Journal of Colloid and Interface Science 332 (2009) 298308

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Journal of Colloid and Interface Science

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Synthesis and characterization of an analogue of heulandite: Sorption applications

for thorium(IV), europium(III), samarium(II) and iron(III) recovery from aqueous
waste
Pankaj Sharma a, , Gurpreet Singh b , Radha Tomar a
a
School of Studies in Chemistry, Jiwaji University, Gwalior 474011, Madhya Pradesh, India
b
Department of Metallurgical and Materials Engineering, Indian Institute of Technology, Kharagpur 721302, India

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

Article history: The synthesis of needle/brous particles of analogue of heulandite with particle diameter of
Received 13 October 2008 0.08 m, length 48 m and high specic surface area (478 m2 g1 ) with cation exchange capacity
Accepted 27 December 2008 (3.27 mequiv g1 ) have been achieved. The heulandite needles were obtained by using inorganic salts
Available online 10 January 2009
as a source for silicon and aluminum in the hydrothermal synthesis of the material. Alkalinity of the
Keywords:
medium played an important role in the formation of heulandite bers, as it affects the nucleation rate
Analogue of zeolite synthesis. The analogue of heulandite was characterized using spectroscopic, thermal analysis,
Heulandite scanning and adsorption techniques. After mechanical grinding of crystals of heulandite, obtained powder
Sorption was used for the study of radionuclide recovery from aqueous waste. The adsorption experiments were
Isotherm carried out under batch process with, pH of medium, amount of sorbent, time of contact between sorbate
Morphology and sorbent, metal ion concentration and temperature as the variables. The adsorption was strongly
dependent on pH of the medium and the uptake of all the metal ions increased from pH 1.0 to 9.0 and
the maximum sorption was noticed in the pH range of 5.07.0. The optimum condition for these metal
ions (Th(IV), Eu(III), Sm(II), and Fe(III)) sorption on self synthesized analogue of heulandite was; 0.001 N
metal ion concentration, equilibration time of 4 h, 100 mg sorbent dose and 313323 K temperature.
This sorption process is t to both Langmuir and Freundlich sorption isotherm. Thermodynamic studies
predict the endothermic and spontaneous nature of the same.
2009 Elsevier Inc. All rights reserved.

1. Introduction
Zeolites are playing a prominent role in nuclear waste pro-
cessing and in its management, as they are well known for their
stability at high temperature and radiation elds [1,2]. Meeting the
stringent coolant purity requirements of the nuclear industry is
solely attributable to inorganic ion exchangers. In the last decade,
zeolites have been used extensively in the chemical decontamina-
tion process for radionuclide recovery, regeneration of decontami-
nants and removal of the formulation chemicals from the coolant
[36]. Therefore, there is a continuing need to synthesize ion se-
lective zeolites with uniform morphology and porosity, which are
capable of removing radioactive substances from aqueous euents,
as they have good stability toward temperature, ionizing radiation,
and oxidizing solutions.
Zeolites are inorganic polymers that have great variety in their
structures and have been classied into seven groups, on the
* Corresponding author.
E-mail address: sharmapankaj47@yahoo.com (P. Sharma).
basis of their framework topology, for which the structure are
known. According to this heulandite comes under group 7 [7].
Heulandite is the name of a series of tectosilicate minerals of
the zeolite group. Prior to 1997, heulandite was recognized as
a mineral species, but a reclassication in 1997 by the Inter-
national Mineralogical Association changed it to a series name,
with the mineral species being named heulandite-Ca, heulandite-
Na, heulandite-K, and heulandite-Sr. Heulandite-Ca, the most
common of these, is a hydrous calcium and aluminum silicate,
|Ca2 ,Na4 |[Al8 Si28 O72 ]24H2 O. It belongs to the monoclinic system
with cell dimensions a = 17.70 ; b = 17.94 ; c = 7.42 ; and
= 116 24 . Its space group is C 2/m [8]. According to Boles [9],
the Si/Al mole ratio for heulandite is below 4. The crystal structure
exhibits three types of structural channels conned by tetrahe-
dral ring systems. Ten-membered A-rings and eight membered
B-rings conne the A and B channels running parallel to the c-
axis. Eight-membered C-rings border C channels running parallel
to [100] and [102] [10]. Two eight membered rings of channel B
and two additional eight membered rings of channel C form cage I.
Two ten-membered rings of channel A and two eight-membered
rings of channel C form cage II. This porous solid is of scientic

