Dyes and Pigments 76 (2008) 220e225

www.elsevier.com/locate/dyepig

Investigation of a basic dye adsorption from aqueous solution

onto raw and pre-treated bentonite surfaces
E. Eren*, B. Afsin
Department of Chemistry, Faculty of Arts and Sciences, Ondokuz Mayis University, 55139 Kurupelit, Samsun, Turkey
Received 16 January 2006; received in revised form 21 May 2006; accepted 16 August 2006
Available online 2 November 2006

Abstract

The effects of temperature, pH and ionic strength on the adsorption of crystal violet (CVþ) by raw, Ni-saturated (Ni-), Co-saturated (Co-) and
Zn-saturated (Zn-) bentonite samples were investigated. The amounts of CVþ adsorbed in equilibrium at 298.15 K were 0.27, 0.37, 0.49
and 0.54 mmol g1 bentonite, which correspond to 108%, 148%, 196% and 216% of the cation exchange capacity (CEC) of the raw, Ni-,
Zn- and Co-saturated bentonite samples, respectively. The adsorption of the dye on these samples is pH-independent within the range (2.5e
8.5), and it increases with ionic strength from 0 to 0.6 mol l1. Thermodynamic and Langmuir parameters showed that cation-saturated bentonite
samples have relatively stronger ability than the raw bentonite towards the crystal violet (CVþ) cation.
Ó 2006 Elsevier Ltd. All rights reserved.

Keywords: Metal-saturated bentonite; Adsorption thermodynamics; Charge reversal; Crystal violet; Ionic strength

1. Introduction Adsorption of cationic dyes by clay minerals has been widely

studied to understand the co-adsorption behavior towards pesti-
Cationic dyes, commonly known as basic dyes, are widely cides [4,5], color removal of industrial effluents [6,7], ion type
used in acrylic, nylon, silk, and wool dyeing. This group of inorganic antibacterial material properties [8,9], ecologically
dyes include a broad spectrum of different chemical structures, important intermediates [10], and determination of the surface
primarily based on the substituted aromatic groups. Due to the properties of clays [11e15]. Margulies and co-workers [16]
complex chemical structure of these dyes, they are resistant to showed that when negatively charged clay particles are
breakdown by chemical, physical and biological treatments. introduced into an ionic solution, migration of the ions occurs,
Furthermore, any degradation by physical, chemical or and either neutral or charged complexes may arise from the
biological treatments may produce small amount of toxic and binding of monovalent organic cations to monovalent sites
carcinogenic products. Adsorption is known to be a promising through several mechanisms. Furthermore, a second organic
technique, which has great importance due to the ease of cation bound to a neutral complex by hydrophobic interactions
operation and comparable low cost of application in the decol- leads to a charge reversal of the particle.
oration process. Although activated carbons have been most In this work, the effects of pH, ionic strength of medium
widely used for the adsorption of dyes, clay materials have and adsorption temperature on the interaction of crystal violet
been increasingly gaining attention because they are cheaper with the raw, Ni-saturated (Ni-), Co-saturated (Co-) and Zn-
than activated carbons and their sheet-like structures also saturated (Zn-) bentonite samples were investigated in order
provide highly specific surface area [1e3]. to elucidate the role of bentonite surface in the sorption
process of basic dye (CVþ). Thermodynamic parameters
which were obtained from adsorption equilibrium experiments
* Corresponding author. Tel.: þ90 362 457 6020; fax: þ90 362 457 6081. using the van’t Hoff equation contribute to the driving force
E-mail address: [email protected] (E. Eren). for adsorption reactions.

