658 Clean – Soil, Air, Water 2011, 39 (7), 658–664

Bengi Özkahraman1
Iş¸ıl Acar2
Research Article
Serkan Emik2
Removal of Cu2þ and Pb2þ Ions Using CMC Based
1
Faculty of Engineering, Chemical
Engineering Department, Hitit
Thermoresponsive Nanocomposite Hydrogel
University, Çorum, Turkey
2
Faculty of Engineering, Chemical In this study, carboxymethylcellulose (CMC) based thermoresponsive nanocomposite
Engineering Department, Istanbul hydrogel was synthesized for the removal of Cu2þ and Pb2þ ions from aqueous
University, Avcılar-Istanbul, Turkey solutions. To prepare nanocomposite hydrogel, graft copolymerization of N-isopropyl
acrylamide (NIPAm) and acrylic acid (AA) onto CMC was carried out in Na-montmo-
rillonite (MMT)/water suspension media and ammonium persulfate (APS) used as
initiator. The chemical structures of hydrogels were characterized by Fourier transform
infrared (FT-IR) and X-ray diffraction spectroscopy (XRD). Lower critical solution
temperature (LCST), pH responsivity, swelling, and deswelling properties of the hydro-
gels were also examined. In addition competitive and non-competitive removal of Cu2þ
and Pb2þ studies were carried out. According to heavy metal sorption studies results,
removal capacities of nanocomposite hydrogel for both metal ions were found to be
higher than those of pure hydrogel. The analyzed adsorption data showed that the
adsorption process of Cu2þ and Pb2þ could be explained by pseudo-second order kinetic
model. Moreover, according to competitive sorption studies, it is found to be that both
hydrogels are more selective to Cu2þ ion rather than Pb2þ.
Keywords: CMC; Heavy metal removal; Hydrogel; Montmorillonite; Nanocomposite; NIPAm
Received: December 6, 2010; revised: March 20, 2011; accepted: March 20, 2011
DOI: 10.1002/clen.201000553

1 Introduction cellulose [11–13], starch [14–19], chitosan [20, 21], and alginate
[22, 23] based hydrogels is continuously increasing due to their
Heavy metal ions contamination causes a serious environmental
biodegradability and low costs [24].
problem and presents a threat to human health, living resources,
Carboxymethylcellulose (CMC) is the major commercial derivative
and ecological systems [1]. The removal of these toxic elements from
of cellulose which contains –CH2COOH groups in the main back-
aqueous solutions has received much attention over the past few
bone. It is ionic ether of cellulose and, due its polar carboxyl groups,
years. Various methods exist for the removal of heavy metals from
it is soluble in water. These structural properties provide hydro-
industrial water and natural water such as chemical precipitation,
philicty and pH-responsivity of the network. CMC based hydrogels
ion-exchange, adsorption, and reverse osmosis techniques [2].
widely used in pharmaceuticals, cosmetics, and foods due to their
Among these techniques, it has been recognized that adsorption
low cost and aforementioned properties. To improve the effective
using low-cost adsorbents is a facile, effective, economic, and prom-
usage of CMC as adsorbent, it is generally modified by grafting a
ising method for water decontamination [3–5]. Hydrogels, which
monomer contains hydrophilic or chelating groups [25–30]. Stimuli
defined as three dimensionally crosslinked polymer network struc-
sensitive hydrogels such as poly(N-isopropyl acrylamide) (pNIPAm)
tures composed of hydrophilic homo or hetero copolymers [6] have
exhibit significant changes in their swelling and mechanical proper-
been employed as effective adsorbents for recent years [7–10]. The
ties in response to changes in pH, ionic strength, or temperature of
efficient adsorption process is due to the functional groups, such as
the external environment [6]. CMC can be used as a hydrophilic
–NH2, –COOH, –OH, etc., and unique network structure of the hydro-
and pH responsive polymer to improve swelling ratios of pNIPAm
gel. Hydrogels used as adsorbents can be classified in two main
hydrogel to obtain pH/temperature sensitive hydrogel [31, 32].
classes as synthetic and natural. Beside the widely usage of synthetic
Polymer nanocomposites are normal composites with the differ-
hydrogels as adsorbents for removal of dye and heavy metal ions
ence that they have at least one phase in the nanometer range
from waste water, the demand of using natural hydrogels such as
and this was found to be the key for a significant improvement
in the mechanical and thermal properties [33, 34]. In last
decade substantial attention has been focused on polymer/clay nano-
Correspondence: Dr. S. Emik, Faculty of Engineering, Chemical
Engineering Department, Istanbul University, Avcılar-Istanbul, 34320,
composite hydrogels because of their improved mechanical, ther-
Turkey mal, electrical, and magnetic properties compared to pure polymers
E-mail: [email protected] [31, 35–37].
In this study, we studied the preparation of CMC-g-poly(NIPAm-co-
Abbreviations: AA, acrylic acid; APS, ammonium persulfate; CMC,
carboxymethylcellulose; LCST, lower critical solution temperature; AA)/MMT hydrogel and its potential use as an adsorbent for removal
MMT, montmorillonite; NIPAm, N-isopropyl acrylamide. of Cu2þ and Pb2þ ions from aqueous solutions.

