Journal of Environmental Management 217 (2018) 123e143

Contents lists available at ScienceDirect

Journal of Environmental Management

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

Review

A review on acrylic based hydrogels and their applications in

wastewater treatment
Parisa Mohammadzadeh Pakdel, Seyed Jamaleddin Peighambardoust*
Faculty of Chemical and Petroleum Engineering, University of Tabriz, Tabriz, 51666-16471, Iran

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

Article history: The acrylic based hydrogels have attracted the attention of many researchers in the field of pollutants
Received 5 October 2017 adsorption such as dyes and metal cations due to their high swelling and adsorption capacities. This
Received in revised form review introduces acrylic based hydrogels and focuses on their adsorption properties. We first described
26 February 2018
the methods for synthesizing hydrogels. Usual methods of characterization of acrylic based hydrogels
Accepted 17 March 2018
Available online 5 April 2018
such as swelling, adsorption capacity and desorption efficiency of the pollutants have been investigated.
In addition, the adsorption isotherm and kinetic models which determine the mechanism of pollutants'
adsorption by hydrogels have been introduced and relations that determine the values of thermody-
Keywords:
Acrylic based hydrogels
namic parameters which define accomplishment of adsorption process have been investigated. In the
Wastewater treatment following sections, a perfect insight has been provided on natural and synthetic acrylic based hydrogels.
Adsorption mechanism The effective parameters of swelling and adsorption by acrylic based hydrogels have been reviewed and
Crosslinking. contents the mechanism of pollutant's adsorption by acrylic based hydrogels has been discussed.
© 2018 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
2. Preparation of hydrogels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
2.1. Physical crosslinking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
2.1.1. Crosslinking with hydrogen bonding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
2.1.2. Crosslinking with hydrophobic interactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
2.1.3. Crosslinking by crystallization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
2.1.4. Crosslinking by ionic interactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
2.2. Chemical crosslinking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
2.2.1. Crosslinking by aldehydes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
2.2.2. Crosslinking by condensation reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
2.2.3. Crosslinking by free radical polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
2.2.4. Crosslinking by radiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
3. Methods of measuring and investigating the adsorption properties of hydrogels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
3.1. Swelling measurement of hydrogels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
3.2. Evaluation and measurement of pollutants adsorption properties by hydrogel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
3.3. Study of the regeneration and reusability of hydrogels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
3.4. Determination of the adsorption mechanism by hydrogels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
4. Acrylic based hydrogels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
4.1. Acrylic based natural hydrogels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
4.1.1. Acrylic based chitosan hydrogels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
4.1.2. Acrylic based cellulose hydrogels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
4.1.3. Acrylic based starch hydrogels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133

* Corresponding author.
E-mail address: j.peighambardoust@tabrizu.ac.ir (S.J. Peighambardoust).

https://doi.org/10.1016/j.jenvman.2018.03.076
0301-4797/© 2018 Elsevier Ltd. All rights reserved.
124 P. Mohammadzadeh Pakdel, S.J. Peighambardoust / Journal of Environmental Management 217 (2018) 123e143

4.1.4. Acrylic based alginate hydrogels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134

4.1.5. Other acrylic based natural hydrogels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136
4.2. Acrylic based synthetic hydrogels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136
4.2.1. Acrylic based polyvinyl pyrrolidone hydrogels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136
4.2.2. Acrylic based polyvinyl alcohol hydrogels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138
4.2.3. Acrylic based polyacrylamide hydrogels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139
5. Future perspective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139
6. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140
Abbreviations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140

1. Introduction be noted that by increasing the functional groups of hydrogels, free

ions are increased. On the other hand, electrostatic repulsion be-
The rapid growth of industrial activities has caused environ- tween the ions along the chains causes swelling increment (Bao
mental contaminants. Heavy metals and industrial dyes are the et al., 2012). In polyelectrolyte hydrogels, the osmotic pressure is
main pollutants of water resources in many parts of the world. calculated by equation (1):
Unlike organic pollutants, inorganic pollutants are not biodegrad- X 
g
able. These contaminants cause genetic and physiologic problems p ¼ RT ci  csi (1)
in living organisms even at low concentrations. For example, Pb2þ i
damages nervous system, hematopoietic system, and kidneys or
Ni2þ damages lung and skin. Methods such as chemical deposition, where R is the gas constant, T is the absolute temperature, ci is the
ion exchange, electrochemical removing, adsorption, coagulation, molar concentration of mobile i ion and sigma is the sum of all
flocculation, membrane separation have been proposed to over- moving ions present in the gel phase and the surrounding solution,
come these contaminants (Jang et al., 2008; Fu and Wang, 2011). specified by subscripts g and s, respectively (Su and Okay, 2017).
Among these methods, adsorption due to its low cost, the simplicity External solution properties such as charge capacity and salt con-
of design and high efficiency is better than other methods (Liu et al., centration affect the swelling of hydrogels. Swelling of hydrogels,
2015). The use of polymeric materials as adsorbents has received especially ionic hydrogels, in salt solutions is less than distilled
the attention of many researchers. In this regard, hydrogels are the water. The type of salt and its concentration can be expressed in
newest adsorbents that are used in the adsorption of water pol- terms of ionic strength. Thus, according to the Flory equation (Eq.
lutants. Their unique properties are good mechanical properties, (2)), the rate of swelling decreases with increasing ionic strength.
easy to use and reusability. Hydrogels are three-dimensional, .   
i 2Vu S2 þ 12  c1 V1
1
porous, hydrophilic, physical and chemical crosslinking networks 5
that swell thousands time of their dry weight in the vicinity of Q z 2
VE
(2)
water or biological fluids (Hoffman, 2002). These materials can V0
respond to specific changes in their environment such as temper-
ature, pH, magnetic field, and the electric field which determines where Q is the degree of swelling, Viu is the polymer charge density,
 
their application in the fields of medicine, tissue engineering
S is the ionic strength of the solution, 12  c1 V1 is the affinity of
(Pensalfini et al., 2017), wound dressing (Rakhshaei and Namazi,
2017), biosensors (Jona
sova