0143-7208/$ - see front matter Ó 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.dyepig.2006.08.019
 E. Eren, B. Afsin / Dyes and Pigments 76 (2008) 220e225 221

2. Experimental
M

2.1. Materials

The bentonite sample (from Unye, Turkey) was ground and

Intensity [cps]
washed in deionized water several times at a 1:10 clay/water
ratio. The mixture was stirred for 3 h and then kept standing
overnight. After the clear liquid was decanted off the top, M

the solid was exposed to slow evaporation to dryness, and Mg

then ground and sieved through a 78e120 mm size. Q M
C
Mi Q Mi Mg
D D
Mi MgC;D,Q
2.1.1. Preparation of cation-saturated bentonites
The sample of raw bentonite was rehydrated with deionized
20 40 60
water at a ratio of 10 g raw bentonite:100 ml water and 10 g
2Theta [deg.]
metal chloride of corresponding salts was added to homoionic
form. The resulting mixtures were stirred for 24 h and centri- Fig. 1. The XRD patterns of the raw bentonite (M: montmorillonite, Mi: mica,
fuged at 3000 rpm until attaining chloride-ion-free form, as Q: quartz, C: calcite, Mg: magnesite, and D: dolomite).
shown by the silver nitrate test.
polyethylene bottle. The pH values were adjusted by adding
The cation exchange capacities (CEC) of the samples were
a few drops of dilute NaOH or HCl, and were measured by
determined by the adsorption of Cu(II) ethylene diamine
a Jenway 3040 model pH-meter, and were calibrated to
complex [17]. The values determined for raw bentonite was
pH ¼ 4.0 and 9.0 buffer solutions. The pH increased slightly
0.25 mmol g1.
(0.1e0.3) at the end of the adsorption process. With salt
added, the change in pH was between 0.2 and 0.4.
2.2. Chemical analysis The adsorption process of CVþ cations on each of the
tested samples was completed in 24 h. Rytwo and co-workers
The chemical compositions of the raw and acid activated [19] reported that the adsorption equilibrium of CVþ on Naþ-
bentonites are given in Table 1. The mineralogical composi- and Ca2þ-exchanged montmorillonite was reached within
tion of the raw bentonite sample was determined from X-ray 24 h and 72 h, respectively. Different equilibirium time re-
diffractograms (Fig. 1). X-ray analyses of the samples were sults were given in the literature; e.g., the adsorption process
made using the three principal lines [18]. The following min- of methylene blue cations on the montmorillonite samples
eral phases were identified: montmorillonite, quartz (a), tested by Ma and co-workers [20] and Rytwo and co-workers
calcite, dolomite, magnesite and mica. [19] reached the equilibrium positions in 4 h and 24 h, re-
spectively. Different equilibirium times arise from different
2.3. Thermal analysis
clay content.
The supernatant was centrifuged for 10 min at 5000 rpm at
Air dried clay samples were dispersed in 50 ml water. The
the end of the adsorption period and then it was diluted
suspensions were kept in the dark and after 24 h the organo-
between the ratios of 1:10 and 1:125 with deionized water
clay was separated by centrifugation. Samples were washed
for obeying LamberteBeer’s laws and avoiding from dye
with distilled water to remove excess dye. Thermal studies
aggregation. The amount of the dye adsorbed was determined
were carried out on Rigaku TG 8110 analyzer equipped with
from the difference between initial and equilibrium concentra-
TAS 100 (range: 20e1000  C) under flow of air at a heating
tion values by measuring the absorbance at 590 nm by a Uni-
rate of 10  C min1. Calcinated a-alumina was taken as the
cam UV2-100 spectrophotometer.
reference.
The structure of the dye studied is shown below:
2.4. Adsorption studies

Adsorption of CVþ (analytical grade, chloride salt, N

obtained from Reidel-de Haen) was carried out in a batch
process at various pH, temperature and salt concentration
values of the medium. A 50 mg sample was mixed with N+ Cl
a 50 ml CVþ solution of known concentration in the
Table 1
Chemical composition of raw bentoite
Sample SiO2 Al2O3 Fe2O3 CaO MgO Na2O K2 O N
(%) (%) (%) (%) (%) (%) (%)
Raw bentonite 62.70 20.10 2.16 2.29 3.64 0.27 2.53 Crystal Violet
222 E. Eren, B. Afsin / Dyes and Pigments 76 (2008) 220e225

