Applied Clay Science 18 Ž2001.

205–209
www.elsevier.nlrlocaterclay

Introduction

Pesticide–clay interactions and formulations

Gerhard Lagaly )
Institute of Inorganic Chemistry, UniÕersity of Kiel, Olshausenstr. 40-60, D-24098 Kiel, Germany

Abstract

The papers collected in this issue reveal the diversity of pesticide–clay interactions. The most important bonding
mechanisms are shortly described in this introduction. These mechanisms provide the basis for attempts to design new
pesticide formulations. Several examples of such formulations are reported. q 2001 Published by Elsevier Science B.V.

Keywords: Adsorption; Bentonites; Clay minerals; Environmental aspects; Herbicides; Layered double hydroxides; Metolachlor; Pesticides

1. Introduction Production and uses of pesticides are still increas-

The presence of pesticides in water, soil, and air
has raised concerns for the protection of the environ-
ment, in particular protection of drinking water qual-
ity. Only a part of the applied amount of a pesticide
is bioactive, the rest is distributed in the environ-
ment. For instance, herbicides are sprayed on the
field to impede the growth of weeds. Only a part of
the amount applied exerts this effect. Certain amounts
remain attached to the soil or are adsorbed by dust
particles, are leached out, migrate into the ground
water or are distributed by surface runoff. A certain
quantity reaches the air and can diffuse over long
distances ŽWeber et al., 1973.. This loss requires
higher amounts of herbicides to be applied and causes
environmental problems. There are indications that
certain fungicides, probably also other types of pesti-
cides, act as culture medium of dangerous bacteria.
ing but must be strongly controlled to minimize the
health and environmental problems. It is more eco-
nomical to reduce the applied amounts of pesticides
than to decompose the non-bioactive amounts—if
ever possible. An important way to achieve this aim
is the design of formulations which combine an
optimum of bioactivity with a minimum amount of
pesticides. Stabilization against degradation and pho-
tochemical decomposition also helps to reduce the
amounts of pesticides distributed in the environment.
The study of pesticide–clay interactions with envi-
ronmental aspects in view is a challenge for coming
studies.
2. Clays and pesticides

Clays and clay minerals are wonderful materials!

)
Tel.: q49-431-880-3261; fax: q49-431-880-1608.
E-mail address: h.mittag@email.uni-kiel.de ŽG. Lagaly..
The high adsorption power, the ease with which they
are modified, and their particular colloidal properties
make them the most suitable materials for designing
solid laden pesticide formulations.

0169-1317r01r$ - see front matter q 2001 Published by Elsevier Science B.V.