0021-9797/$ see front matter 2009 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2008.12.074
 P. Sharma et al. / Journal of Colloid and Interface Science 332 (2009) 298308
and technological interest because of their ability to interact with
atoms, ions and molecules not only at their surface but through-
out the bulk of the material and their unique properties such as
the existence of high intracrystalline surface area, the microporous
character of the uniform pore dimensions, the ion exchange prop-
erties, the ability to develop internal acidity, the thermal stability,
the high internal surface area along with their ability to absorb
chemicals/molecules/ionic species in to their structure, gives rise
to great variety of applications which makes them special [1113].
There are only a few papers, which report the sorption charac-
teristics of heulanite and so far reported literature on heulandite
mainly discussed about their structural properties and morpho-
logical changes [1416]. Yilmaz et al. [17] examine the physical,
chemical, mechanical and microstructural properties of mortars
produced by blending clinoptilolite, which is a zeolite mineral
abundantly found in nature, into Portland cement with increasing
ratios and it was observed that plasticity times extend depending
on the blend ratios of clinoptilolite blended cements and that early
strengths change according to Blaine values. Stolz et al. registered
the symmetric changes in SiAl framework of fully Cd-exchanged
heulandite obtained from a Na-heulandite sample by treatment
with 1 M cadmium acetate solution at 373 K [18]. Bresciani-Pahor
et al. [19,20] reported the structures of a partially and a fully Ag-
exchanged heulandite. Ag+ occupies the positions analogous to
Ca2+ and Na+ in natural samples. In addition, a new site with
a low occupancy was assigned to Ag+ [21]. Research concerning
the application of the heulandite to the removal of radionuclide
from different aqueous waste systems has not been reported much.
Fewer studies are available, that only explains the sorption charac-
teristics of heavy metals on the synthetic and natural heulandite,
and its family member clinoplilolite [2225]. Keeping this in mind
it is decided to study the sorption potential of heulandite for these
radionuclides.
Environmental temperature, pH of the medium, metal ion con-
centration, sorbent dose etc., have a remarkable effect on many
processes in an ion exchange system, including service, back wash,
and regeneration cycles. Integrating these effects into the oper-
ation and design of an ion exchange system helps to minimize
leakage and aids in troubleshooting when problems arise. Under-
standing the effect of temperature, pH of the medium, metal ion
concentration, sorbent dose etc., can improve the operating ca-
pacity and euent quality levels of an ion exchange system to a
degree [2635]. It is reasonable to expect that increasing tempera-
ture will result in a sharper exhaustion zone, higher exchange rate,
and, therefore, higher capacity and better quality.
The prime objective of the present work is to synthesize well
organized, regular shaped with good morphological structured,
analogue of heulandite. Apart from this, another objective of this
work is to investigate the sorption characteristic of this synthetic
analogue of heulandite for Th(IV), Eu(III), Sm(II) and Fe(III) metal
ions and to evaluate the effect of temperature, pH of the medium,
metal ion concentration, and sorbent dose on their sorption. This
paper also discussed the sorption isotherm model (Langmuir and
Freundlich isotherm model) and various thermodynamic parame-
ters (Gibbs free energy change (G 0 ), heat of sorption ( H 0 ) and
entropy change ( S 0 )) as applied to the sorption of Th(IV), Eu(III),
Sm(II) and Fe(III) ions onto the synthetic analogue of heulandite.
2. Materials and methods
2.1. Material synthesis
Hydrothermal method is used to synthesize the desired ana-
logue of heulandite having composition; Na2 O:Al2 O3 :7SiO2 :nH2 O,
and the reactants used for this synthesis were sodium silicate
[Na2 SiO3 , Riedel-de Han] as the silica source; aluminum nitrate
299
[Al(NO3 )3 , CDH] as the aluminum source and sodium hydrox-
ide [NaOH, Merck] as the alkali sources. Other materials included
sodium nitrate and double distilled water. This synthesis process
comprises two steps. The rst step includes the preparation of gel
that contains the silica, aluminum and sodium in the same com-
position as mentioned above. This gel was prepared in a 200 mL
borosil beaker by dissolving nely divided silica and aluminum in
2.0 M sodium hydroxide solution. For complete mixing of gel, the
gel solution was magnetically stirred for two hours on a magnetic
stirrer. In the second step, the resultant mixture was immediately
placed in a 100 mL Teon lined stainless steel pressure bomb ves-
sel which was then kept in a preheated oven 443 K, at autogeneous
pressure and for 24 h. After the completion of 24 h period of syn-
thesis, the product was ltered and washed repeatedly with double
distilled water until the pH of the remaining solution was less
than 9. The samples were dried at 323 K and were stored in pow-
der form for further use.
2.2. Characterization
Powder X-ray diffraction (XRD) patterns for was recorded
at room temperature on a PANalytical XPert-PRO diffractome-
ter. Samples were scanned using CuK radiation of wavelength
1.5405 and diffractograms were recorded in the range 2 =
5 50 . Data were collected in a step mode every 0.1 for a 3 s
duration. The phases were identied by comparing the diffrac-
tion peaks with the data reported in literature [36]. The chemical
composition of the synthesized material was checked for metals
like Na, Al and Si using energy dispersive spectroscopy (EDS). The
bulk EDS analysis was performed on a JEOL JSM 5800 scanning
microscope equipped with a microprobe analyzer LINK ISIS (Ox-
ford instrument). The thermal stability and the number of water
molecules bound with the synthetic analogues of heulandite were
ascertained by differential thermal analysis (DTA) and thermogravi-
metric analysis (TGA). DTA-TGA data were recorded simultaneously
on a Netzsch thermobalance STA-409 with an alumina crucible
