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Microporous and Mesoporous Materials 109 (2008) 3848

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Characterization of the binding site anity distribution

of a surfactant-modied clinoptilolite
A.I. Perez Cordoves a, M. Granda Valdes a, J.C. Torres Fernandez b, G. Pina Luis a,
J.A. Garca-Calzon c, M.E. Daz Garca c,*
a
Faculty of Chemistry, University of La Habana, Cuba
b
Faculty of Chemical Engineering, Federal University of San Carlos, Brazil
c
Faculty of Chemistry, University of Oviedo, Spain

Received 13 December 2006; received in revised form 13 March 2007; accepted 17 April 2007
Available online 29 April 2007

Abstract

The kinetics, adsorption isotherms, equilibration time and pH eect of a surfactant-modied activated clinoptilolite (SMZ) on the
removal of toxic Cr(VI) species from aqueous solutions were studied. Simultaneously, the Cr(III) sorption characteristics of the activated
clinoptilolite (NaZ) were also studied. The cation and anion exchange capacities of each zeolite were calculated and in the case of the
Cr(VI)-SMZ system several models were studied for adsorption isotherm description. Experimental binding isotherms were tted by
non-linear regression to Langmuir, Freundlich and Jovanovic as well as to hybrid models isotherms and the anity distribution cor-
responding to the Freundlich isotherm was used to extract binding parameters. It has been demonstrated for the rst time that the anity
distribution analysis combined with the Freundlich binding model allows the characterization of the SMZ binding properties for Cr(VI).
In comparison to other surfactant-modied clinoptilolites, this activated zeolite proved to have improved properties for Cr(VI) adsorp-
tion. The results obtained demonstrate the possibilities of the surfactant-modied activated zeolite for separation of Cr(VI) from Cr(III)
and hence, its speciation. Its potentiality for chromium speciation using a ow injection system with a minicolumn packed with SMZ is
outlined.
 2007 Elsevier Inc. All rights reserved.

Keywords: Surfactant-modied clinoptilolite; Zeolite; Chromium; Anity distribution

1. Introduction In fact, modications with cationic surfactants, such as

Natural zeolites have been used as cationic exchange
materials for the remediation of heavy metals and other
contaminants due to their excellent properties as sorbents,
as demonstrated by their use in bioremediation barriers to
remediate both ground water and soil containing petroleum
hydrocarbons. They also have the advantages of being very
abundant in nature and of having high chemical stability.
During the last decade alternative and novel modica-
tions have been exploited in order to attribute zeolites with
new properties that extend their spectrum of application.
*
Corresponding author. Tel.: +34 985 10 34 71; fax: +34 985 10 31 25.
E-mail address: medg@uniovi.es (M.E. Daz Garca).
high molecular weight quaternary ammonium salts, have
been rapidly gaining in importance since they provide zeo-
lites with the possibility of also behaving as anionic
exchangers [13]. According to studies done by Bowman
et al. [4], the sorption of this type of surfactant on zeolites
is limited to sites of external exchange. This is probably due
to the diameter of the channels, which are suciently large
for exchangeable cations but too small for the surfactant
cations. Surfactants long chain makes them too bulky to
access the internal exchange sites. The molecules of surfac-
tant adsorbed on the zeolite may form bilayers within
which ion exchange, as well as hydrophobic bonds, are
involved [5,6]. The proposed mechanism [3] of adsorption
and cation exchange is shown in Fig. 1a.