PII: S 0 1 6 9 - 1 3 1 7 Ž 0 1 . 0 0 0 4 3 - 6
206 G. Lagalyr Applied Clay Science 18 (2001) 205–209
The interactions of different types of pesticides
with clay minerals were studied long ago. The first
accumulation of papers on pesticide–clay interac-
tions is noted around the 1970s, dominated by many
papers of Weber Ž1970, 1972a,b.. The sense of
responsibility and new or revised directives raised
the quantity of such papers in the last 10 years.
As pesticides are extremely diversified in their
structures and properties, all of the specific bonding
mechanisms apply to organic pesticides ŽMortland,
1970; Weber, 1972a,b; Sawhney, 1996.. Some pesti-
cides are cationic and are adsorbed by clay minerals
by ion exchange processes. A number of studies
were related to the adsorption of diquat and paraquat.
The adsorption and desorption of these herbicides
was thought to be directed by charge pattern interac-
tions ŽLagaly, 1986. between these divalent cations
and the surface charges of the clay mineral ŽWeber
et al., 1965; Weed and Weber, 1968; Philen et al.,
1971..
Many organic pesticides are weak bases. Their
ability to exchange with metal ions on the clay
mineral layers depends on their basicity, i.e. the
degree of protonation as a function of pH in solution.
Surface acidity can also be the source of protons.
These protons may exist on exchange sites on the
clay mineral but most important is proton transfer
from hydration water molecules around the interlayer
cations to the adsorptive. This process is particularly
effective in the presence of multivalent cations, for
instance Al 3q ŽSawhney and Singh, 1997. or transi-
tion metal ions ŽHerwig et al., this issue.. Also,
acid–base pairs wB PPP H PPP Bxq Žcalled Ahemisalt
formationB by Mortland, 1970. can be bound at
exchange sites. It is noted that the molar ratio
basercorresponding acid in the interlayer space dif-
fers from that in solution ŽKarickhoff and Bailey,
1976.. The adsorption of bases as a function of pH
often shows a maximum because acid–base pairs are
formed and protons compete with the protonated
base at low pH values.
Aliphatic and aromatic amines can directly inter-
act with interlayer cations. In this case, the interlayer
cations must be soft acids Žconcept of hard and soft
acids and bases. such as Zn2q, Cd 2q, Agq. Hard
cations like Naq, Mg 2q, Al 3q coordinate the amino
group by H 2 O bridges. For instance, the pyridinium
nitrogen atom is directly coordinated to the copper
ion but bound by a water molecule to the Mg 2q
cation ŽFarmer and Mortland, 1966..
Many pesticide molecules contain functional polar
groups Ž`OH, 5O, `Cl, `NO 2 . which are bound
by electrostatic forces Ždipole-ion. or coordination
type interactions. Coordination bonds are formed
directly between the adsorptive and the cation or via
water molecules as bridging ligands. As in the case
of base adsorption, the concept of hard and soft acids
and bases indicates if the ligand is directly coordi-
nated to the metal ions or via water molecules. The
reaction can also be described as ligand exchange: a
water molecule in the coordination shell around the
exchangeable cations is replaced by, for instance, an
alcohol molecule. The oxidation state of structural
iron can also exert an effect on pesticide adsorption
because it influences the Brønsted base character of
the surface ŽCervini-Silva et al., 2000..
Hydrogen bonds play an important role in all
cases where water bridges are formed between the
exchangeable cations and the adsorptive. Hydrogen
bonds can be accepted from OH groups at the edges
but can also be donated to the siloxane oxygen atoms
of the silicate layers. It was noted very early that
stronger hydrogen bonds to the oxygen atoms only
exist in case of tetrahedral charge and not when
charge arises from the octahedral layer ŽMortland,
1970.. The higher basicity of the Si–O–Al groups
Žas in the case of tetrahedral substitution. in compar-
ison with Si–O–Si groups Žoctahedral substitution.
was explained Yariv Ž1992. and Garfinkel-Shweky
and Yariv Ž1997..
Pesticide molecules often contain more or less
large hydrophobic moieties. If these groups can ap-
proach closely to the surface oxygen atoms, van der
Waals interaction becomes very strong. The influ-
ence of surface charges often dominates the influ-
ence of the hydrophobic binding sites. Screening of
the surface charges by salt addition then raises the
impact of the van der Waals interaction ŽJaynes and
Boyd, 1991; Nennemann, Kulbach et al., this issue..
When organic cations are exchanged for the metal
ions, the van der Waals forces also operate between
these cations and the organic adsorptive and can
dominate the adsorption process. If long chain cations
such as alkylammonium ions are bound in the inter-
layer space, entropic effects can also play an impor-
tant role ŽRegdon et al., 1998..
 G. Lagalyr Applied Clay Science 18 (2001) 205–209
Anionic pesticides may also be adsorbed. Impor-
tant, but less numerous adsorption sites, are the
positive edge charges of the silicate lamellae if pH is
below ; 5. An anionic pesticide can also be ad-
sorbed by hydrogen bonds or attached to multivalent
metal ions at exchange sites. At appropriate condi-
tions, anionic species may be adsorbed due to the
dominance of the van der Waals attraction. Layered
double hydroxides bind anionic pesticides by anion
exchange ŽLakraimi et al., 1999, 2000; Inacio et al.,
this issue..
Interactions of pesticides with clay minerals can
also include surface and volume effects. Mingelgrin
and Tsvetkov Ž1985. attributed an enhanced adsorp-
tion of organophosphate esters to Asurface condensa-
tionB, a reaction which is comparable to the process
leading to type III gas adsorption isotherms: at weak
adsorbate–adsorbent forces the uptake at low pres-
sures Žor concentrations. is small but once a molecule
has become adsorbed, the adsorbate–adsorbent forces
will promote the adsorption of further molecules in a
cooperative process ŽGregg and Sing, 1982..
