R. Celis

Interactions of pesticides with clays and layered double hydroxides: a review

Abstract The increasing presence of pesticides in natural ecosystems has stimulated research to look for improved adsorbent materials which can be used to remediate and prevent soil and water contamination by these compounds. Among the different materials that have been assayed as adsorbents of pesticides are natural clay minerals, particularly 2:1 phyllosilicates and their structurally complementary synthetic analogues layered double hydroxides (LDHs). The great interest in natural clays and LDHs as adsorbent materials is mainly related to the large specific surface areas associated with their layered structure, the ease with which they are obtained or synthesized, and the possibility of modifying their surfaces to increase their affinity for specific adsorbates. This review summarizes the adsorptive properties of natural clays and LDHs for pesticides and related organic compounds. Particular emphasis is given to the surface modification of clay minerals and LDHs with organic ions as a strategy to improve the efficiency of these materials as pesticide adsorbents. Potential applications of unmodified and modified clays and LDHs as adsorbents to prevent and remediate soil and water contamination by pesticides are also discussed.

Montmorillonite–chitosan bionanocomposites as adsorbents of the herbicide clopyralid in aqueous solution and soil/water suspensions

Montmorillonite (SWy-2)-chitosan bionanocomposites (SW-CH) were prepared following different methodologies, characterized, and assayed as adsorbents of the herbicide clopyralid (3,6-dichloropyridine-2-carboxylic acid) in aqueous solution and soil/water suspensions, to assess the potential of the materials to prevent and remediate soil and water contamination by anionic pesticides. The SW-CH bionanocomposites were good adsorbents for the herbicide at pH levels where both the anionic form of the herbicide (pK(a)=2.3) and the cationic form of CH (pK(a)=6.3) predominated. The performance of the SW-CH bionanocomposites as adsorbents of clopyralid depended on the amount and arrangement of chitosan in the samples. Clopyralid adsorption was rapid and mostly linear up to herbicide concentrations as high as 0.5mM. High salt concentrations (0.1M NaCl) promoted desorption of the adsorbed pesticide from SW-CH, strongly suggesting that adsorption of clopyralid occurred primarily through an ion exchange mechanism on positively charged CH sites at the montmorillonite surface. Amendment of an acidic soil (pH=4.5) with SW-CH at rates of 5% and 10% led to a significant increase in clopyralid adsorption, whereas this effect was negligible when SW-CH was added to an alkaline soil (pH=8.0), reflecting the absence of positively charged sites in SW-CH at high pH values. Montmorillonite-CH bionanocomposites can be useful as adsorbents for the removal and/or immobilization of anionic pesticides in soil and water under mild acidic conditions.

Sorption of two polar herbicides in soils and soil clays suspensions

Abstract Adsorption of the polar herbicides thiazafluron (1,3-dimethyl-1-(5-trifluromethyl-1,3,4-thia-diazol-2-yl)urea) and metamitron (4-amino-4,5-dihydro-3-methyl-6-phenyl-1,2,4-triazin-5-one) in the aqueous suspension of five soils of southern Spain, their respective clay fractions (with diverse organic carbon content and clay mineralogy) and model pure clay minerals has been monitored as an integrated study to assess the role of the diverse colloidal soil components and their solid/solution ratio, as relevant to the transport of contaminants by particulate matter in water. Adsorption isotherms obtained were analysed and fitted to the logarithmic form of the Freundlich equation and adsorption coefficients Kf calculated. Thiazafluron adsorbs on soils, soil clays and model mineral sorbents to a higher extent than the herbicide metamitron due to their different molecular structure. The sorption of both herbicides in clay fractions increases with decreasing solid/solution ratio. The highest Kf value at high solid/solution ratio for both herbicides is found in a saline soil with its clay fraction predominantly composed of an altered illite mineral which behaves as a montmorillonite. Thiazafluron and metamitron also show the highest adsorption capacity (at low solid/solution ratio) on a predominantly montmorillonitic clay fraction of low cation exchange capacity (CEC), whereas low adsorption is found on a montmorillonitic clay fraction of high CEC. The negative influence of the clay CEC is confirmed in adsorption studies on pure clay minerals suspensions. The sorption of both herbicides by soil clays after removing organic matter (OM), shows that contribution of the colloidal OM is very low for thiazafluon, although rather important for metamitron. The influence of the different nature of the OM associated to the clay fractions of diverse soils is suggested. The mineral components of the soil clays, especially expandable layer silicates such as montmorillonite and a type of altered illite, are revealed to be responsible for the adsorption and hence the transport of these polar herbicides by waters in contact with soils or fine-size soil separates. Not only the relative amounts of the organic and inorganic components are important, but also the surface properties and the accessibility of the functional active groups of the herbicide molecule to those surfaces.

Layered double hydroxides as adsorbents and carriers of the herbicide (4-chloro-2-methylphenoxy)acetic acid (MCPA): systems Mg-Al, Mg-Fe and Mg-Al-Fe.

