Applied Clay Science 20 (2002) 273 – 282

www.elsevier.com/locate/clay

Adsorption of diquat, paraquat and methyl green on sepiolite:

experimental results and model calculations
Giora Rytwo a,*, Dvora Tropp b, Carina Serban b
a
Tel Hai Academic College, School of Biotechnology and Environmental Sciences, Upper Galilee, 12210, Israel
b
The Seagram Center for Soil and Water Sciences, The Faculty of Agriculture, The Hebrew University of Jerusalem,
Rehovot, Jerusalem 76100, Israel
Received 8 December 2000; received in revised form 8 May 2001; accepted 28 May 2001

Abstract

Adsorption of the divalent organic cations paraquat (PQ), diquat (DQ) and methyl green (MG) on sepiolite was determined
experimentally and investigated with an adsorption model. The largest amounts of DQ, PQ and MG adsorbed were between
100% and 140% of the cation exchange capacity (CEC) of sepiolite. In previous experiments with monovalent organic cations
(dyes), the largest amounts of dyes adsorbed were about 400% of the CEC of sepiolite. Consequently, it was proposed that most
of this adsorption was to neutral sites of the clay. The large differences between the adsorption of these divalent organic cations
and the monovalent dyes may indicate that there is almost no interaction between DQ, PQ and MG and the neutral sites of
sepiolite. This assumption was confirmed by infrared (IR) spectroscopy measurements, that did not show changes in the peaks
arising from the vibrations of external SiUOH groups of the clay when the divalent organic cations were added. Adsorption
results were compared with calculations of an adsorption model that combines the Gouy – Chapman solution and specific
binding in a closed system. The model considers cation adsorption on neutral sites of the clay, in addition to adsorption to
mono- or divalent negatively charged sites, forming neutral or charged complexes. The model could adequately simulate the
adsorption of the divalent organic cations DQ and PQ when added alone, and could yield good fit for the competitive adsorption
experiment between the monovalent dye methylene blue and DQ. In competitive adsorption experiments, when total cationic
charges exceeded the CEC, monovalent organic cations were preferentially adsorbed on the clay at the expense of the divalent
cations. D 2002 Elsevier Science B.V. All rights reserved.

Keywords: Sepiolite; Diquat; Paraquat; Methyl green; Adsorption model

Abbreviations: CEC, cation exchange capacity; CV, N-[4-[bis[4- 1. Introduction

(dimethylamino)-phenyl]methylene]-2,5-cyclohexadien -1-ylidine]-
N-methyl-methanaminium chloride (crystal violet); DQ, 1,1V-ethy-
lene-2,2V-dipyridilium dibromide (diquat); FTIR, Fourier transform Sepiolite is a clay mineral with a unit cell formula
infrared; MB, 3,7-bis(dimethylamino)phenazathionium chloride Si12O30Mg8(OH,F)4(H2O)4
8H2O (Brauner and Prei-
(methylene blue); MG, 4-[[4-(dimethylamino)phenyl][4-(dimethyli- singer, 1956; Santaren et al., 1990), and a general
mino)-2,5-cyclohexadien-l-ylidene] methyl]-N-ethyl-N,N-dimethyl- structure formed by an alternation of blocks and
benzenaminium bromide chloride (methyl green); PQ, 1,1V-dime-
thyl-4,4V-bypiridinium (paraquat); UV, ultraviolet.
tunnels that grow up in the fibre direction (c-axis).
*
Corresponding author. Fax: +972-4-6988499. Each block is constructed by two tetrahedral silica
E-mail address: rytwo@yiron.org.il (G. Rytwo). sheets enclosing a central magnesia sheet. In some

0169-1317/02/$ - see front matter D 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 1 6 9 - 1 3 1 7 ( 0 1 ) 0 0 0 6 8 - 0
274 G. Rytwo et al. / Applied Clay Science 20 (2002) 273–282
aspects sepiolite is similar to other 2:1 trioctahedral
silicates, such as talc, but it has discontinuities and
inversions of the silica sheets that give rise to structural
tunnels. In the inner blocks, all corners of silica
tetrahedra are connected to adjacent blocks, but in
outer blocks some of the corners are Si atoms bound to
hydroxyls (SiUOH). These silanol groups at the
‘‘external surface’’ of the silicate (Alrichs et al.,
1975), are usually accessible to organic species, acting
as neutral adsorption sites (denoted as N). In addition
to that, some isomorphic substitutions in the tetrahe-
dral sheet of the lattice of the mineral, such as Al3 +
instead of Si4 + , form negatively charged adsorption
sites (P sites). Such sites are occupied by exchangeable
cations that compensate for the electrical charge.
