Journal of Colloid and Interface Science 261 (2003) 32–39

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Adsorptive removal of methylene blue from colored effluents

on fuller’s earth
G. Atun,a,∗ G. Hisarli,a W.S. Sheldrick,b and M. Muhler c
a Department of Physical Chemistry, Faculty of Engineering, University of Istanbul, 34850 Avcilar-Istanbul, Turkey
b Department of Analytical Chemistry, Faculty of Chemistry, University of Ruhr, D-44780 Bochum, Germany
c Department of Technical Chemistry, Faculty of Chemistry, University of Ruhr, D-44780 Bochum, Germany

Received 3 July 2002; accepted 9 January 2003

Abstract
The adsorption behavior of methylene blue (MB) on four fuller’s earth (FE) samples of varying compositions was investigated using a
spectrophotometric technique to obtain information on the color removal. The distribution coefficient (KD ) increased with an increase in the
initial concentration (C0 ) of the dye, attained a maximum value, and decreased again at higher initial concentrations. Dye solutions became
colorless for a C0 value corresponding to maximum KD . A progressively increased flocculation behavior in the clay suspensions was observed
and the maximum value of KD corresponds to optimum flocculation of the clay. The KD values were found to decrease exponentially after of
the solution again became colored while the amount adsorbed increased with an increase in the initial concentration of MB. Only adsorption
data obtained for this region could be defined by adsorption isotherm equations. The shifts of the C0 values corresponding to KD max toward
higher concentrations were correlated with the composition of FE samples by using XRF, XRD patterns, and SEM images. The influence of
temperature on MB adsorption was also studied and thermodynamic parameters were calculated.
 2003 Elsevier Science (USA). All rights reserved.

Keywords: Fuller’s earth; Dye adsorption; Methylene blue; Adsorption isotherm; Distribution coefficient

