Sorption of Pesticides on Kaolinite and Montmorillonite as a Function of Hydrophilicity

Pesticides and other organic species are adsorbed by soil via different mechanisms, with bond strengths that depend on the properties of both the soil and the pesticide. Since the clay fraction in soil is a preferential sorbent for organic matter, reference kaolinite and montmorillonite are useful models for studying the mechanism and the strength of sorption. This paper presents the results of batch experiments to investigate the interactions of kaolinite KGa-1 and montmorillonite SWy-1 with the following pesticides and organic species resulting from the natural degradation of pesticides in the environment: atrazine (1-chloro-3-ethylamino-5-isopropylamino-2,4,6-triazine), simazine (1-chloro-3,5-bisethylamino-2,4,6-triazine), diuron [1,1-dimethyl-3-(3,4-dichlorophenyl)urea], aniline, 4-chlorophenol, 2,4-dichlorophenol, and 2,4,6-trichlorophenol. Each of these chemicals has different hydrophilicity. Systems containing 2.0 g of clay were put in contact with 100.0 mL of solutions of the pesticides at known concentration ranging from 1.0 to 5.0 mg/L, and the amount of solute adsorbed was evaluated through RP-HPLC analysis of the pesticide still present in the aqueous suspension. To test for electrostatic interactions between the clay surface and the pesticides, potentiometric titration was used to determine the permanent surface charge of clays. Experiments were performed at different pH values. The results indicate that, for the chemicals studied, neutral molecules are preferentially retained relative to ionized ones, and that montmorillonite is a more effective sorbent than kaolinite.     

Sorption and desorption behavior of chloroanilines and chlorophenols on montmorillonite and kaolinite

The bioavailability of pollutants, pesticides and/or their degradation products in soil depends on the strength of their sorption by the different soil components, particularly by the clay minerals. This study reports the sorption-desorption behavior of the environmentally hazardous industrial pollutants and certain pesticides degradation products, 3-chloroaniline, 3,4-dichloroaniline, 2,4,6-trichloroaniline, 4-chlorophenol, 2,4-dichlorophenol and 2,4,6-trichlorophenol on the reference clays kaolinite KGa-1 and Na-montmorillonite SWy-l. In batch studies, 2.0 g of clay were equilibrated with 100.0 mL solutions of each chemical at concentrations ranging from 10.0 to 200.0 mg/L. The uptake of the compounds was deduced from the results of HPLC-UV-Vis analysis. The lipophilic species were best retained by both clay materials. The most lipophilic chemical used in the study, 2,4,6-trichloroaniline, was also the most strongly retained, with sorption of up to 8 mg/g. In desorption experiments, which also relied on HPLC-UV-Vis technique, 2,4,6-trichloroaniline was the least desorbed from montmorillonite. However, on kaolinite all of the compounds under study were irreversibly retained. The experimental data have been modelled according to the Langmuir and Freundlich isotherms. A hypothesis is proposed concerning the sorption mechanism and potential applications of the findings in remediation strategies have been suggested.     

Sorption and Desorption Behavior of Chloroanilines and Chlorophenols on Montmorillonite and Kaolinite

The bioavailability of pollutants, pesticides and/or their degradation products in soil depends on the strength of their sorption by the different soil components, particularly by the clay minerals. This study reports the sorption-desorption behavior of the environmentally hazardous industrial pollutants and certain pesticides degradation products, 3-chloroaniline, 3,4-dichloroaniline, 2,4,6-trichloroaniline, 4-chlorophenol, 2,4-dichlorophenol and 2,4,6-trichlorophenol on the reference clays kaolinite KGa-1 and Na-montmorillonite SWy-l. In batch studies, 2.0 g of clay were equilibrated with 100.0 mL solutions of each chemical at concentrations ranging from 10.0 to 200.0 mg/L. The uptake of the compounds was deduced from the results of HPLC-UV-Vis analysis. The lipophilic species were best retained by both clay materials. The most lipophilic chemical used in the study, 2,4,6-trichloroaniline, was also the most strongly retained, with sorption of up to 8 mg/g. In desorption experiments, which also relied on HPLC-UV-Vis technique, 2,4,6-trichloroaniline was the least desorbed from montmorillonite. However, on kaolinite all of the compounds under study were irreversibly retained. The experimental data have been modelled according to the Langmuir and Freundlich isotherms. A hypothesis is proposed concerning the sorption mechanism and potential applications of the findings in remediation strategies have been suggested.     