1387-1811/$ - see front matter  2007 Elsevier Inc. All rights reserved.
doi:10.1016/j.micromeso.2007.04.029
 A.I. Perez Cordoves et al. / Microporous and Mesoporous Materials 109 (2008) 3848
The sorption of inorganic anions on surfactant-modied
zeolites has been attributed to the formation of a complex
formed on the zeolite surface [79]. For this, the modied
surface must have positively charged exchange sites formed
by the positive groups NR 3 of the surfactant directed
towards the surrounding solution in the bilayer. The posi-
tively charged head groups are balanced by counterions
(e.g. bromide, chloride), and the sorption or exchange of
other anionic components entails the substitution of these
weakly bonded counterions [7]. Fig. 1b shows this
mechanism.
The use of surfactant-modied zeolites as sorbents to
remove multiple types of contaminants from water has
attracted great attention recently [10,11] as this modica-
tion of zeolites (organo-zeolites) makes it possible to use
these materials not only in their traditional form as cationic
exchangers but also for the exchange of anions and non-
polar organic compounds, resulting this property very
interesting for the remediation and/or separation of dier-
ently charged chemical species. Surfactant-modied zeo-
lites have even been used for removing viruses and
bacteria from ground water [12].
Clinoptilolite samples from dierent regions exhibit dif-
ferent sorption (ion-exchange) processes. The goal of this
work was to study the adsorption properties of a Cuban
modied clinoptilolite with a cationic surfactant to be used
for the eective sorption/speciation of trace toxic metals in
water. Also, the adsorption properties of the activated
plain clinoptilolite were investigated. As a proof of the
Fig. 1. (a) Sorption mechanism of surfactant on clinoptilolite surface, (b) Sorption mechanism of anions on the surfactant-modied clinoptilolite, (c)
Silanol active binding sites in conditioned clinoptilolite.
39
principle, Cr(VI) and Cr(III) were selected as model toxic
metal species for several reasons. Firstly, works aimed to
environmental studies demonstrated that surfactant-modi-
ed zeolites, as permeable barriers for remediation, may
control chromate migration by sorption [1,8,13]. Second,
as it is well known, while Cr(III) plays an essential role
in plant and animal metabolism, Cr(VI) aects biological
functions and is extremely carcinogenic. On the other
hand, there are a great variety of industrial processes that
generate chromium contamination [14,15]. Chromium spe-
cies persistence in the environment and its bioaccumula-
tion, as well as its capacity to change from one oxidation
state to another, make strict monitoring necessary. Finally,
dierent electrostatic interactions are expected for each
species with the surfactant-modied clinoptilolite due to
their dierent charge, thus allowing separation of both
species.
In this paper, a surfactant-modied clinoptilolite (SMZ)
was prepared and investigated for sorption of toxic Cr(VI)
species from aqueous solutions. The kinetics, adsorption
isotherms, equilibration time and pH eect on the removal
were studied from non-competitive aqueous solution. In
this work, we have chosen to consider dierent isotherm
models, taking into account not only the simple ones, but
also lowhigh anity models. Experimental binding iso-
therms were tted by non-linear regression to Langmuir,
Freundlich and Jovanovic isotherms, as well as to the
hybrid LangmuirFreundlich and JovanovicFreundlich
isotherms. The anity distribution (AD) corresponding
40 A.I. Perez Cordoves et al. / Microporous and Mesoporous Materials 109 (2008) 3848
to the Freundlich isotherm was used to extract binding
parameters for the Cr(VI)-SMZ system. Simultaneously,
the sorption and desorption conditions of Cr(III) on the
plain activated zeolite (NaZ) were also studied. The cation
and anion exchange capacities of each zeolite were calcu-
lated and based on the results a ow injection system is
outlined for chromium speciation using a minicolumn
packed with SMZ.
2. Experimental section
2.1. Reagents
All the reagents used were of analytical grade. The
1000 mg L1 chromium standards were prepared from
K2CrO4 and Cr(NO3)3 9H2O, both Merck. These stock
solutions were diluted appropriately as necessary. The sur-
factant, hexadecyltrimethylammonium bromide (HDTMA),
was prepared 0.06 mol L1 for modication of zeolite.
2.2. Experimental
2.2.1. Zeolite source and conditioning
The raw material used for this work was a clinoptilolite
extracted from the Tasajera deposits, in the central region
of Cuba. The mineral was initially grounded, dried and
sieved till the desired fraction (0.20.5 mm). Zeolite (50 g)
was treated with 250 ml 1 M HCl/1 M citric acid (1:10 v/
v) solution, boiling for 6 h ( 2). The sample was ltered
and washed with deionized water. The zeolite was subse-
quently treated with 200 ml of an aqueous solution of
2 M NH4Cl, boiling for 6 h ( 2), after which the sample
was washed with deionized water and dried at 60 C for
12 h. The zeolite was calcined at 500 C for 15 h and
after a cool-down period the sample was washed with
deionized water. This activating procedure is new for this
type of material [16]. The chemical composition of the
raw and the conditioned clinoptilolite was performed by
ICP analysis using an ICP Spectroame (Spectro GmbH)
spectrometer.
2.2.2. Zeolite surfactant modication
Once the zeolites surface has been activated, the organic
modication with HDTMA was done according to Li [3] so
that the zeolites external cation capacity is exceeded. In
brief, the procedure was as follows: 20 g of conditioned
zeolite and 170 ml of 0.06 M HDTMA-Br solution was
placed in a 500-ml bottle and shaken at room temperature
for 8 h, a time sucient to reach sorption equilibrium. The
mixture was then centrifuged and the solid was washed
with deionized water (2 100 ml) in order to remove unre-
acted monomers. Finally, the material was air-dried. In the
case of the conditioned natural zeolite, conversion to the
sodium form was carried out in order to increase cation
exchange [17]. Hereafter, the organo-zeolite is abbreviated
as SMZ and the conditioned clinoptilolite without surfac-
tant as NaZ. The X-ray diraction patterns of the surfac-
tant treated, the conditioned and the plain-clinoptilolites
were recorded on a Philips PW 17291710 diractometer
