surface area,
favorable pore size distribution, and high adsorptive capacity (Ahmed, 2017). AC is currently one of the most widely used
210 N.B. Singh et al. / Environmental Technology & Innovation 11 (2018) 187–240

Table 14
Adsorption capacities of various industrial waste materials for removal of organic compounds.
Adsorbents Type of pollutants Conditions Adsorption Adsorption Refrences
efficiency isotherm
(mg/g) model
Red mud Phenol pH-7, 1.580 Freundlich Shirzad-Siboni
adsorbate conc et al. (2013)
– 60 mg/L

Blast furnace Phenol Contact time – 22.0 Langmuir Jain et al.


slag 2-chlorophenol 8 h, temp – 64.9 (2004)
4-chlorophenol 45o C 70.4
2,4-dichlorophenol 150.2

Modified Phenol pH-8, 101 Langmuir Akl et al.


sugarcane adsorbent dose (2014)
bagasse – 4 g/L, contact
time – 60 min

Sewage sludge Phenol pH-6-8, 94 Langmuir Thawornchaisit


adsorbate conc and pakulanon
– 110 mg/L, (2007)
adsorbent dose
– 0.5 g/L

Leather Phenol pH-7 78.74 Langmuir Onenc et al.


industry waste (2011)
sludge

Fertilizer 4-bromophenol Contact time – 40.7 Langmuir Bhatnagar


industry waste 2-bromophenol 480 min 170.4 (2007)
2.4-dibromophenol 190.2

Table 15
Adsorption capacities of biomass materials for removal of Heavy metals, dyes and organic compounds.
Adsorbents Type of Conditions Adsorption Adsorption Refrences
pollutants efficiency isotherm
(mg/g) model
Thiobacillus Zn2+ pH-6, 95.24 – Liu et al.
thiooxidans Cu2+ pH-5, 39.84 (2004)
adsorbent dose
0.25 g/L

Rhizopus Methylene pH-10, 370.3 Freundlich Aksu et al.


arrhizus blue adsorbent dose 1666.6 (2010)
SDS modified – 1 g/L

Geobacillus Cu2+ pH-4, 48.5 Langmuir Ozdermir et al.


toebii adsorbent dose 41.5 (2009)
Geobacillus – 2.5 g/L, temp
thermoleovo- – 60o C
rans

Saccharomyces Phenol adsorbate conc 26.95 Langmuir Moyo et al.


cerevisiae – 120 mg/L, (2012)
contact
time-4 h

Sargassum Phenol pH-10 88.10 Langmuir Navarro et al.


Chaetomorpha 17.7 (2017)

adsorbents for water and air purification on an industrial scale. Almost all carbonaceous materials can be used to produce
AC, but the properties vary with its raw materials and activation method. Although AC is a very good adsorbent for water
purification but its high cost limits its use.
Carbon nanotubes (CNTs) are the materials which belong to the carbon family. The CNTs are categorized as single-walled
nanotubes (SWCNTs) and multiwalled nanotubes (MWCNTs). The structure of CNTs is given in Fig. 12 (Mubarak et al., 2013).

Carbon nanotubes (CNTs) are being used as adsorbents for removal of metal ions, and organic and inorganic impurities
present in natural sources of water (Singh et al., 2010). CNTs effectively adsorb metal ions from wastewater. The adsorption
capacity for heavy metals on SWCNTs is higher than MWCNTs. In most of the adsorption studies, the Langmuir isotherm
model fitted best to the equilibrium data suggesting monolayer adsorption over the surface of adsorbent and obeys the
pseudo-second order kinetic model. Generally, adsorption increases with increase in pH of the solution (for cations) and
N.B. Singh et al. / Environmental Technology & Innovation 11 (2018) 187–240 211

Table 16
Adsorption capacity of Nanomaterials used for the removal of heavy metals, dyes and organic compounds.
Nanomaterials Pollutants Adsorption capacity References
(mg/g)
Anatase nanoadsorbent Pb2+ 31.25 Kocabaş-Atakli and Yürüm (2013)
Cu2+ 3.74
As3+ 16.98

Iron oxide nanoparticles Cu2+ 17.3 Hua et al. (2011)


Cd2+ 14.7
Ni2+ 7.8
Pb2+ 42.4

Carbon nanotubes Methylene blue 9.7 Wang et al. (2012)


Acid red 183 49.2
Congo red 148.0 Mishra et al. (2010)
Reactive green 19 152.0
Reactive Yellow 44 148 Gupta et al. (2013)
Methyl Orange 27.6

Nano-TiO2 Reactive red 195 86.96 Belessi et al. (2009)


Basic green 5 377.9 Lee et al. (2008)
Basic violet 10 294
Methylene blue 133.33 Xiong et al. (2010)
Zn(II) 15.3 Hua et al. (2011)
Cd(II), 7.9

Nano-MgO Congo red 131.3 Hu et al. (2010)


Reactive blue 19 166.7 Moussavi and Mahmoudi (2009)
Reactive red 198 123.5
Cu(II) 58.44 Hua et al. (2011)

Nano-Fe3 O4 Methylene blue 93.08 Iram et al. (2010)


Reactive red 120 166.67 Absalan et al. (2011)
Rhodamine 6G 55.8 Zhang et al. (2013)
Cu(II) 47.2 Hua et al. (2011)

Nanochitosan Reactive red 120 910 Momenzadeh et al. (2011)


Acid green 27 2103 Hu et al. (2006)
Remazol black 5 5572 Chen et al. (2011a, b)

Gold nanoparticles coated with palladium tri-chloroethane 100 Tiwari et al. (2008)

Silver nanoparticles supported on alumina Pesticides and halogenated organics 100 Pradeep and Anshup (2009)

N-TiO2 4-chlorophenol 100 Nolan et al. (2012)

N doped TiO2 Phenol 65 Cheng et al. (2012)

N doped TiO2 Lindane 100 Senthilnathan and Philip (2010)

decreases with increase in ionic strength of the solution (Kumar et al., 2014). The maximum regeneration capacity of CNTs
can be obtained at lower pH for metal cations while in case of radionuclide, the regeneration is very poor due to strong
complexation between CNTs surface and radionuclide. This is the major drawback for regeneration of radionuclide saturated
CNTs (Kumar et al., 2014).
SWCNTs exhibit a strong affinity towards many organic compounds because of their very large specific surface areas.
However, a disadvantage with respect to the application of SWCNTs in adsorption technologies is their high cost. MWCNTs
are less expensive, but their relatively low adsorption capacity limits their potential applications. The modification of
MWCNTs can enhance their adsorption capacity for various organics, and they can also be further tuned by selective
functionalization. Moreover, surface chemistry, solution chemistry, and properties of adsorbates influence the adsorption
process (Yu et al., 2014). Gupta et al. reported that CNTs are good adsorbents for removing dyes from aqueous solution and
show maximum potential for the removal of dyes and could be used for commercial purpose (Gupta et al., 2013). Adsorption
of Rhodamine dye and methyl orange on CNT as a function of time is given in Fig. 13 (Banerjeea et al., 2017).
CNTs adsorb bacteria with three unique features. Firstly, microbial adsorption capacities on CNTs so far reported are
higher than any other commercially available adsorbent media. Secondly, CNTs express selective adsorption of bacteria,
a feature which is not generally seen in other adsorbents. Finally, adsorption kinetics of bacteria on CNTs is almost
instantaneous suggesting their use in applications such as pathogen sensors, where it is desired to rapidly concentrate the
target contaminant (Upadhyayula et al., 2009). Adsorption of natural organic matter (NOM) on CNTs is an exothermic process
and yet has positive entropy values.
CNTs strongly adsorb many organic compounds due to interactions including hydrophobic effect, π –π interactions,
hydrogen bonding, covalent bonding, and electrostatic interactions. The π electron rich CNT surface allows π -π interactions
212 N.B. Singh et al. / Environmental Technology & Innovation 11 (2018) 187–240

Fig. 12. Carbon nanotubes, Top: molecular structure and typical dimension of (left) singlewalled carbon nanotubes (SWCNTs) and (right) multiwalled
carbon nanotubes (MWCNTs). Bottom: Scanning electron micrograph pictures of (left) SWCNT and (right) MWCNT samples.

