Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 133 (2014) 876882

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Spectrochimica Acta Part A: Molecular and

Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa

Studies of anions sorption on natural zeolites q

K. Barczyk , W. Mozgawa, M. Krl
Faculty of Material Science and Ceramics, AGH University of Science and Technology, Al. Mickiewicza 30, 30-059 Krakw, Poland

h i g h l i g h t s

g r a p h i c a l a b s t r a c t

 We modied different natural

zeolites with the

hexadecyltrimethylammonium
cations.
 Surfactant-modied zeolites were
used to immobilization of inorganic
anions.
 We showed that anions sorption
causes changes in IR spectra of the
HDTMAzeolites.

a r t i c l e

i n f o

Article history:
Received 1 December 2013
Received in revised form 2 May 2014
Accepted 9 June 2014
Available online 19 June 2014
Keywords:
Natural zeolite
Surfactant modication
Anions sorption
FT-IR spectra

a b s t r a c t
This work presents results of FT-IR spectroscopic studies of anionschromate, phosphate and
arsenate sorbed from aqueous solutions (different concentrations of anions) on zeolites. The sorption
has been conducted on natural zeolites from different structural groups, i.e. chabazite, mordenite,
ferrierite and clinoptilolite. The Na-forms of sorbents were exchanged with hexadecyltrimethylammonium cations (HDTMA+) and organo-zeolites were obtained. External cation exchange capacities (ECEC) of
organo-zeolites were measured. Their values are 17 mmol/100 g for chabazite, 4 mmol/100 g for mordenite and ferrierite and 10 mmol/100 g for clinoptilolite. The used initial inputs of HDTMA correspond to
100% and 200% ECEC of the minerals. Organo-modicated sorbents were subsequently used for immobilization of mentioned anions.
It was proven that aforementioned anions sorption causes changes in IR spectra of the HDTMAzeolites. These alterations are dependent on the kind of anions that were sorbed. In all cases, variations
are due to bands corresponding to the characteristic SiO(Si,Al) vibrations (occurring in alumino- and
silicooxygen tetrahedra building spatial framework of zeolites). Alkylammonium surfactant vibrations
have also been observed. Systematic changes in the spectra connected with the anion concentration in
the initial solution have been revealed.
3
3
The amounts of sorbed CrO2
4 , AsO4 and PO4 ions were calculated from the difference between their
concentrations in solutions before (initial concentration) and after (equilibrium concentration) sorption
experiments. Concentrations of anions were determined by spectrophotometric method.
2014 Elsevier B.V. All rights reserved.

Introduction

Selected paper presented at XIIth International Conference on Molecular

spectroscopy, Krakw Biaka Tatrzanska, Poland, September 812, 2013.
Corresponding author. Tel.: +48 126175220; fax: +48 126337161.
E-mail address: barczyk@agh.edu.pl (K. Barczyk).
http://dx.doi.org/10.1016/j.saa.2014.06.065
1386-1425/ 2014 Elsevier B.V. All rights reserved.

Natural zeolites are a group of crystalline, hydrated tectoaluminosilicates characterized by varied and extremely valuable physicochemical properties. One of the most signicant is the ability
of sorption and separation of ions and molecules. Due to the high