with low angle facilities using Cu Ka1 (k = 1.54178 A)
radiation and equipped with a Ni lter and a graphite
monochromator. Data were collected stepwise over 2h 3
40 angular region, at a scanning rate of 2 min1. Crystal-
linity was obtained by comparing the X-ray diraction
peak intensities of the modied clinoptilolites with those
of the plain zeolite which was considered to be 100%
crystallinity.
2.2.3. Sorption of chromium species
Sorption of Cr(VI) and/or Cr(III) on the NaZ and on
the SMZ was conducted using a batch equilibration tech-
nique. 1 g of SMZ and 2.5 g of NaZ were contacted with
20 ml 0.05 mg mL1 solutions of hexa- and trivalent chro-
mium standards, respectively. Samples were shaken at
160 rpm and 25 C until equilibrium was reached and then
centrifuged. After equilibration, supernatants were ana-
lysed for remnant chromium as described below. For both
systems, the inuence of pH and time of contact on the
sorption process were studied.
In order to evaluate the behaviour of SMZ and NaZ in a
ow format, a dynamic study was done. For this, 0.5 g of
the respective material were packed in a glass column
(20 cm long by 0.6 cm of internal diameter) and a
100 mg L1 Cr(VI) or Cr(III) solution was made to ow
through at 1.5 mL min1. Fractions of 5 mL were collected
and the concentration of chromium in the eluates was
determined. This process was continued until Cr concentra-
tion in eluates corresponded with the inlet value, which
indicated that the corresponding zeolite was saturated with
the metal ion. From the results of these experiments, the
anion exchange capacity (AEC), in the case of hexavalent
chromium, and the cation exchange capacity (CEC), in
the case of trivalent chromium, were determined. Break-
through curves were also constructed from these data.
The desorption process was studied passing the eluant
(KCl 3 mol L1) at a rate of 1.5 mL min1 through the
chromium loaded zeolite column. Fractions of 5 mL were
collected and chromium determined in each. This process
was continued until chromium was not detected in the
eluates.
All chromium determinations in solution were done
spectrophotometrically with diphenyl carbazide (DPhC)
at k = 540 nm using a Karl-Zeiss UVVis spectrophotom-
eter, Model 210, employing a 1 cm cuvette. In the case of
Cr(III) a previous oxidation process with (NH4)2S2O8
(0.1% solution in sulphuric acid) and heating was neces-
sary. All the data presented are the result of at least three
independent experiments.
2.2.4. Characterization of adsorption isotherms
Adsorption isotherms were obtained by shaking for the
appropriate periods of time a xed mass of each zeolite
with solutions of dierent initial concentrations of the cor-
responding ion, and then remnant chromium in solution
 A.I. Perez Cordoves et al. / Microporous and Mesoporous Materials 109 (2008) 3848
was determined. The amount of adsorbed Cr(VI) at equi-
librium,, was calculated from the simple mass balance
equation as follows:
C0  C
BV
M
where C0 is the initial chromium concentration, C is the
equilibrium concentration of the corresponding ion, V is
the volume of the solution and M is the mass of the zeolite.
2.2.4.1. Adsorption isotherm models. In order to character-
ize the surface, we estimated isotherm parameters as the
anity constant (K), the binding site density (Nt), or the
heterogeneity parameter (m), by using the most adequate
adsorption isotherm model between the following seven
equilibrium models: Langmuir (L), Bi-Langmuir (Bi-L),
Jovanovic (J), Bi-Jovanovic (Bi-J), Freundlich (F), Lang-
muirFreundlich (LF), and JovanovicFreundlich (JF)
isotherms. It is important to highlight here that Langmuir
isotherm has been extensively used to study adsorption
properties of zeolitic materials [1820]. Langmuir and
Jovanovic models were considered in this study because
heterogeneous surfaces can be considered as a juxtaposi-
tion of a large number of adsorption centres with the same
properties. These centres are supposed to be grouped in
large patches on the surface constituting independent ther-
modynamic adsorption sub-systems. On each of these
patches the isotherm may be given by the Langmuir or
the Jovanovic isotherm model. The adsorption constant
on each homogeneous surface is dierent and the calcula-
tion of this distribution of adsorption energy is key in the
determination of the most appropriate isotherm model that
may best describe the experimental adsorption data [21].
2.2.4.2. Langmuir (L) and Bi-Langmuir (Bi-L) isotherms.
The Langmuir (L) sorption isotherm [22] assumes that
sorption takes place at specic homogeneous sites within
the adsorbent. Also, it assumes that once a chromium ion
occupies a site, no further sorption can take place at that
site, that all sites are energetically equivalent and that there
is no interaction between ions adsorbed on neighbouring
sites. Theoretically, the zeolite has a nite capacity for
the metal ion. Therefore, a saturation value should be
reached beyond which no further sorption can take place.
While the Langmuir model assumes that there is only a sin-
gle class of binding sites, the bi-Langmuir (Bi-L) model [23]
assumes that there are two classes of sites within the zeolite.
It is straightforward to implement the Langmuir and bi-
Langmuir models using Scatchard plots [24] to determine
the binding parameters, using the general expression:
B chromium concentration in solution, C, such that:
KN t  KB
C B
In homogeneous systems with only one type of binding
sites, by plotting B/C against B it is possible to obtain the
value of Nt from the x-intercept and the value of K from
the slope.
41
In heterogeneous systems, Scatchard plots are not linear
and the simplest model in this case is a material with two
dierent kinds of adsorption sites. Langmuir equation is
then extended to an equation with two Langmuir terms
1 (bi-Langmuir equation):
N 1K 1C N 2K 2C
B 3
1 K 1C 1 K 2C
Thus, the plot B/C versus B is composed of two straight
lines, from which two sets of binding parameters (K1, N1,
and K2, N2) for the two classes of binding sites within the
zeolite can be obtained. The steeper line corresponds to
the high-anity sites while the atter line measures the
low-anity ones.
2.2.4.3. Jovanovic (J) and Bi-Jovanovic (Bi-J) isotherms.
The Jovanovic (J) isotherm [25] is expressed by the follow-
ing equation:
 