and alumina powder reference. The heating prole consisted of a
10 K min1 in nitrogen atmosphere up to the desired temperature
(1600 K). FT-IR spectroscopy was performed on an Irprestige-21
Shimadzu FT-IR spectrometer. The samples were prepared with
KBr and pressed into pellets. Spectra were collected in the mid-
IR range from 400 to 4000 cm1 with a resolution of 1 cm1 .
The cation exchange capacity (CEC) of the material was evalu-
ated by the batch process. The morphology and crystal size of the
synthetic MOR were examined by scanning electron microscopy
(SEM). For SEM, the samples were dispersed onto carbon tape
and coated with gold using a sputter coater system to prevent
charge accumulation on the sample. The heulandite crystals were
then observed on a JEOL JSM-5800 microscope operating in the
SEM mode at 20 kV. The specic surface areas and micropore vol-
ume were determined by physical adsorption of nitrogen with the
BrunauerEmmettTeller (BET) method at 77 K temperature using
a Micromeritics ASAP 2400 automatic analyzer.
2.3. Sorption studies
The thoriumnitrate [Th(NO3 )4 5H2 O, CDH], europium(III) oxide
(Eu2 O3 , Himedia 99.99%), samarium metal powder [CDH] and fer-
ric nitrate [Fe(NO3 )3 , Rankem] were used as a source of Th(IV),
Eu(III), Sm(II) and Fe(III) respectively. Arsenazo-III [2,7-bis(2-
arsenophenylazo)chromotopic acid, C22 H18 As2 N4 Na2 O14 S2 4H2 O,
Merck] was used to determine the concentration of Th(IV). Ana-
lytical grade alizarin red-S [sodium alizarinsulfonate, COC6 H4 CO-
C6 H(OH)2 SO3 NaH2 O, CDH] was used for the estimation of rare
earth metal ions [Eu(III) and Sm(II)]. Other chemicals and re-
gents such as ammonium thiocyanate, hydrochloric acid, nitric
300 P. Sharma et al. / Journal of Colloid and Interface Science 332 (2009) 298308
acid, potassium hydroxide, potassium hydrogen phthalate etc used
were of analytical grade from Rankem, BDH, CDH, Aldrich and no
further purication was made before their use.
Sorption experiments were conducted by equilibrating weighed
amount of sorbent with 25 mL of metal ion solution of known
concentration for 4 h (except kinetic study experiment) there-
fore metal ion sorption i.e. Th(IV), Eu(III), Sm(II) and Fe(III) on
an analogue of heulandite in liquidsolid system was a stan-
dard and strictly adhered to batch technique. Constant stirring
and constant temperature of the liquidsolid system during the
whole experiment was maintained with the help of reciprocating
thermostated water bath shaker. The shaking rate was the same
for all experiments. The pH of the solution was adjusted prior
to the experiments by adding a small amount of NaOH/HNO3 .
Once the equilibrium was established, supernatant liquid was l-
tered off using Whatman lter paper number 42, and care has
been taken to repeatedly centrifuge the solution at high speed
(10,000 rpm, German made Heraeus Biofuge Stratos Centrifuge D-
37520 Osterode) to avoid any solid particle in the aqueous phase.
The metal ions concentration in the solution phase was deter-
mined spectrophotometrically. The percentage removal of metal
ions was estimated from the difference of the metal ion concen-
tration in the aqueous phase before and after the sorption and
expressed in terms of sorption percentage: Sorption percentage =
(C 0 C e )/C 0 100; where, C 0 denotes the concentration of the
initial solution (mequiv mL1 ) and C e concentration of solution
(mequiv mL1 ) at equilibrium. To optimize the sorption process the
inuence of specic process parameters such as pH of the solution,
weight of sorbent, contact time, initial metal ion concentration,
and temperature, was investigated by changing one parameter and
keeping other parameters constant. All the experiments were car-
ried out in duplicate and each experimental result was obtained
by averaging the data for two parallel experiments.
2.4. Sorption isotherm
Sorption process involves an array of phenomena that can al-
ter the distribution of pollutants among the constituent phases
and interfaces of the subsurface system [37]. Sorption at surface
or interface is mainly the result of binding forces between the in-
dividual atoms, molecules or ions of the sorbate and the surface.
The behavior of the sorption process was studied by carrying out
a set of experiments at pH 5 and three different temperatures. The
nature of the sorption process and the relation between the equi-
librium concentrations of the sorbate in the liquid phase and in the
solid phase was tested with respect to the following well-known
sorption models [38,39].
Langmuir isotherm:
C e /qe = 1/( K a qm ) + C e /qm (linear form)
where, qe is the amount of metal ion sorbed per unit weight
of sorbent (mequiv g1 ), C e (mequiv L1 ) is the equilibrium con-
centration of the metal ions in the solution. K a and qm are the
Langmuir coecients representing the equilibrium constant for the
sorbatesorbent equilibrium and the monolayer capacity respec-
tively. The constants were obtained from the slope and intercepts
of the plots of C e /qe against C e . The value of qm represents the
practical limiting sorption capacity, i.e. the maximum value of qe .
Weber and Chakraborti suggested a method to evaluate the fea-
sibility of adsorption processes [40]. Langmuir constants are also
used to obtain the dimensionless constant called equilibrium pa-
rameter or separation factor, R L which can be calculated by the
following equation [41]:
R L = 1/(1 + K a C 0 ),
where C 0 is the highest initial solute concentration (mequiv L1 ).
Freundlich isotherm:
log qe = log K F + 1/n log C e (linear form) (3)
where, K F and 1/n are the Freundlich constants. The value of K F
(mmol g1 ) can be taken as a relative indicator of sorption capac-
ity, while 1/n shows the energy or intensity of sorption. These are
the experimental parameters which depend on the system of sor-
bent and sorbate.
2.5. Thermodynamic parameter
Spontaneity of the sorption can only be predicted by study-
ing its thermodynamic parameters. The distribution coecient
(Eq. (4)) data were used for calculating the thermodynamic pa-
rameters of each sorption system using the following equations
[42,43]:
K d = (C i C e )/C e x( V / W ) mL/g, (4)
where, V is the volume of the solution in mL, and W is the weight
of the exchanger in g.
   