1. Introduction octahedral alumina layer, which is separated from aque-

Fuller’s earth (FE) used as an adsorbent has been known
to exist in the Mihaliccik region of Turkey. It contains vari-
ous amounts of dioctahedral smectites (Ca-montmorillonite),
natural zeolites (analcime), and loughlinite, which is a kind
of sepiolite [1]. All of these minerals exhibit a strong affin-
ity for heteroaromatic cationic dyes. The visible absorp-
tion spectrum of cationic basic dyes such as methylene
blue (MB) [2–11], thionine (TH) [12–15], crystal violet
(CV) [9–11], acridine orange (AO) [7,16,17], and rhodamine
6G (R6G) [18] has been used recently in the determina-
tion of surface properties of several types of clay minerals
such as smectites [2–8,12,15–17], zeolites [13,14], and sepi-
olite [9,10,18]. Smectites are specified as 2:1 layered clays
and swell in water. Surface charge of smectites arises from
proton adsorption–desorption reactions on surface hydroxyl
groups while layer charge results from substitutions in the
* Corresponding author.
E-mail address: gultena@istanbul.edu.tr (G. Atun).
0021-9797/03/$ – see front matter  2003 Elsevier Science (USA). All rights reserved.
doi:10.1016/S0021-9797(03)00059-6
ous solution by a tetrahedral silicate layer [19]. The struc-
ture of zeolite channels contains large cages with windows
showing different openings [13]. Sepiolite is a fibrous clay
mineral with fine channels running parallel to its fibers. It
has an open structure exhibiting microfibrous morphology
with a large micropore volume due to the existence of in-
tercrystalline cavities [9,21]. Monomers, protonated cations,
dimers, and higher aggregates of dye occur on the external
surface or in the basal plane, cages, cavities, or channels
of these minerals depending on the size of the dye mole-
cule, dye loading, solution pH, the type of exchangeable
cations, surface acidity, and the swelling properties of the
clay. Since each form of dye absorbs visible light at a differ-
ent wavelength, a visible spectroscopic technique has been
successfully used to study clay–dye interactions in clay sus-
pensions. The MB–clay interaction has been claimed to be
an extremely sensitive fingerprint for the detection of sur-
face properties of clays such as surface charge, layer charge,
surface area, and exchange capacity [3,6,8,9]. There is, how-
ever, some disagreement about the correct value of surface
 G. Atun et al. / Journal of Colloid and Interface Science 261 (2003) 32–39
area calculations because it was recently shown that the gen-
erally accepted adsorption geometry is questionable and the
MB molecules adsorb a tilted arrangement [6,8]. Visible
MB spectra in dilute solution show a band associated with
monomeric MB at 665 nm with a shoulder at 605 nm. The
observed red shift of the MB monomer band in clay suspen-
sions arises from the interaction of dye molecules in the in-
ternal domains of tactoids. MB in aqueous clay suspensions
shows metachromatic behavior even at lower concentrations
with respect to the aqueous dye solution. The decrease in the
monomer band and the appearance of bands at lower wave-
lengths are attributed to formation of dimers and higher ag-
gregates on the external surface [2,4–8].
The aim of this study is to produce a satisfactory effluent
for discharge into receiving waters or for reuse as a water
supply from highly concentrated MB solutions by using FE
samples with different compositions. The adsorption data
have also been correlated to the ratio of clay minerals in
FE samples and have been used to determine the adsorption
capacity for MB of the adsorbents.
2. Experimental
Four FE samples from different deposits in the Mihal-
liccik region were used for batch experiments. FE samples
were kindly provided by Professor M. Yeniyol from the Ge-
ology Department of Istanbul University and Y. Bilge from
Bensan A.S. X-ray diffraction (XRD) paterns of the four FE
samples revealed that they were composed mainly of Ca-
montmorillonite, loughlinite, and analcime [1]. The chemi-
cal composition of the FE samples was analyzed by X-ray
fluorescence spectrometry (XRF). Analyses of the FE sam-
ples are given in Table 1. The surface morphology of the raw
material and the product obtained after MB treatment of FE
were examined by scanning electron microscopy (SEM).
Adsorption of MB was performed by using a batch
method. The clay samples were crushed and sieved through
a 200-µm sieve. A liquid–solid ratio V /m of 100 cm3 g−1
was chosen. Thus 0.05 g of clay was put into contact with
5 cm3 of dye solution in a polypropylene beaker of 25 cm3
for 4 h (i.e., a time period long enough to reach equilib-
rium) at a given temperature in a thermostatic shaker/water
bath and left overnight. Later, the clay suspensions were
centrifuged at 4000 rpm for 30 min and the equilibrium
MB concentration was determined by using a Perkin Elmer
UV–vis. spectrophotometer model 554 with silica cells of
length 1 cm. The initial MB concentrations were changed
Table 1
Chemical analyses (wt%) of the FE samples used in this study
Clay SiO2 Al2 O3 MgO CaO Na2 O
FE-1 51.09 10.09 10.57 4.38 3.83
FE-2 51.70 9.51 11.06 4.10 4.85
FE-3 52.42 7.73 12.55 1.90 6.60
FE-4 50.23 6.29 13.61 1.84 6.81
33
in the range of (5 × 10−5 )–(2 × 10−2 ) M. Except for
the largest concentrations generally no dilution of the su-
pernatant was required prior to spectrophotometric mea-
surements. Absorbances were determined a wavelength of
665 nm, which corresponds to the maximum absorption peak
of MB monomers in water, or at the maximum of the red-
shifted monomer peak.
Kinetic experiments were made to compare adsorption
rates of MB on FE and on commercial activated carbon
(CAC). Beakers containing 5 cm3 of MB solution of 3.25 ×
10−3 mol dm−3 were immersed in a thermostatic shaker
controlled at 298 K. Adsorbents were added to the beakers
and the timing was started. The suspensions were shaken as a