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Clean – Soil, Air, Water 2011, 39 (7), 658–664 Removal of metal ions by CMC based nanocomposite hydrogel 659

2 Experimental 2.5 LCST determination

Lower critical solution temperatures (LCST) of the hydrogels were
2.1 Materials determined by using DSC technique [39, 40]. Swollen gels were
The monomers, carboxy methyl cellulose (CMC), (low molecular heated from 10 to 708C, with a heating rate of 0.58C/min under
weight), acrylic acid (AA), lead(II) acetate trihydrate, (PbAc), and static atmosphere, using distilled water as reference.
copper(II)acetate monohydrate (CuAc) were all purchased from
Merck (Germany). Ammonium persulfate (APS) was also purchased 2.6 Swelling properties
from Merck and used as initiator. N-Isopropyl acrylamide (NIPAm)
was obtained from Sigma–Aldrich (USA) and recrystallized from The equilibrium swelling ratio of hydrogels was measured gravi-
cyclohexane/toluene (60:40 v/v) before used. Na-montmorillonite metrically by tea bag method described in our previous studies [14,
(MMT) was kindly provided by Kenan Çinku from the Mining 41]. Dry hydrogel samples in a tea bag were immersed in distilled
Engineering Department of Istanbul University. Its cation water at room temperature, held for 24 h and after weighted. The
exchange capacity was found to be 93.1 mequiv/100 g according to equilibrium swelling ratio (Qe) was calculated from the following
measurement by adsorption of copper ethylenediamine complex equation:
method [38]. The other reagents were all in analytical grade. All

Wwet
Wdry
solutions and standards were prepared using distilled water. Qe ¼  100 (1)
Wdry

where Wwet and Wdry are the weights of the swollen gel and the dry
2.2 Preparation of hydrogels sample, respectively.
To determine the pH sensitivity of hydrogels, dry hydrogel samples
To prepare nanocomposite hydrogel, firstly a calculated amount of
were immersed in buffer solutions at different pH values (1.95, 4.83,
MMT (1 wt% of total charge) was dispersed in 50 mL of distilled water
7.00, 9.06, and 9.94) and kept for 24 h to obtain equilibrium swelling
by Bandelin UW 2200 ultrasonic irradiation equipment. Then, this
at room temperature. After 24 h, the hydrogel samples were
well-dispersed suspension was taken in a 250-mL four-necked flask
weighted and the pH dependent swelling ratio (Qe) was calculated
equipped with a mechanical stirrer, a thermometer, a reflux con-
using Eq. (1).
denser, and a nitrogen inlet. The graft polymerization of NIPAm and
Deswelling experiments were carried out at 558C using a thermo-
AA onto CMC was carried out in this system. Approximately 0.2 g
stated water-bath by gravimetric method. A given amount of swollen
CMC was dissolved in the clay suspension, degassed, heated up to
hydrogel at room temperature was immersed in water at 558C for
358C, and stirred till a sticky solution was obtained. To facilitate free
1 h. The water retention value for 1 h was calculated using Eq. (2):
radical formation on CMC, a calculated amount of APS (1 wt% of total
charge) was added to solution and stirred for 15 min. This treatment