K. Barczyk et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 133 (2014) 876882

cation exchange capacity (CEC), these minerals are widely used in

the process removing of heavy metal cations from aqueous solution [1,2]. One the other hand, the presence of uncompensated
negative charge of zeolites crystal lattice, causes their very low
afnity for inorganic anions or nonpolar particles. The increasing
of the anion exchange capacity can be achieved by changing the
chemical surface properties. The treatment of these minerals with
large cationic surfactants, such like hexadecyltrimethylammonium
amine (HDTMA), leads to changes in the external surface charge of
the zeolite from negative to positive [3]. Molecules of HDTMA type
are long-chain forms, which dissolve in water and hydrolyze to the
organic cation and inorganic ion (Br or Cl). Surfactant cations
exchange with inorganic cations (i.e. Na+, K+, Ca2+), which occupy
ion exchange position on the outer surface of the zeolite and form
full or partial surfactant bilayer. In this way net charge of zeolite is
changed from negative to positive [46], which provides sites for
exchange of inorganic anions. Such modication does not limit cation exchange capacity of sorbents, so they can be used in double
role. Thus, the result of surfactant modication is ability of organo-zeolites to sorb both anions and cations and non-polar organic
molecules from aqueous solutions [7]. Some of the related papers
describe changes on IR spectra caused HDTMA-modication
[810].
Organo-zeolites can be successfully used in the processes of
sorption such anions like: chromate [11,12], arsenate [13,14],
phosphate [15], nitrate [16,17], sulphate [18], etc. from aqueous
solutions.
The aim of this work was to compare the sorption properties of
natural zeolites modied with the hexadecyltrimethylammonium
cations (HDTMA+), to the selected inorganic anions (CrO24 , AsO34
and PO34 ), with results of IR spectroscopic studies of sorbents.
The results of sorption and structural studies of modied clinoptilolite, presented in the paper [19] shows that comparison of the
spectra before and after the organic modication and before and
after the sorption of various inorganic anions, allows to determine
their inuence on the structure of sorbents.
In the presented work, studies were extended to concern zeolites from different structural groups, i.e. chabazite, mordenite, ferrierite and clinoptilolite. The typical chemical composition of
chabazite is given by Ca2[Al4Si8O24]
12H2O formula and its aluminosilicate structure (framework type code CHA) consist SBU (Secondary Building Units) built of double 6-ring (D6R). Mordenite
(Na8[Al8Si40O96]
24H2O) and ferrierite (Mg2Na2[Al6Si30O72]
18H2O), which framework type code is MOR and FER respectively, are
example of the group of zeolite in which SBU is the 51 complex
(T8O16 units). Clinoptilolite ((K2,Na2,Ca)3[Al6Si30O72]
20H2O)
belongs to heulandite group (framework HEU) of zeolites and its
SBU is the 44 = 1 complex (T10O20 units) [20].

877

Organic modication was carried out in the following way:

aqueous suspensions of the zeolites and the organic salts were stirred for 24 h at 80 C, left for 24 h at 30 C, after which the supernatants were removed by decanting and the samples were washed
twice with a small amount of redistilled water to a negative reaction for bromide ions. The residues were then dried and homogenized. The effectiveness of modication has been conrmed by
measurement of electrokinetic (zeta) potential and infrared spectroscopy (FT-IR) studies.
Obtained organo-zeolites were subsequently used for immobilization of CrO24 , AsO34 , PO34 ions. Anions were introduced into the
sorbents structure from aqueous solutions with the initial concentrations from 0.01 to 5 mmol/dm3 at a weight sorbent/solution
ratio of 1:50. For this purpose 0.1 g (0.00001 g) of the organo-silicate was placed in a tube and 5 cm3 of appropriate anions solution
was added. The pH 4 was adjusted with 1 M hydrochloric acid. The
mixture was shaken for 24 h at 25 C and centrifuged. All the sorption experiments were done in triplicates for each anion
concentration.
The amounts of sorbed anions were calculated from the difference between their concentrations in solutions before (initial concentration) and after (equilibrium concentration) sorption
experiments. Concentrations of all ions were determined spectrophotometrically (UVVIS HITACHI U-1800) using the biphenylcarbazide method for chromates and molybdenum blue method for
phosphates and arsenates.
The change in the surface charge of sorbents from negative to
positive was conrmed by measurement of electrokinetic potential, which was made using Zetasizer Nano ZS Instrument. The
medium of measurement was an aqueous solution of NaCl at a concentration of 10 2 mol/dm3. The zeta potential value was estimated as an average of 5 measurements.
Spectroscopic studies of organo-zeolite before and after anions
sorption were measured on a Bruker Vertex 70v spectrometer.
Infrared spectra were collected in the mid infrared (MIR) region
(4000400 cm 1) after 512 scans at 1 cm 1 resolution. Samples
were prepared using the standard KBr (Merck) pellets method.

Experimental
Studies presented in this work were divided into several stages:
(1) transformation zeolites into sodium form; (2) modication of
them with HDTMA-Br; (3) sorption of selected anions using
obtained sorbents; and (4) MIR spectroscopic studies of organozeolites after anions sorption.
In order to improve the ion exchange properties, all zeolites
were transformed into sodium forms. The Na-forms of sorbents
were exchanged with hexadecyltrimethylammonium cations
(HDTMA+) [8,10] in amount equivalent to 100% (1.0) and 200%
(2.0) ECEC of each of the zeolites. The value of ECEC in relation to
HDTMA+, determined by sorption of alkylammonium ions, are
17 mmol/100 g, 4 mmol/100 g, 4 mmol/100 g and 10 mmol/100 g
respectively for chabazite, mordenite, ferrierite and clinoptilolite.

Fig. 1. FT-IR spectra of mordenite modied with increasing amount of HDMTA-Br.