These characteristics of sepiolite make it a power-
ful sorbent (Alvarez, 1984) for neutral organic mole-
cules and organic cations.
In this work we present results for the adsorption to
sepiolite of three divalent organic cations: methyl
green (MG), diquat (DQ) and paraquat (PQ) (Fig. 1).
Methyl green is basic triphenylmethane-type dica-
tionic dye, usually used for staining solutions in
medicine and biology (Green, 1990). Preadsorbing it
on clay minerals was also proposed as means to
stabilize pesticides against photodecomposition (Mar-
gulies et al., 1985, 1987). Previous studies (Rytwo et
al., 1998a, 2000) addressed the issue of MG adsorp-
tion on montmorillonite and sepiolite by elucidating
the existence of pH-dependent transformations of MG
Fig. 1. Chemical formula of the organic molecules.
between mono- and di-valent states, which may result
in two patterns of adsorption.
Diquat and paraquat are divalent contact herbicides
widely used with several crops. However, in soils,
strong interactions between DQ and PQ and certain
clays drastically reduce their herbicidal activity (Cal-
derbank, 1968). The environmental impact of these
herbicides is highly influenced by their interactions
with the clay components of the soil (Basile et al.,
1990; Moyer and Lindwall, 1985).
The main aim of the current study has been to
visualize the pattern of adsorption of these divalent
organic cations on sepiolite. The adsorption was
measured experimentally, and the results were com-
pared with calculated adsorption amounts evaluated
by a computer model that considers cation adsorption
on neutral and charged sites of sepiolite (Rytwo et al.,
1998b).
2. Methods and materials
2.1. Materials
The clay used was Yunclillos sepiolite ( < 200
mesh), provided by Tolsa (Madrid, Spain) and with
a 99% content of pure mineral. The chemical compo-
sition of the clay is described in Ruiz-Hitzky and
Casal (1985). The surface area (N2, BET) is 340 m2
g  1 and the cation exchange capacity (CEC) is near
 G. Rytwo et al. / Applied Clay Science 20 (2002) 273–282
0.14 molc kg  1. Analyzes performed to the clay in
previous studies (Rytwo et al., 1998b), showed that
Na + contributed to the CEC 0.03 molc kg  1, and the
rest of the CEC is contributed by Mg2 + . The neutral
N sites content for this sepiolite is 0.60 mol kg  1 as
was determined from grafting reaction of organo-
chlorosilanes on the silanol groups covering the
sepiolite surface (Ruiz-Hitzky and Fripiat, 1976).
Diquat was purchased as the dibromide salt from
Chem Service (West Chester, PA). Paraquat was
obtained as the dichloride salt from Sigma (St. Louis,
MO). Methylene blue was manufactured by Merck
(Darmstadt, Germany). Methyl green (MG) was pur-
chased as dichloride salt from Fluka Chemica (Buchs,
Switzerland). The molecular structures of the four
organic cations used are shown in Fig. 1. All materials
were used without further treatment or purification.