Fig. 13. (a) Effect of contact time on adsorption of (a) Rhodamine B (RhB) and (b) methyl orange (MO) by a-CNTs with corresponding colour change of the
solution shown inset.

with organic molecules with C=C bonds or benzene rings, such as polycyclic aromatic hydrocarbons and polar aromatic
compounds (Qu et al., 2013).
CNTs exhibit excellent physicochemical, mechanical, thermal, and electrical properties that can be maximized for appli-
cations in environmental adsorbents. Designer CNTs, which are prepared through various functionalization or modification
processes, demonstrate remarkable enhancement in contaminant removal efficiency and offer easy nanomaterial recovery
and regeneration. However, the use of CNT for water remediation is costly and depends on different parameters (Sarkar et
al., 2017). Further research is needed to optimize the process parameters for cutting costs in CNT-based water treatment
technologies.
Graphene (Gh), a monolayer (or few layers, <10) of hexagonally arrayed sp2 -bonded carbon atoms, due to its excellent
physical and chemical properties, has been studied world-wide for several purposes, since its discovery in 2004. Following
N.B. Singh et al. / Environmental Technology & Innovation 11 (2018) 187–240 213

Fig. 14. Possible adsorption interactions between GO and ATL or PRO.

this trend, graphite oxide has attracted attention from many researchers, because of its role as a precursor for the cost-
effective mass production of graphene-based materials. For this reason, graphene-based materials are applied to a wide range
of sciences. Graphene oxide (GO) has a layered structure similar to that of graphite, but the plane of carbon atoms in graphite
oxide is heavily decorated by oxygen containing groups, which can be exfoliated in water under moderate ultrasonication. If
the exfoliated sheets contain only one or few layers of carbon atoms as in graphene, these sheets are called graphene oxide
(GO). Graphene and graphene oxide are recently used as adsorbents to remove different groups of pollutants from water
(Kyzas and Bikiaris, 2015). Adsorption of Atenolol (ATL) and propranolol (PRO) drug molecules on GO surfaces was studied
and found to depend on number of factors. The mechanism of adsorption is given in Fig. 14 (Qu et al., 2013).
Number of metal ions from solutions have been removed by GO. For example adsorption of Pb2+ on GO was very much
dependent on the initial concentration of the Pb2+ , and increased with increasing initial concentration. The multi-feature
characteristic of GO like large surface area, existence of various oxygen functional groups, and multi-layered configurations
plays the crucial role in rapid adsorption of Pb2+ from aqueous solution. The mechanism of adsorption of Pb2+ , on GO surface
is given in Fig. 15 (Raghubanshi et al., 2017).
The high specific surface area and large number of oxygen-containing functional groups of graphene oxides (GOs)
make them suitable in the preconcentration and solidification of radionuclides from wastewater (Wang et al., 2016). The
theoretical calculations can further evidence the interaction of different kind of radionuclides with different functional
groups of GOs, which is helpful to modify the GOs with special functional groups to improve the selective removal of
radionuclides from solutions to GOs and GO-based materials. Such information is crucial to understand the interaction
mechanism of radionuclides with GOs, and to evaluate the behavior of radionuclides in the natural environment. However,
with the large application of GOs in multidisciplinary areas, parts of GOs can be released into the natural environment
inevitably and thereby become environmental pollutants (Wang et al., 2016).
Graphene oxide (GO) has attracted considerable attention because of its remarkable enhanced adsorption and multifunc-
tional properties. However, the toxic properties of GO nanosheets released into the environment could lead to the instability
of biological system. Layered double hydroxides (LDHs) is a family of two dimensional anionic clays, which can coagulate
GO and minimise its toxicity. The coagulation of GO on LDH and removal of pollutants is shown in Fig. 16 (Zou et al., 2016a,
b, c).
Pristine graphene and graphene doped with transition metals (Zr, Mo, Ti, Mn, Fe, Co) were utilized for adsorption of
phosgene molecule (Zhang et al., 2017a, b). The adsorption was observed to be more with transition metal doped pristine
grapheme. It was due to strong chemical bond formation between phosgene molecule and transition metal doped pristine
graphene. Maximum adsorption occurred with Mn-doped pristine graphene with adsorption energy −1.677 ev.
Zr-based metal-organic frameworks (MOFs), showed high adsorption capacity for GO in aqueous solution, and hence it
can be a promising material to remove GO efficiently from aqueous solutions by using a simple and rapid coagulation process.
Electrostatic attractions combined with nonnegligible π –π interactions, hydrogen-bonding and acid–base interactions lead
to the heteroaggregation between GO and Zr-based MOFs (Li et al., 2017).

6.6.2. Boron nitride materials


Boron nitride (BN) with a structure similar to graphene possesses many extraordinary properties such as high surface
areas, high oxidization resistance at high temperature, and high chemical stability. It is an environmentally benign material
and the porous BN nanomaterials can treat a wide range of pollutants (such as dyes, organic solvents, heavy metal ions, oils,
etc.) from water.
BN is isostructural to carbon and generally exists in four crystalline forms including graphite-like hexagonal BN (h- BN),
diamond-like cubic BN (c-BN), rhombohedral BN (r-BN), and wurtzite BN (w-BN). Among them, h-BN has attracted special
214 N.B. Singh et al. / Environmental Technology & Innovation 11 (2018) 187–240

Fig. 15. Schematic diagram for the adsorption of Pb2+ on GO.

Fig. 16. Optimized geometrical structures and the coagulation processes of GO on LDHs (Zou et al., 2016a, b, c).

interests because it is analogue of graphite, so-called ‘‘white’’ graphite. Additionally, two-dimensional (2D) crystals of h-BN
can be wrapped up into 0D BN fullerenes and rolled into 1D BN nanotubes (BNNTs) (Fig. 17) (Yu et al., 2018).
Despite the structural similarity between BN and graphene, less attention is given on BN materials on the removal of
contaminants from water. Different kinds of BN-based materials have exhibited efficient sorption capacity for organic and
inorganic pollutants. The excellent sorption capacity of BN was due to high specific surface area (1687 m2 /g), structural
defects and pore volume (0.45 cm3 /g). BN very efficiently remove metal ions and organic pollutants from wastewater. It is
reported that efficiency of removal of different metal ions by activated BN is much higher than that of BN itself and activated
carbon (Fig. 18) (Yu et al., 2018). It is reported that during the removal of heavy metal ions by BN, there is electrostatic
interaction between the two. Organic pollutants have also been removed by BN in an effective way.
N.B. Singh et al. / Environmental Technology & Innovation 11 (2018) 187–240 215

Fig. 17. Structural models of 2D, 1D and 0D BN nanostructures (Yu et al., 2018).

Fig. 18. Comparison of sorption capacities of the activated BN, porous BN and activated carbon for Cr (III), Co(II), Ni(II), Ce(III), and Pb(II) (Yu et al., 2018).

Studies have shown that the sorption of heavy metal ions on BN-based materials was mainly dominated by strong surface
complexation and electrostatic interaction whereas the sorption of organic pollutants was mainly governed by π -π stacking
interactions. Organic molecules with benzene-containing structures have strong π -π stacking, which increases with the
increase of benzene number. In fact, various mechanisms may simultaneously control pollutants’ sorption on BN-based
materials. The overall mechanism of interaction of metal ions and organic contaminants on the surface of BN is represented
in Fig. 19 (Yu et al., 2018).
The feasibility of applying the adsorbent systems in large-scale operations is determined by the cost of their disposal or
regeneration. A large number of investigations have indicated that the BN-based materials could be readily cleaned for reuse
by burning or heating in air due to their strong resistance to oxidation.
However, despite the bright future of BN-based materials in water purification, the preparation methods of functionalized
BN and BN-based nanomaterials are still difficult compared to graphene analogues. Therefore, its utility as an adsorbent is
less explored.