Removal of fenhexamid and pyrimethanil from aqueous solutions by clays and organoclays

The ability of a sodium montmorillonite (CLONa) and two commercial available organoclays having interlayer organic cations possessing different functional groups (CLO20A and CLO30B) was investigated for adsorbing two pesticides namely fenexamid (FEX) and pyrimethanyl (PMT). The two organoclays displayed a higher affinity with the pesticides than the unmodified clay, but the improvement in adsorption capacity varied according to the characteristics of the pesticide and the interlayer organic cation. FEX was adsorbed to a greater extent than PMT by both organoclays, which may be due to the higher hydrophobicity of FEX thereby indicating considerable hydrophobic interaction between the adsorbent/adsorbate systems. Our findings may find application in the removal of water-soluble pesticides from aquifers.     

Effects of surface coatings on electrochemical properties and contaminant sorption of clay minerals

Surface charges play a major role in determining the interactions of contaminants with soils. The most important sources of soil charges are clay mineral colloids, whose electrochemical properties are usually modified by metal-oxides and organic matter in natural environments. In this study, effects of coatings of organic matter and Fe- and Al-oxides on a series of electrochemical properties and heavy metal sorption of three clay minerals (kaolinite, montmorillonite and illite) predominant in natural soils were investigated using batch techniques. The results indicate that the coatings increased the specific surface area of the clay minerals, except for the Al-oxide coated montmorillonite and organic matter coated 2:1 clay minerals. The sesquioxide coatings increased amount of positive charges but decreased negative charges. This causes great reduction of the negative potential on the clay surfaces, shift of the zero point of charge to a higher pH, and promotion of fluoride sorption due to presence of more OH- and OH2 on the oxide surfaces than on the clay surfaces. In contrast, the organic coating significantly increased the negativity of surface charges, and thus the zero point of charge and zeta-potential of the clays dropped down. The organic coating also induced a reduction of fluoride sorption on the clays. With respect to the sorption of lead and cadmium, the sesquioxide coatings produced insignificant effects. The experiments of lead/cadmium competitive sorption show that on both the oxide-coated surface and the original clay surface there exist different types of sites, each of which preferentially binds with a heavy metal.     

Influence of pH on pesticide sorption by soil containing wheat residue-derived char

Field burning of crop residues incorporates resulting chars into soil and may thus influence the environmental fate of pesticides in the soil. This study evaluated the influence of pH on the sorption of diuron, bromoxynil, and ametryne by a soil in the presence and absence of a wheat residue-derived char. The sorption was measured at pHs approximately 3.0 and approximately 7.0. Wheat char was found to be a highly effective sorbent for the pesticides, and its presence (1% by weight) in soil contributed >70% to the pesticide sorption (with one exception). The sorption of diuron was not influenced by pH, due to its electroneutrality. Bromoxynil becomes dissociated at high pHs to form anionic species. Its sorption by soil and wheat char was lower at pH approximately 7.0 than at pH approximately 3.0, probably due to reduced partition of the anionic species of bromoxynil into soil organic matter and its weak interaction with the carbon surface of the char. Ametryne in its molecular form at pH approximately 7.0 was sorbed by char-amended soil via partitioning into soil organic matter and interaction with the carbon surface of the char. Protonated ametryne at pH approximately 3.0 was substantially sorbed by soil primarily via electrostatic forces. Sorption of protonated ametryne by wheat char was also significant, likely due not only to the interaction with the carbon surface but also to interactions with hydrated silica and surface functional groups of the char. Sorption of ametryne by char-amended soil at pH approximately 3.0 was thus influenced by both the soil and the char. Environmental conditions may thus significantly influence the sorption and behavior of pesticides in agricultural soils containing crop residue-derived chars.     