B N t 1  eKC 4
As in the Langmuir model, there are several (J) isotherm
equations available for analysing experimental sorption
data, particularly those from chromatographic analysis.
However, these Jovanovic extensions require multicompo-
nent data in order to identify the interaction parameters.
One of the most widely used is the bi-Jovanovic isotherm,
represented as follows:
B N 1 1  eK 1 C N 2 1  eK 2 C 5
where N1 and N2 are the saturation capacities (binding site
densities) for the rst and the second type of sites, respec-
tively, and K1 and K2 are the corresponding adsorption
constants.
2.2.4.4. Freundlich (F) isotherm. The (F) isotherm is an
empirical power function for non-ideal sorption on hetero-
geneous surfaces [26] and is expressed by the equation:
B aC m 6
where a is a Freundlich parameter (related with the sorp-
tion capacity, Nt, and the average anity, K0) and m is
the heterogeneity index and varies from zero to one (values
approaching zero indicate increasing heterogeneity and one
being homogeneous). The Freundlich equation has been
derived by assuming an exponentially decaying sorption
site energy distribution.
2.2.4.5. LangmuirFreundlich (LF) isotherm. This model
[27] describes an equilibrium relationship between the con-
centration of bound chromium, B, and the equilibrium
2 N t K m0 C m
7
1 K m0 C m
where K0 is the median binding anity. The variable a is
related to K0 via K0 = a1/m. The tting parameter, m, is
identical to the heterogeneity index of site energies from
42 A.I. Perez Cordoves et al. / Microporous and Mesoporous Materials 109 (2008) 3848
the (F) isotherm. The dierence between the (LF) model
and the Freundlich one is evident at high chromium con-
centrations, for which the (LF) model is able to represent
the saturation behaviour. At low sorbate concentrations
the (LF) equation reduces to the classical (F) equation.
On the other hand, as m approaches unity, indicative of
a completely homogeneous zeolite surface (i.e. energetic
equivalence of all binding sites), the (LF) equation re-
duces to the classical (L) equation. Thus, the hybridised
(LF) isotherm is able to model adsorption of solutes at
high and low concentrations onto homogeneous and heter-
ogeneous materials.
2.2.4.6. JovanovicFreundlich (JF) isotherm. The Jova-
novicFreundlich (JF) is a new isotherm model [28] for
describing single-component adsorption equilibrium on
heterogeneous surfaces. In this model the heterogeneous
surface can be divided into heterogeneous patch-like
domains, each domain being characterized by its own
energy distribution. So, the total adsorption isotherm rep-
resents the average over all values of the adsorption ener-
gies and can be expressed as follows:
m sites, N K min K max , and the apparent average association con-
B N t 1  eKC
where m is the heterogeneity index and K is a constant that
only depends on temperature and its magnitude indicates a
measure of the sorbentadsorbate interaction energy. The
equation reduces to the Jovanovic equation when the sur-
face becomes homogeneous (m = 1). At low adsorbate con-
centrations, the equation reduces to the Freundlich
isotherm but at high concentrations, monolayer coverage
is achieved.
2.2.4.7. Fitting parameters. The best-t values for the iso-
therm parameters were obtained by a numerical procedure
that minimizes the dierences between the theoretical data
for B predicted from the dierent isotherm equations and
the experimental data, using a non-linear regression
method. The selection of the most adequate adsorption iso-
therm models was made by minimizing the non-linear Mar-
quardt error function [29] across the concentration range
using a Fisher test calculated as
P
n
2
Bexp;i  Bi
n  p i1
F 9
n1 P n
Bexp;i  Bcalc;i 2
i1
where n is the number of experimental points, p is the num-
ber of parameters within the isotherm equation, Bexp,i are
the experimental points, B i are the average of the experi-
mental data points, and Bcalc,i are the corresponding calcu-
lated values. The second factor in the denominator of the
Fisher parameter contains the residual sum of squares.
Consequently, the higher F, the higher correlation between
the model and the experimental data. On the other hand,
the rst factor in the numerator of the Fisher parameter de-
creases as the number of parameters in the model (p) in-
creases. This means that the Fisher parameter shows to
which extent the introduction of a new parameter in the
model can actually decrease the residual sum of squares
in a signicant way, allowing a comparison of models hav-
ing dierent number of parameters. According to this Fish-
er test, the model that better correlates the data is the one
that exhibits the highest values of F.
2.2.4.8. Anity distribution (AD) analysis. A number of
researchers [3033] in the eld of molecularly imprinted
polymers (MIPs) have used an analytical expression to cal-
culate ADs for materials that better t to a Freundlich (F)
isotherm. This, together with the fact that zeolites present
similarities in heterogeneity to MIPs, led us to use the same
expression.
The equation is:
sinpm m
N K i a Ki 10
p
where Ki = 1/Ci. From this equation, two additional bind-
ing parameters may be calculated, the number of binding
8 stant, Kn:
 