ln K d =  S 0 / R  H 0 / R T , (5)
where, R is the universal gas constant, 8.314 J mol1 K1 and T is
the absolute temperature in Kelvin. The free energy (G 0 ) for the
specic sorption was calculated by
G 0 =  H 0 T  S 0 . (6)
The apparent thermodynamic parameters, enthalpy change
( H 0 ), and entropy change ( S 0 ) for the Th(IV), Eu(III), Sm(II) and
Fe(III) sorption on analogue of heulandite were calculated from the
slopes and intercepts of the linear variation of ln K d vs. 1/ T by
Eq. (5). The values of  H 0 , and  S 0 so obtained from the values
of slope and intercept respectively, are used to calculate the value
of G 0 by the use of Eq. (6).
3. Results and discussion
3.1. Heulandite characterization
The stability of the laboratory synthesized analogue of heulan-
dite is checked by shaking weighed amount of material in acidic,
basic and organic solvents. From the weight loss calculations we
nd that this material is highly stable in basic solutions as well as
in organic solvents, but shows instability above 6.0 M HNO3 acidic
concentration.
Examination of the powder X-ray diffraction pattern (Fig. 1)
shows a characteristic peak of heulandite at 2 values of 9.85 . The
d-spacing values for this material correspond to 2 = 9.85 comes
(1)
out to be 8.98 . In addition to heulandite phases (95%) pres-
ence of unreacted silicates, was also reported in the nal powder.
The crystallite size obtained with X-ray method (calculated from
Scherrers equation; D = 0.9/( B cos ), where, 0.9 is the Scher-
rer constant, is the wavelength of X-ray, B is the breadth of
the pure diffraction prole and is the incidence angle of X-ray.
The breadth B is calculated as the full width half-maximum of X-
ray diffraction pattern) comes out to be 27.08 nm, which is the
effective length, measured in the diffraction vector, along which
diffraction is coherent [44]. The term crystal size is preferred over
particle size, since individual particles may contain crystals or do-
mains having different orientations [45]. The crystal size obtained
by applying Scherrers equation is interpreted as an average crys-
tal dimension. The accuracy of crystal size determined is usually
of 6080%, in case of heulandite because of the uniformity in the
(2)
crystal size analyzed by scanning electron microscopy. Powders
with needle shape crystals tend to aligned with the specimen axis
 P. Sharma et al. / Journal of Colloid and Interface Science 332 (2009) 298308
Fig. 1. Powder X-ray diffraction pattern of laboratory synthesized analogue of
heulandite.
Fig. 2. Energy dispersive spectroscopic analysis of laboratory synthesized analogue
of heulandite.
in the preparation of sample [46]. The crystal dimension measured
by X-ray diffraction could be the crystal diameter instead of crystal
length.
The exibility in the synthesis to produce the desired compo-
sition of heulandite represents a critical step in the improvement
of this material for many experimental processes in which Si/Al
ratio is the key for maximizing performance. Energy dispersive
spectroscopy was used to quantitatively determine the composi-
tion of metal oxides in the synthesized materials. The compositions
of Na2 O, Al2 O3 , and SiO2 in the nal synthesized product are pro-
vided in Fig. 2. The observed ratio of SiO2 /Al2 O3 for heulandite
is 6.58. EDS results show that molar ratio of SiO2 /Al2 O3 is almost
same as reported in the literature [47].
DTA/TGA curves of analogue of heulandite were presented in
Fig. 3, where it can be seen that heulandite exhibits a clear mass
loss of 22 wt% within 100800 C temperature range. This event
is associated with the dehydrogenation and dehydroxylation of
the aluminosilicate framework [4850]. This mass loss of 22 wt%
corresponds to 19 water molecules associated with the nal
heulandite product. The characteristic DTA peaks for analogue of
heulandite are also presented in Fig. 3. DTA peak observed within
150175 and 550600 C temperature range correspond to the two
dehydration step in case of nal heulandite product. The posi-
tion of these DTA peaks as well as the number of dehydration
steps can be attributed to different compensating cationwater
301
Fig. 3. DTA/TGA analysis of laboratory synthesized analogue of heulandite.
binding energies as well as to the different energy associated
with the diffusion of the desorbed water through different zeo-
lite channel system [51]. Most of the physisorbed water was lost
between 50 to 200 C and in the broad interval between 200 to
600 C more strongly associated water was lost. Additionally ana-
logue of heulandite exhibited DTA peak after 600 C, which are as-
signed to dehydroxylation of the heulandite structure and a conse-
quence of structural changes. DTA thermogram did not indicate any
high temperature exothermic characteristic of lattice breakdown
at least up to 1100 C. It indicates that the synthetic analogue of
heulandite was structurally stable up to 1100 C temperature.
FTIR spectra of the synthetic analogues of heulandite revealed
that synthesis condition can cause several changes in the var-
ious stretching and bending vibrations of the active modes of
the nal products given in Fig. 4 [52,53]. Heulandite can also be
readily distinguished from other zeolites by difference in posi-
tion and relative intensities of their stretching and bending vibra-
tion bands [54]. The OH stretching occurring around the 3700
3620 cm1 lies well separate from those of most other zeolite
bands. The OH stretching occurring around the 37003620 cm1
singlet might be characteristic of heulandite. A detail assignment of
all the bands arising from the presence of different metaloxygen