Sorption studies of chloroanilines on kaolinite and montmorillonite

Batch experiments have been performed in order to evaluate the ability of the two reference clays kaolinite (KGa-1) and Na-montmorillonite (SWy-1) to retain three representative chloroanilines: 3-chloroaniline, 3,4-dichloroaniline and 2,4,6-trichloroaniline. Systems containing the clay mineral and the pollutant solution (at concentration levels ranging between 1.0 and 10.0mg/L) were considered and RP-HPLC methods were employed to follow the sorption processes as a function of time. The results indicate that montmorillonite shows a general higher sorption capacity with respect to kaolinite and that for both the reference clays, in the concentration range investigated, the amount of pollutant sorbed increases with concentration. The sorption coefficient K(d) ranges between 0.0030 L/g for the system 3-chloroaniline-kaolinite and 0.0488L/g for the system 2,4,6-trichloroaniline-montmorrillonite. The most lipophilic trichloroaniline shows the greater sorption. X-ray analyses suggest for kaolinite a preferential sorption onto the mineral surface, while for montmorillonite a progressive swelling of the structure is observed, likely due to sorption processes that also take place in the interlayer.     

Calculating pesticide sorption coefficients (Kd) using selected soil properties

Pesticide soil/solution distribution coefficients ( Kd values), commonly referred to as pesticide soil sorption values, are utilized in computer and decision aid models to predict soil mobility of the compounds. The values are specific for a given chemical in a given soil sample, normally taken from surface soil, a selected soil horizon, or at a specific soil depth, and are normally related to selected soil properties. Pesticide databases provide Kd values for each chemical, but the values vary widely depending on the soil sample on which the chemicals were tested. We have correlated Kd values reported in the literature with the reported soil properties for an assortment of pesticides in an attempt to improve the accuracy of a Kd value for a specific chemical in a soil with known soil properties. Mathematical equations were developed from regression equations for the related properties. Soil properties that were correlated included organic matter content, clay mineral content, and/or soil pH, depending on the chemical properties of the pesticide. Pesticide families for which Kd equations were developed for 57 pesticides include the following: Carboxy acid, amino sulfonyl acid, hydroxy acid, weakly basic compounds and nonionizable amide/anilide, carbamate, dinitroaniline, organochlorine, organophosphate, and phenylurea compounds. Mean Kd values for 32 additional pesticides, many of which had Kd values that were correlated with specific soil properties but for which no significant Kd equations could be developed are also included.     

Glyphosate adsorption on soils of different characteristics. Influence of copper addition

Results of glyphosate (GPS) adsorption on three soils of different characteristics show that the interaction of this pesticide with the soils was not related to their CEC and clay minerals content, but to the content of iron and aluminum amorphous oxides and organic matter. The presence of Cu in treatment solutions enhanced GPS adsorption, due to several reasons: GPS coordinates strongly to Cu, and Cu GPS complexes formed seem to have higher ability to be adsorbed on the soil than free GPS; GPS adsorption can take place on sites where Cu was previously adsorbed, acting as a bridge between the soil and GPS; when Cu was present the solution pH decreased, and GPS adsorption increased, since lower pHs lead to the formation of GPS species with lower negative charge, which are adsorbed more easily on the negatively charged soil surfaces.     

Atrazine biodegradation modulated by clays and clay/humic acid complexes

The fate of pesticides in the environment is strongly related to the soil sorption processes that control not only their transfer but also their bioavailability. Cationic (Ca-bentonite) and anionic (Layered Double Hydroxide) clays behave towards the ionisable pesticide atrazine (AT) sorption with opposite tendencies: a noticeable sorption capacity for the first whereas the highly hydrophilic LDH showed no interactions with AT. These clays were modified with different humic acid (HA) contents. HA sorbed on the clay surface and increased AT interactions. The sorption effect on AT biodegradation and on its metabolite formation was studied with Pseudomonas sp. ADP. The biodegradation rate was greatly modulated by the material's sorption capacity and was clearly limited by the desorption rate. More surprisingly, it increased dramatically with LDH. Adsorption of bacterial cells on clay particles facilitates the degradation of non-sorbed chemical, and should be considered for predicting pesticide fate in the environment.     