6.6.3. Nobel metal based nanomaterials


The noble metal nanoparticles like silver and gold are used in drinking water purification (Pradeep and Anshup, 2009).
Silver nanoparticles have been used in removing a number of toxic contaminants from drinking water. Removal of Hg from
water by gold nanoparticles is shown in Fig. 20 (Pradeep and Anshup, 2009).

6.6.4. Nanoscale zerovalent iron (NZVI)


Nanoscale zerovalent iron (NZVI) has been used for the removal of toxic heavy metal ions, present both in the surface and
underground wastewater. Nanoscale zerovalent iron (NZVI), an environmentally benign material, has been used successfully
to treat various metal ions in aqueous solutions (e.g., Pb(II), Ba(II), Zn(II), As(III), Cr(VI), As(V), Cu(II), Cd(II), and Co(II)), via
its controllable particle size, high reactivity and abundant reactive surface sites (Zou et al., 2016a, b, c).

6.6.5. Metal oxide based nanomaterials


A large number of metal oxide nanomaterials like Fe3 O4 , TiO2 , ZnO as well as their composites have been used in the
removal of toxic metal ions and organic pollutants from water and wastewater (Singh et al., 2013). Magnetic nanomaterials
216 N.B. Singh et al. / Environmental Technology & Innovation 11 (2018) 187–240

Fig. 19. Schematic of the interaction mechanism of pollutants with BN-based materials (Yu et al., 2018).

Fig. 20. (a) TEM picture of gold nanoparticles before Hg(0) treatment, (b) TEM picture of gold nanoparticles after the Hg(0) treatment and (c) UV–vis
absorption spectra of gold nanoparticles before and after mercury treatment. Inset of (c): photographs of gold nanoparticles and mercury treated gold
nanoparticles (d) XRD patterns of gold nanoparticles before and after mercury treatment. (a) XRD pattern of gold nanoparticles before reaction. (b) XRD
pattern of mercury-treated gold nanoparticles.

Fig. 21. Photocatalytic process on the surface of semiconductor nanoparticles.

have been also used as adsorbents as they have feasibility of magnetic separation and can be reused. Some of the nano oxides
work as a good photo catalyst for degradation of dyes and organic compounds (Fig. 21) (Singh et al., 2013).
N.B. Singh et al. / Environmental Technology & Innovation 11 (2018) 187–240 217

Table 17
Adsorptive performance of SFs for metal ion removal.
Adsorbent Size (nm) PZC SA (m2 /g) Ms (emu/g) Pollutant qe (mg/g) Qel (mg/m2 ) pH
2+
MBC – – – – Pb 25.3 – 5.0
Cd2+ 15.0 – 5.0
MnFe2 O4 – 7.7 – – Pb2+ 69.1 – 6.0
Cu2+ 60.5 – 6.0
Zn Fe2 O4 20a – 65 29.8 Cr6+ 34.2 0.53 2.5
3D porous Ni Fe2 O4 – – 6.2 15.0 Cu2+ 55.8 9.0 5
Cr6+ 37 6.0 7
Ni2+ 37 6.0 2
Nano 21a 6.2 – 21.82 Fe2+ 70 – 5
Ni Fe2 O4
Mn Fe2 O4 30–50a 7.5 138 32.0 As3+ 93.8 0.68 3
As5+ 90.4 0.66 7
a
CoFe2 O4 10–30 7.0 101 47 As3+ 100 0.99 3
As5+ 73.8 0.73 7
Mn Fe2 O4 4–6a – – 30.7–51.1 Pb2+ 5.2 – 6.8 ± 0.4
Mn Fe2 O4 20–40a – – 1.3–31.4 Cr6+ – – 2
NiFe2 O4 <10a – – 49 Pb2+ – – –
CoFe2 O4 <100b – – 53 Pb2+ – – –
CuFe2 O4 20–90b – 69.1 62.5 Cd2+ 17.54 0.25 6.0
CuFe2 O4 60b 7.3 48.3 62.5 As3+ 41.2 0.85 4.2
CuFe2 O4 20–120b 7.3 48.3 62.5 As5+ 45.7 0.95 3.7
CuFe2 O4 20–120b 7.3 48.3 61.4 Mo 30.6 0.63 2.75
Surface-modified Mn Fe2 O4 10a 6.5 208 3.6 Cr6+ 31.6 0.15 2.0
Mn Fe2 O4 ∼11c 91 – Pb2+ 488 5.36 5
As3+ 97 1.07 6.5
As5+ 136 1.49 4
Isoelectric point; a, b, c are size from TEM [a], SEM [b], and XRD [c].

Table 18
Adsorptive performance of SFs for dye removal.
Adsorbent Size (nm) PZC SA (m2 /g) Ms (emu/g ) Pollutant qe (mg/g) Qel (mg/m2 ) pH
b
Hollow 127.3 – – 76.2 CR 16.6 – 6.0
Zn–Fe2 O4 nanospheres
3D porous NiFe2 O4 – – 6.2 15.0 MB 138 22.3 9.0
FR 14.61 2.35 5.0
MV 19.06 3.09 3.0
Zn Fe2 O4 30–50 6.5 132 69.5 AF 150 1.14 2.0
hollow fibers
Ni Fe2 O4 – – 302 4.0 AO7 159 0.53 –
CuFe2 O4 11.7 µmc – 88.6 22.8 AR B 86.8 0.97 4.8
SPM60 – – 29.8 27.9 MB 20.7 0.69 3.5
CoFe2 O4 30–40b – – 86.1 CR 244 – –
NiFe2 O4 80–100b – – 58.0 CR 97.1 – –
MnFe2 O4 80–100b – – 78.4 CR 92.4 – –
NiFe2 O4 17a – – – RB5 472 – –
MnZnFe 10a 8.5 139 AR 88 111 0.8 –
MnFe2 O4 54.3–74.7b 6.6 – 22.4 CR 42 – 4.0–9.0
MnFe2 O4 200–290b 6.6 2.9–156 27.4 MB 498 3.0–9.0
CR 25.8 3.0–9.0

6.6.6. Spinel ferrite based nanomaterials


Now a days, spinel ferrites (SFs) have been most widely employed nanomaterials for water treatment applications due
to superparamagnetic properties, high surface to volume ratio and nanometer-sized. Different types of pollutants have been
removed from water by using different spinels (Reddy and Yun, 2016). Removal of some metal ions by SFs is given in Table 17
(Reddy and Yun, 2016).
It is reported that NiFe2 O4 nanosheets grown on the surface of the Ni foam have 3D flower type structure and is a very
good adsorbent removing the contaminants from water (Luo et al., 2017). The SEM pictures are given in Fig. 22. This shows
that a typical morphology is related to adsorption efficiency.
Recently, SFs have been extensively used as magnetic adsorbents to remove both cationic and anionic dye molecules from
aqueous solutions. Some examples are given in Table 18.
Physicochemical interactions of the adsorbate–adsorbent such as (i) hydrogen bonding, (ii) π –π interactions (iii) surface
complexation, (iv) electrostatic interactions, (v) chemisorption, and (vi) ion-exchange play an important role. In the case of
spinel metal oxides, surface hydroxyl groups and surface charge play a vital role in adsorption. Depending on the pH of the
solution, the charge of the metal oxide may change (Fig. 23) (Reddy and Yun, 2016).
218 N.B. Singh et al. / Environmental Technology & Innovation 11 (2018) 187–240

Fig. 22. (a), (b), (c) SEM images of NiFe2 O4 /Ni; (d) TEM image of NiFe2 O4 /Ni (Luo et al., 2017).