and Stokke, 2016), pharmaceutical the polymer and solvent and VE
is the crosslinking density. The
V0
(Treenate and Monvisade, 2017), agriculture (Guilherme et al., diffusion process in hydrogels depends on the solvent diffusion rate
2015) and adsorption (Khan and Lo, 2017). Recently, hydrogels and the relaxation of the polymer chains so it is categorized into
have found a special place in the field of wastewater treatments. three types:
Factors affecting heavy metals and dyes adsorption of hydrogels are
the structure and composition of them, the type of pollutant, initial 1) Fickian diffusion: solvent diffusion rate is less than the rate of
concentration of pollutants in the feed solution, treatment time, chain relaxation ðRdiff < Rrelax Þ:
temperature and pH of pollutant solution so the effect of these 2) Non-Fickian diffusion: the solvent diffusion rate is greater than
parameters on adsorption properties of hydrogels should be stud- the rate of the chain relaxation ðRrelax < Rdiff Þ:
ied (Abd El-Mohdy et al., 2013). Common functional groups that are 3) Anomalous diffusion: the solvent diffusion rate is approximately
used in synthesizing hydrogels include carboxylic acids, amides, equal to the rate of chain relaxation.
amines, hydroxyl and sulfonic acid. Super-absorbent hydrogels
swell because of water penetration at pre-existing or dynamically To determine the type of diffusion process, the following rela-
formed distances between polymer chains (Zheng et al., 2011). Due tion is used:
to ionization of hydrogel's functional groups, certain charges in the
polymer's chains and free counter ions in the gel phase are created F ¼ Kt n (3)
that these free counter ions can't go out of the hydrogel network.
The existence of charge in the network of this hydrogel which is where F is fractional uptake at time t, k is the polymer network
called polyelectrolyte leads to the osmotic pressure difference be- constant and n is diffusion power which determines the type of
tween the gel and the aqueous phase. The osmotic pressure dif- diffusion process. If 0.45 < n < 0.5, then diffusion type is Fickian and
ference acts as the driving force that leads to the penetration of if 0.5 < n < 1, then there is a Non-Fickian diffusion (Thakur et al.,
water until the pressure difference gets zero. As a result, whatever 2016). Acrylic acid and methacrylic acid, as shown their structure
free counter ions concentration increases, the pressure difference in Fig. 1, are common monomers in the synthesis of superabsorbent
will be enhanced so this leads to high swelling of the gel. It should hydrogels (Ferfera-Harrar et al., 2015). In the structure of these
 P. Mohammadzadeh Pakdel, S.J. Peighambardoust / Journal of Environmental Management 217 (2018) 123e143
Fig. 1. Common acrylic base monomers in preparing hydrogels; a) acrylic acid b)
methacrylic acid.
monomers, there is an acidic group eCOOH, which plays an
important role in the adsorption and swelling properties of
hydrogels. These monomers can be present in the structure of
hydrogel structure in the form of graft, copolymer, and IPN
network, and change the charges, molecular chain aggregation,
hydrophobicity, response to stimuli, rheological behavior, and
application extent of the hydrogel (Sharma et al., 2015).
Due to the presence of oxygen atoms, acrylics have the ability to
form complex with metal cations and cationic dyes (Yetimog lu
et al., 2007). Also, the hydrogen bond between the polymer
chains, water molecules and dyes are established because of the
presence of eOH group. Due to the weak acidity of the carboxylic
group, the behavior of acrylic based hydrogels is sensitive to pH
(Sakthivel et al., 2016; Wang et al., 2010). pH-sensitive hydrogels
are classified into two groups anionic and cationic. Anionic
hydrogels have carboxylic or sulfonic acid pendant groups and
cationic hydrogels have pendant groups such as amines (Ullah et al.,
2015). Acrylics are anionic polyelectrolytes whose carboxylic group
is not ionized at pH values less than pKa. So, the rate of swelling and
adsorption of cationic metals and dyes by acrylic based hydrogel is
low. In the pH values greater than pKa, this group is ionized and the
hydrogen bond between the polymeric chains is broken up which
leads to hydrogel swelling increment. The created carboxylate
group (eCOO-) improves the cationic metal and dye adsorption.
Also, electrostatic repulsion between the polymeric chains in-
creases the amount of hydrogel swelling (Şolpan and Ko €lge, 2006).
The mechanism of metal cations adsorption for polymers con-
taining this group is as follows.
RCOOH4RCOO þ Hþ
nRCOO þ Mnþ 4ðRCOOÞn M
In this review article, we have investigated recent efforts on
acrylic based hydrogels for the preparation, swelling, adsorption of
dyes and heavy metals. For easiness of pollutants adsorption
investigation, acrylic based hydrogels are classified into two
categories:
- Natural acrylic based hydrogels
- Synthetic acrylic based hydrogels
2. Preparation of hydrogels
Hydrogels depend on nature of polymer were prepared by two
methods of physical and chemical crosslinking. In the physical
crosslinking method that leads to the production of reversible
hydrogels, there are physical interactions and in the chemical
crosslinking method, there are covalent bonds between the poly-
mer chains. Crosslinked hydrogels do not dissolve in various
125
solvents, but swell in the presence of them. Physically networked
hydrogels have been widely used in medical and pharmaceutical
fields due to the lack of use of the crosslinking agent, which is toxic
in most cases. Chemical crosslinking methods are effective and
common methods for preparation of hydrogels. The chemical
crosslinked hydrogels have better mechanical properties and sta-
bility compared to the crosslinked physical hydrogels. Researchers
have shown that crosslinking degree of hydrogels increment leads
to mechanical strength improvement, but it reduces swelling and
adsorption capacity by decreasing the elasticity of the polymer
chains. Therefore, in synthesis of hydrogels, the optimal crosslinker
amount should be determined (Ebara et al., 2014). Physical
networking methods for the synthesis of hydrogels include the
following, which are described below (Maitra and Shukla, 2014).
2.1. Physical crosslinking
2.1.1. Crosslinking with hydrogen bonding
Hydrogen bonding is one of the methods used to generate
physical cross-linking networks. Blends of polymers such as chi-
tosan, itaconic acid, and methacrylic acid because of the presence of
the amino group in chitosan, and carboxylic group in itaconic acid
and methacrylic acid, create networks with hydrogen bonding in
acidic mediums. This bond is sensitive to pH and is deactivated by
the deprotonation of the carboxylic group (Milosavljevi
c et al.,
2011b). Therefore, other networking methods are recommended
especially when hydrogels are used for purifying alkaline
wastewaters.
2.1.2. Crosslinking with hydrophobic interactions
Creating crosslink bonds with hydrophobic interactions is a
common method for the preparation of hydrogels and micelles.
One of the methods for improvement of hydrogel's toughness is the
addition of hydrophobic monomers as graft and block copolymers
to hydrophobic monomers. Researchers have shown that hydro-
phobic interactions between hydrophobic chains act as reversible
crosslinking and effectively eliminate crack energy (Chen et al.,
2016). Energy dissipation by this links prevents hydrogel
breakage. By increasing hydrophobic monomers, the entanglement
of chains increases, resulting in more energy dissipation due to
applying load (Liu et al., 2017).
(4)
2.1.3. Crosslinking by crystallization
In this method, formed gels with low mechanical strength and
(5) resistance are subjected to freeze and thawing process which in-
duces crystallization. Mechanical strength and swelling of the
formed gels depend on the number of cycles and the duration of
each cycle. For example, a suspension of PVA/PVP/HA stays for
10 h at a temperature of 15  C. Then they are placed at room
temperature for 2 h. This freeze and thawing cycles is repeated 5
times to produce the desired hydrogel (Ma et al., 2016).
2.1.4. Crosslinking by ionic interactions
Physical crosslinked networks by ionic interactions depending
on the type of used crosslinker are classified into two groups
anionic and cationic. Cationic crosslinkers are usually metal cations
such as Naþ, Ca2þ, Pt2þ, Mo6þ, Fe3þ and the common anionic
crosslinkers are phosphate groups such as b-glycerophosphate and
tripolyphosphate. For example, the chitosan biopolymer is a poly-
cation that can be crosslinked by ionic interaction. In the acidic
medium, amine groups of this polymer are converted into cationic
ammonium groups which by establishing an electrostatic interac-
tion with anionic crosslinkers such as sodium triphosphate, chito-
san becomes water-insoluble gels and deposits as beads in these
126 P. Mohammadzadeh Pakdel, S.J. Peighambardoust / Journal of Environmental Management 217 (2018) 123e143
crosslinker solution (Farhoudian et al., 2016). Another method for
crosslinking with electrostatic interactions is the use of polymers
with opposite charges, which results in the formation of poly-
electrolyte complexes. The stability of polyelectrolyte complexes
depends on temperature, pH, density, ion strength and solvent
(Aminabhavi and Dharupaneedi, 2017). Chitosan and alginate
hydrogels are a polyelectrolyte complex because chitosan is a
cationic polysaccharide and alginate is an anionic polysaccharide
(Martins et al., 2015).
2.2. Chemical crosslinking
2.2.1. Crosslinking by aldehydes