3. Results and discussion respectively, and the exothermic DTA peaks at 622  C may
be related to the dehydroxylation of the simectite mineral
3.1. Thermal analysis of organo-bentonite complexes and the last stages of the oxidation of the organic matter.
From the present results it seems plausible that p-interactions
Representative DTA curves of bentonites saturated with between the aromatic entity and the oxygen plane contribute to
CVþ are shown in Fig. 2. According to directions of the the thermal stability of the carbon skeleton of the aromatic
various peaks, the DTA curves of the organo-clay can be di- matter, and consequently, the exothermic peak appears
vided into three regions. In the first region, up to 100  C, en- together the dehydroxylation reaction of the bentonites.
dothermic dehydration of clay is the major thermal reaction
(the mass losses for raw and treated bentonite samples are 3.2. CVþ adsorption on cation-saturated bentonite
4.90% and 3.12%, respectively). The second region is between surfaces
330 and 600  C, and the mass losses for CVþ adsorbed raw
and Co-saturated bentonite samples in this region are The amounts of adsorbed CVþ on bentonite samples are
13.10% and 16.17%, respectively. The exothermic oxidation shown in Fig. 3. In the present study, when the amount of
of adsorbed CVþ is the principial thermal reaction of this CVþ added was between 0.01 and 1.0 mmol dye g1 bentonite,
region. Exothermic peaks are associated with weight loss the adsorbed amounts of adsorbed CVþ cations onto raw, Ni-,
which increases with increasing degrees of saturation. The Co- and Zn-saturated bentonite samples were 0.27, 0.37, 0.49
third region occurs at temperatures above 600  C. The mass and 0.54 mmol g1 bentonite, which correspond to 108%,
loss for raw and Co-saturated samples is 7.13% and 7.80%, 148%, 196% and 216% of CEC, respectively. This result is
different comparing to that of Rytwo and co-workers [21],
who showed that the amount of adsorbed CVþ on montmoril-
lonite was 200% of the clay CEC. The difference observed
here may arise from the clay crystallinity, morphology and
TG size of the particles and the total surface area of the clays used.
The adsorption behavior of CVþ on bentonite samples may
be divided into two parts depending on the concentration
(c) ranges: (i) adsorption occurs at the external surfaces of the
clay by ion exchange at CVþ concentration below the CEC
of the clay; (ii) a second organic cation adsorbs by non-co-
DTA lumbic interactions onto clayeorganic complex, giving rise
to a singly positively charged structure with two organic cat-
ions and one negatively charged site in CVþ concentration
above the CEC of the clay. In cation-saturated bentonite sam-
Exo

TG ples, binding of a CVþ cation to a negative surface site re-

quires saturation of the CEC first. The dye adsorbed well
(b) above the CEC value results in charge reversal and increasing

0,6
Endo

DTA
Amount Adsorbed (mmol g-1 bentonite)

0,4
TG
(a)

0,2
Raw
DTA Ni-
Co-
Zn-

20 100 200 300 400 500 600 700 800 900 1000 0
Temperature/ºC 0 0,2 0,4 0,6 0,8 1 1,2

þ
Amount of CV added (mmol g-1 clay)
Fig. 2. Thermal analysis of raw- and CV -treated bentonite samples. (a) Raw
bentonite; (b) CVþ adsorbed raw bentonite; (c) CVþ adsorbed Co-saturated Fig. 3. Adsorption of CVþ on the bentonite samples as a function of the initial
bentonite. CVþ concentration. Contact time, 24 h; temperature, 295.15 K.
 E. Eren, B. Afsin / Dyes and Pigments 76 (2008) 220e225 223

