Montmorillonite-phenyltrimethylammonium yields environmentally improved formulations of hydrophobic herbicides

This study aimed to design formulations of hydrophobic herbicides, alachlor and metolachlor, by adsorbing them on the clay mineral montmorillonite preadsorbed by the small organic cation phenyltrimethylammonium (PTMA). An adsorption model that considers electrostatics and specific binding and the possibility of cation adsorption above the cation exchange capacity (CEC) could explain and yield predictions for PTMA adsorption in the presence of NaCl concentrations from 0 to 500 mM. Adsorption of alachlor and metolachlor from aqueous solution on a clay mineral preadsorbed by PTMA was determined by GC and modeled by Langmuir equation. Herbicide interactions with the organoclay were studied by Fourier transform infrared spectroscopy. Leaching of herbicides was determined by a bioassay using a column technique and Setaria viridis as a test plant. The adsorbed amounts of alachlor and metolachlor on montmorillonite preadsorbed by PTMA at a loading of 0. 5 mol/kg (Mont-PTMA0.5) were higher than at a loading up to the CEC, that is, 0.8 mol/kg, and were higher than those obtained by using several other organic cations. Herbicide formulations based on Mont-PTMA0.5 yielded the largest shifts of the infrared peaks of the herbicides. These formulations based on Mont-PTMA0.5 gave slower release and showed improved weed control in comparison with formulations based on other organoclays. These formulations maintained herbicidal activity in the topsoil and yielded the most significant reduction in herbicide leaching.     

Bioavailability of organoclay formulations of atrazine in soil

Pesticide formulations based on organoclays have been proposed to prolong the efficacy and reduce the environmental impact of pesticides in soil. This research addressed the question of whether atrazine in organoclay-based formulations is irreversibly sorbed or is bioavailable for bacterial degradation in soil. Different cations of l-carnitine (CAR), tyramine (TYRAM), hexadimethrine (HEXADIM), phenyltrimethylammonium (PTMA), hexadecyltrimethylammonium (HDTMA), and Fe(III) were incorporated into Na-rich Wyoming montmorillonite (SWy-2) and Ca-rich Arizona montmorillonite (SAz-1) at 100% of the cation exchange capacity (CEC) of the clays as a strategy to enhance the affinity of the clay minerals for atrazine. A Buse loam soil from Becker, MN, was treated with three organoclay-based formulations of 14C-atrazine or free herbicide and incubated for 2 weeks. To determine the bioavailability of 14C-atrazine, the soil was inoculated with Pseudomonas sp. strain ADP, which rapidly mineralizes atrazine. At day 0, and after a 2 week incubation, mineralization and the amount of 14C-atrazine residues distributed between the aqueous-extractable, methanol-extractable, and bound fractions in the soil were determined to characterize the availability of nonaged and aged atrazine residues. By the end of the 2 week incubation, the microorganisms had mineralized >80% of the initial readily available (water-extractable) and >70% of the less readily available (methanol-extractable) 14C-atrazine in the soil. Bound residues increased from <4% at day 0 to ～17% after the 2 week incubation for both the formulated and free forms of atrazine. The results of these incubation experiments show that the bioavailabilities of atrazine were similar in the case of the organoclay formulations and as free atrazine. This indicated that whereas more atrazine was sorbed and less likely to be transported in soil, when formulated as organoclay complexes, it was ultimately accessible to degrading bacteria, so that the herbicide is likely to be naturally attenuated by soil microorganisms.     

Cosorption of atrazine and a lauryl polyoxyethylene oxide nonionic surfactant on smectite

Commercial atrazine formulations commonly contain nonionic surfactants that serve as solubilizing and wetting agents for enhancing the stability and efficacy of the herbicide. The fate of atrazine in soils has been extensively investigated; yet, few studies have considered the effects of formulation components on the fate of atrazine in soils. In this study, we investigated the influence of the nonionic surfactant, Brij 35 (Brij), on the sorption of atrazine on Ca- and K-saturated samples of a reference smectite, Panther Creek (PC). In general, Brij concentrations of 50 and 200 mg L(-1) had little effect on atrazine sorption, but sorption was substantially inhibited by Brij concentrations of 2100 mg L(-1). For Brij concentrations of 6300 mg L(-1), atrazine sorption was intermediate between that observed for the 200 and 2100 mg L(-1) Brij systems. Brij molecules themselves were very strongly sorbed by PC, with sorption maxima exceeding 200 g kg(-1). X-ray diffraction analysis of Brij-treated PC indicated that the sorbed Brij was intercalated into interlayers of the smectite. At Brij concentrations of 2100 mg L(-1), Brij competed with atrazine for interlayer sorption sites. In contrast, at the initial Brij concentration of 6300 mg L(-1), the clay interlayers were largely filled with Brij, and excess Brij probably accumulated on external surfaces of the clay as surface micelles. We hypothesize that atrazine partitioning into surfactant micelles on external surfaces of the clay led to enhanced retention by the solid phase.     