function of time from 1 min to 4 h. At various time intervals,
samples were taken and MB concentration was measured,
after centrifugation as already described.
The distribution coefficient for adsorption KD (cm3 g−1 )
was derived using the formula
C0 − C V
KD = , (1)
C0 m
where C0 and C are the initial and final concentration of the
dye solution (mol dm−3 ), respectively, m (g) is the weight of
adsorbent, and V (cm3 ) is the volume of the aqueous phase.
3. Results and discussion
3.1. MB adsorption isotherms
As an example of the adsorption isotherms of FE samples,
Fig. 1 depicts the amounts of MB adsorbed by FE-2 against
the equilibrium concentrations for various temperatures.
Three regions can be distinguished on the isotherm curves.
In the first region (I), an S-shaped isotherm which corre-
sponds to a slow increase, followed by a fast growth, and a
region growing to a plateau is observed at very low dye load-
ing, except for the lowest temperature. After that, the curves
show a behavior in which at lower equilibrium concentra-
tions the adsorption is higher than at higher equilibrium con-
centrations in the second region. However, the amount of
adsorbed dye increases depending on the initial concentra-
tion for all cases. The adsorption of MB on FE leads to
changes in the absorption spectra of the dye. As may be
seen from visible spectra for the first region in Fig. 2 the
maximum wavelength of the monomer peak is observed at
675 nm. This represents a red shift by about 10 nm with
Fe2 O3 TiO2 MnO K2 O P 2 O5
4.19 0.42 0.06 2.45 0.01
3.95 0.38 0.06 2.00 0.01
3.14 0.29 0.05 1.64 0.01
2.25 0.22 0.04 1.07 0.00
34 G. Atun et al. / Journal of Colloid and Interface Science 261 (2003) 32–39
Fig. 1. Equilibrium profiles for MB solution in contact with FE-2 samples at
various temperatures. The curves in the first and second regions were drawn
by hand through the data.
Fig. 2. Visible spectra of MB in aqueous solution and after equilibration at
a point corresponding to the first, second, and third regions.
respect to the maximum observed for dilute aqueous solu-
tions. At this stage dye penetrates into the interlayer space
where the bathochromic shift could be due to p-interactions
between the aromatic entity and the oxygen plane of the
clay minerals and/or micropolarity/microacidity of the in-
terlayer surface. In our unpublished study, the average pH
value at the zero point of charge (i.e., pHzpc ) of FE sam-
ples was determined as 8.7. Since solution pH changes in
the range of 6 to 8 during sorption experiments it is believed
that the positively charged surface hydroxyl groups on the
edges of clay repel the similarly charged MB cations and
hence they enter the interlayer of minerals without covering
of outer exchange sites [12]. The dye molecules must ori-
ent themselves to find a suitable position in the interlamellar
spaces of the adsorbent. Since this is a difficult process an
S-shaped isotherm is observed in this region and the color
changes from light blue to dark with increasing dye con-
centration. However, an absence of S-shaped behavior at the
lowest temperature may be due to the competition of dye
molecules with water molecules in the interlamellar spaces
because it is well known that the adsorption of water mole-
cules on a solid is higher at lower temperatures. Although
there are positively charged surface sites on FE, no peak is
observed at the longer wavelength corresponding to the pro-
tonated form of adsorbed dye.
In the second region (II), as the initial MB concentration
increases the equilibrium concentration of MB in solution
decreases and finally reaches zero. This does not character-
ize an adsorption behavior. In this region the change of color
from dark blue to colorless can be followed by the naked
eye. The clay flocculates due to aggregation of the cations in
the interparticle space of the flocs. At an excess of MB, FE is
gradually peptized, forming small tactoids with monomeric
MB in the interlayer space and at the same time adsorb-
ing dimeric and polymeric MB cationic species at the solid–
liquid interfaces. Colorless solution (CS) appears at the point
of optimum flocculation of FE, indicating the highest rate of
sedimentation due to size of the flocs forming. This behav-
ior suggests that all structural negative charges of FE in the
suspension are neutralized by cationic MB species. Time-
dependent spectra for the second region show that the shoul-
der at 610 nm starts to decrease, and at 575 nm a new large
peak appears. At equilibrium, the 610-nm peak completely
disappears while the 575-nm peak increases. It is assumed
that the 575-nm band in the MB spectra in Fig. 2 corresponds
to trimers or higher aggregates of dye on the external surface
and 610-nm band corresponds to dimers at the outer and in-
ternal surfaces of the clay [7,15]. The amount of adsorbed
dye (qcs ) at the optimum flocculation point (i.e., at CS) is
considered to correspond to coverage of the clay surface
with MB molecules. The layer charge distribution on the FE
layers is heterogeneous because of its heterogeneous nature.
Neutralization of the higher negative layer charge density by
cationic MB species promotes greater agglomeration and the
value of qcs increases as the layer charge of FE increases.
In the third stage of adsorption (III), the MB solutions in
equilibrium are once again colored and the H type isotherm
is observed, indicating that the adsorbent surface has a very
high affinity for MB molecules. The wavelengths of the
absorption maximum and shoulder of the supernatant are
665 and 605 nm, respectively. These values are similar to
those of MB in water rather than to those of MB adsorbed
on dispersed clay particles, indicating the presence of free
MB molecules in the water phase. The interaction of the
montmorillonite, sepiolite, and some zeolite with MB and
 G. Atun et al. / Journal of Colloid and Interface Science 261 (2003) 32–39 35