Aldehydes, such as formaldehyde, acetaldehyde and glutaral-
dehyde are used for the crosslinking of hydrogels because of their
low cost and availability. Polymers that have hydroxyl groups
require strict conditions (low pH, high temperature, etc.) for cross-
linking with aldehydes while polymers that have an amine group in
their structure are crosslinked with these crosslinking agents in
conventional conditions (Singh et al., 2006). For example, the
mechanism of cross-linking chitosan by formaldehyde has been
shown in Fig. 2.
2.2.2. Crosslinking by condensation reactions
In condensation reactions, two molecules that contain func-
tional groups are combined together. In addition to the large
molecule production by this reaction, other side products such as
water are produced (Marsh et al., 1977).
2.2.3. Crosslinking by free radical polymerization
One of the methods of crosslinking for hydrogels preparing is
free radical polymerization in the vicinity of a crosslinking agent
such as MBA. This method consists of three stages of initiation,
propagation, and termination. In the first step, a chemical initiator
such as potassium persulfate and tetramethylene-diamine
(TEMED) that generates free radicals in the vicinity of heat, or
gamma (Fekete et al., 2016) or ultraviolet radiation, is used to
initiate the reaction. By free radical reaction with the monomers,
radicals of monomers are produced and react with other mono-
mers, so the growth of the chains occurs. During the growth of the
chains, the crosslinker is added and randomly reacts with chains
and the three-dimensional network is generated. Finally, termina-
tion is accomplished by combination or disproportionation
Fig. 2. The crosslinking mechanism of chitosan by formaldehyde (reprinted with permission from (Sadeghi et al., 2016)).
reactions. In the combination reaction, growing chains constitutes a
long chain and in the disproportionation reaction, a hydrogen atom
is reduced from the end of a chain and is added to the end of the
other chain resulting in a polymer with the saturated end group
and a polymer with an unsaturated end group (Khan and Lo, 2016).
This crosslinking method results in the fast preparation of hydrogel
even under mild conditions (room temperature and pH 7) (Hennink
and van Nostrum, 2012).
2.2.4. Crosslinking by radiation
In this method, cross-linking of the hydrogel by g radiation,
electron beams, and ultraviolet light radiation is carried out at room
temperature without the need of the crosslinking agent and cata-
lyst (Delbecq et al., 2013). This method is a safe and effective way to
prepare a hydrogel due to easiness of controlling the process
without the use of crosslinking agent. Proposed synthetic and
natural polymers for the synthesis of crosslinked hydrogels by this
method include PEG, PVA, PVP, HA, Gelatin, Alg, CS, and CMC (Abd
El-Mohdy, 2007; Gaharwar et al., 2013). For example, with g radi-
ating, PVP and MAA solutions covalent crosslinked network forms
that crosslinking density, swelling, and gelatinizing depend on the
dose and duration of the radiation (Şolpan and Ko €lge, 2006). This
method of crosslinking like free radical polymerization method is
composed of three stages of initiation, propagation, and termina-
tion. When the polymer solution is exposed to radiation, a free
radical of hydroxyl formed which results in the production of free
radical monomers. When the network reaches the critical point of
gelling, the hydrogel is formed (Maitra and Shukla, 2014).
3. Methods of measuring and investigating the adsorption
properties of hydrogels
In this section, methods for measuring and evaluating the
properties of hydrogels such as swelling, pollutant adsorption,
regeneration, reusability, and adsorption mechanism are
presented.
3.1. Swelling measurement of hydrogels
The performance of hydrogels depends on the amount of water
adsorption which in turn affects the adsorption of pollutants. As
water adsorption by the hydrogel is increased, the pollutants
adsorption is improved, but high swelling reduces the mechanical
 P. Mohammadzadeh Pakdel, S.J. Peighambardoust / Journal of Environmental Management 217 (2018) 123e143
strength of the hydrogel. Water as a carrier of contaminants makes
them easy to penetrate into hydrogels. Therefore, the quantitative
measurement of swelling can be as a quantitative measure of
acrylic based hydrogel performance. Weight measurement is the
most common method for measuring the swelling of hydrogels. In
this method, a specific amount of hydrogel (Wdry) is placed in
distilled water and distilled water is discharged in certain time
periods and the water present on the surface is taken by filter paper
and its weight (Wwet) was measured. This process continues as long
as water adsorption gets constant. The equilibrium water adsorp-
tion value is determined by the difference between the weights of
wet hydrogel from the dry hydrogel, as follows (Sheikh et al., 2010):
Wwet Wdry
Water uptake ¼  100
Wdry
The most important factors affecting water adsorption of
hydrogel include pH, crosslinker, and temperature.
3.2. Evaluation and measurement of pollutants adsorption
properties by hydrogel
A quantitative study of the rate of adsorption by hydrogels is
very important because it shows their application. In order to
determine the adsorption capacity, acrylic based hydrogels are kept
in contact with a dye or metal cation solution with a specified
concentration in a batch state. Then, the concentration of residual
pollutants in the solution is measured as a function of the various
parameters by vis spectrophotometry until the amount of equilib-
rium adsorption is obtained. The following relationships are used to
determine the equilibrium adsorption capacity (qe), removal effi-
ciency (R%), retention capacity (Qr) and uptake percent (Pu):
ðC0 Ce ÞV mg
qe ¼ ; (7)
W g
C0 Ce
R¼  100
C0
Amount of metal ion in polymer ðmEqÞ
Retention capacityðQrÞ ¼
Weight of dry polymer ðgÞ
Amount of metal ion in the polymer
Percent uptakeðPuÞ ¼
Amount of metal ion in feed
 100
(10)
In the above relations, C0 is initial concentration of the pollutant
and Ce is the final concentration of the pollutant, V is the volume of
solution and W represents the amount of dry hydrogel
(Bhattacharyya and Ray, 2015). The hydrogel adsorption capacity is
a function of different parameters such as temperature, pH, con-
centration, adsorbent amount, contact time and ionic strength of
the contaminating solution. Adsorption kinetics is one of the
important aspects of the design of adsorbents. An adsorbent for
127
industrial use should not only have high adsorption capacity but
also a high adsorption rate. In order to investigate the adsorption
rate, the amount of adsorption of the pollutant is determined at
specific times and the data are fitted to different models.
Commonly used models for the study of adsorption of pollutants by
hydrogels include pseudo first order (PFO) (Azizian, 2004), pseudo
second order (PSO) (Ho, 2006), intraparticle diffusion (IPD) (Wu
et al., 2009b), and Elovich (Wu et al., 2009a). Table 1 shows the
linear and nonlinear forms of these models. By determining the
kinetic model governing the process, the adsorption mechanism
and the potential adsorption rate limiting steps can be understood
(Zhang et al., 2016). According to Tables 3 and 4, it can be seen that
the pseudo-second order, which represents adsorption by electro-
static interaction, is the governing model in most of the adsorption
(6)
process by hydrogels. Comparison of Tables 3 and 4 shows that
acrylic based polysaccharide hydrogels have a higher rate of
adsorption than acrylic based synthetic hydrogels.
The adsorption isotherms show how the adsorbed molecules
are distributed in the liquid and solid phases when the adsorption
process reaches equilibrium (Li et al., 2013). The adsorption
isotherm is measured by determining equilibrium concentrations
and the equilibrium adsorption capacity at a constant temperature.
Isotherms that are commonly used to examine the adsorption
process include Langmuir (Mittal and Ray, 2016), Freundlich (Wang
et al., 2016), Tempkin (Sharma et al., 2017a,b), and Redlich-Peterson
(Zheng and Wang, 2009), which R2 (Linear Regression Coefficient)
determines the governing model. The mathematical equations for
these isotherms are shown linearly and nonlinearly in Table 2.
Langmuir isotherm is the most common isotherm that is consistent
with experimental data (Tables 3 and 4).
The study of thermodynamic parameters variation during the
adsorption process is important because it determines the feasi-
bility and the mechanism of the adsorption process. The thermo-
dynamic parameters include the standard free Gibbs energy of
(DG0), the standard enthalpy change (DH0), and the standard en-
tropy change (DS0) which is calculated by the following
relationships:
(8)
DH0 DS0
LnKC ¼  þ (11)
RT R
(9)
DG0 ¼ DH0  TDS0 (12)
In the above relations, KC is equilibrium constant, R is the global
gas constant and T is absolute temperature. DH0 and DS0 are ob-
tained by the slope and intercept of the LnKC versus 1/T plot,
respectively (Nandi et al., 2009; Sharma et al., 2017a,b). The DG0
sign specifies the feasibility of the process so that the negative value
of this parameter indicates the spontaneous adsorption process.
Negative and positive values of DH0 represent exothermic and
endothermic adsorption process, respectively and positive DS0 in-
dicates randomness increment at the interface between the
contaminated solution and the gel during the adsorption process
(Yu et al., 2013; Ge et al., 2017).
128 P. Mohammadzadeh Pakdel, S.J. Peighambardoust / Journal of Environmental Management 217 (2018) 123e143