2.1.1. Adsorption isotherms
To measure adsorption amounts of the divalent
cations, aliquots of aqueous 1  10  2 M solution of
each organic cation were added under continuous
stirring to 5 ml of a 5-g sepiolite kg  1 suspension
in 20-ml polyethylene bottles. The final volume was
brought to 15 ml with deionized water. The bottles
were sealed and kept at 25 F 0.2
C under continuous
agitation. The pH was measured and found to be
between 6.7 and 7.4 for all samples. Previous inves-
tigators (Narine and Guy, 1981) have reported that the
adsorption of DQ and PQ was essentially independent
of pH in the range of 4.5 – 8.5. Adsorbed amounts
were measured after 1 and 7 days, by sampling 3 ml
of suspension from each bottle and filtering through
S&S FP030/2 disposable filters (Schleicher & Schuell,
Dassel, Germany), with 0.45-mm pore diameter cellu-
lose-acetate membranes. Adsorption of the used
organic cations to the filters was insignificant, as was
tested by filtering low concentrations of pure solutions
of DQ, PQ, MG and MB. In the case of MG, the initial
dye solution had a pH of 5.8, ensuring that most of the
MG adsorption was as a divalent cation (Rytwo et al.,
1998a, 2000).
The concentration of the cations in each of the
filtrates was determined by measuring the absorption
at 308 nm (DQ, e = 1,8300 M  1 cm  1), 258 nm (PQ,
e = 20,500 M  1 cm  1), and 248 nm (MG, e = 13,600
M  1cm  1) by using an HP 8452A diode array UV –
VIS spectrophotometer (Hewlett-Packard, Palo Alto,
275
CA). To avoid analytical problems observed in the
measurements of MG concentrations (Rytwo et al.,
2000), the samples with this cation were diluted with a
buffer solution (pH 7.0), and left to stabilize for 24 h
at room temperature, under darkness.
Limits of detection of the cations were 5.5  10  7,
4.9  10  7 and 7.4  10  7 M for DQ, PQ, and MG,
respectively, corresponding to an optical density of
0.01 with 10-mm quartz cuvettes. All experiments
were carried out in triplicate.
2.1.2. Competitive adsorption
To evaluate the competitive adsorption between the
monovalent dye MB and the divalent herbicide DQ,
separate aqueous 2  10  2 molc l  1 solutions of
each cation were prepared. Binary solutions contain-
ing equal volumes of DQ and MB were prepared to
yield a final concentration of 0.01 molc l  1 of each
organic cation. Aliquots of these solutions were added
to sepiolite suspensions as described above. Separa-
tion and spectroscopic measurements were performed
after 1 and 7 days. The spectra were mathematically
deconvoluted, to determine the concentration of each
organic cation. Subtraction of the spectrum of DQ
from the measured spectrum yielded results highly
correlated with that of MB (R2 > 0.99), and vice versa.
This led to the conclusion that there was no chemical
interaction between the two organic cations in the
solution that might affect their spectra. Concentrations
of MB were determined by measuring the absorption
at 662 nm (MB, e = 61,000 M  1 cm  1), using the
HP 8452A spectrophotometer. The limit of detection
for MB was 1.6  10  7 M, corresponding to an
optical density of 0.01 in a 10-mm cuvette.
2.1.3. IR spectra
Volumes of 1 ml from the suspensions prepared for
the adsorption isotherms of DQ and PQ were sampled
and dropped onto ZnS (Irtran-2) plates. The organic
cation– clay mixture was allowed air dry for 4 days.
IR spectra in the range of 700– 4000 cm  1 were
measured with a Magna-IR 550 FTIR spectrophotom-
eter, (Nicolet Analytical Instruments, Madison, WI).
2.1.4. Adsorption model
The model employed is fully described in Rytwo et
al. (1998b). It is essentially an extension of that
described by Nir (1986), Margulies et al. (1988) and
276 G. Rytwo et al. / Applied Clay Science 20 (2002) 273–282
Rytwo et al. (1995), which accounts for the ability of
charged organic monovalent cations to adsorb to
neutral binding sites on the silicate layer. In general
it is based on the following main elements:
1. The total amount of cations sorbed is composed
of cations bound specifically to the surface (cations in
the Stern layer) and those residing in the diffuse
double layer.
2. The electrostatic Gouy –Chapman equations are
solved for the suspension considering all cations and
anions, with their respective valencies. Changes in the
actual surface charge density that occur due to the
specific cation binding are iteratively considered
while solving the equations.
3. The model considered the system as closed—
thus a mass conservation balance for each ion in the
system is constantly calculated, and adsorption of a
molecule causes a reduction of it in the equilibrium
solution.