other basic dyes has been studied by several authors with

similar results [7,13,15,18].
The curves show clear plateaus corresponding to maxi-
mum adsorption capacity (qm ) of FE. Although the S-shaped
curves in the first region move toward the right, indicat-
ing a lower coverage for higher temperature, the adsorbed
amount of MB increases with increasing temperature in the
third region. This may be attributed to the difficulty of the
monomers attaining a suitable orientation in the interlamel-
lar space at higher temperature. On the other hand, the ad-
sorption mechanism in the third region is considered to be
ion exchange and in general the exchange capacity increases
as the temperature increases.
Only adsorption data for the third region in Fig. 1 could
be fitted to Freundlich and Langmuir isotherm equations.
The linear form of the Freundlich isotherm is defined by

log q = log k + n log C, (2)

where q is the amount of dye adsorbed per unit mass of ad-

sorbent (in mol g−1 ) and C is the equilibrium concentration
of dye (mol dm−3 ).
As is seen in Fig. 3, log q vs log C curves give straight
lines according to the Freundlich isotherm equation. The
Freundlich isotherm parameters k and n are shown in
Table 2. The Freundlich exponent n gives information about
surface heterogenity and surface affinity for the solute.
For favorable adsorption, 0 < n < 1. Since the degree of
favorability increases as n approaches zero all four FE
samples show a very high affinity for MB species.
Since the Freundlich isotherm equation does not take into
account the maximum adsorption capacity, as an alternative,
data for the H type isotherm were fitted to the Langmuir
equation. The adsorption data were analyzed with the help
Fig. 3. Freundlich isotherms for third region of MB adsorption at various
temperatures.
of the linear form of the Langmuir isotherm,
C/q = 1/Kqm + (1/qm )C, (3)
where qm is the maximum adsorption capacity of dye (in
mol g−1 ), and if the equilibrium concentration C is referred
to standard concentration C 0 = 1 mol dm−3 , the adsorption
equilibrium constant K is found to be nondimensional.
As seen in Fig. 4 from the linear relation between C/q
and C, the adsorption equilibrium constant K and maximum
adsorption capacity qm of adsorbents were calculated and

Table 2
max
Isotherm parameters of MB adsorption on FE samples and parameters for KD
Clay sample T Freundlich parameters Langmuir parameters max
Parameters for KD
n k × 104 r qm × 104 K × 10−4 r C0 × 103 qcs × 104
(K) (mol g−1 ) (M) (mol g−1 )
FE-1 290 0.116 2.94 0.982 1.50 3.77 0.999 0.85 0.84
298 0.093 5.20 0.992 3.15 6.17 0.999 1.50 1.49
318 0.083 6.95 0.951 4.25 3.13 0.999 2.00 1.90
333 0.080 9.15 0.948 4.48 14.00 0.999 2.35 2.30

FE-2 290 0.079 3.09 0.961 1.78 16.27 0.999 0.90 0.98
298 0.068 5.89 0.962 3.47 20.48 0.999 2.00 2.00
318 0.050 8.13 0.958 5.65 21.53 0.999 3.60 3.50
333 0.061 9.42 0.994 6.11 36.58 0.999 3.80 3.79