Qe;RT
Qe;55
was followed by the addition of 1 g NIPAm and AA (3 mol% of NIPAm) Water retention ð%Þ ¼  100 (2)
Qe;RT
and NMBA (0.5 mol% of total monomer). In 4 h, the reaction solution
was completely gelatinized and the obtained hydrogel put into where Qe,RT and Qe,55 are the equilibrium swelling ratios calculated
distilled water and held at room temperature for 4 days. To remove by Eq. (1) at room temperature and 558C, respectively.
any unreacted monomers and initiators, water was changed with The all swelling/deswelling experiments were repeated three
fresh water periodically (twice a day). After 4 days, the hydrogels times for each hydrogel sample and the averages of the results were
were dried under vacuum at 508C during 24 h for using in sorption reported.
experiments. The procedure of preparation of pure hydrogel that
does not contain MMT was similar to that of nanocomposite hydro-
2.7 Adsorption kinetics and isotherm experiments
gel, except without addition of MMT. Here after, the pure hydrogel
and the nanocomposite hydrogel expressed as H and H–C, Adsorption kinetics experiments were carried out in 8 mmol/L aque-
respectively. ous metal solutions at pH 4 at room temperature. Stock solutions
containing Cu2þ and Pb2þ or both of these ions were prepared by
dissolving metal acetate salts in distilled water and for pH adjust-
2.3 Fourier transform infrared analysis ment diluted HNO3 was used. Approximately 0.05 g hydrogel
samples were added in 50 mL of stock solution and the mixture
The IR spectra of samples were obtained with Digilab, Exalibur-FTS was stirred with a magnetic stirrer. The concentration of residual
3000 MX (USA) Fourier transform infrared (FT-IR) spectrophotometer metal ions in the aliquots of withdrawn solution was followed by
in the range 400–4000 cm
1, at a resolution 2 cm
1. In order to atomic absorption spectrometer (Perkin Elmer, Analyst 200) up to
prepare the sample pellets, the samples were diluted with IR grade 48 h. Metal ion removal capacities of the copolymers were calculated
Merck KBr (samples/KBr: 1:200 w/w). as follows:
  ðCi
Ct Þ
Metal ion removal capacity mmol=ghydrogel ¼ V (3)
2.4 X-ray diffraction analysis Mhydrogel

X-ray diffraction (XRD) patterns were obtained using powdered, where Ci is the initial concentration of metal ions in the solution
dried hydrogel samples with a Rigaku D/Max Ultimaþ X-ray diffrac- (mmol/L), Ct the concentration of metal ions in the solution after
tometer equipped with Cu Ka radiation (k ¼ 1.5405) scanning from 2 metal ion removal (mmol/L), V the volume of the solution (L), and
to 208 at 0.018/s. Mhydrogel is the weight of nanocomposite hydrogel (g).

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660 B. Özkahraman et al. Clean – Soil, Air, Water 2011, 39 (7), 658–664