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K. Barczyk et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 133 (2014) 876882

Fig. 2. Sorption isotherm of: (a) chromate, (b) phosphate and (c) arsenate ions on chabazite, mordenite, ferrierite and clinoptilolite after HDTMA-modication.

K. Barczyk et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 133 (2014) 876882

879

Fig. 2 (continued)

Result and discussion

The results of the zeta potential measurements indicated that
the negative surface charge of natural zeolites ( 39 mV for chabazite, 59 mV for ferrierite, 53 mV for mordenite and 45 mV for
clinoptilolite) was changed to positive after organic modication.
When the HDTMA+ loading equals to 100% (1.0) ECEC of each of
the zeolites, the initial negative charge was neutralized by surfactant cations. Introduction of additional amount of surfactant cations resulted in a gradual increase of the zeta potential. At
maximum load with HDTMA+, the zeta potential reached: +38,
+22, +22 and +47 mV for chabazite, ferrierite, mordenite and
clinoptilolite respectively. The charge reversal conrmed that surfactant cations form an organic bilayer or patchy bilayer coating on
the external surface of zeolite.
Chabazite, mordenite, ferrierite and clinoptilolite modied with
different amount of HDTMA-Br were mainly investigated with the
use of infrared spectroscopy (FT-IR). Due to the fact that HDTMA+
sorption process occurs only on the surface of sorbents, the bands
connected with the internal SiO(Si) and SiO(Al) vibrations in
tetrahedra or alumino- and silico-oxygen (in the range of
1200400 cm 1) remain unchanged.
However, organic modication causes that in the MIR spectra of
zeolites bands associated with the presence of HDTMA appear.
In the range of 30602820 cm1 (Fig. 1), the two intense bands,
at about 2920 cm 1 and 2851 cm 1, are associated respectively
with asymmetric and symmetric stretching vibrations of CH2
groups [21]. With the increase in the initial concentration of surfactant, these bands are shifted towards lower wavenumbers to
about 2920 and 2851 cm 1, respectively. Simultaneously, their
integral intensity increases with increase of HDTMA+ packing density. The observed shift is a consequence of the conformational
changes of the chain on the zeolite surface (transition from gauche

to trans conformation) [10]. At small amount of surfactant cations

on the zeolite surface, these bands appear at higher wavenumbers.
This is due to disordered arrangement of chains of HDTMA+, which
adopt gauche conformations. With the increase of the content of
surfactant on the surface, chains gradually adopt highly ordered
trans conformations characteristic of crystalline HDTMA Br, for
which these bands are respectively at 2918 and 2850 cm 1 [22].
Fig. 2 presents spectrophotometric study (UVVIS) results of
chromates, arsenates and phosphates sorption on chabazite, mordenite, ferrierite and clinoptilolite unmodied and modied with
HDTMA-Br in amount equivalent to 1.0 and 2.0 of ECEC of each
of the zeolites, as a function of the equilibrium anions concentration in the solution. Sorption of mentioned anions depends on
the kind of anion and its initial concentration in the solution, as
well as on the type of zeolite and its surfactant loading level.
As shown in Fig. 2, all anions are slightly exchanged on the
unmodied zeolites. The low afnity of natural zeolites for anionic species results from negative charge of their crystal lattice,
which provides sites for exchanging cations but not for anions.
In contrast, surfactant-modied zeolites (SMZ) show signicant
sorption of all three oxyanions from aqueous solution. The ability
of SMZ to sorb anions is due to anion exchange with chargebalancing anions (initially Br ) on the headgroups of the
surfactant bilayer.
The removal capacity of anions gradually increased with
increasing of the initial concentration of the solution. It relates to
both the zeolites treated with HDTMA at amount equal to 1.0
and 2.0 the ECEC of each of the sorbents. This trend can be easy
explained by the increase in the amount of ions in solution, which
can be adsorbed. Additionally, higher difference in the initial solution concentration is the driving force mass diffusion from the
solution to the solid phase, which in turn increases the probability
of contact the anion with exchange site on SMZ surface [12].

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K. Barczyk et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 133 (2014) 876882

Fig. 4. MIR spectra of: (a) clinoptilolite and (b) mordenite modied with 2.0 ECEC of
HDTMA before and after sorption of different ions form the aqueous solution with
5 mmol/dm3 initial concentration in the range of 30402800 cm 1.
Fig. 3. MIR spectra of: (a) chabazite and (b) clinoptilolite modied with 2.0 ECEC of
HDTMA before and after sorption of different ions form the aqueous solution with
5 mmol/dm3 initial concentration.