the CVþ concentration induces the hydrophobic interactions Table 2

among large organic molecules. Isotherm constants of CVþ adsorption on bentonite samples
Sorption of CVþ molecules on cation-saturated bentonite Sample b (mmol g1) k (L g1) R2
samples showed different sorption behavior from that of the Raw 0.35 0.64 0.99
raw bentonite which may be explained by two reasons. (i) It Ni- 0.41 8.96 0.99
is known that hydrated or partially hydrated metal cations Co- 0.56 14.86 0.99
Zn- 0.50 51.29 0.99
could provide more spaces due to the pore opening effect.
The insertion of metal cations into the clay sheets increases
the pore size and gives rise to permanent charges at the basal According to the b parameter (mmol g1), sorption on
surface [22e25]. The differences in the adsorption capacities bentonites occurs following the sequence: Co- (0.56) > Zn-
of raw and cation-saturated bentonites may be attributed to (0.50) > Ni- (0.41) > raw (0.35) bentonite. Adsorption iso-
pore diameters and distortions in the electrical potential therms of CVþ on metal-saturated bentonite are different
influence the adsorption capacity directly. (ii) The increase from that on the raw bentonite, suggesting that metal satura-
in the adsorption amounts of CVþ molecules may also arise tion may influence the adsorptive properties of the bentonites.
from enhancing reactivity of XOH (X ¼ Si, Al) groups
[26,27], which may be responsible for the particle aggregation, 3.4. Effects of ionic strength and pH
and which is increased by the electrical interaction energy of
the clay double layers. Aggregation refers to the collapse of The effect of ionic strength on the adsorption ability of the
the diffuse double layers and the formation of aggregates of samples towards CVþ was investigated using NaCl solutions
higher spaced parallel platelets. from 0.2 to 0.6 mol l1 in the presence of 1.2 mmol g1 at
pH 6.0 for 24 h. The increase in the ionic strength of the
3.3. Adsorption isotherms medium had different effects on the adsorbed amounts on
the bentonite samples (Fig. 5). The increase in the ionic
The Langmuir model effectively describes the sorption data strength also favors the approximation-association process of
with all R2 values >0.98. the clay particles, through which the dye molecules can be
entrapped by newly generated centers [12]. It is known that
in a clay suspension, the particles are suspended in pure water
Ce 1 Ce and do not agglomerate, due to the interaction of the diffuse
¼ þ ð1Þ
ðx=mÞ kb b double layers. In the presence of an electrolyte the particles
may approach each other so closely that they aggregate. The
where Ce is the equilibrium concentration of CVþ remaining addition of the electrolyte led to an increase of the mean
in the solution and x/m is the quantity of CVþ adsorbed per aggregate radius. Luckham and Rossi [28] showed that a small
unit weight of adsorbent. The Langmuir constants are called addition of Na concentration led to the formation of edge-to-
adsorption capacity (b) and bonding energy constant (k). The edge type aggregates, whereas a more concentrated solution
Langmuir lines for each adsorbate are shown in Fig. 4, and resulted in the formation of very compact irregular aggregates
Langmuir constants and correlation coefficients are given in having a multilayer structure of the face-to-face type.
Table 2. To study the influence of pH on the adsorption capacities of
the samples towards CVþ, experiments were performed for
3
1,2
Adsorbed Amount (mmol g-1 bentonite)

Raw

Raw

Raw

0,8
Co-

2
Co-

Co-
Ce/(x/m)

Zn-

Zn-
Zn-
Co-

0,6
Zn-

Ni-

Ni-

Ni-
Ni-

0,4
Raw

1
Raw 0,2
Ni-
Co-
0
Zn-
Cl Cl Cl Cl
t Na Na Na Na
0 ou M M M
th 2 4 6
0 0,2 0,4 0,6 0,8
wi 0. 0. 0.
Ce (mmol g-1 bentonite)
Fig. 5. Adsorption of CVþ on the bentonite samples with NaCl concentration
þ
Fig. 4. Langmuir isotherm plots for the adsorption of CV on the bentonite in medium. Contact time, 24 h; temperature, 295.15 K; initial CVþ concentra-
samples. Contact time, 24 h; temperature, 298.15 K. tion, 1.2 mmol g1 bentonite.
224 E. Eren, B. Afsin / Dyes and Pigments 76 (2008) 220e225