Hydrotalcite-like compounds [Mg(3)Al(OH)(8)]Cl x 4H(2)O; [Mg(3)Fe(OH)(8)]Cl x 4H(2)O; [Mg(3)Al(0.5)Fe(0.5)(OH)(8)]Cl x 4H(2)O (LDHs) and calcined product of [Mg(3)Al(OH)(8)]Cl x 4H(2)O, Mg(3)AlO(4.5) (HT500), were studied as potential adsorbents of the herbicide MCPA [(4-chloro-2-methylphenoxy)acetic acid] as a function of pH, contact time and pesticide concentration, and also as support for the slow release of this pesticide, with the aim to reduce the hazardous effects that it can pose to the environment. The information obtained in the adsorption study was used for the preparation of LDH-MCPA complexes. The results showed high and rapid adsorption of MCPA on the adsorbents as well as that MCPA formulations based on LDHs and HT500 as pesticide supports displayed controlled release properties and reduced herbicide leaching in soil columns compared to a standard commercial MCPA formulation. Thereby, we conclude that the LDHs employed in this study can be used not only as adsorbents to remove MCPA from aqueous solutions, but also as supports for the slow release of this highly mobile herbicide, thus controlling its immediate availability and leaching.

Organo/LDH nanocomposite as an adsorbent of polycyclic aromatic hydrocarbons in water and soil–water systems

Polycyclic aromatic hydrocarbons (PAHs) are considered as priority pollutants because of their high risk to human health. In this paper, we addressed the issue of using hydrotalcite-based nanocomposites as adsorbents of six low molecular weight PAHs (acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene and pyrene) to reduce their negative effects on the environment. A nanocomposite (HT-DDS) was prepared by intercalating the organic anion dodecylsulfate (DDS) in a Mg-Al hydrotalcite (HT), and then characterized using several analytical techniques. A Mediterranean soil was selected for being a high-risk scenario of groundwater contamination by leaching of pollutants. The nanocomposite displayed enhanced affinity for the PAHs in water as compared to carbonate-hydrotalcite (HTCO(3)) and its calcined product (HT500), and showed a high irreversibility of the adsorption process (hysteresis coefficient, H<0.15). The results revealed an increase of the pollutants retention in the soil by the addition of the nanocomposite that depended on the nanocomposite application rate and also on the hydrophobicity of each PAH. Accordingly, the use of HT-DDS as an amendment or barrier in contaminated soil is proposed for reducing the mobility of PAHs and, consequently, the adverse effect derived from rapid transport losses of the pollutants to the adjoining environmental compartments.

Clay-Herbicide Complexes to Retard Picloram Leaching in Soil

An approach for minimizing the risk of ground water contamination for highly mobile pesticides is to enhance the soil sorption process through the application of the pesticide together with a sorbent which limits the amount of pesticide immediately available for undesirable leaching losses. In this work, a number of clays exchanged with different inorganic and organic cations were assayed as sorbents of the acidic herbicide picloram (4-amino-3,5,6-trichloropyridine-2-carboxylic acid) and the ability of three selected clays to retard the release of picloram into water and to reduce picloram leaching through a soil column was investigated. For the selected clays, Fe3þ-saturated Wyoming montmorillonite (Fe-SW), octadecylammonium-treated Arizona montmorillonite (ODA-SA1) and hexadecyltrimethylammonium-saturated Arizona montomorillonite (HDTMA-SA2), two types of clay–picloram complexes (a physical mixture, PM, and a strongly-sorbed complex, SC) were prepared. All clay–picloram complexes yielded slow release of the herbicide and retarded its vertical movement through soil columns compared to the free technical compound, showing that clay– pesticide complexes prepared from selectively-modified clays may be useful in reducing rapid leaching of highly mobile pesticides such as picloram.

Environmental behavior of the enantiomers of the chiral fungicide metalaxyl in Mediterranean agricultural soils

Improving the existing knowledge on the enantioselectivity of processes affecting chiral pesticide enantiomers in the environment is necessary to maximize the efficacy and minimize the environmental impact caused by the use of pesticides with chiral properties. In this work, the enantioselectivity of the sorption, degradation, and leaching processes of the chiral fungicide metalaxyl in three slightly alkaline, agricultural soils from southern Spain was studied. Batch sorption experiments indicated that the sorption of racemic-metalaxyl on soils, their clay (<2 μm) fractions, and a number of model sorbents simulating naturally-occurring soil colloidal particles was non-enantioselective; the S-enantiomer was sorbed to the same extent as the R-enantiomer on all soil materials. Soil incubation experiments revealed that the R-enantiomer of metalaxyl was degraded faster than the S-enantiomer in all three soils, but the extent and enantioselectivity of metalaxyl degradation was soil-dependent, occurring more slowly and with less enantioselectivity in the fine-textured soil (soil 1) than in the coarse-textured soils (soils 2 and 3). For soils 2 and 3, S- and R-metalaxyl dissipation data were very well described by single first-order kinetics, whereas for soil 1 dissipation data were better fitted by two coupled first-order equations. It is suggested that sorption and entrapment of metalaxyl enantiomers in the abundant small-size pores of soil 1 (i.e., pore radius<100 nm) could have resulted in a fraction of the fungicide of reduced bioavailability, and consequently, protected from enantioselective degradation. Metalaxyl leaching through soil columns was also enantioselective; the concentration of S-metalaxyl in all leachates collected was greater than that of R-metalaxyl. Despite being non-enantioselective, sorption influenced the enantioselectivity of metalaxyl leaching, as it determined the residence time of the fungicide within the soil column, and consequently, the extent and enantioselectivity of its degradation during leaching.