Fig. 23. Schematic of the surface charge of SF at low and high pH conditions.

Fig. 24. Magnetic separation of used PPy/Fe3 O4 nanocomposite after Cr(VI) removal.

6.6.7. Nanocomposites
Nanoparticles possess a series of unique physical and chemical properties. Metals, metal oxides, polymers and ceramics,
and carbon derivatives (carbon nanotubes and fullerenes) at nanoscale have higher ratio of surface area to particle size and
exhibit different optical, electrical, and magnetic properties as compared to that of macroscopic particles (Shelley, 2005). As
the size decrease from scale of micrometer to nanometer, it results in increase in surface energy which reduces their stability.
As a result nanoparticles are susceptible to agglomeration due to Van der Waals forces or other interactions (IPCS, 2001). It
also results in reduction or loss of capacity and selectivity of nanoparticles. Moreover, it also leads to excessive decrease in
N.B. Singh et al. / Environmental Technology & Innovation 11 (2018) 187–240 219

Fig. 25. A tentative mechanism for the removal of Cr(VI) ions from water solution.

Fig. 26. Adsorption of Cr (VI) and Cu (II) ions from aqueous on Polypyrrole/maghemite (PPY/γ -Fe2 O3 ) and polyaniline/maghemite (PANi/γ -Fe2 O3 ) magnetic
nanocomposites surfaces.

pressure and mechanical strength which makes nanoparticles useless in fixed beds and other flowing systems. To improve
the usability of nanoparticles in real wastewater treatment, they are permeated into other matrices particularly polymers
to obtain nanocomposite adsorbents (Pan et al., 2009). The polymer nanocomposites are much better adsorbents and are
discussed in detail in the next para. A large number of nanomaterials have been used for water remediation (Ambashta
and Sillanpaa, 2010). Nanocomposites have applications in various sectors including water purification (Chowdhury and
Balasubramanian, 2014; Bhaumik et al., 2013; Thatai et al., 2014; Gupta et al., 2014; Li et al., 2014; Singh et al., 2013).
The magnetic properties of nanoparticles can be modified by using functionalized polymers which improve the removal of
pollutants (Bhaumik et al., 2011a). Polypyrrole (PPy)-based nanocomposites have been extensively used (Bai et al., 2015). PPy
can be coated onto Fe3 O4 to make a magnetic PPy nanocomposite. The magnetic PPy nanocomposite can then be collected and
separated by using an external magnetic field, without requiring filtration or centrifugation. Polypyrrole (PPy), a conducting
polymer, has a tendency to aggregate but its nanocomposite may minimize the aggregation as well as may increase the
surface area, so it may work as a good adsorbent.
Fe3 O4 coated polypyrrole (PPy) magnetic nanocomposite is reported to be an efficient adsorbent for the adsorption of
Cr(VI) from water solution. 100% removal is possible at pH 2 (Bhaumik et al., 2011b). Cr (VI) removal by the PPy/Fe3 O4
nanocomposite may be due to reduction on the surface of the nanocomposite and ion exchange mechanism. Fig. 24 shows
magnetic separation of PPy/Fe3 O4 nanocomposite adsorbent after adsorption of Cr(VI) on magnet bar, indicating that the
adsorbent after adsorption can easily be separated (Bhaumik et al., 2011b).
The adsorption of Cr(VI) from water solution depends mainly on pH. Cr(VI) is predominantly as monovalent bichromate
ions (HCrO4 − ) and divalent dichromate (Cr2 O7 2− ) ions in the pH range of 2–6 and above pH 6, the dominant species is
chromate (CrO24− ) ions (Bhaumik et al., 2011b). The higher removal efficiency in the acidic pH (2–6) range is due to the anion
220 N.B. Singh et al. / Environmental Technology & Innovation 11 (2018) 187–240

Fig. 27. Possible mechanism of removal of Cr(VI) from aqueous solution by PPy–PANi nanofibers (Bhaumik et al., 2012).

Fig. 28. pH dependent removal of Cr(VI) from aqueous solution by PPy–PANi nanofibers and PPY homopolymer (Bhaumik et al., 2012).

exchange property of the PPy/Fe3 O4 nanocomposite by replacing the doped Cl− ions with either HCrO4 − or Cr2 O7 2− ions.
The removal of HCrO4 − can be visualized by Fig. 25.
Negative value of free energy of Cr(VI) adsorption on the surface of PPy/Fe3 O4 nanocomposite suggested spontaneity of
the process and adsorption followed pseudo-second-order kinetics and fitted well the Langmuir adsorption isotherm model.
After desorption, the nanocomposite can successfully be used for readsorption process (Bhaumik et al., 2011b).
Polypyrrole/maghemite (PPY/γ -Fe2 O3 ) and polyaniline/maghemite (PANi/γ -Fe2 O3 ) magnetic nanocomposites (MNCs)
have been used for removal of Cr (VI) and Cu (II) ions from aqueous solutions (Fig. 26) (Chávez-Guajardo et al., 2015).
These MNCs can adsorb a high amount of Cr (VI) and Cu (II) ions in a relatively short time and can be easily recycled and
reused. However, PPY/γ -Fe2 O3 showed higher adsorption capacities and shorter times to reach the saturation equilibrium
for adsorption.
It is reported that core–shell structured Fe3 O4 /PANi microspheres with high magnetization have a strong Cr(VI) ion
adsorption capacity, and show an excellent regenerability to offer rapid Cr(VI) removal from water within 30 min (Han
et al., 2013).
Polypyrrole–polyaniline (PPy–PANi) nanofibers have been used as an adsorbent for removal of Cr(VI) from aqueous
solution (Bhaumik et al., 2012). Possible process of removal of Cr(VI) from aqueous solution by PPy–PANi nanofibers is shown
in Fig. 27. The removal is pH dependent and much higher for PPy–PANi nanofibers (Fig. 28).
N.B. Singh et al. / Environmental Technology & Innovation 11 (2018) 187–240 221

Fig. 29. Cr(VI) removal mechanism using PANi- Fe3 O4 nanocomposite.

Fig. 30. Cationic polymer–TiO2 nanocomposite, synthesized by using functionalized TiO2 nanoparticles as filler and a quaternary ammonium-based
polymer.

PANI/zeolite nanocomposite was considered to be a good adsorbent for Cr(VI) metal ions. The chromium removal in-
creases with increase of metal ion concentration (20–100 ppm) and Freundlich isotherm model fitted well the experimental
data (Shyaa et al., 2015).
Polyaniline–magnetite nanocomposites was also used as an adsorbent for the removal of Cr(VI) from contaminated water.
The mechanism of removal is given in Fig. 29 (Guo et al., 2013).
Arsenic pollution is a worldwide problem due to its high toxicity. Cationic polymer–TiO2 nanocomposite, synthesized by
using functionalized TiO2 nanoparticles as filler and a quaternary ammonium-based polymer (Fig. 30) was used for arsenic
removal (Bruno et al., 2015). The removal was found 99% in less than 10 min. The experiment conducted in the presence of
sulfate showed a strong decrease in arsenic sorption (Fig. 31).
The core–shell nanocomposite PS–Fe3 O4 is reported to have high capacity and fast kinetics for arsenate adsorption. It
could be effectively separated from water in the presence of a low magnetic field (Jiang et al., 2012). Additionally, the
composite could be employed for repeated use for arsenate removal after regeneration with alkaline solution.
222 N.B. Singh et al. / Environmental Technology & Innovation 11 (2018) 187–240

Fig. 31. Arsenate sorption in the presence of sulfate for NC 15%.