Table 1
Common kinetic models of heavy metal and dye adsorption.

Nonlinear form Linear form Plot

Pseudo-first order dqt

¼ k1 ðqe  qt Þ Lnðqe  qt Þ ¼ Lnqe  k1 t Lnðqe  qt Þ vs t
dt
Pseudo-second order t 1 1 t
dqt 2
¼ k1 ðqe  qt Þ qt ¼ qe tþ k2 q2e qt vs t
dt
Intraparticle diffusion qt ¼ kdi t 0:5 þ B qt vs t 0:5
 
Elovich dqt
¼ a expð  bqt Þ 1 lnðabÞ þ 1 LnðtÞ qt vs LnðtÞ
dt qt ¼ b b

Table 2
Common isotherm models of heavy metal and dyes adsorption.

Isotherm Nonlinear form Linear form Plot Assumptions

Langmuir qe ¼ q m KL C e Ce
¼ Ce
þ 1 Ce
vs Ce Homogeneous distribution of the sorption sites and
1þKL Ce qe qm qm KL qe
sorption energies, monolayer adsorption
Freundlich qe ¼ KF Cen
1
Lnðqe Þ ¼ LnðKF Þ þ 1n LnðCe Þ Logqe vs log Ce Heterogeneous surface with non-uniform heat of
adsorption, multilayer adsorption
Tempkin qe ¼ RT LnaC qe ¼ RT LnKT þ RT LnCe qe vs Ce Uniform distribution of binding energies
bt e
 bT  bT  
Redlich-Peterson qe ¼ kRP Ce Combination of Langmuir and Freundlich model
1þaR Ce
bRP Ln kRP Cqee  1 ¼ bRP LnðCe Þ þ LnðaRP Þ LnðCe Þ vs Ln kRP Cqee  1

3.3. Study of the regeneration and reusability of hydrogels
The ability to recover and reuse are the most important
hydrogel's properties for the industrial application. In addition to
having a high capacity and absorption rate, a hydrogel must be able
to be regenerated to be economically affordable. Solutions that are
used to regenerate the hydrogel are usually based on acids or al-
kalines (Khan and Lo, 2017). HCl, HNO3, and NaOH are the most
important solutions used to regenerate hydrogels. Selection of
appropriate solution, concentration, optimal time and volume are
the most important parameters that should be considered in the
regeneration of hydrogels. The quantitative measurement of
desorption efficiency is performed by the following relationships:
Mdesorbed Cr  Vr
Desorption efficiency ¼  100 ¼
Msorbed ðC0 Ce Þ  V
q of dye and eOH of hydrogel (Thakur et al., 2016). Adsorption
Desorption ratio ¼
qe
In the above relations, Msorbed is the amount of adsorbed
contaminant into the hydrogel, Mdesorbed is the amount of desorbed
contaminant from the hydrogel, Cr is the concentration of the
contaminated solution after the regeneration, Ce is equilibrium
concentration of the contaminated solution, C0 is the initial con-
centration of the contaminate in the solution, V is volume of the
feed solution, Vr is volume of the regeneration solution, q is the
desorption capacity and qe is the adsorption capacity. To study the
reusability of hydrogels, adsorption and desorption experiments
should be carried out over several successive cycles (Sahraei et al.,
2016; Khan and Lo, 2017).
3.4. Determination of the adsorption mechanism by hydrogels
Understanding the mechanism of adsorption is very important
for further investigating the process of dyes and heavy metals
removal onto different adsorbents, however it is a difficult and
challenging work to characterize the adsorption mechanism of dyes
and heavy metals by hydrogels. Some researchers have studied in
the areas. They suggest that the most of adsorption mechanisms of
dyes and heavy metals onto the hydrogels depending on the
chemical structure of them include different interactions like
electrostatic interaction, hydrogen bonding, hydrophobic interac-
tion between non-polar components of dye molecules and hydro-
gels, complexation, ion exchanging, and the combination of
proposed mechanisms (Khan and Lo, 2016). Ngwabebhoh et al.
(2016a,b) investigate adsorption mechanism of Cu2þ and anionic
nitrazine yellow (NY) dye by chitosan-montmorillonite hydrogel.
They implied that eNH2 groups of chitosan are more responsible to
adsorption of Cu2þ and NY dye. At pH < 5.6, eNH2 groups are in
protonated form (eNHþ 3 ) so NY dye is adsorbed to hydrogel through
electrostatic interaction. As the pH is increased, eNHþ 3 groups are
transformed to NH2 groups, so nitrogen atoms share their lone pair
of electrons with Cu2þ and NY dye to form complex (Ngwabebhoh
et al., 2016a,b). Thakur et al. (2016) proposed that the adsorption
mechanism of methyl blue (MB) on sodium alginate-cl-poly (acrylic
 100
acid)/ TiO2 hydrogel might be due to electrostatic attraction be-
(13) tween cationic dye and carboxylate groups on hydrogel and
hydrogen bonding interaction between imines groups eRCH]NR
(14) mechanism of Pb2þ on sodium alginate-carboxymethyl cellulose
gel beads was investigated by Ren et al. (2016) They reported that
the adsorption mechanisms of Pb2þ on hydrogel consist of the
following: 1) Complexation: given that O ineOH and CeOO- of gel
beads could share its lone pair electron with Pb2þ ions; 2) Elec-
trostatic attraction: Gel bead surface is negatively charged, but
pollutant is a positively charged heavy metal (Ren et al., 2016).
Various methods have been suggested to determine adsorption
mechanism such as FTIR, XPS, SEM-EDX, and XRD. Investigating the
results of these analyses before and after the adsorption of pol-
lutants provides useful information about the adsorption mecha-
nism. For example, Wang et al. (2009) employed XPS to
characterize adsorption mechanism of Sr2þ by carboxymethyl cel-
lulose, carboxymethylated chitosan and hydroxypropyl methylcel-
lulose phthalate hydrogels. Analysis results show that Naþ peaks
gets weakened or disappear after heavy metal adsorption, so
adsorption mechanism is ion exchange and Sr2þ ions replace Naþ
ions (Wang et al., 2009). In another study, Orozco-Guaren ~ o et al.
(2010) analyzed the FTIR spectra of poly (acrylic acid-co-
acrylamide) hydrogel before and after Cu2þ adsorption and their
analysis results showed that eNH2 and eOH groups of hydrogels
are involved in the complexation with Cu2þ ions (Orozco-Guaren ~o
et al., 2010).
 P. Mohammadzadeh Pakdel, S.J. Peighambardoust / Journal of Environmental Management 217 (2018) 123e143 129

4. Acrylic based hydrogels
4.1. Acrylic based natural hydrogels
Natural hydrogels are widely used in various fields, such as
wastewater treatment, drug delivery, and agriculture, due to their
biodegradability, non-toxicity, biocompatibility, and hydrophilicity.
These hydrogels are based on polysaccharides (hyaluronic acid,
starch, alginate, chitosan, and cellulose), proteins (collagen,
gelatin), and DNA (Shi et al., 2016). As protein hydrogels are more
widely used in the medical field and little research has been done
on the wastewater treatment of these type hydrogels, in this sec-
tion only polysaccharide hydrogels will be investigated. Due to
their unique properties, polysaccharide hydrogels have received
special attention in the field of industrial wastewater treatment.
Due to the presence of oxygen atoms and, in some cases, nitrogen
atoms in their structure, polysaccharides are chelating polymers
that can form complexes with metal cations. One of the
disadvantages of these natural hydrogels is their low mechanical
strength which is enhanced by the addition of inorganic materials
or synthetic polymers. A lot of research has been carried out on the
adsorption of pollutants by acrylic based polysaccharide hydrogels.
Table 3 shows the comparison of adsorption properties of acrylic
based polysaccharide hydrogels.
4.1.1. Acrylic based chitosan hydrogels
Chitosan (CS) is a linear polysaccharide that is produced by the
random distribution of b- (1 / 4) -linked ɒ-glucosamine (deace-
tylation unit) and N-acetyl-ɒ-glucosamine (acetylated unit). It is
the second most abundant natural polymer after cellulose that is
obtained by deacetylation of chitin. Nowadays, chitosan due to its
non-toxicity, high adsorption potential, biodegradability, biocom-
patibility, economic cost-effectiveness, the ability to remove a wide
range of dyes and cationic heavy metals, fast kinetics, and finally
the availability of producing many derivatives from it has found a
special place in industrial wastewater treatment. Chitosan has

Table 3
Natural acrylic based hydrogel adsorption properties.