linkages (TOT, OTO, TO, etc., T = Si/Al) in the analogue of
heulandite synthesized in alkaline medium is given as follow:
Band position (cm1 ) Vibration assignment
3622 OH stretching
1630 HOH bending
Internal tetrahedral
1120,960 Asymmetrical stretching
680 Symmetrical stretching
500,460 TO bending
External linkages
623,575 Double ring vibrations
420 Pore opening vibration
1050 Asymmetrical stretching
816,761 Symmetrical stretching
One of the peculiar characteristic of the zeolite is the ion ex-
change capacity dened as the capacity to locate specic cation in
the framework of zeolites. The ion exchange capacity of zeolites
depends on the chemical composition and varies with the struc-
ture of zeolite and with the nature of cation. The CEC depends on
the number of exchangeable position and these values depend on
the ratio SiO2 /Al2 O3 .
Cation exchange capacity of synthetic analogue of heulandite
in solution where the ions mobility is spontaneous has been car-
302 P. Sharma et al. / Journal of Colloid and Interface Science 332 (2009) 298308
Fig. 4. FTIR spectra of laboratory synthesized analogue of heulandite.
Fig. 5. SEM micrograph of laboratory synthesized analogue of heulandite.
ried out for Fe(III) only. The CEC of the analogue of heulandite
was estimated following the procedure that involved the equili-
bration of analogues of heulandite, 1.0 g, with 25 mL of 0.25 N
solution of Fe(III) at pH 3. The process was followed for 24 h with
constant stirring at room temperature. The amount of Fe(III), cap-
tured in the analogue of heulandite is determined by estimating
the Fe(III) ions left in the solution after equilibration time. CEC
for analogues of heulandite is calculated to be 3.27 mequiv g1 .
This high value of CEC for this synthetic analogue is because of its
regular framework geometry, comparable cavity dimensions, good
structural properties, cation positions in the framework and num-
ber of exchangeable cations [55].
Typical SEM microimage of powder sample of the analogue
of heulandite is shown in Fig. 5. These micrographs reveal the
homogeneous nature of surface morphology of the analogues of
heulandite which also shows that heulandite crystals to possess a
needle like morphology. The rod/needle like morphology of crys-
tallites of synthetic analogue of heulandites can be explained on
the bases of nucleation and crystallization rate. The alkalinity of
the medium affects both these processes. The synthesis medium
of 2 M NaOH concentration may results in a poor nucleation rate
and faster crystallization leading to larger crystal sizes as well as
elongated needle like crystallites [56]; this can be seen in Fig. 5.
The gure illustrates the fact that a poor nucleation rate with rapid
crystallization results in a larger crystal size with a rod/needle like
morphology. Crystallites grown with needle/rod like morphology
with rod diameter 0.08 m and length of about 24 m.
Fig. 6. Effect of pH on the sorption of Th(IV), Eu(III), Sm(II) and Fe(III) onto analogue
of heulandite.
Specic surface area (S BET ) and the total pore volume mea-
surements of nal product of synthetic analogue of heulandite are
478 m2 g1 and 0.026 cm3 g1 respectively. The preliminary inves-
tigation of the analogue of heulandite by the N2 sorption isotherm
data (obtained via Micromeritics ASAP 2400, automatic analyzer)
showed that analogue of heulandite may resolutely refer to meso-
porous material with mesopore diameter 30 nm.
3.2. Effect of initial pH on sorption
The sorptive properties of zeolites are expected to depend
strongly on their surface functionality, and charge. Depending on
pH, metal oxide group present in zeolite materials may be pro-
tonated/deprotonated, creating a net charge on the surface of the
zeolite. As such, material pH is also expected to inuence the sorp-
tion of metal ions, in particular when the metal ions are in the
ionic state or in molecular state. Low sorption of metal ions by
the synthetic analogue of heulandite at lower pH than at higher
pH was in accord with the fact that exchanger surface was largely
protonated at low pH, which enhanced the electrical repulsion be-
tween the metal cations and positively charged surface of analogue
of heulandite. Therefore in order to optimize the pH for maximum
removal/sorption eciency, experiments were conducted in the pH
range 19 at constant temperature (30 1 C), 4 h equilibration
time, 0.001 N metal ions concentration and aqueous to sorbent
ratio 1:4 (mL/mg). As shown in Fig. 6, aqueous phase pH was a
controlling factor in metal ions sorption. Selected metal ions may
exist in solution, either in neutral or positively charged species
within the experimental pH range. pH of the solution may also
affect the surface charge of the sorbent as well as the degree of
ionization of the metal ions present in the framework of materi-
als. pH therefore affects the structural stability and selectivity of
sorbent.
Depending on the pH metal ions may form complexes with
OH , for example, M(OH)n , M(OH)n+1 and M(OH)n2+
2 , at higher
pHs and as a result, metal hydroxyl species may participate in the
adsorption and precipitate onto the adsorbent surface. It is well
known that the different metal ion species can form the metal-
lic cations in solution as a function of pH and metal concentra-
tion [57]. The following equations for metal ions as a function of
pH have been expected [58,59].
 n+  (n1)+
M(H2 O)6 + OH M(OH)(H2 O)5 + H2 O, (7)
 (n1)+
M(OH)(H)2 O)5 + OH
 (n2)+
M(OH)2 (H2 O)4 + H2 O, (8)
 P. Sharma et al. / Journal of Colloid and Interface Science 332 (2009) 298308 303