FE-3 290 0.059 3.55 0.950 2.95 22.19 0.999 2.50 2.50
298 0.057 6.62 0.911 4.15 36.58 0.999 3.25 3.22
318 0.051 7.84 0.986 5.79 29.65 0.999 3.63 3.62
333 0.060 9.33 0.995 6.00 56.81 0.999 3.80 3.79

FE-4 290 0.058 5.15 0.967 3.96 38.08 0.991 3.00 2.99
298 0.061 8.51 0.977 6.02 45.59 0.999 3.35 3.30
318 0.069 9.12 0.977 6.23 56.24 0.999 3.70 3.69
333 0.065 10.47 0.999 6.34 79.02 0.995 3.80 3.79
36 G. Atun et al. / Journal of Colloid and Interface Science 261 (2003) 32–39
Fig. 4. Langmuir isotherms for third region of MB adsorption at various
temperatures.
these are also shown in Table 2. Both K and qm increased
from FE-1 to FE-4.
Using the appropriate constants for the Freundlich and
Langmuir equations, the theoretical isotherm curves were
predicted using known values of C. Figure 1 shows a com-
parison of the experimental points with the Freundlich and
Langmuir isotherms. Both isotherms gave good agreement
with the experimental data for the four temperatures.
3.2. Distribution coefficients dependence on initial
concentration of MB
Our investigation has focused particularly on determin-
ing the initial concentration of MB for the appearance of
colorless solution depending on clay composition and tem-
perature. This can be easily determined from the C0 value
corresponding to the maximum of the log KD vs C0 curves.
Before the appearance of colorless solution (BCS) the val-
ues of KD increased exponentially with increasing C0 while
after coloring appeared (ACS) they decreased. The curves
for BCS and ACS intersect at a point corresponding to C0
for the occurrence of CS. These points for CS shifted toward
higher C0 values from FE-1 to FE-4 (see Fig. 5 and Table 2).
As can be seen in Table 1, the amounts of MgO and Na2 O
increase from FE-1 to FE-4 whereas the amounts of Al2 O3 ,
CaO, and Fe2 O3 decrease. This suggests that the amount of
loughlinite, which is a Na-sepiolite, in the FE samples in-
creases toward FE-4. Sepiolite is a natural hydrated magne-
sium silicate mineral with a needle-like morphology [20,21].
These microscopic fibers have dimensions ranging in length
from 0.2 to 2 µm. A comparison of SEM images for FE-1
and FE-4 in Fig. 6 shows fibrous loughlinite particles inter-
spersed with a larger fraction in FE-4. Since both loughlin-
Fig. 5. The change of log KD values against initial concentration of MB
solution for FE samples.
ite and montmorillonite have a d spacing of 12.9 Å, peaks
corresponding to 2θ of 6.8◦ overlap in the XRD patterns in
Fig. 7 for the FE samples. These XRD patterns also show
that this peak increases from FE-1 to FE-4, indicating that
the fraction of these minerals increases. On the other hand,
the XRF data in Table 1 support the fact that especially the
fraction of loughlinite increases rather than that of montmo-
rillonite. The increase in the maximum adsorption capacities
toward FE-4 may be correlated with the enhanced loughlin-
ite fraction (Table 2).
To better understand the interaction of dye with FE,
SEM images and XRD patterns of a raw clay surface
were compared with the MB adsorbed surface at BCS, CS,
and ACS. At the BCS, the intensity of peaks of MB and
loughlinite in the XRD patterns decreases with respect to
the raw materials. On the other hand, at the CS, the basal
spacing is hardly ever observed for MB adsorbed loughlinite
and montmorillonite. Since at this point the adsorbed amount
of MB is equal to the point producing optimum flocculation,
silicate layers arranged very irregularly with respect to one
another [3]. At ACS, the peaks of MB adsorbed clay appear
again. This suggests that MB aggregates adsorbed on the
surface are diffused interparticles and clay silicate layers are
reoriented. The SEM images corresponding to these XRD
patterns indicate that the surfaces at BCS and CS are covered
by MB aggregates while at ACS some of the dye molecules
are diffused inside and the surface shows some similarity to
the raw material.
3.3. Effect of temperature on MB adsorption
The values listed in Table 2 show that the values of C0
corresponding to KDmax shift toward higher concentrations as
 G. Atun et al. / Journal of Colloid and Interface Science 261 (2003) 32–39 37