Fig. 32. In-situ preparation of PANi/HMS nanocomposite.

FeOOH@GO-COOH nanocomposite has been used as an efficient adsorbent for removal of arsenite and arsenate and
adsorption capacities were found to be 77.5 mg g−1 for As(III) and 45.7 mg g−1 for As(V), respectively (Chen et al., 2015a, b).
Polyaniline (PANi) is an important conducting polymer and it has high affinity for metal ions due to large amount of
amine and imine functional groups. It can remove heavy metal contaminants from aqueous solutions readily and effectively.
However, it is found that Polyaniline/Hexagonal Mesoporous Silica (PANi/HMS) nanocomposite is a successful adsorbent for
Ni(II) ions removal from water solutions. In-situ preparation of PANi/HMS nanocomposite is shown in Fig. 32 (Javadian et
al., 2013).
Optimum pH and contact time for 99.87% removal of Ni(II) from water solution were found to be 8 and 16 min respectively.
Freundlich adsorption isotherm model and pseudo-second-order model fitted the data for adsorption of Ni(II) on PANi/HMS
nanocomposite surface. Desorption of Ni(II) from PANI/HMS has been investigated using 0.1 M H2 SO4 and maximum
desorption efficiency was 86%.
Macroporous nanocomposite biomass was used for the removal of toxic ions and the adsorption capacity for different
ions is given in Fig. 33 (Ma et al., 2015).
MnFe2 O4 -G ferrites have been used for the effective removal of Pb and Cd ions. Sorption of Pb and Cd ions onto MnFe2 O4 -G
surface followed pseudo second order kinetic model and the monolayer adsorption capacity of Pb and Cd on MnFe2 O4 -G was
found to be 100 and 76.90 mg/g at pH 5 and 7 respectively (Santhosh et al., 2016). Effect of MnFe2 O4 -G on bacterial model
E. coli was also investigated with 82% loss of viability after 2 h of treatment with 100 mg/L MnFe2 O4 -G (Fig. 34).
Bentonites and its modified nanocomposites have been found to remove inorganic contaminants from drinking water
with very high removal efficiency. In most of the cases, they proved to be better or comparable with the existing commercial
adsorbents. Being natural and their abundance presence makes them a low-cost green, nontoxic adsorbent which can be
N.B. Singh et al. / Environmental Technology & Innovation 11 (2018) 187–240 223

Fig. 33. The adsorption capacity of different ions on Macroporous nanocomposite biomass.

Fig. 34. Schematic diagram showing the adsorption of heavy metal ions and antibacterial activity on MnFe2 O4 -G.

used for removal of different contaminants from water and making clean and pure drinking water available for developed
and developing nations (Pandey, 2017).
There are variety of other nanocomposites which have been used as effective adsorbents for the removal of toxic
metal ions and dyes from waste water. Nanosized tungsten oxide (WOx ) is a multifunctional material and has various
structures such as hierarchical flowers, nanoplates, hollow nanospheres, nanodiscs and nanowires. Nanowires were found
as good adsorbents for the removal of many pollutants from water. To further improve their adsorption capacity, organic
functional groups with favorable affinity to heavy metal ions and organic dyes may be incorporated into the WOx to produce
inorganic–organic hybrid WOx based composites (Zhang et al., 2017a, b). These organic functional groups including thiol,
amino, carboxylic and sulfur groups commonly possess stronger complexation or chelating ability toward heavy metal ions,
and have been used to functionalize the inorganic adsorbents to improve their adsorption performance. WOx /C nanowire
networks were found to be exceptionally effective and efficient in the removal of Pb2+ and methylene blue (MB) from
224 N.B. Singh et al. / Environmental Technology & Innovation 11 (2018) 187–240

Fig. 35. Schematic description of six subclasses of dendritic polymers (Sajid et al., 2018).

aqueous solution, with rapid adsorption equilibrium (within 1 min) and exceptionally high adsorption capacity. The ion
exchange, π –π interaction, hydrogen bonding and/or electrostatic attraction are the contributions to the fast and high
capacity removal of Pb2+ and MB by the WOx /C nanowire networks (Zhang et al., 2017a, b).
Fe3 O4 – polydopamine (PDA) — Mg–Al LDH (MPL) has been used for the simultaneous removal of heavy metal ions and
anionic dyes from waste water. Removal efficiency depends on number of factors (Li et al., 2016).
Hierarchical porous ZnO–Al2 O3 composites were utilized as adsorbents to remove organic dyes from waste water. The
efficiency of the ZnO–Al2 O3 composite depends on its morphology and microstructure. The ZnO–Al2 O3 composites exhibited
higher adsorption performance than the pure ZnO and Al2 O3 (Lei et al., 2017a, b, c, d). Hollow microspheres and hierarchical
porous nanostructured materials like NiO–SiO2 composite particles were found to be powerful adsorbents for removal of
Congo red from water (Lei et al., 2016). Hierarchically porous nickel–iron-layered double hydroxide (NiFe–LDH) was also
found as an effective adsorbent for removal of congo red dye from water (Lei et al., 2017a, b, c, d).
β -cyclodextrin polymer crosslinked with aromatic groups were utilized as low cost adsorbents for removal of Pb(II), Cu(II)
and Cd(II) from aqueous solution. Adsorption process was found to be very fast and completed within 5 min with maximum
adsorption capacity of 196.42, 164.43 and 136.43 mg/g (He et al., 2017).

6.6.8. Dendritic polymers based adsorbents


Dendrimers are novel nanostructured synthetic polymers that possess a highly branched structure with a unique three-
dimensional molecular configuration and a large number of (reactive) end groups (Fig. 35). Dendrimers are an excellent
addition to the world of adsorbents. They have high internal and external specific areas. Both surface and internal cavities
can entrap and bind with target pollutants through a wide variety of interactions. They have shown extra-ordinary potential
in water remediation. Dendrimers can be used alone or supported on different materials. They can be immobilized over
the membranes in dynamic systems. Their performance is affected by dendrimer generation, solution pH, contact time, etc.
(Sajid et al., 2018).
Nanomaterials in general have number of properties that make them useful as adsorbents for water purification. The
properties are high surface area, ability of functionalization, high selectivity and reusability. Carbon nanotubes are found
to be good adsorbent for water purification but their practical applications are restricted due to economic considerations.
Recently graphene and its nanocomposites have drawn considerable attention for water purification. Mass production of
nanomaterials is difficult and at the same time it is costly. This can be a serious bottleneck for industrial applications.
Another important issue is the prevention of release of nanoparticles into the environment because they can accumulate
for long periods of time and can be toxic for living system. The research in this area is still at an early developmental stage.
Nevertheless, nanomaterials could offer great potential in water treatment and environmental remediation in the coming
decades.

6.7. Geopolymer cement as adsorbent

Adsorption of wastewater by zeolite is feasible due to its unique three-dimensional network structure, with fixed-sized
pores and paths that allow only certain heavy metals to pass through. Similar to zeolite, geopolymer, an inorganic polymer,
N.B. Singh et al. / Environmental Technology & Innovation 11 (2018) 187–240 225

Fig. 36. Preparation of geopolymer cement.

has three-dimensional polymeric structure and pores. Geopolymer cement is an innovative material and a real alternative
to conventional Portland cement. Its preparation is represented in Fig. 36.
Wastewater treatment using a geopolymer as an adsorbent should be more feasible.In recent years, the adsorption of
methylene blue dye on a fly ash based geopolymer adsorbent was studied (Cheng et al., 2012). The synthesized geopolymer
demonstrated an adsorption capacity of approximately 0.12 mmol/g. Fly ash-based geopolymer was also used for Cu2+ and
Pb2+ removal from an aqueous solution (Zhang and Liu, 2013).
Fly ash-based geopolymers as adsorbents can also remove poisonous and harmful organic materials from the environ-
ment and aqueous solution. The organic molecules adsorbed on the surface of geopolymers have not been degraded and
easily cause secondary pollution (Ma et al., 2015). In view to explore a new approach for degradation of organic pollutants,
geopolymer have been used as a photocatalyst for the degradation of methylene blue (MB) dye from wastewater under UV
irradiation (Ma et al., 2015).