A comparative study of adsorption of an anionic and a non-ionic surfactant by soils based on physicochemical and mineralogical properties of soils

In the present work we performed a comparative study on the adsorption of the surfactants sodium dodecyl sulphate (SDS) (anionic), and octylphenoxypolyethoxyethanol (Triton X-100) (non-ionic) to 18 soils with organic matter (OM) and clay fraction contents varying over a broad range. The objective of the study was to gain further insight into the influence of the physicochemical and mineralogical properties of soils on the adsorption of surfactants by soils. Adsorption isotherms were obtained using concentrations below the critical micellar concentration (cmc) of the surfactants. The adsorption coefficients, Kf, determined from the Freundlich equation were lower for SDS (range 1.77-82.1, mean value 36.3) than for Triton X-100 (range 0.01-913, mean value 257). Simple and multiple correlation coefficients were obtained between Kf values and soil characteristics. The results obtained indicate the influence of the OM content on the adsorption of SDS (r=0.64, p<0.01) and of the clay fraction content on that of Triton X-100 (r=0.83, p<0.001). Additionally, we observed a preferential adsorption of SDS by the 1:1 mineral kaolinite (r=0.54, p<0.05), while Triton X-100 was adsorbed mainly by the 2:1 minerals, montmorillonite (r=0.66, p<0.01) and illite (r=0.87, p<0.001). According to the influence of different soil parameters on adsorption, different mechanisms of adsorption are proposed for each surfactant. Our findings point to the interest of considering the physicochemical properties of soils and also the mineralogy of the soil clay fraction when selecting a surfactant in technologies involving enhanced solubilization and removal of contaminants from soils and sediments.     

Effects of organic acids on adsorption of lead onto montmorillonite,goethite and humic acid

Adsorption isotherms for Pb onto six soil components (quartz, feldspar, kaolinite, montmorillonite, goethite and humic acid) were studied. The influence of pH, EDTA and citric acid on the adsorption of Pb onto montmorillonite, goethite and humic acid were considered. Results indicate that the experimental data fit the Langmuir Adsorption Isotherm. The adsorption capacity for Pb at pH 6 was found to be in the order: humic acid (22.7 mg g(-1)) > goethite (11.04 mg g(-1)) > montmorillonite (10.4 mg g(-1)) > kaolinite (0.91 mg g(-1)) > feldspar (0.503 mg g(-1)) > quartz (0.148 mg g(-1)). Generally, the amount of Pb adsorbed onto montmorillonite, goethite and humic acid decreased with increasing concentrations of EDTA and citric acid and with increases in alkality. However, there were two exceptions: (1) addition of citric acid increased the amount of Pb adsorbed onto humic acid; and (2) the amount of Pb adsorbed onto goethite decreased with increasing pH in the presence of EDTA. Some mechanisms involved in the adsorption reactions are discussed.     

Destruction of halogen-containing pesticides by means of detonation combustion

Pesticides that contain a halogen functional group have been destructed by means of detonative combustion. The following compounds were examined: (1) atrazine—2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine—herbicide; (2) bromophos—O,4-bromo-2,5-dichlorophenyl O,O-dimethyl phosphorothioate—insecticide; (3) chloridazon—5-amino-4-chloro-2-phenylopyridazin-3(2H)-one—herbicide; (4) linuron—3-(3,4-dichlorophenyl)-1-metoxy-1-methylurea—herbicide; (5) metoxychlor—1,1,1-trichloro-2,2-bis(4-metoxyphenyl)ethane—insecticide and acaricide; and (6) trichlorfon—dimethyl 2,2,2-trichloro-1-hydroxyethylphosphonate—insecticide. Explosive material has been produced on the basis of ammonium nitrate, which served as an oxidizer while the pesticides were used as fuels. Composition of the explosive was adjusted in such a way as to respect thermodynamic parameters. Detonative decomposition of the mixtures has been carried out in shot-holes pre-drilled in soil. Efficiency of the pesticide decomposition has been examined with gas chromatography in order to determine pesticides residues in the environment. It was found that for some, the amount of pesticides in some compounds in the analyzed samples after decomposition was below the determination threshold of the applied method.     

The use of clays to sequestrate organic pollutants. Leaching experiments

Leaching experiments are performed from clay-pollutant systems in order to evaluate the capability of clays to sequestrate organic pollutants from wastewaters. Reference kaolinite KGa-1b, montmorrillonite SWy-2 and reference soil BCR^®-700 are the sorbent materials. 2,4,6-trichloroaniline (2,4,6-TCA) and 4-chlorophenol (4-CP) are the typical pollutants, sorbed at amounts of 10.0 mg g⁻¹ and 5.8 mg g⁻¹ on SWy-2 and 7.3 mg g⁻¹ and 2.2 mg g⁻¹ on KGa-1b, respectively.The leaching agents are ultrapure water and model solutions of acid rain and surface waters that simulate meteoric leaching. 1.0 mM HNO₃, 1.0 mM H₂SO₄ solutions and a methanol/water 50/50 (v/v) mixture simulate leaching agents of industrial source.The results are compared and the preferential capability of the clays to sequestrate the more lipophilic 2,4,6-TCA is evidenced.The bond interactions are discussed and explained through preferential adsorption reactions. For montmorrillonite also a simultaneous intercalation in the phyllosilicate interlayer is proposed.     