3 Results and discussion

3.1 Fourier transform infrared studies
The FTIR spectra of MMT, CMC, H, and H–C hydrogel are shown in
Fig. 1. The spectrum of MMT shows a characteristic band at
1036 cm
1 that ascribed to Si–O stretching vibrations of MMT. The
other two characteristic absorption bands at 528 and 463 cm
1 may
result from Al–O stretching and Si–O bending vibrations of MMT [42].
At the spectrum of CMC, the band at 1059 cm
1 attributed to the
stretching vibrations of C–O–C groups but by grafting of AA and
NIPAm onto the CMC backbone this band shifted to 1084 cm
1.
Beside this, in the spectra of H and H–C, the characteristic absorption
bands of NIPAm (amide (II) band at 1550 cm
1), AA (COO
vibrations
at 1720 cm
1) were also observed that suggested the grafting of these
monomers onto the CMC backbone was successfully done [43].
Additionally, according to comparison of the spectra of H and
H–C, due to incorporation of MMT into the network there are some Figure 2. X-ray diffraction patterns of MMT and H–C hydrogel.
discrepancies were recognized. In the spectrum of H–C, a shoulder at
1032 cm
1 due to Si–O vibrations and an intensity increase at the
peak at 463 cm
1 were observed. Also a new peak was appeared at intense diffraction peak at 2u ¼ 7.48. Contrarily, there is no distinct
538 cm
1 which attributed to Si–O stretching vibrations that shifted diffraction peak existed in the range of 2u from 5 to 208 in H–C
to higher wavenumber due to the interaction of COO
groups of the pattern which means that clay sheets are exfoliated and uniformly
polymeric network and Si–O groups of MMT. As a result, these so- dispersed in organic network [41].
called IR bands confirm the presence of all components in the
hydrogel structure.
3.3 Swelling properties and LCST behaviors of
3.2 X-ray diffraction studies the hydrogels
Figure 2 illustrates the XRD patterns of MMT and H–C nanocompo- The swelling mechanism of a hydrogel is affected by several factors
site hydrogel. As it seen from the figure, MMT powder shows an such as hydrophilic and hydrophobic character of the network,
ionization degree of the hydrophilic groups, dynamic volume, etc.
[44, 45]. In case of stimuli sensitive hydrogels, the medium
parameters such as temperature and pH take important roles on
swelling properties of the hydrogels. The synthesized hydrogels in
this study are both thermo and pH sensitive because of the nature of
the monomers used, thus they exhibited significant swelling
changes when temperature or pH of the medium changed. All
swelling properties of the hydrogels were given in Tab. 1 and Fig. 3.
The effect of incorporation of MMT in the polymer network on the
water absorbency of the hydrogel can be easily seen in Tab. 1. As it
seen from the table, adding 1 wt% of hydrophilic MMT increased the
Qe of the H–C hydrogel 1.4 times greater than that of H. This case is
compatible with similar previous works in the literature; increasing
hydrophilic clay content of the network up to a certain value
enhances the water absorbency. MMT contains many easily ionizable
cations and when they ionized and dispersed into the polymeric
network an enhanced swelling is attained [46–49].
In case of investigating thermoresponsive characteristic of hydro-
gels DSC technique was employed. In DSC curves of both hydrogels,
large endothermic peaks between 40 and 508C were observed which
indicate continuous phase transition. According to these findings,
the LCST values of both hydrogel are very close to each other and
higher than that of pNIPAm (LCST of pNIPAm is 328C). As it known
that, increasing the hydrophilic character of the network causes a
significant increase in LCST. Since, CMC and AA have hydrophilic
characters, higher LCST values for both H and H–C hydrogels are
expected results. H–C hydrogel contains 1 wt% hydrophilic MMT and
it should be an expected result if the LCST of H–C was higher than
Figure 1. Fourier transform infrared spectra of CMC, MMT, H, and H–C that of H. However, LCST of both hydrogels are almost same, thus it is
hydrogels. concluded that MMT has no significant effect on LCST behavior.

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Clean – Soil, Air, Water 2011, 39 (7), 658–664 Removal of metal ions by CMC based nanocomposite hydrogel 661

Table 1. Swelling properties of H and H–C hydrogels.

Hydrogel Qe,RT Qe,558C Water Retention (%) LCST range

(g H2O/g hydrogel) (g H2O/g hydrogel) (Qe,RT – Qe,558C)/Qe,RT  100 (8C)