 
M(OH)2 (H2 O)6 M(OH)2 + 4H2 O, (9)
 
M(OH)n (H2 O)6n M(OH)n + (6 n)H2 O, (10)

where M = Th(IV), Eu(III), Sm(II) and Fe(III). Precipitation of

M(OH)2 on the solid surface;
 n+
M(H2 O)6 + nOH M(OH)n + 6H2 O. (11)

Results emphasize that with increase in pH of the solution sorp-

tion percentage increases. The reason for low sorption in acidic
solution is the competition between the excess of H+ ions, in the
medium and positively charged cationic species present in solu-
tion [60]. Also higher acid concentrations suppress hydrolysis of
the metal ions. In addition, as pH is increased there is decrease of
positive surface charge, which results in lower coulombic repulsion
of the sorbing metal ions [6163]. The difference in the sorption
percentage of these metal ions onto synthetic analogue of heulan-
dite at high pH can also be explained on the basis of anity of Fig. 7. Effect of sorbent does on the sorption of Th(IV), Eu(III), Sm(II) and Fe(III) onto
surface and aqueous speciation: it is well known that aqueous and analogue of heulandite.

surfaces species/ligands compete for the complexation with metal

ions. Out of these four metal ions, heulandite exhibit maximum
sorption potential for Fe(III), may be because of weaker tendency
of Fe(III) to form aqueous complexes and stronger interaction with
the solid surface as having smaller ionic size and high charge. This
trend in pH dependence suggests that the removal of metal ions is
favored by high pH values [6466]. The maximum uptake of metal
ions was observed around pH 5.0 and this pH value is considered
to be the optimum pH for upcoming metal ion/heulandite studies.

3.3. Effect of sorbent dose

Sorbent dose plays an important role in the sorption process

of metal ions onto sorbent. As it is well known fact that sorp-
tion of metal ions onto the sorbent is mainly due to the presence
of active sites on the surface of the sorbent. When sorbent dose
is increased, percentage sorption of the metal ions also increases,
this is only because of the greater surface area and availability of
Fig. 8. Effect of equilibration time on the sorption of Th(IV), Eu(III), Sm(II) and Fe(III)
more number of active sorption sites with the increase in sorbent
onto analogue of heulandite.
does. In the present study, effect of sorbent dose was checked at
six different sorbent doses viz., 25, 50, 100, 150, 200, and 250 mg
3.5. Effect of initial metal ion concentration and temperature of the
for all the four metal ions in this study, keeping all other con-
system
ditions constant like; initial metal ion concentration of 0.001 N,
medium pH 5, equilibration time of 4 h and constant temperature
The effect of initial metal ion concentration and the temper-
of 30 1 C. It is clear from the plot (Fig. 7) of data obtained
ature of the sorption system are the two important parameters
from this study that amount of the sorbent used has a signi-
which affects the sorption process considerably. Fig. 9 represents
cant impact on the sorption process and this synthetic analogue
the changes in the sorption behavior of all the metal ions viz.,
of heulandite shows maximum removal eciency for Fe(III) at all
Th(IV), Eu(III), Sm(II), and Fe(III) under different metal ion concen-
adsorbent doses in comparison to other metal ions. The sorption
tration and system temperatures. On reviewing the data we nd
was found to be more or less maximum at 100 mg sorbent dose
out that, an increase in the metal ion concentration leads to de-
and therefore for further studies, it was decided to check the sorp-
crease in the metal uptake onto synthetic analogue of heulandite.
tion behavior of Th(IV), Eu(III), Sm(II), and Fe(III) onto synthetic
The maximum sorption of all the metal ions was obtained at ini-
analogue of heulandite by taking 100 mg of sorbent does.
tial metal ion concentration of 0.001 N, but as we go on increasing
the initial metal ion concentration, the sorption process depresses.
3.4. Effect of equilibration time This is because of the surface saturation of the sorbent with metal
ions. We can also say that as concentration of metal ion increases
The effect of equilibration time on the removal of Th(IV), Eu(III), then there is increase in the positive charge species in the aqueous
Sm(II), and Fe(III) by synthetic analogue of heulandite at C i = phase. These positive charge species gives rise to coulombic repul-
0.001 N and pH 5 is shown in Fig. 8. It can be seen that the re- sion which results in decrease in sorption which is even less than
moval of all the metal ions increased up to a certain time limit the sorption at 0.001 N initial metal ion concentrations.
and then it remained almost constant. An increase in the sorption According to adsorption theory adsorption decreases with rise
with the passing of time can be attributed to greater contact time in temperature and molecules adsorbed earlier on a surface tend
between the sorbate and sorbent. At 4 h equilibration time, the to desorbed from the sorbent surface at elevated temperature. But
sorbent surface becomes saturated with respective metal and the for activated carbon, inorganic and organic ion exchangers differ-
removal eciency becomes almost constant. ent results are noticed [6769], where decreasing viscosity and
304 P. Sharma et al. / Journal of Colloid and Interface Science 332 (2009) 298308

Fig. 10. Langmuir adsorption isotherm for Th(IV) sorption on synthetic analogue of
Fig. 9. Effect of initial metal ion concentration and system temperature on the sorp- heulandite at three different temperatures.
tion of Th(IV), Eu(III), Sm(II) and Fe(III) onto analogue of heulandite.