7. Fluoride removal

Presence of Fluoride (F− ) in groundwater has been identified as one of the acute problems worldwide (Cheng et al.,
2012). It results in severe effects on teeth and bones. Fluoride is considered beneficial at levels around 0.7 mg L−1 but it
is hazardous if it exceeds 1.5 mg L−1 , which is the World Health Organization (WHO) limit in drinking water and this is
followed in most nations. Theoretically, the adsorption of fluoride on to solid particles normally occurs in three steps (Fan
et al., 2003; Mohapatra et al., 2009).
(i) diffusion of fluoride ions to the external surface of the adsorbent from bulk;
(ii) adsorption of fluoride ions on to particle surfaces;
(iii) the adsorbed fluoride ions probably exchange with the structural elements inside adsorbent particles.
Variety of adsorbants has been used for the removal of fluoride from water (Velazquez-Jimenez et al., 2015) and is given
in Table 19 (Bhatnagar et al., 2015).
Excess amounts of fluoride in potable water have been recognized as a major public health hazard. Various adsorbents
have been used for the removal of fluoride from water but a particular adsorbent which shows higher removal efficiency for
fluoride in the laboratory, may fail in field conditions. Therefore, the choice of a suitable adsorbent and the technology is a
difficult task.

8. Phosphate removal

Fertilizers are used to increase the yield, but their excessive use has led to pollution of water and environmental resources
(Lin et al., 2013, 2011). Among fertilizers, those of nitrogen and phosphorus are used more frequently. However, the increased
concentration of phosphorus in water (above 0.02 mg/L) can result in eutrophication, causing degradation of water quality
and menancing the life of aquatic animals (Ismail, 2012; Jyothi et al., 2012). Thus, the excessive quantity of phosphorus should
be removed (Anirudhan et al., 2006; Zhang et al., 2012). The reAgricultural waste/by-products (AWBs) has been found as a
biosorbent for removal of phosphate from water (Nguyen et al., 2014; Ning et al., 2008). There are number of properties
in AWBs which make them good adsorbent for phosphorus removal. Recovery of phosphorus by means of adsorption onto
AWBs is presented in Fig. 37 (Nguyen et al., 2014).
Metal loaded AWBs were found to be effective biosorbents for removal of phosphate from aqueous solutions. Some
examples are given in Table 20 (Nguyen et al., 2014).
In recent years, magnetic nanoparticles have emerged as a novel material for phosphate adsorbents (Lai et al., 2016; Gu
et al., 2016). Zinc ferrite (ZnFe2 O4 ) was used for phosphate removal. Phosphate adsorption by zinc ferrite was enhanced at
lower pH and with increasing ionic strength (Gu et al., 2016).
Phosphate was also removed by using La-Zeolite as adsorbent (He et al., 2017). The removal efficiency was observed to
be 95%. It was due to the formation of inner sphere complexation between Oh group of phosphate and La-Zeolite.
226 N.B. Singh et al. / Environmental Technology & Innovation 11 (2018) 187–240

Table 19
Adsorption capacities and other parameters for the removal of fluoride by different sorbents (Mohapatra et al., 2009).
Adsorbent pHpzc Adsorption Concentration Contact time pH Temperature
capacity range
Basic oxygen – 4.58–8.07 1–50 mg/L 35 min 7.0 25–45 ◦ C
furnace slag mg/g
Alum sludge – 5.394 mg/g 5–35 mg/L 240 min 6.0 305 K
Activated alumina ca. 8.0 0.86 mmol/g 15–100 mg/L 16–24 h 5.0–6.0 30◦ C
(Y-Al2 O3 )
Metallurgical grade – 12.57 mg/g – – 5.0–6.0 20◦ C
alumina
La(III) impregnated – 0.350 mM/g 2 mM/L 20 h 5.7–8.0 Room
on Alumina temperature
Alum-impregnated – 40.68 mg/g 1–35 mg/L 3h 6.5 Room
activated alumina temperature
Manganese 7.2 ± 0.1 7.2 ± 0.1 2.5–30 mg/L 3h 7.0 ± 0.2 30 ± 2◦ C
oxide-coated
alumina
Hydrousmanganeseoxide- 5.9 7.09 mg/g 10–70 mg/L 4h 5.2 ± 0.05 ca. 25◦ C
coated
alumina
Magnesia amended 8.6 ± 0.2 10.12 mg/g 5–150 mg/L 3h 6.5–7.0 30 ± 1◦ C
activated alumina
Alkoxide origin – 2.0 mg/g 0–25 mg/L 24 h 7.0 30 ± 2◦ C
alumina
Quick lime – 16.67 mg/g 10–50 mg/L 75 min – 25 ± 2◦ C
Lime stone (LS) and 9.23 43.10 mg/g 0–100 mg/L 5h 8.0 298 K
aluminum and and 84.03
hydroxide 10.17 mg/g
impregnated lime
stone
Schwertmannite 4.2 50.2–55.3 10–90 mg/L 24 h 3.8 295.6–313.0 K
mg/g
Nano-geothite – 59 mg/g 5–150 mg/L 2h 5.75 303 K
Synthetic siderite – 1.775 mg/g 3–20 mg/L 8–12 h 4.0–9.0 25◦ C
Magnesia amended ca. 10 12.6 mg/g – 60 min 3.0 25◦ C
silicon dioxide
granules
Iron(III)-tin(IV) 6.5 ± 0.3 10.47 mg/g 10–50 mg/L 2h 6.4 ± 0.2 303 ± 1.6 K
mixed oxide
Al–Ce hybrid 9.6 91.4 mg/g 2–15 mg/L 24 h 6.0 25◦ C
adsorbent
Fe–Al–Ce trimetal 5.8 178 mg/g 2–110 mg/L 24 h 7.0 ± 0.1 25◦ C
oxide
Fe–Al mixed 5.4 91.7 mg/g 10–90 mg/L 2h 4.0 30◦ C
hydroxide (Molar
ratio:1)
Aluminum titanate 7.4 3.01 mg/g 2–10 mg/L 40 min 7.0 30◦ C
Bismuth aluminate 7.1 7.09 mg/g
Various grades of 6.89– 0.16–3.13 2–10 mg/L 60 min 7.0 30 ±0.5◦ C
graphite 7.34 mg/g
Lignite (LN) – 6.9–7.44 mg/g 3–90 mg/dm3 10 h 5–10 30◦ C
Fine coke (FC)
Bituminous coal
(BC)
Fired clay chips – 70%–90% 5–20 mg/L – 5–7 22 ± 2◦ C
Montmorillonite 2.5 1.485 mg/g 3.0 mg/L 50 min Neutral pH 30◦ C
clay
Montmorillonite – 0.263 mg/g 2–120 mg/L 180 min 6.0 25◦ C
Clay minerals 6.5 69.44–93.45 23.6–2360.0 3-4 days ∼3.0 25◦ C
mg/g mg/L
Laterite 3.98 0.8461 mg/g 10–50 mg/dm3 – 7.5 303 K
Acid activated – 0.0450 mg/g 3.0 mg/L 100 min Low pH 25◦ C
kaolinite clay
Al3+ pretreated 6.0– 28.21–41.35 5–80 mg/L 2 days 4.0–8.0 298 K
low-silica 8.2 mg/g
synthetic zeolites
(continued on next page)
N.B. Singh et al. / Environmental Technology & Innovation 11 (2018) 187–240 227