Sorption and desorption of imidazolium based ionic liquids in different soil types

This study investigates the influence of the two different clay minerals kaolinite and smectite as well as of organic matter on the cation sorption and desorption behaviour of three imidazolium based ionic liquids -1-butyl-3-methyl-imidazolium tetrafluoroborate (IM14 BF(4)), 1-methyl-3-octyl-imidazolium tetrafluoroborate (IM18 BF(4)) and 1-butyl-3-methyl-imidazolium bis[(trifluoromethyl)sulfonyl]imide (IM14 (CF(3)SO(2))(2)N) - in soil. The German standard soil Lufa 2.2 - a natural soil classified as a loamy sand - was the basis substrate for the different soil compositions and also served as a reference soil. The addition of organic matter and clays increases the sorption of the substances and in particular smectite had striking effects on the sorption capacity for all three ionic liquids indicating that ionic interactions play an important role for sorption and desorption processes of ionic liquids in soil. One exception was for kaolinite-containing soils and the IM14 cation: with (CF(3)SO(2))(2)N(-) as an anion the sorption was identical at either 10 wt% or 15 wt% clay content, and with BF(4)(-) sorption was even lower at 15 wt% kaolinite than at 10 wt%. Desorption was weak for IM18 BF(4), presumably owing to the longer alkyl side chain. With regard to the influence of kaolinite on desorption, the same pattern was observed as it was found for the sorption of IM14 BF(4) and IM14 (CF(3)SO(2))(2)N.     

Adsorption studies of the herbicide simazine in agricultural soils of the Aconcagua valley, central Chile

Simazine is a s-triazine herbicide that has been applied worldwide for agriculture. This herbicide is the second most commonly detected pesticide in surface and groundwater in the United States, Europe and Australia. In this study, simazine adsorption behaviour was studied in two agricultural soils of the Aconcagua valley, central Chile. The two studied soils were soil A (loam, 8.5% organic matter content) and soil B (clay-loam, 3.5% organic matter content). Three times higher simazine adsorption capacity was observed in soil A (68.03 mg kg⁻¹) compared to soil B (22.03 mg kg⁻¹). The simazine adsorption distribution coefficients (K_d) were 9.32 L kg⁻¹ for soil A and 7.74 L kg⁻¹ for soil B. The simazine adsorption enthalpy in soil A was −21.0 kJ mol⁻¹ while in soil B the adsorption enthalpy value was −11.5 kJ mol⁻¹. These results indicate that simazine adsorption process in these soils is exothermic, governing H bonds the adsorption process of simazine in both the loam and clay-loam soils. These results and the potentiometric profiles of both soils, suggest that simazine adsorption in soil A is mainly governed by simazine–organic matter interactions and in soil B by simazine–clay interactions. The understanding of simazine sorption–desorption processes is essential to determine the pesticide fate and availability in soil for pest control, biodegradation, runoff and leaching.     

A lysimeter experiment to investigate temporal changes in the availability of pesticide residues for leaching

Leaching of three pesticides (isoproturon, chlorotoluron and triasulfuron) and a tracer (bromide) were determined in four contrasting soils ranging in texture from sandy loam to clay. The compounds were applied to undisturbed columns of soil and four columns for each soil were randomly selected and leached with 24-mm equivalent of water at prescribed time intervals (3, 9, 24, 37 and 57 d after application). A rapid decline in leached loads of isoproturon and chlorotoluron as time from application to irrigation increased was observed in all soils. In contrast, triasulfuron and bromide loads only decreased rapidly in the clay soil. Bromide losses decreased with decreasing clay contents of the soil and therefore with a decrease in structural development. Magnitudes of pesticide losses varied from soil to soil, depending on structural development and the organic carbon content. Pesticide degradation experiments on disturbed and undisturbed soil samples showed that the rapid decline of leached loads with time was faster than could be explained by degradation alone. Five physico-chemical processes are put forward to explain the different patterns of pesticide leached loads observed in the soils: (1) relative extent of preferential flow, (2) sorption capacity of the compounds to the different soils, (3) extent of degradation of the compounds in the soil, (4) variation in sorption kinetics between compounds associated with pesticide diffusion into soil aggregates, and (5) protection of the compounds by a combination of intra-aggregate diffusion and the presence of preferential flow pathways.     