H 9.5 1.2 87 40–50

H–C 13.5 3.6 73 40–50

Figure 4. The effect of treatment time on non-competitive removal of heavy

metal ions by H and H–C hydrogels.
Figure 3. The effect of pH on equilibrium swelling ratios of H and H–C
and H–C hydrogels, it can be easily recognized that Cu2þ removal
hydrogels.
capacity of H–C nanocomposite hydrogel is almost same but a little
The water release properties of the hydrogels were also summa- bit higher than that of H (2.23 and 2.14 mmol/g, respectively). Similar
rized in Tab. 1. As it seen from this table, holding the hydrogels for behavior was observed for Pb2þ removal, and for H and H–C hydro-
1 h at 558C causes a dramatic decrease in Qe values. H and H–C gels the sorption capacities were found to be 1.40 and 1.51 mmol/g,
hydrogels desorb 87 and 73% of water (determined according to respectively. Metal ion removal process from aqueous solutions by
Eq. (2)) that absorbed at lower temperatures, respectively. nanocomposite hydrogels involves two main sorption mechanisms:
The variation of equilibrium swelling ratios of the hydrogels at Adsorption and ion exchange. In the adsorption process, the
different pH values were illustrated in Fig. 3. As it seen from the carboxyl groups on the polymer network are the main functional
figure, minimum swelling ratios were observed at pH 2, and Qe groups for adsorption of metal ions; in case of ion exchange process
values of H and H–C were found to be 1.3 and 1.9 g H2O/ghydrogel, the CEC of the clay plays an important role in removal of metal ions.
respectively. The swelling ratios of the hydrogels continuously In this study, the sorption capacity of H–C is approximately 0.1 mmol
increased with increasing pH values up to pH 9, and after this value (4%) higher than that of H. Since the main difference between H
a decrease in swelling ratios was observed. This behavior is the and H–C is the presence of MMT in H–C structure, increment in
standard behavior of pH sensitive hydrogels that contain COO
ions sorption capacity of H–C can be possibly explained by the incor-
in their backbone. At lower pH values the COO
groups are proto- poration of MMT into gel network. As it known, clays like MMT have
nated to COOH groups, which leads to minimizing electrostatic cation exchange ability, and using a certain amount of them in
repulsions between the molecular chains and also formation of preparation of hydrogel composites could increase sorption capacity
hydrogen bonds between COOH and CONH groups, thus at [3, 50]. Moreover, as reported by Yi et al., when the sorption capacities
lower pH values smaller swelling ratios were observed. Observing of nanocomposite hydrogels and physical mixtures of pure polymer/
a decrease in swelling ratios above pH 9 is due to the screening effect clay with equal clay content were compared, the nanocomposite
of counter ions, i.e., Naþ that shielding the charge of the carboxylate hydrogels have higher sorption capacities than those of physical
anions and prevents an efficient repulsion. mixtures [3]. The authors concluded that nanocomposite hydrogels
with three-dimensional crosslinked network as adsorbents could
increase sorption capacity. In addition, in a similar study, Ma
3.4 Non-competitive heavy metal removal studies
et al. [31] reported that the initiator could strongly interact with
Figure 4 shows the effect of treatment time on the non-competitive clay platelets to give radicalic points on the clay surface. And during
removal of Cu2þ and Pb2þ ions with H and H–C hydrogels (deter- the polymerization, radicals existed near the clay surface could react
mined according to Eq. (3)). It is clearly seen that the removal with clay, thus the pNIPAm chains attached to the clay platelets
capacity of metal ions increased with the treatment time during forming a network structure. Also they confirmed that CMC was not
48 h. Also, the metal ion removal capacities of both hydrogels show a cross-linked by clay and still as linear chains incorporated in the
rapid increase with increasing treatment time during 7 h and then hydrogel. According to these conclusions, we concluded that in
slow down and reach almost equilibrium value in 48 h (Fig. 4). In case the pure hydrogel all NIPAm and AA moieties grafted onto CMC
of comparative investigation of non-competitive Cu2þ removal by H backbone to give long polymeric chains on CMC backbone and also

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662 B. Özkahraman et al. Clean – Soil, Air, Water 2011, 39 (7), 658–664