N K min K max a1  m2 K m m
min  K max 11
 m K 1m  K 1m 
min max
Kn 12
m  1 K m m
min  K max
where Kmax and Kmin are limited by the measured free con-
centration of template, being equal to the reciprocal corre-
sponding concentrations: Kmax = 1/Cmin and Kmin = 1/
Cmax.
2.2.4.9. Anity spectrum. The tting parameters were then
substituted into the anity distribution Eq. (10) and plot-
ted in a Ln(N(K)) versus Ln(K) format. The anity distri-
bution for the zeolite was obtained for chromium sorption.
Numbers of binding sites N(K) were calculated using Eq.
(10) and employing the same Kmin and Kmax. Specic
details concerning the calculation of the anity spectrum
from raw adsorption data as those collected in this work
are given in a recent review [33].
3. Results and discussion
3.1. Batch studies
pH studies were done by equilibrating the zeolitic mate-
rial with the corresponding chromium solutions at dierent
pH values, in the conditions described previously in which
zeolite active sites were in excess with respect to total metal
concentration. In the case of Cr(VI) this experiment was
repeated for three dierent concentrations of the anion.
Figs. 2a and b show the results for Cr(VI) and Cr(III),
respectively. As can be seen in (a), the sorption of Cr(VI)
was practically constant in the whole pH range studied,
 A.I. Perez Cordoves et al. / Microporous and Mesoporous Materials 109 (2008) 3848 43