Hydrogel Pollutant Initial pollutant Sample qae tbe pHc Kinetic Isotherme Adsorption mechanism Ref.
concentration dose modeld

CS-g-PAA/Fe2O3 Cd2þ 400 mg/L 0.8 g/L 308.84 mg/g 10 min 7 P-2 L e (Zhu et al.,
2016)
CS-g-PAA/Fe2O3 Pb2þ 600 mg/L 0.8 g/L 695.22 mg/g 5 min 7 P-2 L e (Zhu et al.,
2016)
CS-g-PAA Ni2þ 100 mg/L 2 g/L 46.52 mg/g 30 min 7 p-2 e Chelating interactions (Zhu et al.,
2016)
CS-g-PAA/VMT MB 1000 mg/L 0.25 g/L 1683.7 mg/g 90 min 7 P-2 L Electrostatic interactions (Liu et al.,
2010b)
CS/IA/MAA Cu 2þ
408 mg/L 0.7 g/L 122.6 mg/g 40 h 5.5 P-2 RP Combination of chelation and (Milosavljevi
c
electrostatic interactions et al., 2011a)
CPCS CR 100 mg/L 1 g/L 84 mg/g 1700 min 7 P-2 Combined Combination of hydrogen bonding (Mandal and
L-F and electrostatic interactions Ray, 2014)
SCPCS CR 100 mg/L 1 g/L 88 mg/g 1700 min 7 P-2 Combined Combination of hydrogen bonding (Mandal and
L-F and electrostatic interactions Ray, 2014)
CPCS MV 100 mg/L 1 g/L 75 mg/g 1400 min 7 P-2 Combined Electrostatic interactions (Mandal and
L-F Ray, 2014)
SCPCS MV 100 mg/L 1 g/L 78 mg/g 1400 min 7 P-2 Combined Electrostatic interactions (Mandal and
L-F Ray, 2014)
CMC-g-PAA/ATP Pb2þ 3000-4500 mg/L 4 g/L 847.46 mg/g 60 min 5.55 P-2 L Combination of Complexation and (Liu et al.,
ion exchange 2010a)
2þ
St-g-PAA/SH Cu 0.02 mol/L 2 g/L 2.8 mmole/ 10 min 4.68 P-2 L Combination of ion exchange and (Zheng et al.,
gr chelation 2010)
2þ
St-g-PAA/MMT Cu 8 mmol/L 4 g/L 1.6 mmol/g 24 h 4 P-2 F Electrostatic interactions (Güçlü et al.,
2010)
NaAlg-g-P(AA-co-AAm)/ MB 25 mg/L 2 g/L 12.46 mg/g 8h e P-2 F Electrostatic interactions (Rashidzadeh
Clin et al., 2015)
P(AA-co-HEMA)/ NaAlg CR 10-140 mg/L 1 g/L 85 mg/g 1800 min 7 P-2 & L& F-S Electrostatic interactions (Mandal and
IPD Ray, 2013)
P(AA-co-HEMA)/ NaAlg MV 10-140 mg/L 1 g/L 81 mg/g 1800 min 7 P-2 & L & F-S Electrostatic interactions (Mandal and
IPD Ray, 2013)
P(NaA-co-HEMA)/ NaAlg CR 10-140 mg/L 1 g/L 93 mg/g 1800 min 7 P-2 & L & F-Sr Electrostatic interactions (Mandal and
IPD Ray, 2013)
P(NaA-co-HEMA)/ NaAlg MV 10-140 mg/L 1 g/L 85 mg/g 1800 min 7 P-2 & L & FeS Electrostatic interactions (Mandal and
IPD Ray, 2013)
NaAlg-cl-PAA/TiO2 MB 75 mg/L 0.2 g/L 372.45 mg/g 100 min 7 P-2 L Combination of hydrogen bonding (Thakur et al.,
and electrostatic interactions 2016)
NaAlg-g-P(AA-co-St)/ MB 1000 mg/L 0.5 g/L 1843.46 mg/ 30 min 4 P-2 L Electrostatic interactions (Wang et al.,
(Organo-I/S) g e10 2013)
k-carrageenan-g- CV 30 mg/L 0.5 g/L 27.42 mg/g 15 min 7 P-2 L Electrostatic interactions (Gholami et al.,
poly(methacrylic acid)/ 2016)
Fe2O3
Gg-cl-PAA MB 50 mg/L 0.2 g/L 313.855 mg/ 75 min 7 P-2 L Electrostatic interactions (Fosso-Kankeu
g et al., 2015)
Gg-cl-PAA RhB 50 mg/L 0.4 g/L 141.88 mg/g 45 min 7 P-2 L Electrostatic interactions (Fosso-Kankeu
et al., 2015)
St-g-PAA/MMT Cu2þ 8 mmol/L 4 g/L 1.9 mmol/g 24 h 4 P-2 F Electrostatic interactions (Güçlü et al.,
2010)

Adsorption Capacity (a), Equilibrium time (b), pH value (or range) at which maximum adsorption occurs (c), P-1¼ Pseudo first order; P-2¼ Pseudo second order; E ¼ Elovich;
IPD¼ Intraparticle diffusion (d), L ¼ Langmuir; F¼ Freundlich; F-Z¼ FritzeSchlünder (e).
130 P. Mohammadzadeh Pakdel, S.J. Peighambardoust / Journal of Environmental Management 217 (2018) 123e143
reactive hydroxyl and amino groups which acts as a chelating site
for adsorption of metal cations and cationic and anionic dyes.
Therefore, it is an excellent agent for the synthesis of superabsor-
bent hydrogels. The number of free amino groups found in chitosan,
which determines the pka of this polymer, depends on the degree
and method of deacetylation process. By increasing DDA, chitosan
solubility is increased. Chitosan adsorbs proton in the acidic me-
dium due to presence of amino groups, so it is a cationic poly-
electrolyte capable of absorbing cationic dyes such as methyl blue
and anionic dyes like Congo red (Mandal and Ray, 2014; Yang et al.,
2016). The chitosan chemical structure is shown in Fig. 3.
Chitosan hydrogels are dissolved in weak acids, so chemical
crosslinking is used to increase the stability of these hydrogels, but
chitosan crosslinking, especially in lower pHs, reduces adsorption
capacity due to the use of amine groups during the crosslinking
process. Therefore, selecting the appropriate crosslinking method is
essential (Li and Bai, 2005). Chemical crosslinking agents are
commonly used to synthesize chitosan hydrogels, including
glutaraldehyde (GLA), epichlorohydrin (ECH), and ethylene glycol
diglycidyl ether (EGDE) (Li and Bai, 2006). Fig. 4 shows the struc-
ture of crosslinked chitosan hydrogel with GLA.
It should be noted that swelling of chitosan hydrogels is not only
pH responsive but also is temperature responsive. The
temperature-sensitive behavior of these hydrogels is due to the
presence of hydrogen bonding between amine groups of chitosan
which this bond dissociation is decreased by increasing tempera-
ture, so the relaxation of polymeric chains is reduced. By reducing
the relaxation of polymeric chains, the amount of water diffusion in
the network of these hydrogels is limited (Ngwabebhoh et al.,
2016a). The methods of chemical modification of chitosan hydro-
gels are grafting, creating IPN and semi-IPN networks with syn-
thetic monomers such as acrylics to improve mechanical
properties, adsorption of heavy metals and dyes of these hydrogels.
Zheng et al. (2011) reported the adsorption of Ni2þ by CS-g-PAA
hydrogel. They showed that pH is one of the important parameters
in adsorbing metal cations by this hydrogel because the surface
charge of the hydrogel is controlled by pH. At pH < 3, the carboxylic
group of hydrogels does not lose its proton, and there is hydrogen
bonding between polymeric chains. On the other hand, there is an
electrostatic repulsion between the protonated amine group and
the metal cations. Therefore, the adsorption capacity of Ni2þ is low.
They showed that by pH increment, the metal adsorption of
hydrogel capacity is increased which results from the deprotona-
tion of the carboxylic group and the formation of chelate in-
teractions between the polymer and the metal cations. The
operational pH should be in the range of 3e7 during the Ni2þ metal
adsorption process because at pH more than 7, this metal cation
precipitates (Zheng et al., 2011). As aforementioned, one of the
Fig. 3. Chemical structure of chitosan.
Fig. 4. The structure of crosslinked chitosan hydrogel with GLA (reprinted with
permission from (Ngwabebhoh et al., 2016b).
methods to improve the properties of hydrogels is the combination
of polymers network. These kinds of hydrogels are morphologically
classified into three types of full IPN, IPN, and semi-IPN (Hou and
Siow, 2001). IPN networks consist of a combination of two or
more separate crosslinked networks, and semi-IPN networks
interfere with the penetration of a linear polymer in a crosslinked
polymer network. The semi- IPN CS/PAA-GLA hydrogel was suc-
cessfully developed by Dai et al. (2010). The CS and PAA are miscible
due to the strong electrostatic interactions between the amino and
the carboxylic groups. The researchers investigated the adsorption
of Cu2þ by CS/PAA-GLA and CS-GLA hydrogels. The results showed
that blending of chitosan with polyacrylic acid increased the
adsorption of Cu2þ and improved its mechanical properties
compared to chitosan hydrogel (Dai et al., 2010). pH is not only a
factor affecting the surface charge of the hydrogel but also affects
the hydrogel morphology. In most studies, pH has been used to
control the porosity and pore size of pH-sensitive hydrogels.
Porosity is one of the important factors affecting the selectivity,
adsorption capacity, and the swelling of the hydrogel. High swelling
and adsorption capacity can be achieved by a well-defined porous
structure. Milosavljevi
c et al. (2011a) prepared CS/IA/MAA hydrogel
in two steps. At first step, CS was ionically crosslinked by IA. Then
free radical polymerization and crosslinking of CS/IA network were
performed with MAA and MBA. They investigated swelling of this
hydrogel in buffer solutions with pH 2.2 and 6.8. The results
showed that the swelling of this hydrogel in a buffer solution with
pH 6.8 was greater than pH 2.2, because according to the results of
the SEM analysis shown in Fig. 5, the hydrogel pore size at PH 6.8
was greater than pH 2.2 (Milosavljevi
c et al., 2011a). Later,
Milosavljevi
c et al. (2011c) examined the adsorption of Cu2þ by this
hydrogel. Their results showed that the absorption rate of Cu2þ at
pH 6.8 was greater compare to pH 2.2 and the optimum pH, in
which the highest adsorption value was equivalent to qe 7.5 mg/g
occurs, is 5.5 (Milosavljevi
c et al., 2011c).
Composite hydrogels have attracted the attention of many re-
searchers because of their low cost, high thermal stability, high
mechanical stability, high swelling, and adsorption capacity. Com-
mon non-organic materials in nano and micro sizes for the incor-
poration to hydrogels include clay (Zhang et al., 2014), GO (Huang
et al., 2012), Fe2O3 (Yu et al., 2013), TiO2 (Zhou et al., 2017), ZnO
(Wu et al., 2016), MnO2 (Hong et al., 2017) and so on. Clays, such as
montmorillonite, kaolin, mica, attapulgite, vermiculite are high-
surface silicate layers that contain reactive hydroxyl groups and
exchangeable cations. Clays show high affinity with cationic and
anionic dyes, but due to their negative charges, they exhibit higher
adsorption capacity for anionic dyes than cationic dyes. The dis-
tribution and weight fraction of clay particles affect the hydrogel
 P. Mohammadzadeh Pakdel, S.J. Peighambardoust / Journal of Environmental Management 217 (2018) 123e143
Fig. 5. SEM analysis of CS/IA/MAA hydrogels a) pH 2.2 b) pH 6.8 (reprinted with permission from (Milosavljevi
c et al., 2011a)).
adsorption capacity. The addition of clay to acrylic based hydrogels
can partially increase the adsorption capacity and its optimum
amount should be determined. The eOH group on the clay surface
reacts with eCOOH group of acrylic monomers which increases the
adsorption capacity. On the other hand, part of the eOH group on
the clay surface acts as cross-linking points. Therefore, by
increasing the weight percentage of clay, the elasticity of polymeric
chains is decreased which leads to a reduction in the adsorption
capacity of acrylic based hydrogels. Also, the number of hydrophilic
groups is decreased by increasing the amount of clay which leads to
the shrinkage of hydrogels and thus reduces the adsorption ca-
pacity of the hydrogel (Wang et al., 2011). Liu et al. (2010b) syn-
thesized CS-g-PAA/VMT composite hydrogels and investigated the
effect of weight percent of VMT on MB adsorption. The results
showed that by increment of the weight percentage of VMT up to
10%, the dye adsorption increased from 1571.21 to 1612.32 mg/g.
More than 10% increment of this clay resulted in adsorption
reduction of this cationic dye by hydrogel (Liu et al., 2010b). One of
the problems of hydrogel adsorbents, especially in the nano and
micro scales, is their separation after the adsorption process.
Various methods have been proposed for the separation of these
adsorbents, such as deposition, membrane technology, centrifugal
separation and magnetic separation. Magnetic separation is an
inexpensive, effective and rapid method for separating magnetic
hydrogels by applying external magnetic field. Zhu et al. (2016)
used an interesting method for the synthesis of CS-g-PAA macro-
porous hydrogel. They investigated the adsorption of Pb2þ and Cd2þ
metal cations by magnetic hydrogels synthesized from pickering
high internal phase emulsions template (HIPEs) stabilized by
modified Fe2O3 nanoparticles. Their results showed that these
hydrogels have a high adsorption rate for both cations due to the
excellent porosity of the hydrogel and the presence of sufficient
functional groups. The researchers used HCl to regenerate this
hydrogel. They showed that after five cycles of adsorption and
desorption, a slight change was observed in the adsorption capacity
of metal cations by the hydrogel, indicating its excellent reusability.
Fig. 6 shows adsorption capacity versus contact time at initial
concentrations of 50, 300 and 600 mg/L for Pb2þ and 50, 200 and
400 mg/L for Cd2þ at neutral pH and 30  C temperature (Zhu et al.,
2016).
Comparison of the adsorption capacity of anionic CR and
cationic MV dyes by poly (AA-co-HEMA), poly (NaA-co-HEMA) and
IPN of CS and P (AA-co-HEMA) and IPN of CS and P(NaA-co-HEMA)
hydrogels prepared by Mandal and Ray (2014) showed that the CR
adsorption rate is greater than MV in all hydrogels. In all hydrogels,
the highest adsorption capacity of both dyes occurs at pH 7. The
131
adsorption of CR by these hydrogels is in the order of
SCPCS > CPCS > SCP > CP. CS/P (NaA-co-HEMA) hydrogel has high-
est adsorption capacity for CR because there are the electrostatic
interaction between sulfonate (eSO2-
3 ) functional group of CR and
the amino group of protonated chitosan and the hydrogen bonding
between the protonated amine group of dye and hydroxyl group of
chitosan (Mandal and Ray, 2014).
4.1.2. Acrylic based cellulose hydrogels
Cellulose is the first abundant renewable source in nature that is
found in plants and natural fibers. Cellulose, due to the numerous
eOH groups in its structure, easily prepares hydrogen crosslinked
networks. But on the other hand, the presence of these links leads
to a reduction in the solubility of cellulose in water. Therefore, the
basic problem in preparing cellulose hydrogels is to determine the
solvent (Chang and Zhang, 2011). Cellulose derivatives derived
from the esterification of cellulose, such as carboxymethylcellulose,
methylcellulose, hydroxyethyl cellulose, hydroxypropyl methyl
cellulose, have various functional groups in their structure and high
solubility in water. So, they are good options for hydrogel prepa-
ration. Fig. 7 shows the structure of cellulose derivatives.
Among cellulose derivatives, carboxymethylcellulose (CMC) is a
good candidate for hydrogel preparation because it has carboxylic
groups that can be ionized. But other cellulose derivatives have
hydroxyl groups, which is not ionized. It should be noted that the
hydrophilicity of the carboxylic group is higher than the hydroxyl
group. Carboxymethyl cellulose is an important category of poly-
saccharides that is produced by the cellulose reaction with mono-
chloro acetate in the alkaline medium (Bao et al., 2011). CMC is a
biodegradable and biocompatible linear anionic polymer that the H
atom of the hydroxyl cellulose group was replaced with carbox-
ymethyl (eCH2-COOHe) group (Barbucci et al., 2000). Because of
its acidic group, CMC is a high-swollen smart polyelectrolyte that is
sensitive to pH and ion strength of swelling medium (Raafat et al.,
2012). This polymer is most often found in the form of sodium salts
(NaCMC) (Hebeish et al., 2010). The presence of sodium counterion
(Naþ) causes more swelling of these hydrogels by the effect of
Donnan. CMC hydrogels have high swelling due to their eCOO-
group repulsion. Commonly used crosslinking agents for the syn-
thesis of CMC hydrogels include epichlorohydrin, bifunctional
epoxy, acids, and ethers. Crosslinked CMC hydrogels do not have
high mechanical strength, so in addition to cross-linking, other
common approaches such as grafting with synthetic polymers or
synthesizing IPN networks with synthetic polymers are used to
overcome this drawback (Mandal and Ray, 2016). Fig. 8 shows the
chemical structure of NaCMC.
132 P. Mohammadzadeh Pakdel, S.J. Peighambardoust / Journal of Environmental Management 217 (2018) 123e143