The most effectively sorbed anions are chromates, which sorption capacities on zeolites modied with 2.0 of ECEC are 198, 112,
77 and 56 mmol/kg, respectively for chabazite, clinoptilolite, ferrierite and mordenite. In contrast, sorbents modied with HDTMA
in amount equivalent to 1.0 the ECEC removed little more than a
half of maximum amount sorbed anions on zeolites modied with
double layer of HDTMA. Trivalent anions, like phosphates and arsenates, are removed to a much lesser extent, and their anion
exchange capacities do not exceed 50 mmol/kg for AsO34 and
35 mmol/kg for PO34 .
These results clearly show that differences in sorption capacity
are caused by many factors, like the type of anion, its charge and
speciation in aqueous solution. The removal of oxyanions from
aqueous solution depends strongly on the pH of the solution,

which affects the surface charge of the sorbent and determines

the kind of anion species [11]. The pH of each of anions solution
was adjusted to pH 4. According to the Cr(VI) speciation diagram
[23], at this value of pH, predominant Cr(VI) species are HCrO4
anions. These univalent forms require one exchange site from
SMZ for sorption one molecule of HCrO4 on zeolite surface at that
pH. At the higher pH predominant forms of Cr(VI) are divalent ions
(CrO24 and Cr2O27 ), which need two surface sites from SMZ. This
causes, that more chromate ions can be removed by organo-zeolites at pH 4 than at higher pH.
In contrast, at the pH study, arsenates(V) and phosphates(V)
exist mostly also as univalent ions, H2AsO4 and H2PO4 respectively. However, neutral forms: H3AsO4 and H3PO4 are also common in the aqueous solution [24,25]. Probably, the presence of
these neutral forms results in lower removal capacity of As(V)
and P(V) than Cr(VI) at pH = 4. This follows from mechanism of

K. Barczyk et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 133 (2014) 876882

retaining these anions, which is mainly limited to ion exchange

with charge-balancing anions (Br ) in surfactant bilayer on zeolites
surface, therefore physical sorption of neutral form does not occur.
However, other potential sorption mechanisms cannot be
excluded. The surface precipitation of oxyanions with HDTMA
and/or chemical reduction of anions to less soluble forms may
inuence the removal of inorganic anions form aqueous solution
[6].
The anion sorption properties also strongly depend on the type
of zeolites. Among the analyzed minerals, chabazite has the highest
anion exchange capacity, while mordenite and ferrierite have the
lowest. These differences result from i.a. the value of the negative
surface charge of aluminosilicate network. The higher the charge,
the lower the ratio of Si/Al, which causes the zeolite to have more
exchange sites and thus enables it to sorb more HDTMA+ to cover
the surface, and to exhibit higher value ions sorption capacity.
Chabazite has the lowest Si/Al ratio from examined zeolites
(Si/Al = 6.9) and shows the highest anion exchange capacities,
whilst for mordenite and ferrierite (zeolites belonging to high silica
minerals) this ratio is the highest (in case of mordenite Si/Al = 12.1
and ferrierite Si/Al = 19.3), so their anion sorption properties are
lower.
The results of anion sorption properties of zeolites indicated
spectrophotometrically (UV/VIS) have been compared with those
obtained by FT-IR spectroscopy studies. The MIR spectra of different zeolites modied with 2.0 ECEC of HDTMA before and after
anion sorption from the solution with the maximum initial concentration equal to 5 mmol/dm3, are presented in Fig. 3.
All bands occurring in the spectra can be divided into several
groups [19] associated with different types of vibrations realized
in samples structure:
 38001600 cm 1
vibrations related to the presence of OH
groups and zeolite water in the structure;
 30402800 cm 1
vibrations associated with the presence of
HDTMA+ on the external surface of zeolites;
 1300800 cm 1
internal, anti-symmetric SiO(Si) and Si
O(Al) vibrations in tetrahedra or alumino- and silicooxygen
bridges;
 820680 cm 1
pseudolattice vibrations of aluminosilicate
structure and vibrations characteristic for HDTMA+;
 15001400 cm 1
internal vibrations connected with methylene chains of surfactant molecules.
Due to small amount of ions retained on zeolite surface, the
bands originating from the anions were not observed.
Comparison of the spectra presented in Fig. 3 and detailed analysis in particular ranges of wavenumbers show that noticeable differences between them are observed in the second and fourth
group of mentioned bands.
In the region of 30402800 cm 1 (Fig. 4) bands connected
directly with the organic modication of the sorbents occur. The
two most intense of them at ca. 2922 and 2852 cm 1 correspond
to the anti-symmetric and symmetric CH2 stretching modes of
amine respectively. As was mentioned, their intensity strongly
depends on the packing density of amine chains, thus visible
changes in the spectra are observed mainly for organo-zeolites
modied with 2.0 ECEC of HDTMA+. Comparison of the spectra of
organo-zeolites before and after sorption of different anions shows
that their presence in zeolite structure causes change in the position of these bands. Replacement of the small Br ions by large
inorganic anions (HCrO4 , H2AsO4 and H2PO4 ) results in a shift of
the bands responsible for CH stretching vibrations toward higher
wavenumbers. The magnitude of this shift depends on amount of
anions retained on external zeolite surface. The maximum anion
sorption capacities are obtained in the case of chromates, hence