decreased in this pH zone. It is known that zeolites do

a8 not necessarily follow the typical behaviour of other ion
exchange materials and it has been reported [17] that they
present high-anity for ions that exactly counterbalance
6 the charge of the zeolitic lattice, this being the reason
mg Cr(VI)/g zeolite

why the Cr3+ ions may be more dicult to exchange. Also,

in this zone of high acidity, protons strongly compete with
4 the dierent cationic species of chromium.
The inuence of contact time for each system was stud-
ied shaking for dierent periods of time, at the selected pH
2
in each case. As presented in Fig. 3a, the sorption equilib-
rium for Cr(VI) on the SMZ was reached in less than
10 min of contact. In the case of the Cr(III)-NaZ system,
0 10
8 sorption equilibrium occurred only after ca. 72 h of contact
7
300 6 (Fig. 3b), a typical lapse of time for most cation exchange
200 4 pH
50 2 processes with zeolites.
mg Cr(VI) L-1
Other authors have found that equilibrium for the same
Cr(VI)-HDTMA-modied clinoptilolite system was
b
4 obtained only when contact time was much longer. Thus,
Warchol [11] reports 24 h for equilibration, the same as
mg Cr(III)/ g zeolite

Ghiaci [8], Li and Bowman [39] and Haggerty [7]. On the

other hand, Majdan et al. [9] obtained adsorption equilib-
2 rium for Cr(VI) on a surfactant-modied chabazite in 2 h.

1.5

0
2 3 4 5 6
pH
mg Cr(VI ) /g zeolite

Fig. 2. Inuence of pH on adsorption (a) for Cr(VI)-SMZ, (b) for Cr(III)-

NaZ.
0.75

independently of the Cr(VI) concentration used in the

experiment. This study also showed that Cr(VI) sorption
is independent of the predominant species at each pH
(HCrO 2
4 between pH 2 and 6, or CrO4 at higher pH) [34].
Several authors have found dierences in the pH depen-
dence of Cr(VI) adsorption on organo-zeolites and similar 0
clay materials. Krishna et al. [35,36] have reported maxi- 0 20 40 60
mum adsorption of chromates on HDTMA-modied ben- Minutes
tonite and montmorillonite only at pH values below 1,
while Li [13] found optimum range for the same anion on b 5