Organic cations may bind to the clay by different
modes. In the case of monovalent organic cations, the
following three kinds of clay –organic complexes can
be found.
(i) A neutral complex may form by the binding of a
cation to a monovalent negative site on the clay block
(Fig. 2a). Such reaction is mainly electrostatic, and
should be considered for both organic and inorganic
cations.
(ii) A second organic cation may bind to a neutral
clay – organic complex by non-coulombic interactions
(Fig. 2b), forming a single positively charged complex
with two organic cations and one charged site. This
Fig. 2. Patterns of adsorption for the different clay organic com-
plexes. See details in the text.
type of binding arises from hydrophobic interactions
between large organic molecules, and may lead at
high loads to charge reversal (Margulies et al., 1988).
The model does not considers the possibility of
formation of such complexes in the adsorption of
inorganic cations, and the assumption is that they
occur only in organic molecules.
(iii) In sepiolite, where neutral sites occur at the
external surface, a monovalently charged complex
may form by the binding of one organic cation and
a neutral site (Fig. 2c). Such binding was found to be
responsible for the very large amount of monovalent
organic cations adsorbed to sepiolite, that reached up
to 400% of the CEC (Alvarez et al., 1987; Aznar et
al., 1992; Rytwo et al., 1998b).
For neutral organic molecules, the model considers
only the possibility of a neutral complex that may
arise by the binding of a neutral organic molecule and
a neutral site (Fig. 2d).
Several clay – organic complexes can be formed by
divalent organic cations.
(i) A neutral complex may form by the binding of a
cation and a divalent negative site on the clay (Fig.
2e). Such reaction is mainly electrostatic, and was
already considered by previous versions of the model
that evaluated adsorption of divalent inorganic (Hirsch
et al., 1989; Undabeytia et al., 1998) and organic
(Rytwo et al., 1996a) cations.
(ii) A monovalent charged complex may form by
the electrostatic binding of one divalent cation and a
monovalent negative site on the clay (Fig. 2f). Such
complexes were considered for inorganic di- and tri-
valent cations by previous users of the adsorption
model (Yermiyahu et al., 1994; Kinraide et al., 1998).
Charged complexes while adsorbing divalent organic
cations can arise by non-coulombic interactions
between two divalent cations and a divalent site, as
they appear in Fig. 2b for the case of monovalent
organic cations (ii). Such complexes would form
positively divalent charged complex, and were con-
sidered for adsorption of DQ and PQ to montmor-
illonite. However, when evaluating the influence of
high ionic strength solutions on the amounts of DQ
and PQ adsorbed, the possibility of their formation
was rejected (Rytwo et al., 1996a).
(iii) Theoretically, in the case of sepiolite, a diva-
lent charged complex might form by the binding of
one organic cation and a neutral site (Fig. 2g). Results
 G. Rytwo et al. / Applied Clay Science 20 (2002) 273–282
of this study will show that such a complex was not
observed in the case of DQ and PQ.
3. Results and discussion
Fig. 3 shows the amounts of DQ, PQ and MG
adsorbed on sepiolite after 7 days, as a function of
total divalent cation added amount. This is not a
classic isotherm representation, but it helps to empha-
size that when the added amounts were lower than the
CEC of the sepiolite (0.14 molc kg  1), all cations
were completely adsorbed. Similar results were ob-
served for the adsorption of these cations on smectites
(Tomlinson et al., 1969; Narine and Guy, 1981;
Margulies and Rozen, 1986), indicating a very large
affinity of those molecules to the clay. When the
added amounts were higher than the CEC, the amount
of MG and DQ adsorbed increased, up to a saturation
level of 0.20 and 0.16 molc kg  1, respectively (about
140% and 115% of the CEC). Unlike the adsorption
of MG and DQ, PQ adsorbed amounts approached the
CEC. Adsorption isotherms after 1 day were almost
identical to those in Fig. 3, indicating that the equi-
libration time for the adsorption of all three divalent
organic cations was less than 1 day (results not
shown).
Fig. 3. Adsorption isotherms of MG, PQ and DQ on sepiolite.