24 h using 0.6 mmol g1 dye solutions with pH values the capability of a clay to retain a solute and also the extent of
changing from 2.5 to 8.5 (Fig. 6). The pH increased slightly its movement in a solution phase [30]. According to Gomes
(0.1e0.3) following the adsorption. and co-workers [31], Kd is a useful parameter for comparing
Fig. 6 points out that adsorption of the CVþ species on ben- the sorptive capacities of different clays or materials for any
tonite samples is controlled by a pH-independent adsorption particular ion, when measured under the same experimental
mechanism, which occurs partly by ion exchange releasing conditions.
exchangeable cations in the interlayer and on basal plane The DH, DS and DG values are negative for adsorption of
surfaces and partly via non-columbic interactions between CVþ on raw bentonite (Table 3) in agreement with the results
an adsorbed cation and a neutralized site. of Rytwo and Ruiz-Hitzky [32], who used a concentration
value well above 0.6 mmol dye g1 clay for adsorption on
3.5. Thermodynamic parameters Wyoming montmorillonite. But Ma and co-workers [20]
reached positive DH and DS values using 2.5 mmol dye g1
To study the influence of the temperature on the adsorption clay for adsorption on Na-, Ca- and Cu-montmorillonite sam-
capacities of the samples towards CVþ, experiments were per- ples. Generally, the change in adsorption enthalpy for physi-
formed using 0.8 mmol g1 dye solutions with pH 6.0 for 24 h sorption is between 20 and 40 kJ mol1, but chemisorption
at various temperatures. is in the range of 80 to 400 kJ mol1. The negative value
The thermodynamic parameters of the adsorption process of the change in enthalpy (83.81 kJ mol1) indicate that
were determined from the experimental data obtained using the adsorption is chemical in nature involving strong forces
the following equations: of attraction, and is also exothermic, thereby demonstrating
that the process is stable energetically. The negative DG values
DS DH found here indicate that the adsorption process is thermody-
ln Kd ¼  ð2Þ
R RT namically feasible at room temperature. In this study, the pos-
itive DH and DS values were obtained for pre-treated bentonite
DG ¼ DH  TDS ð3Þ samples. The positive value of DH reflects that the adsorption
process is endothermic in nature, but the activation energy
Ca necessary for it is not very large. The negative value of DH
Kd ¼ ð4Þ
Ce for CVþ adsorption on raw bentonite indicates that the adsorp-
tion of CVþ cations on this surface occurs mainly through an
where Kd is the distribution coefficient for the adsorption, DS, ion-exchange mechanism, whereas the positive values of the
DH and DG are the changes of entropy, enthalpy and the Gibbs adsorption heats observed on the metal-saturated samples
energy, T is the absolute temperature, R is the gas constant, Ce show that the adsorption on these samples are accompanied
(mmol g1) is the equilibrium adsorbate concentration in the not only by the ion exchange but also by the release of water
aqueous phase and Ca (mmol g1) is the amount of CVþ molecules hydrated around the exchangeable cations. The pos-
adsorbed per unit mass of the adsorbent. The values of DH itive values of DS suggest the increased randomness at the
and DS were determined from the slopes and intercepts of solidesolution interface during the adsorption of CVþ on
the plots of ln Kd vs. 1/T. Distribution coefficient (Kd) indicate pre-treated bentonites, since adsorbed CVþ led to decreasing
0,6
number of water molecules surrounding CVþ cations and
thus the degree of freedom of the water molecules increases.
Because the reorientation or restructuring of water around
CVþebentonite complex is very unfavorable in terms of
Amount Adsorbed (mmol g-1 bentonite)

0,5 entropy, since it disturbs the existing water structure and im-
poses a new and more disordered structure on the surrounding
water molecules. The large differences in the values of the
thermodynamic parameters between raw and pre-treated
0,4 bentonite samples suggest that a non-uniform thermodynamic
process participate in the bentoniteeCVþ interaction. Further-
more, slightly positive entropy values of CVþ adsorption
Raw process on treated bentonite samples indicate an irregular
0,3
Ni- increase of the randomness at the bentoniteesolution interface
Co- during adsorption.
Zn-