increasing molecular motion at higher temperature allows the up-

take of molecules into the pores more easily, causing adsorption to
increase as the temperature increases. Therefore system tempera-
ture is considered to be a crucial parameter in sorption reaction. So
the purpose of this study is to ascertain the effect of temperature
on the sorption of metal ions by synthetic analogue of heulandite.
The effect of temperature on the removal of Th(IV), Eu(III), Sm(II),
and Fe(III) in aqueous solution by synthetic analogue of heulandite
was studied by varying the temperature between 303323 K. The
data presented in Fig. 9 showed that sorption of metal ion by the
synthetic analogue of heulandite increased with increase in tem-
perature, which is generally expected for the sorption/ion exchange
of most metal ions from their solution [7079]. However, the mag-
nitude of such increase continues to decline at higher initial metal
ions concentration, as temperatures are increased from 303 to
323 K. This is because with increasing temperature, the attractive
forces between sorbent surface and metal ions are weakened and
the sorption decreases. For lower temperatures, equilibrium sorp- Fig. 11. Langmuir adsorption isotherm for Eu(III) sorption on synthetic analogue of
heulandite at three different temperatures.
tion occurs rapidly at lower metal ion concentrations in the rst
phase and becomes relatively constant at higher concentrations.
The equilibrium concentrations for higher temperatures were not This thermal study also conrms the endothermic nature of the
signicantly different for those of lower temperatures. This indi- sorption process.
cates that increasing the initial metal ion concentrations above the
equilibrium concentrations may not have any signicant increase 3.6. Langmuir and Freundlich isotherm
in the sorption of metal ions by synthetic analogue of heulandite.
Although we have not studied the effect of temperature beyond
To facilitate the estimation of the sorption capacities at various
323 K, but it is expected that further increase of temperature re-
sults in decrease in sorption. It is only because of that, at high temperatures, experimental data were tted into equilibrium sorp-
temperature, the thickness of the boundary layer decreases, due to tion isotherm models of Langmuir and Freundlich. The Langmuir
the increased tendency of the metal ion to escape from the sor- adsorption equilibrium constant K a and maximum monolayer ca-
bent surface to the solution phase, which results in a decrease in pacity qm at three different temperatures were recorded from the
sorption as temperature increases (>323 K). On the other hand graphs (Figs. 1012, and 13) plotted between C e /qe and C e for
the high sorption at 323 K is because of increasing the tempera- each metal ion and are tabulated in Table 1. The values of cor-
ture is known to increase the rate of diffusion of sorbate across relation coecient (R 2 ) were expressed on the graphs for each
the external boundary layer and in the internal pores of the sor- temperature. These high value of R 2 (0.98) reveals that the ob-
bent particles, as zeolites are well known for their porous character tained sorption data best t to Langmuir adsorption isotherm at
and they can sorb water or other sorbate molecules even more all temperatures. The Langmuir maximum adsorption, qm , for a
than that of their weight. In addition changing the temperature monomolecular surface coverage is found to be highest for Fe(III)
will change the equilibrium capacity of the sorbent for particular sorption onto synthetic analogue of heulandite at all tempera-
sorbate [80]. This could also be due to acceleration of some origi- tures and it increases with increase in temperature. The order
nally slow sorption steps or due to thermal agitation of the system, of qm values for respective metal ion sorption onto synthetic ana-
processes such as association of ions, aggregation of molecules, logue of heulandite at 323 K is as; Fe(III) (0.24 mequiv g1 ) >
ion pairing and complex formation are discouraged in the system Sm(II) (0.17 mequiv g1 ) > Eu(III) (0.15 mequiv g1 ) > Th(IV)
[8183]. According to Barrow, temperature also affect the rate of (0.10 mequiv g1 ). The calculated values of R L , from Langmuir con-
approach to equilibrium and position or state of equilibrium [84]. stant K a are reported in Table 2, which emphasizes the feasibility
 P. Sharma et al. / Journal of Colloid and Interface Science 332 (2009) 298308 305

of the sorption process, as these R L values comes out less than
that of unity for each metal ion at all temperatures.
The results obtained from sorption of Th(IV), Eu(III), Sm(II), and
Fe(III) over synthetic analogue of heulandite have also been tried
to correlated with Freundlich sorption isotherm (Eq. (3)).
Sorption data were also tted by Freundlich sorption isotherm
(Figs. 1416, and 17) at all temperatures (R 2 values were greater
than 0.96). The values of n were found to be less than unity at all
temperatures except for Th(IV) and Sm(II) sorption, indicating that
desorption may also occurs during the sorption process of these
metal ions. This implies that signicant sorption took place in case
of Eu(III) and Fe(III). The value of K F (Table 1), which is a measure
of the degree of sorption, is high at higher temperatures indicate
that more sorption would be expected at these temperatures.

3.7. Thermodynamic parameters

The data obtained from thermal study is used to calculate

the thermodynamic parameters. The calculated apparent enthalpy
change ( H 0 ) and entropy change ( S 0 ) for sorption process of

Fig. 12. Langmuir adsorption isotherm for Sm(II) sorption on synthetic analogue of
heulandite at three different temperatures.

Fig. 14. Freundlich adsorption isotherm for Th(IV) sorption on synthetic analogue of
heulandite at three different temperatures.

Fig. 13. Langmuir adsorption isotherm for Fe(III) sorption on synthetic analogue of
heulandite at three different temperatures.

Table 2
R L values from Langmuir adsorption isotherm for Th(IV), Eu(III), Sm(II), and Fe(III)
sorption onto synthetic analogue of heulandite.

Metal ion 303 K 313 K 323 K

Th(IV) 0.1017 0.0985 0.0821
Eu(III) 0.0551 0.0622 0.0615
Sm(II) 0.0646 0.0538 0.0533
Fe(III) 0.0459 0.0483 0.0373 Fig. 15. Freundlich adsorption isotherm for Eu(III) sorption on synthetic analogue of
heulandite at three different temperatures.

Table 1
Langmuir and Freundlich adsorption constants for Th(IV), Eu(III), Sm(II), and Fe(III) sorption onto synthetic analogue of heulandites at three different temperatures.