Adsorption studies of pesticides in relation to the
pore structure should gain importance in the future.
It is expected that pesticide molecules assemble into
small mesopores of clay mineral aggregates. An
example is the adsorption of metolachlor on calcined
bentonites ŽBojemueller et al., this issue.. Adsorption
in porous aggregates retards the liberation of the
adsorptive in comparison to external surfaces ŽSawh-
ney and Gent, 1990; Sawhney, 1996.. Pillared clays
offer meso- and micropores but also reactive surface
sites for pesticide adsorption ŽGerstl et al., 1998a;
Nennemann, Mishael et al., this issue..
3. Clay-based pesticide formulations
The knowledge of the diversity of clay–pesticide
interactions should be helpful in developing new
pesticide formulations which fulfil the actual require-
ments of environmental control. An optimal pesticide
formulation signifies that a minimum amount of a
pesticide produces the maximum effect at the right
moment with a minimum of the pesticide being
dispersed in the environment. Many pesticides are
oil-like liquids and are applied in form of emulsions.
Other formulations contain particulate mater or poly-
207
mers. However, the potential of clay minerals as
carriers in pesticide formulations is not nearly ex-
ploited. It is one subject of this issue to show new
designs of pesticide formulations on the basis of
surface modified clay minerals such as bentonites,
montmorillonites, and sepiolite ŽCasal et al., this
issue.. Layered double hydroxides are considered the
most suitable adsorbents for anionic pesticides
ŽLakraimi et al., 1999, 2000; Inacio et al., this issue..
Unmodified, raw bentonites may be used as pesti-
cide carriers. The success of such formulations de-
pends on the type of bentonite, i.e. its origin ŽNenne-
mann, Mishael et al., this issue.. As many pesticide
molecules contain nonpolar moieties, van der Waals
interaction will be an important, often decisive, con-
tribution to the adsorption enthalpy. The hydropho-
bicity of the unmodified bentonites depends not only
on their layer charge but, even more strongly, on the
origin of the charges Žtetrahedral or octahedral. as
discussed above. Thus, the interaction with pesti-
cides can be strongly influenced by subtle differ-
ences in the clay mineral structure Žsee also Laird et
al. 1992; Sawhney, 1996..
Cation exchange with organic cations is the most
important reaction to modify the adsorbent in a way
that the interaction between the pesticide and the
clay mineral becomes optimal. A demonstrative ex-
ample is the adsorption of metolachlor on bentonite
modified with benzyl trimethylammonium ions
ŽBTMA. ŽEl-Nahhal et al., 1999a; Nennemann,
Mishael et al., this issue.. This example also reveals
the influence of the packing density of the organic
interlayer cations on adsorption. The amounts ad-
sorbed Žsometimes also the binding constants. are
not always in linear relation to the packing density
Žamounts of organic cations per formula unit. but
show a maximum. If swelling is restricted, the in-
creasing number of organic cations reduces the space
available to the adsorptive. An exchange of about
50–80% yielded the best formulations of meto-
lachlor on BTMA bentonite. Thus, optimal adsorp-
tion of a pesticide molecule may not only depend on
the tight fit of the interlayer cation to the pesticide
structure but also on the packing mode and density
of the cations ŽVimond-Laboudigue et al., 1996;
Carrizosa et al., this issue..
Rytwo and Tropp Žthis issue. developed the idea
to reduce the adsorption of the contact herbicide
208 G. Lagalyr Applied Clay Science 18 (2001) 205–209
diquat on dust particles by competition with monova-
lent organic cations and to lower the amount of this
herbicide which is inactivated by adsorption on dust
particles.
Bentonites modified with polymers can offer ad-
sorption sites in the interlayer space but the shell of
polymers around the particles often provides the
most important adsorption sites. This field of investi-
gation needs further studies. In most cases, however,
the pesticide molecules are trapped in the voids of
the polymer network which retards their liberation
ŽGerstl et al., 1998a,b..
The fascination in preparing clay based pesticide
formulations arises from the diversity of mechanisms
which operate. For instance, a different approach to
reduce leaching is entrapping of pesticide molecules
in clay mineral aggregates during coagulation of
dispersed montmorillonite lamellae ŽNennemann,
Kulbach et al., this issue.. At higher metolachlor
contents the clay mineral particles from large,
Apotato-likeB aggregates. These aggregates flow in-
dependently and the yield value of the dispersion
decreases and, eventually, disappears with increasing
metolachlor content.
The system just described also reveals that the
pesticides do influence the flow behavior of dis-
persed clay minerals. They can reduce viscosity and
yield value or increase these properties. For instance,
addition of multivalent cationic pesticides strongly
increases the viscosity and yield value of montmoril-
lonite dispersions ŽPenner and Lagaly, 2000.. Thus,
the presence of larger amounts of herbicides in soils
may influence the migration of soil clay particles.
Adsorption of pesticides on clay minerals can
reduce photodegradation and volatilization ŽEl-
Nahhal et al., 1999b.. Effective photoprotection was
achieved by energy transfer to coadsorbed molecules
ŽMargulies et al., 1987, 1988..
4. Conclusion
The diversity of pesticide–clay interactions pro-
vides the basis of attempts to reduce the hazardous
distribution of these materials in the environment.
This special issue reveals how pesticide molecules
interact with clay minerals, and demonstrates, for a
few herbicides, the design of new formulations de-
veloped on the knowledge of pesticide–clay interac-
tions. However, these efforts are lost if the aware-
ness of the society towards these problems cannot be
raised.
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