0,2
4. Conclusions
2,0 4,0 6,0 8,0 10,0
pH This study investigated the adsorption of a basic dye, namely
þ
Fig. 6. Adsorption of CV on the bentonite samples with equilibrium pH. Con- crystal violet, onto raw and cation-saturated bentonite samples.
tact time, 24 h; temperature, 295.15 K; initial CVþ concentration, Increasing the ionic strength increased the adsorption of CVþ
0.8 mmol g1 bentonite. onto bentonite samples. Adsorption equilibrium was correlated
 E. Eren, B. Afsin / Dyes and Pigments 76 (2008) 220e225 225

Table 3
Calculated thermodynamic parameters for adsorption of CVþ on bentonite samples
Sample DH (kJ/mol) DS (kJ/mol K) DG (kJ/mol) R2
295.15 K 300.15 K 305.15 K 309.15 K
Raw 83.81 0.26 4.41 3.06 1.72 0.64 0.97
Ni- 54.58 0.18 0.39 1.32 2.25 3.00 0.98
Co- 41.94 0.14 0.99 1.71 2.44 3.02 0.98
Zn- 39.03 0.13 0.66 1.33 2.00 2.54 0.99
Contact time, 24 h; temperature, 295.15 K; initial CVþ concentration, 0.8 mmol g1 bentonite.