881

Fig. 5. MIR spectra of chabazite modied with 2.0 ECEC of HDTMA before and after
sorption of different ions form the aqueous solution with 5 mmol/dm3 initial
concentration in the range of 840680 cm 1.

the biggest shift is visible for these anions (about 4 cm 1), whilst
the smallest shift refers to AsO34 and PO34 ions, which are sorbed
to a much lesser extent.
In the fourth analyzed region (860680 cm 1) bands which concern two types of vibrations realized in zeolites structure occur
(g. 5). The rst type related to bands at ca. 776 cm 1 and
635 cm 1 originates from pseudolattice vibrations of aluminosilicate structure of zeolites. The anion sorption process is limited
only to external surface of organo-zeolites, hence the bands connected with the internal SiO(Si) and SiO(Al) vibrations in tetrahedra or alumino- and silico-oxygen bridges remain unchanged.
The second group of bands is connected with HDTMA+ modication. The bands at ca. 730 and 720 cm 1 correspond to the
CH2-rocking mode [22]. The bands responsible for these vibrations
are splitted, which is a consequence of intermolecular interaction
between the two adjacent hydrocarbon chains in perpendicular
orthorhombic cell [21,22]. As can be noticed, the rocking vibrations
in methylene group are preserved at essentially unchanged frequencies during anions sorption process. At the same time, the
integral intensity of these bands decreases with the increase of
concentration in the initial solution. As in the case of the bands
in the second analyzed region, the most visible changes are
observed for chromates, because CrO24 ions are sorbed the most
effectively form all anions.
Conclusions
Based on obtained results the following conclusions can be
drawn:
 Organic modication with the use of HDTMA+ leads to change
of the surface properties of all analyzed zeolites, giving them
the ability to anions sorption.
 The anion sorption capacity of SMZ depends on the kind of
anion and its initial concentration in the solution, as well as
on the type of zeolite and its surfactant loading level.
 Sorbents modied with 2.0 of ECEC of each of zeolites show
greater anion sorption than materials modied with 1.0 of
ECEC, and have a bigger afnity for chromates than for
arsenates and phosphates.

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K. Barczyk et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 133 (2014) 876882

 In the MIR spectra of all zeolites after surfactant modication

additional bands associated with HDTMA+ appear. With the
increase of the surfactant content, these bands are shifted
toward lower wavenumbers with simultaneous increase of
their integral intensity.
 Anion sorption process causes changes in the MIR spectra of
zeolites. These changes relate to the two ranges of wavenumbers (30402800 cm 1 and 820680 cm 1) and depend on
amount of anions retained on external zeolite surface. In the
region of 30402800 cm 1 (related to the presence of HDTMA+
in the structure) bands at ca. 2922 and 2852 cm 1, correspond
to the anti-symmetric and symmetric CH2 stretching modes
respectively are shifted to higher wave numbers with the
increase of the sorbed anions.
 In the 820680 cm 1 region, the anion sorption process causes a
decrease in the intensity of the bands connected with zeolites
modication by HDTMA+ at 730 and 720 cm 1. The bands at
ca. 776 and 635 cm 1 connected with the internal SiO(Si)
and SiO(Al) vibrations in tetrahedra or alumino- and silicooxygen remain unchanged. This conrms that anions sorption
process occurs only on the surface of sorbents.

Acknowledgments
Financial support this work was provided by AGH University of
Science and Technology in Krakow under Grant No. 15.11.160.114.
The authors would like to thank Dr. T. Bajda from Faculty of
Geology, Geophysics and Environmental Protection AGH University of Science and Technology for his help during measurements
of anion sorption capacity of SMZ.

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