Metal qm (mequiv g1 ) K a (L mequiv1 ) Kf n

ion 303 K 313 K 323 K 303 K 313 K 323 K 303 K 313 K 323 K 303 K 313 K 323 K
Th(IV) 0.07 0.10 0.10 8.83 9.15 11.18 0.07 0.10 0.11 2.13 2.04 2.24
Eu(III) 0.10 0.13 0.15 17.15 15.07 15.27 527.23 387.26 405.51 0.36 0.34 0.32
Sm(II) 0.14 0.15 0.17 14.48 17.59 17.77 1.09 66.07 0.77 1.00 0.40 1.14
Fe(III) 0.17 0.21 0.24 20.77 19.70 25.83 126.18 63.53 178.65 0.35 0.28 0.33
306 P. Sharma et al. / Journal of Colloid and Interface Science 332 (2009) 298308

Fig. 16. Freundlich adsorption isotherm for Sm(II) sorption on synthetic analogue of Fig. 18. Plot of 1/ T vs. ln K d to calculate the thermodynamic parameters for Th(IV)
heulandite at three different temperatures. adsorption onto synthetic analogue of heulandite at ve different concentrations.

Fig. 17. Freundlich adsorption isotherm for Fe(III) sorption on synthetic analogue of Fig. 19. Plot of 1/ T vs. ln K d to calculate the thermodynamic parameters for Eu(III)
heulandite at three different temperatures. adsorption onto synthetic analogue of heulandite at ve different concentrations.

Th(IV), Eu(III), Sm(II), and Fe(III) by synthetic analogue of heulan-
dite are summarized in Table 3. These values of  H 0 and  S 0
were obtained from the slope and intercept of the plot of ln K d
and 1/ T (Figs. 1820, and 21), that satises Eq. (5). The free en-
ergy change, G 0 was calculated from  H 0 and  S 0 value at
each temperature using Eq. (6) and the obtained values were tab-
ulated in Table 4. The observed values of enthalpy change ( H 0 )
for each metal ion indicates that  H 0 of each exchange process
is concentration dependent. The maximum  H 0 values are ob-
tained at initial metal ion concentration of 0.001 N and minimum
at 1.0 N. The positive values of enthalpy change reveal the process
to be endothermic and low magnitude of these values indicates
the physicosorption. The positive values of entropy ( S 0 ) as listed
in Table 3 reects the anity of the ion exchange material for
the metal ion under consideration. It also conrms that random-
ness of the sorption process at solute sorbent interface. The G 0
values (Table 4) becomes more and more negative with rise in re-
action temperature and decrease in initial metal ion concentration
for each metal ion. These results represent the high feasibility and
spontaneity of this exchange process at higher temperature and
low initial metal ion concentration. Based on the values of free
energy, Fe(III) sorption onto synthetic analogue of heulandite is
most spontaneous process in comparison to other three metal ions
(Th(IV), Eu(III), and Sm(II)) sorption onto the same.
4. Summary
In this reported work we able to make the desired analogue
of heulandite by hydrothermal method and the reliability of the
material was conrmed by analyzing the material with different

Table 3
Enthalpy change and entropy change values for Th(IV), Eu(III), Sm(II), and Fe(III) sorption onto an analogue of heulandite at ve different initial metal ion concentrations.

Metal H 0 S0
ion (J mol1 ) (K J mol1 )
0.01 N 0.05 N 0.1 N 0.5 N 1.0 N 0.01 N 0.05 N 0.1 N 0.5 N 1.0 N
Th(IV) 474.14 291.08 263.29 283.62 216.86 2.22 1.58 1.39 1.34 1.06
Eu(III) 1084.20 178.25 267.02 235.27 280.01 4.49 1.35 1.46 1.24 1.32
Sm(II) 1323.31 312.12 147.46 165.02 112.58 5.33 1.83 1.12 1.05 0.81
Fe(III) 1261.73 646.26 338.59 270.39 262.21 5.27 2.93 1.80 1.44 1.33
 P. Sharma et al. / Journal of Colloid and Interface Science 332 (2009) 298308 307

Table 4
Free energy change (G 0 , J mol1 ) values for Th(IV), Eu(III), Sm(II), and Fe(III) sorption onto an analogue of heulandite at ve different initial metal ion concentrations and
three different temperatures.

Metal 0.01 N 0.05 N 0.1 N 0.5 N 1.0 N

ion 303 K 313 K 323 K 303 K 313 K 323 K 303 K 313 K 323 K 303 K 313 K 323 K 303 K 313 K 323 K
Th(IV) 198.63 220.83 243.03 187.44 203.23 219.03 156.91 170.78 184.65 122.37 135.77 149.17 105.45 116.09 126.73
Eu(III) 277.37 322.31 367.25 232.11 245.66 259.20 176.15 190.77 205.40 141.57 154.01 166.44 118.69 131.85 145.01
Sm(II) 292.28 345.60 398.92 241.10 259.36 277.62 191.14 202.32 213.49 153.61 164.13 174.64 133.24 141.35 149.46
Fe(III) 335.27 387.98 440.69 241.17 270.45 299.74 207.72 225.75 243.78 167.31 181.76 196.20 141.23 154.55 167.86

tive waste using synthetic zeolite (heulandite). The equilibrium

isotherms for sorption of Th(IV), Eu(III), Sm(II), and Fe(III) ions
have been modeled successfully using the Langmuir and Freundlich
sorption isotherm. The results of this work indicates that synthetic
analogue of heulandite shows maximum sorption anity for Eu(III)
and Fe(III).

Acknowledgments

This work was nancially supported by UGC, New Delhi. The

authors gratefully acknowledge Dr. R. Maiti, at SEM laboratory,
Central Research Facility, I.I.T. Kharagpur, India for the electron mi-
croscopic facility.

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Fig. 21. Plot of 1/ T vs. ln K d to calculate the thermodynamic parameters for Fe(III)
adsorption onto synthetic analogue of heulandite at ve different concentrations.
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