PeLM: modeling of pesticide-losses through runoff and sediment transport

A GIS-aided pesticide loss model (PeLM) was developed to simulate pesticide losses through surface runoff and sediment transport in watershed systems. The PeLM could tackle the movement of eroded soil along with surface runoff as well as the pesticide losses in adsorbed and dissolved phases. The contributions of different soil types in the sediment were also examined. The model was applied to the Kintore Creek Watershed of southern Ontario, Canada. The simulation results were verified through observed data, indicating a correlation level of 0.89-0.98. The results also showed that clay particles usually held the largest share of contributions to pesticide losses through soil erosion. This study is significant in the efforts for modeling nonpoint source pollution in watershed systems. It provides useful information and support for the related decisions of watershed management.     

Arsenic residue in residential area after cleanup of pesticide illegal dumping sources in Thanh Hoa province,Central Vietnam

In Vietnam, Nicotex's site is perhaps the most infamous case of illegal disposal of toxic pesticides near residential areas. In 2013, affected villagers discovered illegal burials of around 1,000 tons of expired pesticides in the Nicotex factory. Organic pesticides were detected in illegal burial areas (IBAs) around 60 times greater than acceptable levels, but no attention was paid to contamination of metals, metalloids, and other classes of organic contaminants, which could be co-contaminants in pesticide formulation. This study assessed the contaminants remaining in the IBAs and surrounding residential areas two years after the source removal conducted in 2014. Additionally, a preliminary health risk assessment from residual contaminants was performed. Nine classes of chemicals including parental pesticides, inorganic and organic degradation byproducts, and metals and metalloids, comprising 123 chemicals were quantified in soil, sediment, and water samples from Nicotex and surrounding residential areas. Although concentrations of organic pesticides were below acceptable levels, arsenic contamination in the soil in a Nicotex IBA named NCT5 and Nap village (NV) exceeded the acceptable level. The enrichment factor and log-probability plot indicate that arsenic enrichment at NV is not from natural sources but is associated with arsenic contamination in NCT5. Arsenic may be a co-contaminant in pesticide manufacturing or an arsenical pesticide, such as monosodium methanearsonate. Arsenic found in NV was toxic arsenate for which the preliminary risk assessment yielded an unacceptable excess carcinogenic risk (1 × 10^?4). While all attention was paid to investigate and treat contamination of organic pesticides, it turns out that arsenic is the major existing threat which poses an unacceptable cancer risk in good agreement with the high cancer rate claimed by villagers near Nicotex. This justifies the need for further investigation of the extent of the arsenic contamination and restoration of the contaminated land.     

Development of enterosorbents that can be added to food and water to reduce toxin exposures during disasters

Humans and animals can be exposed to mixtures of chemicals from food and water, especially during disasters such as extended droughts, hurricanes and floods. Drought stress facilitates the occurrence of mycotoxins such as aflatoxins B₁ (AfB₁) and zearalenone (ZEN), while hurricanes and floods can mobilize toxic soil and sediments containing important pesticides (such as glyphosate). To address this problem in food, feed and water, we developed broad-acting, clay-based enterosorbents that can reduce toxin exposures when included in the diet. In this study, we processed sodium and calcium montmorillonite clays with high concentrations of sulfuric acid to increase surface areas and porosities, and conducted equilibrium isothermal analyses and dosimetry studies to derive binding parameters and gain insight into: (1) surface capacities and affinities, (2) potential mechanisms of sorption, (3) thermodynamics (enthalpy) of toxin/surface interactions and (4) estimated dose of sorbent required to maintain toxin threshold limits. We have also used a toxin-sensitive living organism (Hydra vulgaris) to predict the safety and efficacy of newly developed sorbents. Our results indicated that acid processed montmorillonites were effective sorbents for AfB₁, ZEN and glyphosate, with high capacity and tight binding, and effectively protected hydra against individual toxins, as well as mixtures of mycotoxins.