Surface fractal dimensions of synthetic clay-hydrous iron oxide associations from nitrogen adsorption isotherms and mercury porosimetry

Abstract Model associations of layer silicates (kaolinite and montmorillonite) and iron oxyhydroxides were obtained by precipitating hydrous iron oxide in clay suspensions at different loading. The porosity of these clay-hydrous iron oxide associations was studied in the macro- and mesopore range by mercury intrusion porosimetry (MIP) and in the micropore region by nitrogen adsorption isotherms, being the fractal geometry applied to the approaches used in porosity studies. Results of nitrogen adsorption isotherms showed that surface area and microporosity of kaolinite and montmorillonite increased upon Fe precipitation, especially for montmorillonite. This process is accompanied by an increase in the surface fractal dimension Ds(N2) by the presence of hydrous iron oxide coating the clay particles. Results of MIP also showed a decrease in the pore volume by Fe precipitation on montmorillonite due to a decrease in the number of large pores and a development of new medium-size pores. An increase of the fractal dimension Ds(Hg) was also observed.

Effect of olive-mill waste addition to soil on sorption, persistence, and mobility of herbicides used in Mediterranean olive groves

Laboratory and field experiments were conducted to evaluate the effect of olive-mill waste (OMW) addition to a Mediterranean olive grove soil on sorption, persistence, and mobility of two herbicides which are simultaneously applied for weed control in olive groves: terbuthylazine (TA) and fluometuron (FM). Laboratory batch sorption experiments showed that OMW addition to the soil at rates of 5 and 10% (w/w) greatly enhanced the sorption of both herbicides, thus suggesting that amendment with OMW could be useful to enhance the retention and reduce the mobility of FM and TA in the soil. Incubation experiments showed that OMW increased the persistence of FM and had little effect on the long persistence of TA in the soil studied. A demonstration field experiment was also conducted in field plots with a slope of about 5%, either unamended or amended with OMW at a rate of 10 kg m⁻², and then treated with a commercial formulation containing a mixture of TA and FM. Extraction of field soil samples, taken from different soil depths (0-5, 5-10, 10-20, and 20-30 cm) at different times after herbicide application, showed that both TA and FM moved deeper in unamended soil than in OMW-amended soil, and that OMW addition affected the persistence of FM in the toplayer, increasing its half-life from 24 to 58 days, while having little effect on the persistence of TA. Thus, data obtained under real field conditions were consistent with those obtained under controlled laboratory conditions. Preliminary herbicide runoff data indicated that the total herbicide runoff losses were also reduced upon OMW addition. Addition of OMW could be beneficial in reducing the mobility of TA and FM in olive grove soils, and also in increasing the persistence of FM in soils where this herbicide could be rapidly degraded.

Assessing factors influencing the release of hexazinone from clay-based formulations

New designs of pesticide formulations based on organoclays are receiving increasing attention in reducing offsite movement of pesticides in the environment and in prolonging the efficacy of soil-applied pesticides. In the present article, we report the results of laboratory and field experiments conducted to evaluate the influence of the saturating cation, the sorbent : herbicide ratio, and the type of preparation on the controlled release properties of organoclay-based formulations of the herbicide hexazinone. Two organoclays with different affinities for hexazinone (hexadecyltrimethylammonium-exchanged Arizona montmorillonite, HDTMA-SA, and phenyltrimethylammonium-exchanged Arizona montmorillonite, PTMA-SA), two herbicide loadings (10% and 20% AI), and three types of preparation were assayed. Laboratory experiments showed that hexazinone formulations based on HDTMA-SA displayed slow-release properties in water, retarded herbicide leaching through soil columns, and maintained a herbicidal efficacy similar to that of the currently available commercial hexazinone formulation (wettable powder). In contrast, PTMA-SA formulations released the herbicide instantaneously and did not display slow-release properties. High organoclay-herbicide ratios and the use of organic solvent made the interaction between HDTMA-SA and the herbicide more intimate and reduced the release rate of hexazinone, suggesting that a range of release and leaching behaviours can be achieved by selecting the type of preparation and the herbicide loading in the formulations. A field experiment confirmed the usefulness of HDTMA-SA formulations of hexazinone to reduce herbicide leaching while maintaining weed-control efficacy.