Table 19 (continued)
Adsorbent pHpzc Adsorption Concentration Contact time pH Temperature
capacity range
Metal ion – 2.04–4.13 1–20 mg/L 24 h – 30◦ C
loaded natural mg/g
zeolite
Neodymiummodified – 22.380 mg/g 10–100 mg/L 24 h 7.0 303 K
Chitosan
Fe(III) loaded 3.22 4230 mg/kg 11–19 mg/L 40 min Neutral pH 303 K
carboxylated
chitosan beads
Calcined – 213.2 mg/g 50 mg/L 4h 6.0 30◦ C
Mg-Al-CO3
layered double
hydroxides
Light weight – 5.15 mg/g – 60 min 6.9 298 K
Concrete
Hydrated Cement – 2.6788 mg/g – 24 h 6.7 30 ± 2◦ C
Hardened alumina 11.32 34.36 mg/g 2.5–100 mg/L 3h – ca. 300 K
Cement granules
(ALC)
Al2 O3 /CNTs – 28.7 mg/g 50 mg/L 12 h 6.0 25◦ C
Aligned carbon – 4.5 mg/g 15 mg/L 180 min 7.0 25◦ C
nanotubes
(CNTs)
nano-AlOOH 7.8 ± 0.1 3259 mg/kg 3–35 mg/L 4h 5.2 ± 0.2 298 K
CaO Nanoparticles – 163.3 mg/g 10–100 mg/L 30 min 2.0–8.0 35 ± 1◦ C
Fe–Al–Ce – 2.22 mg/g 0.001 M 36 h 7.0 25◦ C
nanoadsorbent
MASG – 38 g/kg – – 6.0 298 K
MAHP 8 g/kg
Fe3 O4 @Al(OH)3 – 88.48 mg/g 0–160 mg/L 240 min 6.5 25◦ C
NPs
Nanomagnesia – 267.82 mg/g 5–200 mg/L 90–120 min 7.0 30 ± 2◦ C
Bleaching Powder – 0.1308 mg/g 5.0 mg/L 1h 6.7 30 ± 2◦ C
Conducting – 6.37 mg/g 2–10 mg/L 30 min – 30◦ C
polypyrrole
Granular ceramic 6.0 ± 0.2 12.12 mg/g 5–50 mg/L 72 h 6.9 ± 0.1 20◦ C
PPy/Fe3 O4 – 17.6–22.3 5–100 mg/L 24 h 6.5 25◦ C
nanocomposite mg/g
Glass derived – 17.34 mg/g 100 mg/L 12 h 6.72 35◦ C
Hydroxyapatite
(G-HAP)
Chitosan based – 8.264 mg/g 5.0 mg/L 24 h – 30 ± 2◦ C
mesoporous
Alumina
KMnO4 modified 7.8 15.9 mg/g 20 mg/L 3h 2.0 25◦ C
carbon
Alumina/chitosan – 3809 mg/kg 10 mg/L 30 min Neutral pH 303 K
composite
Zirconium-iron – 9.80 mg/g 10 mg/L 10 h 7.0 25 ± 1◦ C
oxide

9. Nitrate removal

Nitrate is a major nutrient required for plant growth and nitrogenous fertilizers are routinely applied to agricultural lands
worldwide to increase crop production. However, elevated concentrations of nitrate in surface and ground waters, as a result
of firstly, excessive use of nitrogenous fertilizers, and secondly, disposal of untreated municipal and industrial wastes, are a
serious global environmental problem. It causes eutrophication of water bodies such as bays, inland seas, lakes and ponds.
Number of methods has been used for the removal of nitrate from water (Bhatnagara and Sillanpaa, 2011). Comparison of
some nitrate removal technologies is given in Fig. 38 (Bhatnagara and Sillanpaa, 2011).
Different adsorbents used for removal of nitrate are given in Fig. 39 (Bhatnagara and Sillanpaa, 2011).
Adsorption capacities and other parameters for the removal of nitrate by different sorbents are given in Table 21.
Most of the adsorbents’ effectiveness is not high because of their low to medium adsorption capacities. However on
surface modification, adsorption efficiencies are enhanced (Loganathan et al., 2013).
Excess NO− 3 concentrations in drinking water poses serious health problems. A number of adsorbents have been used for
removal of NO− −
3 removal from water and the choice of adsorbents generally depends on NO3 concentrations, presence of
other competing ions, pH of water, and some other factors. A particular adsorbent which shows higher uptake of NO− 3 in the
laboratory, may fail in field conditions. Therefore, further research is needed to optimize the conditions.
228 N.B. Singh et al. / Environmental Technology & Innovation 11 (2018) 187–240

Fig. 37. Phosphorus removal and recovery from aqueous solutions using AWBs based biosorbents.

Fig. 38. Different techniques for Nitrate removal.


N.B. Singh et al. / Environmental Technology & Innovation 11 (2018) 187–240 229

Table 20
Performance of metal loaded AWBs based phosphate biosorbents.
Biosorbents Modifying agents Mechanisms Side effects Phosphate Desorption Operation
uptake efficiency (%) mode
capacity (mg/g)
Apple peels NaOH+0.1M Electrostatic No release of 20.35 Distilled water BSR
ZrO2 Cl-8H2 O interaction Zr(IV) during pH 12 (>70%)
adsorption
Bagasse fibers Monochloroacetic 152 – –
acid + FeCl2
0.9%, 1.8%,
3.6%, and 5.3%
Eggshell FeCl3 .2H2 O5 Diffusion is not No 14.49 – BSR
mg/L only rate information on
controlling Fe(III) leakage
step
Orange waste gel Ca(OH)2 + 0.1 Polynuclear No significant 175 (322 at opt BSR 0.2 M BSR + PBR
M ZrOCl2 .8H2 O complexation leakage of pH) NaOH (95%)
Zr(IV) – no PBR HCl
detailed data (<40%)
NaCl(0%)
Wood particles Carboxymethyl Complexation Fe release 17.38 BSR
cellulose during
(CMC) 4% + sorption
FeCl2 12% increased with
decreasing
particle sizes –
no detailed
data
Orange waste gel Ca(OH)2 + 0.01 Ligand La(III) was 42.72 for all 3 0.4 M HCl BSR + PBR
M exchange eluted during types of gels (85%) (withLa(III)-
La(III)/Ce(III)/Fe(III)- reaction desorption test loaded SOW
gel only)
solutions
Juniper fiber Acid mine Iron release 7.08 – BSR + PBR
drainage was found (synthetic
(AMD) WW) + Field
(real WW)
Juniper fiber 0.1 and 0.01 M Ion exchange + Significant 20.045(La/JB01) – BSR
La(NO3 )3 .6H2 O complexation desorption of 33.35 (La/JB02)
+precipitation La(III) occurred
under acidic
condition (pH
<4.5)
Coir pith AC ZnCl2 Chemisorption 5.1 Distilled water –
+ ion exchange pH 2 (30%) pH
11 (50%) pH
3–11 (<10%)
Sawdust N, N′ - Ligand Reduced 8.9% 28.79 NaOH 0.1M BSR (synthetic
methylenebisacry- exchange of qm after 3 (96.8%) and real WW)
lamide cycles Sorbent
Acrylamide weight loss 3%
oxydisulfate after NaOH
Ethylenedi- treatment
amine
FeCl3 .6H2 O