organo-kaolinite to be 59. Majdan [9,37], on the other

mg Cr(III) / g zeolite

4
hand, reports pH intervals for chromate adsorption on sur-
factant-modied bentonite and chabazite of 26 and
3
approximately 3, 57, respectively. In our case, the high
AEC (vide infra) exhibited by the SMZ could account for
adsorption independence from pH. 2
In the case of Cr(III) (Fig. 2b), maximum sorption
occurred around pH 5.3, which limits the practical use of 1
this system. According to its distribution diagram [38],
around pH 5.3 CrOH2+ predominates in about 90%. At 0
0 0.5 1 1.5 3 12 24 36 60 70 78 90
slightly higher pH values, Cr(OH)3 begins to exist and pre-
cipitates, which reduces sorption. On the other hand at h
pH < 5, together with CrOH2+, the species Cr3+ was pres- Fig. 3. Inuence of time of contact (a) for Cr(VI)-SMZ, (b) for Cr(III)-
ent. Yet, as can be seen in Fig. 2b, sorption rapidly NaZ.
44 A.I. Perez Cordoves et al. / Microporous and Mesoporous Materials 109 (2008) 3848
Again, dierences with the present work may be due to the
better adsorption characteristics acquired through citric
acid activation and calcination of the natural zeolite before
surfactant modication, as mentioned in Section 2.2.
The sorption isotherms of Cr(VI) on SMZ and Cr(III)
on NaZ are shown in Figs. 4a and b, respectively. In these
gures XZ and XS represent the molar fraction of chro-
mium in the corresponding zeolite and in the solution,
respectively. In the case of the Cr(III)-NaZ system,
Fig. 4b is proof of adsorbent non-selectivity for the incom-
ing chromium at the concentration level studied. No fur-
ther treatment of the isotherm was conducted for this
system due to the poor features of this sorption process.
For the Cr(VI)-SMZ system, a typical adsorption isotherm
was obtained (Fig. 4a).
The binding properties of SMZ for Cr(VI) were deter-
mined by measuring the Cr(VI) uptake over a range of con-
centrations, from 10 to 200 mg L1. The Scatchard plot
was constructed for a constant mass of SMZ (0.25 g) and
results demonstrated (Fig. 5) that the plot is not linear
and may be composed of two or more straight lines, thus
indicating that the binding sites in this organic-modied
zeolite are not uniform in nature.
Isotherm constants were determined by non-linear
regression and the corresponding parameters for Cr(VI)
with SMZ are summarized in Table 1.
As can be seen, the higher value of the Fisher test for the
F isotherm when compared to the Langmuir or the Jova-
novic isotherms suggest that the Freundlich isotherm is
a 0.8
0.6
X (z)
0.4
0.2
0 tent with the adsorption energy distribution. In Table 2 the
0 0.1 0.2
X (s)
b 0.2
X (z)
0.1
0 On the other hand, the activated zeolite could be used as a
0 0.1 0.2 0.3
X (s)
Fig. 4. Sorption isotherms (a) for Cr(VI)-SMZ, (b) for Cr(III)-NaZ.
70
60
50
40
B/C
30
20
10
0
0 1 2 3 4 5 6 7
B/mg g-1
Fig. 5. Scatchard plot for SMZ binding to Cr(VI).
an appropriate model in estimating the Cr(VI) adsorption
parameters to the SMZ. Even, for the hybrid models, L
F and JF, the Fisher test values were higher than those
of the single models, suggesting that the Freundlich contri-
bution to the hybrid isotherm improves the t to the exper-
imental data. The heterogeneity parameter is a measure of
the ratio of high-to-low anity sites, that is, it is a measure
of the percentage of high-anity sites. In the system under
study, the heterogeneity parameter values (F, L F andJF
isotherms) were close to 0.5, which suggests that a Cr(VI)
species can occupy two sites with dierent anity on the
surface and/or the surface is heterogeneous.
The anity distribution, based on the Freundlich iso-
therm (which gave the best tting parameters) and pro-
duced by Eq. (10) was plotted in terms of N(K) vs Ln(K)
or Ln(N(K)) vs Ln(K). For SMZ interactions, the anity
distribution in N(K) vs Ln(K) format was an exponentially
decreasing function (Fig. 6). For the highest association
constant, the anity distribution function tends toward
zero while it tends toward innity for the lowest association
constant. The format Ln(N(K)) vs Ln(K) generates straight
lines (Fig. 6), suggesting that the isotherm model is consis-
0.3 Freundlich tting parameters are summarized.
3.2. Dynamic studies
Following the described experimental procedure, the
values of AEC (7.79 mg of Cr g1 SMZ) and CEC
(3.9 mg of Cr g1 NaZ) were calculated. Breakthrough
curves showed that it was possible to achieve quantitative
and rapid Cr(VI) sorption (less than 20 min) and desorp-
tion (around 10 min) using KCl (3 mol L1) (Figs. 7a and
8a, respectively). This, together with very fast equilibrium
periods in batch, show that the adsorption process is typi-
cal of one limited to the external surface of the adsorbent.
0.4
preconcentration sorbent for Cr(III) from water (Fig. 7b)
but the process, as already mentioned, is long and desorp-
tion was not ecient (Fig. 8b).
 A.I. Perez Cordoves et al. / Microporous and Mesoporous Materials 109 (2008) 3848 45

Table 1
Fitting parameters obtained by non-linear regression for the dierent adsorption isotherms of Cr(VI) binding to SMZ
Model Anity constant, Binding site density, Binding Heterogeneity Regression coecient, Fisher test,
isotherm K(g mg1) N (mg g1) capacity,(N K) parameter, m R2 F
L 7.5 6.5 48 0.9332 98
Bi-L 43 2.6 112 0.9784 76
0.77 8.7 6.77
J 5.5 5.6 30 0.8849 54
Bi-J 43 2.0 86 0.9826 94
1.5 5.6 8.3
F 46 0.39 0.9686 216
LF 2.9 17 50 0.49 0.9713 101
JF 4.2 12 48 0.48 0.9711 101

0.35 0.8

0.30

n Cr(VI)/m.AEC
0.6

n Cr(III)/m.CEC
0.25
N(K)/mg g-1

0.20 0.4

0.15
0.2
0.10

0.05 0
0 10 20 30 40 50
0.00 Fraction

-1 0 1 2 3 4 5 6 Fig. 7. Adsorption curve for Cr(VI)-SMZ (e) and for Cr(III)-NaZ (h).
Ln(K)/g mg-1

0.10
1.5

0.05
Ln(N(K))/mg g-1

0.00 1
Co - C1/ Co

-0.05

0.5
-0.10

-0.15
-1 0 1 2 3 4 5 6
0
Ln(K)/g mg-1 0 10 20 30 40
Fraction
Fig. 6. Anity distributions for Cr(VI)-SMZ calculated using the anity
distribution function (Eq. (10)). Fig. 8. Desorption curves for Cr(VI)-SMZ (e) and for Cr(III)-NaZ (h).