reacted with each other to give p(NIPAm-co-AA) copolymeric net- 0.91–0.99 that seem to be significant at first glance. But, the calcu-
works, and the presence of NMBA caused the formation of cross- lated qe values obtained from the first-order kinetic model do not
linked network. Thus, most of the grafted CMC chains crosslinked give reasonable values, which are low compared with experimental
with each other. But, in case of H–C, a definite amount of NIPAm and qe values. This suggests that the adsorption of metal ions onto the
AA monomers could be reacted with clay sheets to give polymeric hydrogels is not a first-order reaction. The determination coefficients
chains attached to the clay surface which could bring about a for the second-order kinetic model are very close to 1.000 for almost
decrease in grafting them onto the CMC backbone that cause a all cases. Also, the calculated qe values almost agree with the exper-
decrease in the crosslinking of CMC chains with each other. This imental data. These findings indicate that the adsorption system
means H–C network has higher amount of non-crosslinked CMC belongs to the second-order kinetic model. By using pseudo-second-
chains than that of H. Since the crosslinks (and also long polymeric order kinetic model data, the initial sorption rate, h0 (mmol/g h), can
chains attached the backbone) in a network may cause hindrance on be calculated as given below:
the active points responsible from adsorption process and the most
of COO
groups consist on the CMC backbone, observation of a bit h0 ¼ k2 q2e (6)
low value in sorption capacity of H than that of H–C is an acceptable
situation. This case also confirms the selectivity of the hydrogels, as it
will be discussed below, both hydrogel are more selective to Cu2þ As it seen from Tab. 2, the initial sorption rates for the adsorption
than Pb2þ. Since Pb2þ ion has bigger ion radius than that of Cu2þ, of Cu2þ onto both hydrogels are greater than those of Pb2þ. The
it is much more affected from this hindrance. Thus the sorption change tendency of adsorption capacities (Fig. 4) and h0 values
capacities of both hydrogels for Pb2þ are lower than those for Cu2þ. versus ion type may be ascribed to the following reasons. Several
To investigate the mechanism of adsorption, the pseudo-first-order parameters such as pH, initial ion concentration, metal ion–adsor-
and pseudo-second-order equations were used to test the experimen- bent interactions, adsorbent’s functional groups, and surface pro-
tal data of adsorption tests. The first-order rate expression of perties, the competition of metal ions with each other, etc., affect the
Lagergren [51] is given as: sorption rate and capacity. And it is generally expected that the
bigger the ion radius the stronger the metal ion–adsorbent inter-
logðqe
qt Þ ¼ log qe
ðk1 tÞ=2:303 (4) action is, because big ion radius causes more electropositivity, which
facilitates electrostatic interaction between metal ion and active
where qe and qt are the amounts of metal ion adsorbed on adsorbent points of the adsorbent [11, 13, 15]. However, in this study the
at equilibrium and at time t, respectively, in mmol/g, and k1 is the removal capacity of metal ions and h0 values followed the order
rate constant of first-order adsorption (h
1). In many cases, the first- of Cu2þ > Pb2þ, which could be described by following reason. As it
order equation of Lagergren does not fit well to the whole range of discussed before, the sorption process can be affected by several
contact time and is generally applicable over the initial stage of the parameters such as metal ion–adsorbent interaction and adsorbent
adsorption processes [51, 52]. The second order kinetic model [47, 48] surface properties. As it known, metal ions that have relatively big
is expressed as: ion radius have stronger metal ions–adsorbent interactions than
! these of relatively smaller ones. Contrarily, this case causes
 
t 1 t more difficult diffusion into the crosslinked hydrogel network.
¼
 þ (5)
qt k2 q2e qe While the ions that have smaller ion radius could easily diffuse into
the polymer network, the ions that have bigger ion radius could not.
where k2 (g/mmol h) is the rate constant of second-order adsorption. This case causes to slower sorption speed and lower sorption
If second-order kinetic is applicable, the plot of t/qt versus t should capacity. In this study, the crosslinked network probably more hin-
give determination coefficient >0.990. This kinetic model is more dered the interaction of Pb2þ ions with active points of the hydrogels
likely to predict the behavior over the whole range of adsorption and than that of Cu2þ. In other words, the ion radius of Cu2þ ions is
is in agreement with chemical sorption being the rate-controlling smaller than that of Pb2þ, which gains itself ease diffusion ability
step [52, 53], which may involve valence forces through sharing or into the crosslinked network, and effective interaction with the
exchange of electrons between metal ions and adsorbent. Table 2 active points. This case yields higher sorption capacity and h0 value
lists the calculated results with the determination coefficients (R2) of Cu2þ than these of Pb2þ. Similar behavior was observed in case of
for first order and second order kinetic models. The determination competitive metal removal study findings and discussed in next
coefficients for the first-order kinetic model are in a range of section.

Table 2. Kinetic parameters for the adsorption of Cu2þ and Pb2þ ions onto hydrogels.

Hydrogel qe,exp (mmol/g) Pseudo first order kinetic model Pseudo second order kinetic model h0 (mmol/g h)

k1 (h
1) qe,teo. (mmol/g) R2 k2 (g/mmol h) qe,teo. (mmol/g) R2

Cu2þ
H 2.14 0.1073 1.36 0.9313 0.2209 2.22 0.9991 1.09
H–C 2.23 0.1125 1.42 0.9332 0.2138 2.31 0.9988 1.14
Pb2þ
H 1.40 0.0971 0.87 0.9916 0.3653 1.44 0.9986 0.76
H–C 1.51 0.1024 0.96 0.9866 0.3275 1.56 0.9987 0.79

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Clean – Soil, Air, Water 2011, 39 (7), 658–664 Removal of metal ions by CMC based nanocomposite hydrogel 663

(iv) Competitive ion removal studies showed that both hydrogels

are selective to Cu2þ.

The authors have declared no conflict of interest.

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