Fig. 6. Adsorption capacity of magnetic macroporous CS-g-PAA hydrogel at different contact times for a) Cd2þ b) Pb2þ (reprinted with permission from (Zhu et al., 2016)).

Fig. 7. The structure of cellulose derivatives (reprinted with permission from (Bao et al., 2012)).

synthetic and natural polymers leads to the formation of hydrogels

Fig. 8. Chemical structure of NaCMC.
As aforementioned, CMC has eCOO- and eOH functional groups
and the acrylic polymers have eCOOH functional group. Therefore,
the integration and preparation of IPN networks with these
that have high mechanical properties, high adsorption rates, and
high swelling. El-Naggar et al. (2006) prepared the CMC/P (AA)
hydrogels by polymerization and cross-linking with electron beam
radiation. They investigated the pH and temperature sensitive
swelling behavior of them. They put the synthesized hydrogels
under different doses of radiation in contact with buffer solutions at
pHs 2, 5, 7, and 10 at room temperature. Their results showed that
the pH-sensitive behavior of these hydrogels is dependent on
electron beam radiation dose. At 80 kGy dose, hydrogels exhibit a
pH-sensitive behavior, while they do not show this behavior at
50 kGy dose. The results of the synthesized hydrogels with 80 kGy
dose showed that at higher pHs, the carboxylic group of the acrylic
 P. Mohammadzadeh Pakdel, S.J. Peighambardoust / Journal of Environmental Management 217 (2018) 123e143 133

acid is ionized and the electrostatic repulsion between the eCOO-

groups results increment in the swelling of the hydrogels. The
highest amount of swelling is observed at pH 7. By the
temperature-sensitive behavior of CMC/AA hydrogels investigation,
the researchers found that the temperature of 25  C is the upper
critical solution temperature (UCST) for crosslinked hydrogels with
50 kGy dose. At temperatures higher and lower than UCST the
hydrogels shrink (El-Naggar et al., 2006). Bao et al. (2011) synthe-
sized CMC-g-P (AA-co-AM-co-AMPS)/MMT composite hydrogels
and studied their swelling behavior in distilled water and saline
solutions of KCl, NaCl, CaCl2, and MgCl2. Their results showed that
the amount of hydrogel's swelling in saline solutions was in the
order of MgCl2< CaCl2< NaCl < KCl because ionic strength of salts
was in the order of Kþ<Naþ<Ca2þ<Mg2þ. On the other hand, the
amount of swelling of these hydrogels in water is more than salt
solutions which is related to the screening effect of added cations,
leading to a decrease in the electrostatic repulsion between anion
and anion. As a result, the osmotic pressure difference between the
hydrogel network and the external solution is decreased (Bao et al.,
2011). Liu et al. (2010a) recently reported the preparation of com-
Fig. 10. Molecular structure of amylose and amylopectin (reprinted with permission
posites hydrogel including grafting PAA onto CMC with attapulgite from (Lu et al., 2013)).
filler and used to Pb2þ adsorption. They used FTIR analysis to
investigate the cation adsorption mechanism by CMC-g-P (Acrylic
acid)/5% APT hydrogel. Investigation of the FTIR spectrum before
and after Pb2þ adsorption showed that the eCOOH, eCOO- and
eNHe are effective groups in adsorbing this metal cation and the
complexation mechanism is the predominant mechanism on the
metal cation adsorption by this composite hydrogel (Liu et al.,
2010a). Fig. 9 illustrates a proposed mechanism for Pb2þ adsorp-
tion by CMC-g-P (AA)/APT hydrogel.