reasonably well by Langmuir isotherm. The adsorption of CVþ methylene blue and clays in an aqueous suspension. J Colloid Interface
on bentonite suspensions is highly affected by the bentonite Sci 2002;255:254e9.
[14] Czimerova A, Jankovic L, Bujdak J. Effect of the exchangeable cations
surface features. Metal cation exchange process leads to pore on the spectral properties of methylene blue in clay dispersions. J Colloid
widening and increase in the reactivities of basal and edge sur- Interface Sci 2004;274:126e32.
face groups. Thus, the adsorption capacities of the cation-satu- [15] Miyamoto N, Kawai R, Kuroda K, Ogawa M. Adsorption and aggrega-
rated bentonites were higher than that of the raw and acid tion of a cationic cyanine dye on layered clay minerals. Appl Clay Sci
activated bentonite. Thermodynamic results indicate that CVþ 2000;16:161e70.
[16] Margulies L, Rozen H, Nir A. Model for competitive adsorption of or-
adsorption onto bentonite samples is spontaneous. The adsorp- ganic cations on clays. Clays Clay Miner 1988;36:270e6.
tion enthalpies and entropies prove that the clay surfaces do not [17] Bergaya F, Vayer M. CEC of clays: measurement by adsorption of a cop-
exhibit a uniform behavior towards the CVþ moieties. per ethylenediamine complex. Appl Clay Sci 1997;12:275e80.
[18] Grimshaw RW. The chemistry and physics of clays and allied ceramic
materials. 4th ed. London: Ernest Benn Lmt, p. 968e78.
References [19] Rytwo G, Serban C, Nir S, Margulies L. Use of methylene blue and crys-
tal violet for determination of exchangeable cations in montmorillonite.
[1] Gupta GS, Shukla SP. An inexpensive adsorption technique for the treat- Clays Clay Miner 1991;39:551e5.
ment of carpet effluents by low cost materials. Adsorpt Sci Technol [20] Ma YL, Xu ZR, Guo T, You P. Adsorption of methylene blue on
1996;13:15e26. Cu-exchanged montmorillonite. J Colloid Interface Sci 2004;280:
[2] Juang RS, Lin SH, Huang FC, Cheng CH. Structural studies of Na-mont- 283e8.
morillonite exchanged with Fe2þ, Cr3þ and Ti4þ by N2 adsorption and [21] Rytwo G, Nir S, Margulies L. Interactions of monovalent organic cations
EXAFS. Environ Technol 2004;18:525e31. with montmorillonite e adsorption and model-calculations. Soil Sci Soc
[3] Tsai WT, Chang CY, Ing CH, Chang CF. Adsorption of acid dyes from Am J 1995;59:554e64.
aqueous solution on activated bleaching earth. J Colloid Interface Sci [22] Huang FC, Lee JF, Lee CK, Chao HP. Effects of cation exchange on the
2004;275:72e8. pore and surface structure and adsorption characteristics of montmoril-
[4] Casal B, Merino J, Serratosa JM, Ruiz-Hitzky E. Sepiolite-based mate- lonite. Colloids Surf A Physicochem Eng Asp 2004;239:41e7.
rials for the photo- and thermal-stabilization of pesticides. Appl Clay [23] Huang FC, Lee JF, Lee CK, Tseng WN, Juang LC. Effects of exchange
Sci 2001;18:245e54. titanium cations on the pore structure and adsorption characteristics of
[5] Banerjee K, Dureja P. Photostabilization of quinalphos by crystal violet on montmorillonite. J Colloid Interface Sci 2002;256:360e6.
the surface of kaolinite and palygorskite. Pesticide Sci 1995;43:333e7. [24] Juang RS, Wu FC, Tseng RL. The ability of activated clay for the adsorp-
[6] Borisover M, Graber ER, Bercovich F, Gerstl Z. Suitability of dyeeclay tion of dyes from aqueous solutions. J Colloid Interface Sci
complexes for removal of non-ionic organic compounds from aqueous 1997;274:337e40.
solutions. Chemosphere 2001;44:1033e40. [25] Lee JF, Lee CK, Juang LC. Size effects of exchange cation on the pore
[7] El-Shishtawy RM, Melegy AA. Geochemistry and utilization of mont- structure and surface fractality of montmorillonite. J Colloid Interface
morillonitic soil for cationic dye removal. Adsorpt Sci Technol Sci 1999;217:172e6.
2001;19:609e20. [26] Schlegel ML, Manceau A, Chateigner D, Charlet L. Sorption of metal
[8] Cik G, Bujdakova H, Sersen F. Study of fungicidal and antibacterial ef- ions on clay minerals. I. Polarized EXAFS evidence for the adsorption
fect of the Cu(II)-complexes of thiophene oligomers synthesized in of Co on the edges of hectorite particles. J Colloid Interface Sci
ZSM-5 zeolite channels. Chemosphere 2001;44:313e9. 1999;215:140e58.
[9] Ohashi F, Oya A, Duclaux L, Beguin F. Structural model calculation of [27] Schlegel ML, Charlet L, Manceau A. Sorption of metal ions on clay min-
antimicrobial and antifungal agents derived from clay minerals. Appl erals II. Mechanism of co sorption on hectorite at high and low ionic
Clay Sci 1998;12:435e45. strength and impact on the sorbent stability. J Colloid Interface Sci
[10] Chattopadhyay S, Traina SJ. Spectroscopic study of sorption of nitro- 1999;220:392e405.
gen heterocyclic compounds on phyllosilicates. Langmuir 1999;15: [28] Luckham PF, Rossi S. The colloidal and rheological properties of benton-
1634e9. ite suspensions. Adv Colloid Interface Sci 1999;82:43e92.
[11] Cione APP, Neumann MG, Gessner F. Time-dependent spectrophotometric [30] Reddy MR, Dunn SJ. Distribution coefficients for nickel and zinc in
study of the interaction of basic dyes with clays III. Mixed dye aggregates soils. Environ Pollut 1986;11:303e13.
on swy-1 and laponite. J Colloid Interface Sci 1998;198:106e12. [31] Gomes PC, Fontes MPF, Silva AG, Mendonc, ES, Netto AR. Selectivity
[12] Cione APP, Schmitt CC, Neumann MG, Gessner F. The effect of added sequence and competitive adsorption of heavy metals by Brazilian soils.
salt on the aggregation of clay particles. J Colloid Interface Sci Soil Sci Soc Am J 2001;65:1115e21.
2000;226:205e9. [32] Rytwo G, Ruiz-Hitzky E. Enthalpies of adsorption of methylene blue and
[13] Neumann MG, Gessner F, Schmitt CC, Sartori R. Influence of the layer crystal violet to montmorillonite e enthalpies of adsorption of dyes to
charge and clay particle size on the interactions between the cationic dye montmorillonite. J Therm Anal Calorim 2003;71:751e9.