277
The adsorbed amounts are considerably lower than
those reported in the past for monovalent organic
cations, such as MB and crystal violet (CV) and even
for neutral molecules such as Triton-X (TX100). The
reported maximal adsorbed amounts were about 0.55,
0.64 and 0.30 mol kg  1 clay for MB (Aznar et al.,
1992), CV (Rytwo et al., 1998b) and TX100 (Alvarez
et al., 1987), respectively. Thus, the amounts of these
monovalent organic cations adsorbed are more than
400% of the CEC of sepiolite. Such large adsorbed
amounts were explained by the possibility of polar
organic molecules adsorbing on neutral silanol
(SiUOUH) sites, whereas monovalent organic cations
can adsorb to both charged sites (isomorphic ex-
changes) and neutral sites. The relatively lower
amounts of divalent organic cations adsorbed might
raise the question whether these molecules adsorb on
both types of sites.
In order to test this hypothesis we performed FTIR
measurements on the clay – organic particles. The
vibrations of the SiUOH bond result in a band at
3700 cm  1, together with a doublet due to OUH
deformation at approximately 800 cm  1 (Nakanishi
and Solomon, 1977; Kodama, 1985). Shifts or
changes of these peaks indicate interactions of the
organic cations with the silanol groups, and can be
interpreted as adsorption on the neutral sites.
278 G. Rytwo et al. / Applied Clay Science 20 (2002) 273–282
Fig. 4. IR spectra of the OUH vibration in pure sepiolite, sepiolite
with 0.05 and 0.15 molc methylene blue/kg clay (sep – MB 0.05 and
sep – MB 0.15), and sepiolite with 0.15 molc diquat/kg clay (sep –
DQ 0.15).
Fig. 4 shows the FTIR spectra of the doublet due to
OUH deformation. Pure sepiolite exhibits two clear
peaks at 789 and 764 cm  1. Adsorption of a mono-
valent organic cation, such as MB at 1/3 of the CEC
(MB 0.05) shows almost no influence on those peaks,
Fig. 5. IR spectra of the SiUOH vibration in (a) pure sepiolite (sep), sepiolite with 0.05 and 0.15 molc methylene blue/kg clay (sep – MB 0.05
and sep – MB 0.15, respectively); (b) pure sepiolite (sep), sepiolite with 0.05 and 0.15 molc diquat/kg clay (sep – DQ 0.05 and sep – DQ 0.15,
respectively).
but at higher loads, for example, at the CEC (MB
0.15), a considerable deformation of the peaks is
observed. Divalent organic cations, for example DQ,
do not affect the OUH doublet at any adsorbed load,
e.g., DQ adsorbed up to the CEC (DQ 0.15 in Fig. 4).
The same results were obtained for FTIR spectra of
PQ (results not shown). When both DQ and MB are
co-adsorbed up to the CEC the deformation appears,
but is ascribed to the binding of the monovalent
organic cation to the neutral sites.
Similar effects can be observed for the main
SiUOH vibration at 3700 cm  1 (Fig. 5). Fig. 5a
shows that with increasing amounts of MB the peak
shifts from 3689 (no MB) to 3680 cm  1 (MB 0.15,
up to the CEC). No shift is observed when DQ is
adsorbed (Fig. 5b).
Our conclusion from Figs. 4 and 5 is that neither
DQ nor PQ adsorb on the neutral sites of sepiolite. We
speculate that this might be a general pattern for
divalent organic cations interacting with sepiolite.
Since the binding coefficients of DQ and PQ to the
charged sites of sepiolite are not known, we assumed
that they were equal to the corresponding binding
coefficients to montmorillonite (Rytwo et al., 1996a).
 G. Rytwo et al. / Applied Clay Science 20 (2002) 273–282
A similar approximation was employed for the ad-
sorption of monovalent organic cations on sepiolite
(Rytwo et al., 1998b). The binding coefficients to
neutral sites were taken as zero based on the FTIR
results presented above. Thus, our calculations did not
introduce any new parameters and might be only be
considered as a test of the model for the adsorption of
divalent organic cations to sepiolite.