4.1.3. Acrylic based starch hydrogels

Starch (St) biopolymer is a neutral polysaccharide that is made
up of ɒ-glucan units. Starch is composed of two main components:
1) amylose, which is a linear polysaccharide with ɒ-glucan units
linked through a-(1,4) bonds and 2) amylopectin, which is a highly
branched polysaccharide with (a- (1-4-linked) -ɒ-glucan) units
with a- 1-6-linked branches. Fig. 10 shows the molecular structure
of amylose and amylopectin (Lu et al., 2013).
There are many hydroxyl groups in the backbone of starch that
are connected to C2, C3, and C6 of glucose units. The existence of
these groups makes it possible for further modification by func-
tional groups (Xiao, 2013). Fig. 11 shows the chemical structure of
this biopolymer.
Starch hydrogels and their derivatives have attracted a lot of
attention in adsorbing heavy metals and dyes due to their non-
Fig. 9. Scheme of Pb2þ adsorption by CMC-g-P (AA)/APT composite hydrogel
(reprinted with permission from (Liu et al., 2010a)).
Fig. 11. The chemical structure of starch (reprinted with permission from (Xiao, 2013)).
toxic, low cost and biodegradable properties. Because of its low
solubility in water at room temperature, high viscosity and high
gelation temperature, starch has limited use in the synthesis of
hydrogels. Starch hydrogels also have a low mechanical strength.
Therefore, to improve this property, chemical modification
methods such as grafting, copolymerization, or creating IPN net-
works with vinyl monomers, such as acrylic monomers, are used
(Zhu et al., 2015). Starch-based hydrogels are crosslinked by radi-
ation (Mahmoud et al., 2014) or chemical crosslinking agents such
as epichlorohydrin (Abdel Halim, 2013), glutaraldehyde, methylene
bisacrylamide and phosphoryl chloride. Fig. 12 shows the proposed
mechanism of AA grafting on the starch in the presence of potas-
sium persulfate as an initiator and MBA as a crosslinker (Lu et al.,
2013). First, thermal decomposition turns persulfate into persul-
fite radical. Then the produced hydrogen radicals are separated
from the starch backbone so macro-radicals are produced. Macro
radicals begin AA grafting and produce St-g-P (AA), and finally, the
MBA leads to the production of a three-dimensional network.
Sodium humate is a crystal or black powder that can adsorb,
exchange, chelate, and complex due to abundant active groups such
as carboxylic and hydroxyl. Zheng et al. (2010) synthesized a series
of starch-g-poly (acrylic acid)/sodium humate hydrogels and
studied the adsorption of Cu2þ by these hydrogels. Their results
showed that the adsorption rate of the metal by hydrogel shows a
sudden increase in the pH 2e7.2 and the highest adsorption occurs
in the pH 4e5, which results from the decomposition of the car-
boxylic groups. Their results also indicated that an increase of 5%
sodium humate in the starch-g-poly (acrylic acid) hydrogels
134 P. Mohammadzadeh Pakdel, S.J. Peighambardoust / Journal of Environmental Management 217 (2018) 123e143
Fig. 12. Grafting mechanism of AA on starch (reprinted with permission from (Lu et al., 2013)).
network would increase the rate and absorption capacity of Cu2þ
and regeneration ratio. The results of FTIR analysis of hydrogels
before and after metal adsorption showed that complexation is the
most important adsorption mechanism. The results of cation
adsorption by these hydrogels showed that Langmuir isotherm and
pseudo-second-order kinetic model dominated on the adsorption
process (Zheng et al., 2010). Güçlü et al. (2010) investigated the
Starch-g-P (AA)/MMT nanocomposite hydrogel synthesis and Pb2þ
and Cu2þ adsorptions. They showed that a hydrogel in which MMT
particles exist do not have the ability to recover due to low me-
chanical resistance. Investigating the adsorption of metal cations by
these hydrogels in uncompetitive and competitive conditions
showed that adsorption of Cu2þ was more than Pb2þ. They used HCl
to regenerate the hydrogels (Güçlü et al., 2010).
4.1.4. Acrylic based alginate hydrogels
Alginate (Alg) is an anionic polysaccharide containing (1,4)-
linked b-ɒ- mannuronic acid (M) and a-L- guluronic (G) acid that
are repeated linearly with irregular patterns and different ratios of
GG, MM and GM blocks in chains length (Benettayeb et al., 2017).
The M/G ratio is an important factor affecting the physical prop-
erties of the alginate and the resulting hydrogels. Biodegradability,
non-toxicity, biocompatibility, low cost and the ability to form gel
has made this polymer to take a special place in the field of drug
delivery (Jabeen et al., 2016), wound dressing (Kamoun et al.,
2015b) and adsorption of pollutant (Hong et al., 2017). Alginate
has free hydroxyl and carboxylate groups in its backbone which
have led to its hydrophilicity. The presence of carboxylate groups in
alginate causes this biopolymer to be an appropriate agent for the
adsorption of metal cations such as Pb2þ, Cu2þ, Ni2þ, Cd2þ and Cr3þ
(An et al., 2015). Due to the ionization of the carboxylic group, the
swelling and adsorption of this polyelectrolyte is sensitive to the pH
of the surrounding medium. The approximate values of pka for
guluronic and mannuronic acids of alginate were reported 3.2 and
4.8, respectively (Bekin et al., 2014). Fig. 13 shows the chemical
structure of sodium alginate.
Alginate can be physically crosslinked and gelated through
divalent cations such as Ca2þ, Zn2þ, and so on (Jiang et al., 2017;
Cerciello et al., 2017). These ions interact intensely with the G
residues of alginate in a two-dimensional plane while they form
weak links with the M and GM residues. Crosslinking of alginate by
Ca2þ is mainly done by diffusion method, so that the alginate so-
lution is dropped in the bath of CaCl2 and gelatinization occurs. In
the crosslinking of alginate hydrogels by divalent metal cations,
carboxylic group participate so adsorption of the pollutants is not
done by the ionic exchange mechanism. Crosslinked hydrogels by
metal cations have low stability and crosslinking is influenced by
the pH of the surrounding medium. Compared to these hydrogels,
gels from chemical crosslinking by networking agents such as MBA
(Pourjavadi et al., 2007), GLA and ECH are more stable and resistant
(Bekin et al., 2014; Pawar and Edgar, 2012). Fig. 14 shows the
mechanism of crosslinking of alginate with GLA.
Alginate hydrogels have a low mechanical strength like other
natural hydrogels. One of the methods of modifying and increasing
the mechanical strength of alginate hydrogels is the use of synthetic
monomers such as acrylics. Mandal and Ray (2013) synthesized
poly (acrylic acid-co-hydroxyethyl methacrylate)/sodium alginate
hydrogels and investigated the swelling, diffusion and network
parameters of these hydrogels. They used these hydrogels for
adsorption of Congo red and methyl violet dyes. Their results
showed that adsorption of the Congo red is more than that of
methyl violet which is due to the difference in the structure of these
two dyes (Mandal and Ray, 2013). Thakur et al. (2016) synthesized
nanocomposite hydrogels of AA-grafted alginate in the presence of
TiO2 nanoparticles, MBA crosslinker, and KPS initiator and inves-
tigated swelling and MB adsorption capacity. Their results showed
that the adsorption of gel without TiO2 was 80% while for gels
containing 0.2 g of nanoparticles, it was 99.4%. It was also shown
that increasing the amount of AA increases the dye adsorption. Two
proposed mechanisms for adsorption of dye by this nanocomposite
 P. Mohammadzadeh Pakdel, S.J. Peighambardoust / Journal of Environmental Management 217 (2018) 123e143 135

Fig. 13. Chemical structure of alginate (reprinted with permission from (Bekin et al., 2014)).

Fig. 14. Crosslinking mechanism of alginate with GLA (reprinted with permission from (Bekin et al., 2014)).

hydrogel are electrostatic interactions and hydrogen bonding be-
tween adsorbent and dye (Thakur et al., 2016). Wang et al. (2013)
have developed a nanocomposite hydrogel of NaAlg-g-P (AA-co-
St)/organo-illite/smectite with mixed nanoparticles of illite and
smectite. They investigated the effect of I/S ratio, pH, concentration,
the temperature of MB solution and contact time. They also
determined optimal value of these parameters. Investigation of
adsorption results at different pH values showed that this hydrogel
at the pH 4e10 shows the highest dye adsorption. Therefore, this
hydrogel can be used in a wide range of pHs. Analysis of FTIR results
of hydrogel before and after dye adsorption showed that the elec-
trostatic interaction between cationic dye and the anionic hydrogel
is the mechanism that governs the adsorption process (Wang et al.,
2013). Thakur and Arotiba (2017) synthesized NaAlg-g-P(AA)/TiO2
nanocomposite hydrogels by using the KPS initiator and the organic
and inorganic crosslinkers, MBA and TiO2. They investigated the
effect of concentration of TiO2, NaAlg, and grafting on the adsorp-
tion of MV. They optimized parameters such as reaction time, re-
action temperature, monomer concentration, initiator
concentration, pH and crosslinker to determine the greatest
amount of grafting. Investigating the results of dye adsorption in
different TiO2 amounts showed that the increase of nanoparticles to
some extent increases the dye adsorption. In higher amounts of
TiO2, the formation of a dense network with low elasticity reduces
the adsorption of dye. Fig. 15 shows the effects of TiO2, treatment
with acrylic monomers and dye adsorption on hydrogel's
morphology using SEM results.
Comparison of ‘a’ and ‘b’ shows that the treatment of NaAlg with
AA monomer increased the surface roughness of the hydrogel, and
the comparison of ‘c’ with ‘b’ shows that the roughness increment
with increasing nanoparticles. Case 4‘d’ shows the highest surface
roughness because of dye adsorption. Investigating the effect of pH
on hydrogels adsorption showed that NaAlg-g-PAA/TiO2 hydrogel
has a valuable use to remove dye in neutral pH (Thakur and Arotiba,
2017). Rashidzadeh et al. (2015) investigated MB adsorption by
NaAlg-g-poly (AA-co-AAm)/Clinoptilolite nanocomposite hydrogel.
The results showed that the presence of zeolite particles not only
increases the swelling and adsorption capacity of the hydrogel but
also improves the reusability of the hydrogel (Rashidzadeh et al.,
2015).
136 P. Mohammadzadeh Pakdel, S.J. Peighambardoust / Journal of Environmental Management 217 (2018) 123e143
Fig. 15. a) NaAlg, b) NaAlg-g-P (AA), c) NaAlg-g-P (AA)/TiO2, d) MV loaded NaAlg-g-P (AA)/TiO2 (reprinted with permission from (Sourbh Thakur, 2017)).
4.1.5. Other acrylic based natural hydrogels
Other natural polymers such as k-carrageenan, guar gum, xan-
than, and gelatin are used to synthesize hydrogels modified with
acrylic monomers. Carrageenan is a linear water-soluble anionic
polysaccharide extracted from red seaweed. This polymer consists
of (1,3)-ɒ-galactopyranose, (1,4)-3,6 anhydro-a-ɒ-galactopyranose
repetitive units and sulfate groups (eOSO-3) which based on the
location and number of sulfate ester groups is divided into three
categories of kappa, iota and lambda (Mahdavinia et al., 2013).
Kappa-carrageenan is a carrageenan derivative that can form a gel
with the coil-helix conformational transitions followed by aggre-
gation of helices (Liu and Li, 2016; Padhi et al., 2016). Carrageenan
gelling is highly susceptible to cations such as Kþ, Naþ, and Ca2þ
which affects the coil-helix conformational transitions and aggre-
gation of helices (Liu and Li, 2016). The results show that Kþ cation
has a great influence on the stability and resistance of gels than
other cations (Zia et al., 2017). k-carrageenan-poly (methacrylic
acid)/Fe3O4 nanocomposite hydrogel was synthesized by Gholami
et al. (2016) for adsorption of crystalline violet dye. They showed
that by adding nanoparticles and increasing their concentration,
the porosity and interaction between particles and copolymer are
enhanced so the adsorption rate is increased. To determine the
adsorption mechanism, the kinetic data were compared with three
models of pseudo-first order, pseudo-second order and intra-
particle diffusion. The fitting of the data with the pseudo-first order
model showed that the electrostatic interactions between the dye
and the carboxylic groups of methacrylic acid and sulfonate of
carrageenan are the main mechanism governing the adsorption
process (Gholami et al., 2016). Gums are polysaccharides that are
used as the raw material of many industries such as food industry,
pharmacy and wastewater treatment. Gham ghatti or Indian gum is
a non-toxic, biodegradable, inexpensive and renewable material
derived from the Anogeissus latifolia tree. It is made from sugars
such as L-arabinose, ɒ-galactose, ɒ-mannose, ɒ-xylose and ɒ-glu-
curonic acid. Gham ghatti is rich in anionic functional groups, so it
has a high potential for adsorbing dyes and cationic metals (Mittal
et al., 2013). Kankeu et al. (2015) developed Gum ghatti-g-PAA
hydrogels by free radical polymerization using KPS and MBA as
initiator and crosslinker, respectively. They studied the adsorption
capacity of MB and rhodamine B solutions during batch experi-
ments. The results showed that in all values of pH the MB
adsorption was higher than RhB. Also, the effect of polymer dose on
dyes adsorption showed that increasing the dose of the polymer to
a degree increases the adsorption of dyes and in higher amounts of
optimal amount, dye adsorption is constant (Fosso-Kankeu et al.,
2015). Sharma et al. (2015) synthesized Gum ghatti-cl-poly (AA)
and Gum ghatti-cl-poly (AA-IPN-aniline) hydrogels using gamma
rays as initiators and MBA as crosslinkers. They examined the
adsorption of anionic methyl orange dye by Gum ghatti-cl-poly
(AA-IPN-aniline) hydrogels at different contact times. The results
showed that as the contact time increases, the dye adsorption is
enhanced until it reaches the equilibrium. They introduced elec-
trostatic interactions between the dye and eOH and eNH groups of
polyacrylic and polyaniline as the governing adsorption mechanism
(Sharma et al., 2015). Fig. 16 illustrates adsorption mechanism of
MO by the Gg-cl-poly (AA-IPN-ANI) hydrogel.
4.2. Acrylic based synthetic hydrogels
Synthetic polymers were the first materials used to prepare
hydrogels. The first synthetic hydrogel was prepared by Wichterle
and Lim (1960) using the HEMA polymer (Wichterle and Lim,
1960). Later, other synthetic polymers such as PVA, PVP, PAA,
were used to synthesize hydrogels. This part of the review article
examines the most important synthesized acrylic based hydrogels
used for the purification of industrial wastewater. Table 4 shows the
absorption properties of acrylic hydrogels.
4.2.1. Acrylic based polyvinyl pyrrolidone hydrogels
Polyvinylpyrrolidone (PVP) is a low toxic, biocompatible,
biodegradable and water soluble polymer which is made up of N-
vinylpyrrolidone monomers (Morariu et al., 2016). Poly-
vinylpyrrolidone hydrogels are widely used in the field of drug
delivery (Krezovi
c et al., 2017), articular cartilage (Shi et al., 2014),
wound dressing (Singh and Pal, 2011) and wastewater treatment
(El-Hag Ali et al., 2003). This uncharged polymer, due to the pres-
ence of O and N atoms in its structure, has the ability to form a
complex with metal cations and dyes. Fig. 17 shows the chemical
structure of vinyl pyrrolidone.
Recently, acrylic monomers are used to increase the adsorption
of vinyl pyrrolidone hydrogels. These monomers are added to PVP
in the form of copolymer, graft and IPN networks. Mohdy et al.
(2013) synthesized PVP/(AAc-co-Sty) hydrogels with different ra-
tios of AAc: Sty by gamma radiation and investigated the adsorp-
tion of Co2þ, Cu2þ, and Fe3þ metals by these hydrogels. The results
showed that by increasing AAc, the amount of gelation, swelling
and metal adsorption are increased. Ion sizes are one of the most
important factors in the amount and rate of adsorption. The small
ions diffuse greater and faster to the porous hydrogel. The com-
parison of adsorption of metal cations by PVP/P (AAc-co-Sty)
hydrogels showed that adsorption rate and capacity were in the
order of Cu2þ<Co2þ<Fe3þ (Abd El-Mohdy et al., 2013). Yetimog lu
et al. (2007) synthesized the NVP/AAc/AMPS hydrogel by UV-
curing and investigated the selectivity of Fe3þ, Cu2þ and Cd2þ.
Their studies showed that the maximum adsorption rate occurred
during 3 h at pH 5. They showed that under the competitive con-
ditions of adsorption of three cations by the hydrogel, the adsorp-
tion rate is lower than single cationic state and the adsorption was
in the order of Fe3þ <Cu2þ<Cd2þ. Finally, they used 2 N HCl to
regenerate hydrogels. More than 90% recovery were observed in
 P. Mohammadzadeh Pakdel, S.J. Peighambardoust / Journal of Environmental Management 217 (2018) 123e143 137