10. Removal of radionuclide’s

Both geogenic and anthropogenic sources are accountable for contagion of water stream by radioactive elements.
Geogenic sources involve natural sources like washout and emission from radioactive materials present in earth crust (rocks,
soils, minerals, marine sediments etc.). Anthropogenic or manmade sources are created by human being such as mining and
processing of radioactive ores, coal fired plants, wide use of radioactive isotopes in medical technology (In X-ray machines
and preparation of some medicine), use of radioactive materials in power plants, radio-active fallout from nuclear outburst,
industrial applications include effluent from nuclear power plants, any leak or accident taking place emit nuclear radiation,
nuclear tests conducted under the ground or under oceans, reprocessing of nuclear fuel.
There are approximately five thousand natural and artificial radioactive isotopes such as uranium235 , uranium238 ,
antimony, thorium232 , radium226 , plutonium239 , Ruthenium106 , Plutonium240 , argon41 , cesium137 , krypton85 , Technetium91 ,
Bismuth214 , etc. Exposure to radiation emitting from radioactive material can lead to various effects on human body such
230 N.B. Singh et al. / Environmental Technology & Innovation 11 (2018) 187–240

Fig. 39. List of different adsorbents used for the removal of nitrate from water.

as brain damage, anemia, infection, hemorrhage, skin irritation, nausea, vomiting, diarrhea, acute sickness, decrease in the
total white blood cells, epilation, mutations, cardiovascular disorders, immune and endocrine system disorders, impairment
of kidney function, premature ageing, tumor production, damage of cell membranes, mitochondria and cell nuclei resulting
in abnormal cell functions, cell division, cancers and cell death, which depends on the type and energy of exposed radiation,
time of exposure, amount of radiation, types of cells and the decay mechanism. Therefore removal of such radionuclides
from water is must. There are number of methods including adsorption technique to remove the radionuclides from water
(Mishra, 2016) and appropriate adsorbents and conditions are yet to be develop.

11. Adsorption mechanism

Different adsorbates adsorb on different adsorbents in different ways. Four step diffusion model for dye adsorption on
porous adsorbents is given in Fig. 40 (Sivakumar and Palanisamy, 2010).
Adsorption mechanism of copper cyanide onto activated carbon is shown in Fig. 41 (Dai et al., 2010).

12. Future prospects

Although the available literature on the use of adsorbents for wastewater treatment is increasing at a tremendous pace,
there are still several gaps which need more attention. More selective, efficient, inexpensive, reusable and eco-friendly
adsorbents should be developed and experiments be conducted with real industrial effluents. Researches are required to
have a comparative study of different adsorbents for the removal of different contaminants from water considering the
feasibility, effectiveness and cost under similar conditions. Different type of adsorbents with greater stability (resistance
to pH changes and concentrations of chemicals present in contaminated water) and the capacity for the simultaneous
removal of multiple contaminants, such as toxic metal ions, organic dyes and bacterial pathogens should be developed.
Despite various drawbacks and challenges that currently exist, a widespread and great progress in this area can be expected
in the future. There is a great need to prepare, optimize and use new generation adsorbents for water treatment at pilot
and commercial levels by using column operations. The future of new generation adsorbents which can be efficient and
economical seems to be quite bright.

13. Conclusions

In the present era of scarcity of water resources, effective treatment of wastewater is a major prerequisite for growing
economy. It is critical to develop and implement advanced wastewater treatment technologies with high efficiency and
N.B. Singh et al. / Environmental Technology & Innovation 11 (2018) 187–240 231

Table 21
Adsorption capacities and other parameters for the removal of nitrate by different sorbents (Bhatnagara and Sillanpaa, 2011).
Adsorbent Amount adsorbed Concentration range Contact time Temperature pH
H2 SO4 treated carbon cloth 2.03 mmol/g 115 mg/L 60 min 25 ◦ C 7.0
Powdered activated carbon 10 mmol/g – 60 min 25◦ C <5.0
Carbon nanotubes 25 mmol/g – 60 min 25◦ C <5.0
Untreated coconut granular activated carbon 1.7 mg/g 5–200 mg/L 2h 25◦ C 5.5
ZnCl2 treated coconut granular activated carbon 10.2 mg/g 5–200 mg/L 2h 25◦ C 5.5
Coconut shell activated carbon 2.66 ×10−1 mmol/g – – 303 K 2-4
Bamboo charcoal 1.04 ×10−1 mmol/g – – 303 K 2-4
Bamboo powder charcoal 1.25 mg/g 0–10 mg/L 120 h 10◦ C –
Halloysite 0.54 mg/g 100 mg/L 17 h Room temp. 5.4
HDTMA modified QLD-bentonite 12.83–14.76 mg/g 100 mg/L 17 h Room temp. 5.4
Calcined hydrotalcite-type compounds 61.7–147.0 g/kg 12.7–236 mg/L 24 h 25◦ C –
Layered double hydroxides 20–35 mg/g 0–1000 mg/L 4h 21◦ C ∼8.5
Chitosan coated zeolite 0.6–0.74mmol/g 10–3100 mg/L 72 h 4◦ C and 20◦ C –
Chitosan hydrobeads 92.1 mg/g 1–1000 mg/L 1440 min 30◦ C 5.0
Chitosan beads 90.7 mg/g 25–1000 mg/L 24 h 30◦ C 5.0
Conditioned cross-linked chitosan beads 104.0 mg/g 25–1000 mg/L 24 h 30◦ C 5.0
Pure alkaline lignin 1.8 mmol/g 1–30 mg/L 48 h 30◦ C –
Sugarcane bagasse 1.41 mmol/g 1–30 mg/L 48 h 30◦ C –
Pure cellulose 1.34 mmol/g 1–30 mg/L 48 h 30◦ C –
Rice hull 1.32 mmol/g 1–30 mg/L 48 h 30◦ C –
Raw wheat residue 0.02 mmol/g 50–500 mg/L 150 min 23 ± 2◦ C 6.8
Modified wheat residue 2.08 mmol/g 50–500 mg/L 150 min 23 ± 2◦ C 6.8
Impregnated almond shell activated carbon 16–17 mg/g 10–50 mg/L 120 min 20◦ C 6.2
Wheat straw charcoal 1.10 mg/g 0–25 mg/L 10 min 15◦ C –
Wheat straw charcoal 1.30 mg/g 0–25 mg/L 10 min 15◦ C –
Commercial activated carbon 1.22 mg/g 0–25 mg/L 10 min 15◦ C –
Zr(IV)-loaded sugar beet pulp 63 mg/g – 24 h 25◦ C 6.0
Chemically modified sugar beet bagasse 9.14–27.55 mg/g 10–200 mg/L – 25◦ C–45◦ C 6.58
Original and activated red mud 1.859 and 5.858 mmol/g 5–250 mg/L 60 min Room temp. 6.0
Sepiolite activated by HCl 38.16 mg/g 100 mg/L 5 min – –
Unmodified sepiolite 408 mmol/kg – – – –
Surfactant-modified sepiolite 453 mmol/kg – – – 2.0
Cross-linked and quaternized chinese reed 7.55 mg/g 10–40 mg/dm3 10 min 25◦ C 5.8
Ammonium-functionalized mesostructured silica 46.0 mg/g 100–700 mg/L 60 min 5◦ C <8.0

Fig. 40. Proposed four stage mechanism of dye adsorption.

low capital requirement. Safe water has become a competitive resource in many parts of the world due to increasing
population, prolonged droughts, climate change, and so forth. Number of methods has been developed for purification of
232 N.B. Singh et al. / Environmental Technology & Innovation 11 (2018) 187–240

Fig. 41. Schematic diagram representing the concept of modelling the equilibrium adsorption of copper cyanide onto activated carbon.

water but adsorption method has been found to be efficient and effective. Various types of adsorbents have been used for
removal of different pollutants from wastewater. In recent years the use of nanomaterials in water remediation has increased
considerably. Adsorption efficiency is found to depend on the type of adsorbent, adsorbate, pH of solution, concentration of
pollutant and temperature. Removal of pollutants has been discussed on the basis of different isotherm and kinetic models.
However, there are various aspects related to adsorbents, which require detailed investigations. Attempts are needed to
optimize the process parameters and laboratory scale experiments require commercialization.

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