Fig. 6 shows calculated and measured results for
the adsorption of DQ (Fig. 6a) and PQ (Fig. 6b) on
sepiolite. All binding coefficients are given in Table 1.
A very good fit between the measured and calculated
values was observed. For the case of DQ, R2 = 0.978
and RMSE = 0.0080 molc kg  1. For PQ, we obtained
R2 = 0.955 and RMSE = 0.0086 molc kg  1.
Fig. 6. Calculated and measured adsorption isotherms of PQ (a) and
DQ (b) on sepiolite. Points are experimental and lines are calculated
values using binding coefficients in Table 1.
279
Table 1
Binding coefficients of the organic cations used for the model
calculations
Organic Binding coefficient to charged sites Binding
cation coefficient to
Neutral Charged neutral sites
complex complex
MB + 3.0  108a 1.0  106a 3.0  106b
DQ2 + 2.7  105c 1.4  105c 0
PQ2 + 4.4  106c 1.0  103c 0
a
Rytwo et al. (1995).
b
Rytwo et al. (1998b).
c
Rytwo et al. (1996a).
No model calculations were performed for the
adsorption of MG. As mentioned before, MG changes
from divalent to monovalent when the pH changes
from 6 to 7 (Rytwo et al., 1998a, 2000). Since the
change is relatively slow if the initial pH of the MG
solution is 6 or less, most of its adsorption is as a
divalent cation (MG2 + ). Under this conditions the
amounts adsorbed were about 140% of the CEC (see
Fig. 3). However, when the pH of the initial MG
solution was changed to 7 by using concentrated
NaOH, its adsorption was mostly as a monovalent
(carbinol + ), reaching a maximal amount of more than
threefold the CEC (Rytwo et al., 2000), similarly to
the results with other monovalent dyes. Even though
the change in the charge of MG is relatively slow, it is
impossible to determine in each case the fraction of
MG adsorbed as a monovalent or a divalent species.
However, albeit MG adsorption was not tested by
model calculations, the adsorption results emphasize
the difference in the general pattern of sorption be-
tween monovalent organic cations that might adsorb
on neutral sites of sepiolite, and divalent organic
cations that do not.
Fig. 7 shows experimental and calculated results
of a competitive adsorption experiment with equiv-
alent amounts of the monovalent dye MB + and the
divalent herbicide DQ2 + . If amounts less than or
equal to the CEC where added, the organic cations
added were completely adsorbed, but at higher added
amounts, a considerable preference for the adsorption
of the monovalent organic cation is evident. When
the total added amounts are about twice the CEC,
almost no DQ is adsorbed by the clay. Similar
280 G. Rytwo et al. / Applied Clay Science 20 (2002) 273–282
Fig. 7. Adsorbed amounts in a competitive adsorption experiment
adding equivalent amounts of the monovalent dye MB + and the
divalent herbicide DQ2 + . Points are experimental and lines are
calculated values using binding coefficients in Table 1.
results, although slightly less pronounced, were
obtained for the CV + /PQ2 + pair (results not shown).
One explanation for this effect is that since divalent
organic cations, such as DQ, do not adsorb on neutral
sites, these sites are occupied only by the monovalent
MB. In addition, binding coefficients of MB to
charged sites are higher than those of DQ (see Table
1). Thus, at high added concentrations the monova-
lent cations displace the divalent ones from the
charged sites, resulting in very low amounts of DQ
adsorbed.
A similar pattern was observed in competitive
adsorption experiments employing montmorillonite
(Rytwo et al., 1996b; Nir et al., 1994), although in
most cases at least part of the divalent organic cations
were adsorbed. In that work an additional explanation
was presented for the preference for the monovalent
over the divalent cation: In general the concentration
of a cation near the surface is expressed by the
Boltzmann’s equation,
eu0
Xið0Þ ¼ Xið1Þ e kT Zi ð1Þ
where Xi(1) and Xi(0) are the molar concentrations of
cation i in the equilibrium solution far away from the
surface and at the surface, respectively, Zi is the
valence of the given ion, e is the absolute magnitude
of an electron charge, u0 is the surface potential, k is
Boltzmann’s factor, and T is the absolute temperature.