Fig. 6. A comparison of SEM images of FE-1 and FE-4 samples.

temperature increases from 290 to 333 K. However, smaller
changes were observed for higher temperatures. A series of
experiments were conducted with water without MB at 298,
318, and 333 K to study the transformation of clay in hot
water.
A comparison of SEM images and XRD patterns of raw
material and hot-water-treated FE showed that peak inten-
sities of XRD patterns increased with increasing tempera-
ture and SEM images showed that clay layers are separated,
forming small tactoids of larger spacing. So, the adsorbent
possesses a higher surface area and a more porous nature.
As a result of these phenomena, the adsorption capacities qcs
at CS, the maximum adsorption capacities qm , and the equi-
librium constants K increased with increasing temperature
(Table 2).
The change of free energy of adsorption can be calculated
from equilibrium adsorption constants:
G0 = −RT ln K. (4)
38 G. Atun et al. / Journal of Colloid and Interface Science 261 (2003) 32–39

Fig. 7. A comparison of XRD patterns of FE samples.

Thermodynamic parameters, standard enthalpy H 0 and Table 3

entropy S 0 of adsorption, were obtained from the slope Thermodynamic parameters for MB adsorption on FE
and intercept of the ln K vs 1/T plot according to the Clay sample H 0 × 102 G0 S 0
relation (kJ mol−1 ) (kJ mol−1 ) ( kJ mol−1 K−1 )
FE-1 1.58 −27.34 0.92
S 0 H 0 FE-2 1.29 −30.30 1.01
ln K = − . (5) FE-3 1.28 −31.74 1.06
R RT FE-4 1.27 −32.28 1.08

The results presented in Table 3 show that the values of

G0 are negative, indicating favorable adsorption. These
values (around −30 kJ mol−1 at 298 K) are in the middle of
physical adsorption and chemisorption [22]. Since H 0 is
close to zero and S 0 is positive, the adsorption mechanism
is an entropy-controlled process.
3.4. Comparison of adsorption rate of MB on FE and
activated carbon
Since the adsorption rate of MB is very high, the dis-
tribution coefficients initially increase exponentially. There-
 G. Atun et al. / Journal of Colloid and Interface Science 261 (2003) 32–39
Fig. 8. Comparison of adsorption rates of two FE samples with CAC in
3.25 × 10−3 M MB solution (i.e., near CS).
fore, log KD was plotted against time. The adsorption rates
of FE-3 and FE-4 samples near CS were compared with that
of the CAC. As shown in Fig. 8 the adsorption capacities of
both FE samples are higher than that of CAC and the time
required to attain equilibrium is much shorter. Furthermore,
FE is a locally available, low-cost adsorbent in Turkey. The
average price of FE samples is $0.04/kg whereas CAC costs
$20/kg.
4. Conclusion
MB is found to adsorb strongly on the surface of FE sam-
ples and the adsorbed amount of MB increases from FE-1
to FE-4. Three regions were observed on the adsorption
isotherm curves. The shape of the isotherm belongs to the
S type for low dye loading, whereas an H-type isotherm is
observed in high concentrations. On the other hand, a floccu-
lation behavior is observed at moderate concentrations. The
interaction of MB with clay in this region cannot be consid-
ered as dye adsorption because the equilibrium concentra-
39
tion of MB in solution decreases as dye-interacted clay in-
creases. The adsorption process of MB on FE, for the treat-
ment of MB effluents, allowed effluent suitable for reuse
to be produced. The results show that MB adsorption on
FE is very fast compared to that on CAC and also that FE
samples have higher adsorption capacity. Furthermore FE
is approximately 500 times cheaper than CAC. Therefore,
FE can be used as a highly effective low-cost adsorbent for
the removal of cationic dyes. The optimum condition for
the production of colorless effluent was determined as about
318 K.
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