Fig. 16. Schematic of the methyl orange adsorption by Gg-cl-poly (AA-IPN-ANI) (reprinted with permission from (Sharma et al., 2015)).

Table 4
Adsorption properties acrylic-based synthetic hydrogels.

Hydrogel Pollutant Initial pollutant Sample qe te pH Kinetic Isotherm Adsorption mechanism Ref
concentration dose model

PVP/P(AA-co-St) Co2þ 200 mg/L 82 mg/g 8h Combination of chelation and (Abd El-Mohdy
ion exchanging et al., 2013)
2þ
PVP/P(AA-co-St) Cu 200 mg/L 75 mg/g 8h Combination of chelation and (Abd El-Mohdy
ion exchanging et al., 2013)
3þ
PVP/P(AA-co-St) Fe 200 mg/L 108 mg/g 8h Combination of chelation and (Abd El-Mohdy
ion exchanging et al., 2013)
NVP/AAc/AMPS Cu2þ 3000 mg/L 125 mg/g 3h 5 Electrostatic interactions (Yetimog lu et al.,
2007)
NVP/AAc/AMPS Fe3þ 3000 mg/L 40 mg/g 3h 2.5 Electrostatic interactions (Yetimog lu et al.,
2007)
NVP/AAc/AMPS Cd 2þ
3000 mg/L 138 mg/g 3h 5 Electrostatic interactions (Yetimog lu et al.,
2007)
P(VP-co-MAA) MV 10 mg/L 4 g/L 5.73 mg/g 4 day 9 P-2 L Electrostatic interactions, (Şolpan and Ko € lge,
Hydrophobic and Hydrogen 2006)
bonding
PVA-g-P(AA-co-AMPS) Pb2þ 300 mg/L 1 g/L 190.1 mg/g 360 min 3 P-2 L Ion exchange (Hui and Ye, 2016)
IPN PVOH/P(AA-co- RB 1 mg/L 0.075 mg/g 10-12 h 7 P-2 L Electrostatic interactions (Mandal et al.,
HEMA) 2012)
IPN PVOH/P(AA-co- MV 1 mg/L 0.085 mg/g 10-12 h 7 P-2 L Electrostatic interactions (Mandal et al.,
HEMA) 2012)
Semi eIPN PVOH/P(AA- RhB 1 mg/L 0.08 mg/g 10-12 h 7 P-2 L Electrostatic interactions (Mandal et al.,
co-HEMA) 2012)
Semi eIPN PVOH/P(AA- MV 1 mg/L 0.1 mg/g 10-12 h 7 P-2 L Electrostatic interactions (Mandal et al.,
co-HEMA) 2012)
2þ
P(NIPAM-co-AA) Cu 80 mg/L 0.5 g/L 58.9552 mg/ 40 min 5 P-2 L Chemisorption (Chen et al., 2013)
g
138 P. Mohammadzadeh Pakdel, S.J. Peighambardoust / Journal of Environmental Management 217 (2018) 123e143
Fig. 17. The chemical structure of vinyl pyrrolidone.
hydrogel regeneration from three cations (Yetimog lu et al., 2007).
Fig. 18 shows the proposed mechanism for the synthesis of P (NVP/
AAc/AMPS) hydrogel.
€ lge (2006) prepared poly (N-vinylpyrrolidone-co-
Şolpan and Ko
methacrylic acid) hydrogels with different ratios of MAA and
investigated swelling and methyl violet adsorption. The results
showed that water and dye penetration to hydrogel is non-Fickian
type. In this hydrogel, increasing MAA monomer leads to an in-
crease in swelling and adsorption at high pHs. The adsorption re-
sults fit the Langmuir isotherm and the electrostatic interaction
between the cationic dye and the carboxylic group is the dominant
€lge,
mechanism on the dye adsorption by hydrogel (Şolpan and Ko
2006).
Fig. 18. Mechanism of synthesizing of P (NVP/AAc/AMPS) hydrogel (reprinted with permission from (Yetimog
4.2.2. Acrylic based polyvinyl alcohol hydrogels
Polyvinyl alcohol (PVA) is a water-soluble, semi-crystalline,
biodegradable and biocompatible polymer with high mechanical
strength and physical gelation ability (Kamoun et al., 2015a). This
polymer has an abundant hydroxyl group in its structure, so it has a
high potential for preparing a hydrogel. Today, PVA hydrogels have
been studied in many fields such as pharmaceutical, tissue engi-
neering, scaffolds, artificial organs and industrial wastewater
treatment. PVA hydrogels can be obtained from physical and
chemical methods. Among the various methods of physical syn-
thesis of hydrogels, the Freeze and Thawing method is a suitable
method for the synthesis of PVA hydrogels and their structure can
be adjusted by PVA molecular weight, PVA concentration, number
and duration of freeze and thawing process (Kamoun et al., 2015b).
PVA hydrogels have a limited application in the field of industrial
water treatment because of low swelling, low adsorption and lack
of ionic pendant groups (Mahdavinia et al., 2014). Therefore, the
introduction of ionic polymers such as acrylics can be an effective
way to solve these problems. Mandal et al. (2012) investigated the
adsorption of methyl violet and rhodamine B by IPN and Semi-IPN
PVOH and poly (acrylic acid-co-hydroxyethyl methacrylate)
hydrogels in different weight ratios of AA and HEMA. Investigation
of adsorption of dyes in the various pH showed that the adsorption
of the dye at pH 5e7 was constant. At pH higher than 8, the
adsorption of dye is reduced and the rate of adsorption of rhoda-
mine B is greater than methyl violet. In all synthesized hydrogels,
the amount of methyl violet adsorption is always higher than that
lu et al., 2007)).
 P. Mohammadzadeh Pakdel, S.J. Peighambardoust / Journal of Environmental Management 217 (2018) 123e143
of rhodamine B and by increasing initial concentration of the dyes,
the adsorption is increased (Mandal et al., 2012). Hui and Ye (2016)
prepared PVA-g-AA-AMPS hydrogels with different AMPS/AA ratios
by NMBA as crosslinker by free radical polymerization. SEM results
showed that by AMPS/AA ratio increment, the size of hydrogel
pores is decreased, and the structure becomes uniform and denser.
They investigated the effect of initial concentration of Pb2þ on
adsorption of the hydrogel. The results showed that by increasing
the initial concentration of the pollutant from 100 to 400 mg/L, the
adsorption rate is increased from 89.3 to 200.7 mg/g because by
increasing the initial concentration, the mass transfer driving force
and the interaction between Pb2þ and the hydrogel are increased,
and desorption efficiency is decreased from 90.2% to 50.98% (Hui
and Ye, 2016).
Nowadays, the use of semiconductive materials such as TiO2,
ZnO, CdS, and ZnS in the field of water purification is common due
to their photocatalytic activity to remove organic dyes. The most
commonly used material in this field is TiO2, which is inexpensive,
non-organic, long-term stability, high surface area and activity
(Thomas et al., 2016). These molecules adsorb ultraviolet wave-
lengths lower than 390 nm and produces active compounds such as
hydroxide radicals that can oxidize and degrade organic dyes. It
should be noted that these particles do not have any effect on the
degradation of metal cations.
Yun et al. (2011) synthesized PVA/PAAc/TiO2 composite hydro-
gel in two composite and nanofiber forms by free radical poly-
merization and electro-spinning methods, respectively. They
investigated the degradation of Coomassie brilliant blue (CBB) in a
glass reactor equipped with a UV lamp at different pH levels. The
results showed that in both forms of the hydrogel, with pH
increasing, the degree of dye degradation is increased and the
amount and the rate of degradation of dye in the fiber hydrogel are
higher than the composite hydrogel (Yun et al., 2011).
Moon et al. (2013) synthesized a PVA/PAAc/TiO2/GO pH-
sensitive nanocomposite hydrogel by free radical polymerization
with ethylene glycol diamethacrylate (EGDMA) and glutaraldehyde
crosslinkers. Studies have shown that TiO2 particles play an
important role in the degradation efficiency of the dyes. They used
sonication to improve the dispersion of these particles in the
hydrogel's cross-section. The results of adsorption and degradation
of MB and Coomassie brilliant blue (CBB) dyes in different amounts
of GO and different pH showed that by increasing GO, the dye
adsorption is increased and by increasing pH, the hydrogel swelling
rate due to electrostatic repulsion between carboxylic groups is
increased which leads to more contact with TiO2 particles. There-
fore, the most photocatalytic activity of the hydrogel is observed at
pH 10 (Moon et al., 2013).
4.2.3. Acrylic based polyacrylamide hydrogels
Acrylamide (AAm) is a hydrophilic polymer, so it a good option
for hydrogels preparing. This polymer has an amide group that
adsorbs proton in the acidic medium and is converted to the amino
group. Therefore, the behavior of acrylamide hydrogels is sensitive
to pH. The first acrylic based acrylamide hydrogels with various
AAm/AA ratios for the removal of textile dyes was developed by
Duran et al. (1999). Later, Şolpan et al. (2003) used these hydrogels
to adsorb the methyl violet at pH 3e8. They observed the highest
amount of swelling and dye adsorption at pH 8 (Şolpan et al., 2003).
Kangwansupamonkon et al. (2010) investigated the adsorption and
degradation of methyl blue by poly (acrylamide-co-acrylic acid)/
TiO2 synthesized hydrogels. Their study showed that TiO2 particles
did not play a role in dye adsorption. They showed that an increase
in TiO2 particles up to 15 wt%. could increase the degradation
139
efficiency of the dye but increasing the concentration of particles
from this amount would reduce the degradation efficiency of the
dye. Because increasing the concentration causes the aggregation of
particles. As a result, the number of active sites of catalyst for dye
degradation is decreased. This cationic dye is absorbed by the ionic
interaction to hydrogel (Kangwansupamonkon et al., 2010). Poly N-
isopropylacrylamide (PNIPAM) is one of the acrylamide derivatives
which consists of two parts, hydrophilic amide (eCONHe) and
hydrophobic propyl (CH-(CH3)2) moieties. This negative
temperature-sensitive polymer indicates that its LCST is approxi-
mately 32  C which is somewhat lower than its volume phase
transition temperature (VPTTz34  C). Around critical temperature
point, PNIPAM turns from the solvated coil to a collapsed globule
conformation. At low temperatures, the amide group binds to water
molecules by hydrogen bonding and this polymer dissolves in
water. At high temperatures, the hydrogen bond is weakened and
the interactions between hydrophobic groups are predominated as
a result, the water is released from the polymer (Haq et al., 2017).
PNIPAM hydrogels, as the most commonly used temperature-
sensitive hydrogels, with the LCST near to the human body tem-
perature, have been widely used in medical fields (Gandhi et al.,
2015). In these hydrogels, by increasing temperature the
hydrogen bond between the polymer and water is broken down
and the dense impermeable layer forms on the surface of the
hydrogel which is called skin effect so the water release from
PNIPAM hydrogel is a slow process (Depa et al., 2012). To increase
the rate of water release from the hydrogel, various methods such
as the incorporation of pore forming additives such as silica parti-
cles during the gel forming, preparation of hydrogels at a temper-
ature higher than LCST, and using a surfactant and its extraction
after preparation are proposed (Serizawa et al., 2002). Chen et al.
(2013) synthesized poly (N-isopropyl acrylamide-co-acrylic acid)
nano-hydrogels by using emulsion polymerization method and
investigated the effects of Cu2þ adsorption on the structure and
behavior of hydrogels. The results showed that due to the pene-
tration of Cu2þ into the hydrogel network and the reduction of
hydrogen bond between water and the acrylic monomer, VPTT of
the hydrogel shifted from 32  C to 27  C. The results of the TEM
analysis show an increase in the size of the hydrogel particles after
the adsorption of Cu2þ. Investigation of adsorption data fitting with
Langmuir, Freundlich, Tempkin, and Dubinin-Radushkevich equi-
librium adsorption isotherms showed that Langmuir isotherm is a
suitable model for describing the adsorption process (Chen et al.,
2013).
5. Future perspective
The adsorption of dyes and heavy metals by acrylic based
hydrogels had been reviewed in this paper. For future researches,
more attention should be focused on improvement of adsorption of
heavy metals and dyes using acrylic based hydrogels. Researchers
could gain useful information to design high efficient hydrogels by
studying adsorption mechanism. Adsorption mechanism study by
kinetics and isotherm models isn't comprehensive and scanning
electron microscope (SEM), X-ray diffraction (XRD) analysis, elec-
tron spin resonance (ESR), X-ray photoelectron spectroscopy (XPS)
and thermogravimetric analysis (TGA) should be examined in
addition. An economic way to synthesize efficient hydrogels will be
needed approach. Investigation of economic feasibility should be
considered to determine whether the selection of acrylic based
hydrogel is suitable to be implemented in large scale. The key factor
in studying economic feasibility is regeneration and stability which
determine hydrogel reusability and should be taken into
140 P. Mohammadzadeh Pakdel, S.J. Peighambardoust / Journal of Environmental Management 217 (2018) 123e143

consideration in more detail. Also, selection of appropriate solvent Abbreviations

for pollutant extraction needs more studies. In most researches,
adsorption investigation has done in batch form so the perfor- AAm Acrylamide
mance of hydrogels should be examined in continuous mode in Alg Alginate
future works. Researchers should investigate adsorption efficiency AMPS 2-Acrylamido-2-methylpropane sulfonic acid
of acrylic based hydrogels in industrial effluents include different ANI Aniline
pollutants, unlike laboratory solutions. In addition, designing of APT Attapulgite
acrylic based hydrogels with higher selectivity towards a specific CBB Coomassie brilliant blue
pollutant is recommended. Clin Clinoptilolite
CMC Carboxymethyl cellulose
6. Conclusion CP P(AA-co-HEMA) hydrogel
CPCS IPN of CS and P (AA-co-HEMA) hydrogel
One of the most important factors that threatens the life of CR Congo red
living creatures is contamination of water resources by industrial CS Chitosan
effluents. Several methods have been proposed to solve this prob- DDA Degree of deacetylation
lem. Hydrogels have received greatest attention in the treatment of ECH Epichlorohydrine
industrial wastewater due to their unique properties. For industrial EGDE Ethylene glycol diglycidyl ether
applications, hydrogels have high swelling, adsorption capacity, EGDMA Ethylene glycol dimethacrylate
adsorption rate, mechanical strength, high thermal, chemical sta- Gg Guar Gum
bility and reusability. This review article examines the properties of GLA Gultaraldehyde
recent synthesized natural and synthetic acrylic based hydrogels HA Hyaluronic acid
that are used to wastewater treatment. Acrylic based hydrogels, HEMA Hydroxyethylmethacrylate
which are obtained by the addition of acrylic monomers in the form HIPEs Pickering high internal phase emulsions
of copolymer, graft and IPN networks have been widely used in this IA Itaconic acid
field due to high swelling, high adsorption capacity and high IPD Intraparticle diffusion
adsorption rate. These polyelectrolytes hydrogels have a pH- KPS Potassium persulfate
sensitive behavior due to the presence of a carboxylic group. LCST Lower critical solution temperature
Therefore, optimum pH should be determined which the highest MAA Methacrylic acid
adsorption rate is occurring. Among the various methods of MB Methyl blue
crosslinking, the chemical crosslinking method by free radical MBA NʹNʹ-Methylenebisacrylamide
polymerization is the most common method for the preparation of MMT Montmorillonite
these hydrogels. The degree of cross-linking is one of the most MO Methyl Orange
important factors affecting the adsorption capacity of these MV Methyl violet
hydrogels. The study of the mechanism of adsorption of pollutants NaA Sodium acrylate
provides useful information on the improvement of the properties NaAlg Sodium alginate
of these hydrogels. Various adsorption mechanisms have been NIPAM N-isopropylacrylamide
proposed by these hydrogels such as electrostatic interactions, NVP N-vinylpyrrolidone
hydrophobic interactions, ion exchange and hydrogen bonding. In NY Nitrazine yellow
the meanwhile, electrostatic interactions are the most common PAA Polyacrylic acid
mechanism for adsorption of pollutants by these hydrogels. Com- PEG Polyethylene glycol
parison of the adsorption capacity of natural and synthetic hydro- PFO Pseudo first order
gels has shown that acrylic based hydrogels have higher efficiency. PSO Pseudo second order
One of the most important problems of natural acrylic based PVA Polyvinyl alcohol
hydrogels is their low mechanical strength. To solve this problem, RhB Rhodamine B
the preparation of composite systems by inorganic particles of clay, SCP P(NaA-co-HEMA) hydrogel
sodium humate (SH) and so on is suggested. These particles not SCPCS IPN of CS and P(NaA-co-HEMA) hydrogel
only increase the mechanical strength of acrylic hydrogels but also SH Sodium Humate
increase the adsorption capacity, thermal and chemical stability of St Starch
hydrogels. They also reduce the cost of hydrogels preparing. The Sty Styrene
preparation of composite systems by TiO2 particles in addition to TEMED Tetramethylene diamine
improvement of mechanical strength, chemical and thermal sta- UCST Upper critical solution temperature
bility, adds the property of photocatalytic degradation of dye con- VMT Vermiculite
taminants to acrylic based hydrogels. One of the most important VPTT Volume phase transition temperature
issues that should be addressed in the development of acrylic based
hydrogels is the regeneration and usability of them. From an
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