For cation adsorption exceeding the CEC, the surface
potential becomes positive. In such case the value in
the exponent in Eq. (1) is negative, and a decrease in
the concentration of cations near the surface is
observed. Since this effect is an exponential function
of the potential and the valence of the ion, divalent
cations are excluded from the clay surface to a larger
extent than monovalent cations; and this effect
increases for larger amounts of adsorbed cations,
i.e., for larger positive potentials. Hence, it can be
anticipated that as cation adsorption exceeds the CEC,
the competition for adsorption on the clay between
monovalent and divalent organic cations should favor
the monovalent organic cations. This effect that can
be observed only when the amounts adsorbed are
larger than the CEC, is general for all surfaces that
form a double layer. In the sepiolite case, since
positively charged complexes may also arise from
the binding of monovalent organic cations to neutral
sites, the positive potential increases furthermore,
causing the concentration of divalent cations to be
very low. As an example, we can present model
calculations for the case where MB and DQ are added
at amounts of 0.2 molc kg  1 clay each. The calcu-
lated surface potential is + 66.2 mV. This potential
would reduce the concentration of a monovalent ion
near the surface to 7.5% of its concentration in the
equilibrium solution, whereas the concentration of a
divalent cation at the surface would be only 0.52% of
its value far from the surface. The calculated adsorbed
amounts of DQ and MB for this case are 0.024 and
0.199 molc kg  1 clay, respectively; close to the
experimentally measured amounts.
The model calculations for the DQ/MB competitive
adsorption experiment are in very good agreement with
the measured results (RDQ2 = 0.961, RMSEDQ = 0.0069
molc kg  1, RMB2 = 0.993, RMSEMB = 0.0075 molc
kg  1).
We may speculate at this point, that in general the
affinity of divalent organic cations for adsorption on
sepiolite are lower than those of monovalent organic
cations. Similar results were shown by Perez-Rodri-
guez et al. (1989) for vermiculite and montmorillon-
ite. They observed the desorption of DQ and PQ
caused by adding low concentrations of monovalent
alkyl-ammonium organic cations.
 G. Rytwo et al. / Applied Clay Science 20 (2002) 273–282
4. Concluding remarks
Our results show that when the added concentra-
tions of MG, DQ and PQ are below the CEC of the
clay, less than 5% of the added concentration remain-
ed in solution. Such behavior corresponds to high-
affinity (H-type) adsorption isotherms, and demon-
strates that the affinity of these divalent organic
cations for sepiolite is very strong.
From FTIR spectra of the silanol groups, we de-
duced that unlike neutral organic compounds and
monovalent organic cations, DQ and PQ do not bind
to the neutral silanol sites. The results presented in this
work emphasize the difference in the patterns of
adsorption between monovalent organic cations that
may bind to charged and neutral sites of sepiolite, and
divalent organic cations that bind to the charged sites
only.
Competition experiments with monovalent organic
cations show that as long as the total organic cation
concentration was less than the CEC, all organic
cations adsorb. With respect to adsorption beyond
the CEC, the monovalent organic cations have a
striking advantage over the divalent ones. This differ-
ence might be explained by the fact that neutral sites
bind to monovalent cations only, together with a
larger exclusion of the divalent cations from the clay
surface, which is positively charged when adsorption
exceeds the CEC.
Model calculations gave a good fit to the adsorbed
amounts of DQ and PQ, and for the competitive
adsorption of DQ with MB. Such good fit was
obtained using binding coefficients that were found
in previous studies for the adsorption of organic ions
to montmorillonite, and without making any adapta-
tion.
Acknowledgements
This research was supported in part by a Grant G-
0405-95 from G.I.F., the German – Israeli Foundation
for Scientific Research and Development, by a grant
for Strategic Research in Environmental and Water
Quality #1317 from Israel’s Ministry of Science, and
by a fellowship from the Sacta-Rashi Foundation. We
are grateful to Prof. Shlomo Nir for reading the ma-
nuscript and for his helpful comments and suggestions.
281
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