In Fig. 7, the Y axis refers to the fraction of chromium

Table 2
Freundlich tting parameters, weighted average anity and number of (tri- or hexavalent) sorbed as the solution ows through the
sites for Cr(VI) binding column, with respect to the maximum possible according to
Parameter Value the exchange capacity of the corresponding zeolite, n refers
to the number of mmoles of the chromium species and the
a 46
m 0.39 capacity is expressed in mmoles/g of the zeolite. In Fig. 8,
Kn 15 g mg1 the Y axis refers to the fraction of chromium species
NKminKmax 4.7 mg g1 adsorbed as the eluent ows through the column. Ci
Kn and NKminKmax calculated in the range Kmin = 0.9875 and Kmax = (mol L1) was the chromium concentration determined in
156.25 g mg1, respectively. the eluate and C0 (mol L1) was the initial concentration
46 A.I. Perez Cordoves et al. / Microporous and Mesoporous Materials 109 (2008) 3848
Table 3
Typical X-ray peaks for plain and treated clinoptilolites in the 2h range
1030
Diraction lines Plain clinoptilolite NaZ SMZ
d (A) RC (%) d (A) RC (%) d (A)
020 9.02 100 9.06 98 9.11
200 7.97 100 7.91 97 7.63
131 3.97 100 3.96 109 3.96
151 2.98 100 2.96 85 2.94
of the analyte. In both gures the X axis refers to the num-
ber of the collected fraction.
3.3. Clinoptilolite characterization and adsorption
mechanisms
The X-ray spectra of conditioned- and surfactant trea-
ted clinoptilolites proved that both materials were highly
crystalline and of ordered structure. In Table 3, the inten-
sity of the X-ray peaks corresponding to the crystallo-
graphic planes (0 2 0), (2 0 0), (1 3 1) and (1 5 1) of the
samples are shown. The values for the plain clinoptilolite
were included for comparison. The results showed that
the structural parameters of the conditioned and the sur-
factant-modied zeolite were very near those of the plain
clinoptilolite and that the crystallinity of the samples was
largely preserved after the dierent treatments.
On the other hand, it has been observed that dealumina-
tion of zeolites by steaming or chemical treatments with
ammonium hexauorosilicate, hydrochloric acid, oxalic
acid, chelating agents (e.g. EDTA) may aect the coordina-
tion state of aluminium or its surroundings, thus changing
the number and types of acid sites [40,41]. In Table 3 the
chemical composition of the raw clinoptilolite and the acti-
vated one used in this work are summarized. As can be seen
a decrease in the bulk aluminium content was observed in
the clinoptilolite activated by the citric acid treatment as
well as an increase in the bulk Si/Al ratio. It was interesting
to observe that in spite of this dealumination observed, the
activated zeolite retained its crystallinity as discussed
above. Similar results have been attributed to the relatively
small changes that occur in the unit cell of the zeolite, even
when all the Al is removed from its framework [42]. There-
fore, it is probable that the framework Al atoms not lea-
ched out of the solid could still generate the native
cationic ion-exchange sites (AlO(M)Si; M = Na, H),
which also constituted adsorption centers for the surfactant
adsorption (Fig. 1a).
Once the surfactant adsorbed onto the activated clinop-
tilolite, adsorption of anionic Cr(VI) species should pro-
ceed as described previously (Fig. 1b). As the surface of
the surfactant-modied clinioptilolite can be viewed as con-
taining isolated surfactant cations separated by free
(uncovered) aluminosilicate surfaces, the interaction of
Cr(III) species with the native cationic ion-exchange sites
(AlO(M)Si; M = Na, H) according to the surface com-
plex model of Stumm et al. [43] could be considered. How-
Table 4
Chemical composition of plain and citric acid conditioned clinoptilolites
Oxide Raw clinoptilolite Activated clinoptilolite
(% w/w) (% w/w)
RC (%) Na2O 1.4 0.2 0.6 0.4
91 K2O 1.3 0.3 0.1 0.3
MgO 0.5 0.4 0.1 0.2
85
CaO 3.8 0.4 0.5 0.6
104
TiO2 0.3 0.4 0.2 0.3
82
Fe2O3 1.4 0.6 0.3 0.5
Al2O3 11.2 0.5 5.8 0.6
SiO2 68.2 0.7 81.8 0.8
H2O 12.0 0.3 10.8 0.2
Bulk Si/Al ratio 5.2 12.0
ever, in our experiments, we could not observe Cr(III)
adsorption onto the surfactant-modied clinoptilolite,
which suggested that the cationic ion-exchange sites were
already saturated with the surfactant monomers and/or
Cr(III) species were not able to compete with surfactant
monomers for the binding sites (see Table 4).
As in other host materials such as catalysts and adsor-
bents, the chemical treatment (usually organic and/or inor-
ganic acids and ion-exchange with concentrated
ammonium salts) followed by heat activation at elevated
temperatures may generate the formation of dierent types
of silanol groups on the clinoptilolite surface [44], in which
the silicon atoms holding the OH groups are within a sili-
con environment, and silanol groups in which one or more
of such silicon atoms are direct neighbour of aluminium
atoms (see Fig. 1c). Thus, the presence of framework Al
in activated aluminosilicate structures increases the number
of probable types of active sites. The mechanisms by which
cations (or cationic surfactants) bond the dierent types of
active sites are not yet elucidated, but some simplied
assumptions can be dropped from the acid-basic character
of the dierent types of silanol groups and the electroneg-
ativity of its oxygen atoms. The dierent types of terminal
silanol groups are expected to impart surface heterogeneity
or site energy distribution on the activated SMZ. The prob-
able modication of hydrogen bonding between the silanol
groups makes them energetically more distinct. This is,
however, speculative and further detailed studies are essen-
tial for understanding the suggested surface heterogeneity.
3.4. Potential of the materials investigated
The surfactant-modied clinoptilolite described in this
paper exhibits a high binding capacity for Cr(VI) compared
to reported surfactant modied zeolites. Santiago et al. [45]
reported unaltered zeolite to be ineective for Cr(VI)
removal and used zeolites tailored with the organic cations
ethylhexadecyldimethylammonium (EHDDMA) and cetyl-
pyridinium (CETYL) to adsorb Cr(VI). Results demon-
strated that CETYL modied zeolite performance was
better than that with EHDDMA: adsorption capacities
were achieved of approximately 0.65 mg Cr g1 zeolite with
 A.I. Perez Cordoves et al. / Microporous and Mesoporous Materials 109 (2008) 3848
Fig. 9. Flow system conguration.
CETYL and 0.42 mg Cr g1 zeolite with EHDDMA. Maj-
dan et al. [9] report maximum adsorption of 5.80 mg chro-
mate g1of HDTMA-chabazite, while Warchol [11] found
maximum capacity for Cr(VI) with a HDTMA-modied
clinoptilolite to be 2.27 mg g1. Ghiaci et al. [8] report that
an organo-clinoptilolite had a capacity of 1.93 mg g1 for
chromate when the surfactant used was again HDTMA,
while Li and Bowman [39] found 1.28 mg g1 as maximum
adsorption for yet another HDTMA-modied clinoptilo-
lite. Dierences must evidently arise from the origin and
treatment of the zeolite used and the amount of HDTMA
adsorbed.
According to a previous study [2], we have found that
although zeolites have been greatly employed for remedia-
tion purposes, they still have to be put to use in separation
methods of analysis, even in ow through systems as an
alternative for expensive ion exchange resins. Taking into
account these considerations and the sorption characteris-
tics of the SMZ, a ow injection system for chromium spe-
ciation has been designed and constructed [2]. A schematic
diagram of the set-up is shown in Fig. 9, in which a mini-
column packed with SMZ was inserted. Cr(VI) determina-
tion was performed spectrophotometrically with DPhC.
The on-line oxidation of Cr(III) with H2O2 in alkaline
medium at room temperature was employed. The surfac-
tant-modied zeolite was tested for Cr(III) and Cr(VI)
determination using the ow injection system proposed
over a period of no less than three months with reproduc-
ible results. Preliminary results are highly promising, oer-
ing potential for chromium speciation studies in polluted
waters (e.g. industrial euents from match industries).
4. Conclusions
A clinoptilolite was pretreated, calcinated and modied
with a cationic surfactant (HDTMA) and the sorption of
Cr(VI) on this organo-zeolite (SMZ) and that of Cr(III)
on the simply activated zeolite (NaZ) were studied. In this
work it has been demonstrated for the rst time that the
anity distribution analysis combined with the Freundlich
binding model allows the characterization of the SMZ
binding properties for Cr(VI). Results reveal SMZ as a het-
erogeneous material with dierent anity binding sites for
47
Cr(VI). Cr(VI) sorption equilibrium on the SMZ took
place in less than 10 min over a wide pH range (210)
and the material exhibited a high anion exchange capacity
(7.79 mg Cr(VI) g1). No Cr(III) was adsorbed on the org-
ano-zeolite due to its positively charged surface and it was
demonstrated that the best conditions for the separation of
chromium species can be obtained when the surfactant-
modied zeolite was used. Based on these dierences, a
SMZ packed minicolumn in an on-line ow injection sys-
tem was designed for the independent and sequential spec-
trophotometric determination of both chromium species
with DPhC. Preliminary results applied to spiked tap
waters are promising and work on the application to dier-
ent environmental samples is currently in progress. This
procedure could open the way to microcolumn eld sam-
pling and preconcentration of Cr(VI) and its on-site
determination.
Acknowledgments
Authors acknowledge University of Oviedo and Univer-
sity of La Habana for support (Convenios de Cooperacion
con Iberoamerica).
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