Influence of herbicide structure,clay acidity,and humic acid coating on acetanilide herbicide adsorption on homoionic clays

Adsorption of chloroacetanilide herbicides on homoionic montmorillonite was studied by coupling batch equilibration and FT-IR analysis. Adsorption decreased in the order metolachlor > acetochlor > alachlor > propachlor on Ca(2+)- or Mg(2+)-saturated clays and in the order metolachlor > alachlor > acetachlor > propachlor on Al(3+)- or Fe(3+)-saturated clays. FT-IR spectra showed that the carbonyl group of the herbicide molecule was involved in bonding. For the same herbicide, adsorption of alachlor, acetachlor, and metolachlor on clay followed the order Ca(2+) approximately Mg(2+) < Al(3+) < or = Fe(3+), which coincided with the increasing acidity of homoionic clays. Adsorption of propachlor, however, showed an opposite dependence, suggesting a different governing interaction. In clay and humic acid mixtures, herbicide adsorption was less than that expected from independent additive adsorption by the individual constituents, and the deviation was dependent on the clay-to-humic acid ratio, with the greatest deviation consistently occurring at a 60:40 clay-to-humic acid ratio.     

Photostabilization of the herbicide norflurazon by using organoclays

Photostable formulations of the herbicide norflurazon [4-chloro-5-(methylamino)-2-(alpha,alpha, alpha-trifluoro-m-tolyl)pyridazin-3-(2H)-one] were achieved by adsorbing it on pillared clay or on montmorillonite preadsorbed with the organic cation thioflavin T (TFT). Diffuse reflectance Fourier transform infrared spectra showed the existence of strong interactions between the aromatic moieties of preadsorbed TFT and the herbicide, particularly after irradiation. The photostabilization of norflurazon obtained with TFT-clay was mainly due to energy transfer from the herbicide to the organic cation via pi-pi interactions. An additional mechanism is the lower production of radicals from the clay when the clay mineral surface is covered with the organic cation. These radicals are responsible for the enhanced photodegradation observed when norflurazon was irradiated in the presence of untreated montmorillonite.     

Organo-clay formulations of the hydrophobic herbicide norflurazon yield reduced leaching

The study aimed to reduce leaching of the hydrophobic herbicide norflurazon (4-chloro-5-methylamino-2-(alpha,alpha, alpha)-trifluoro-m-tolylpyridazin-3-(2H)-one) by adsorbing it on clays or organo-clays. The surface of the clay mineral montmorillonite was modified from hydrophilic to hydrophobic by preadsorbing it with organic cations, of which thioflavin-T (TFT) at a loading corresponding to (5)/(8) of the cation-exchange capacity of the clay mineral yielded the highest affinity of adsorption of norflurazon. Pillared clay (PC) used without organic cations exhibited enhanced affinity for norflurazon adsorption, much higher than that of montmorillonite or sepiolite. Fourier transform infrared (FTIR) results showed interactions between aromatic moieties of preadsorbed TFT and the herbicide. Stronger interaction of the herbicide with a clay mineral or organo-clay corresponded to its slower release. Formulations prepared on the basis of montmorillonite-TFT and PC were more effective in reducing herbicide leaching in soil columns in comparison to the commercial formulation, whereas the herbicidal efficiencies were comparable.     

Organo-clay formulation of acetochlor for reduced movement in soil.

This study aimed to design ecologically acceptable formulations of acetochlor by adsorbing it on montmorillonite exchanged by a small organic cation, phenyltrimethylammonium (PTMA). Adsorption of acetochlor on the clay mineral exchanged with different organic cations and its release from these complexes were determined by GC and modeled by Langmuir equation. Interactions between acetochlor molecules and the exchanged organic cation on the clay surface were studied by Fourier transform infrared spectroscopy. Leaching of acetochlor in soil was determined by a bioassay using a column technique and Setaria viridis as a test plant. The adsorbed amounts of acetochlor on montmorillonite exchanged by PTMA at a loading of 0.5 mmol/g of clay were higher than at a loading up to the cation-exchange capacity, i.e., 0.8 mmol/g, and were higher than obtained by using a clay mineral exchanged by other organic cations. Preloading montmorillonite by PTMA at 0.5 mmol/g yielded maximal shifts of the infrared peaks of the herbicide. The above formulation of acetochlor yielded slow release in water and showed improved weed control in field and greenhouse experiments in comparison with the commercial formulation. The PTMA-clay formulation of acetochlor maintained herbicidal activity in the topsoil and yielded the most significant reduction in herbicide leaching and persistence under field conditions. The application of this formulation can minimize the risk to groundwater and can reduce the applied rates.     

Ethylcellulose formulations for controlled release of the herbicide alachlor in a sandy soil

The development of controlled-release formulations of alachlor to diminish its leaching in sandy soils, avoiding groundwater contamination and maintaining its efficacy, was studied. For this purpose, ethylcellulose (EC) microencapsulated formulations (MEFs) of alachlor were prepared under different conditions and applied to soil columns to study their mobility. The results show that in all cases the release into water of alachlor from MEFs was retarded when compared with commercial formulation. Total leaching losses in soil columns were reduced to 59% from 98%. The mobility of alachlor from EC microspheres into soil columns has been greatly diminished in comparison with its current commercial formulation (CF), above all with increasing EC/herbicide ratios. Distribution of alachlor applied as MEFs at different depths in the soil was higher in the soil surface (66.3-81.3% of herbicide applied at the first 12 cm). In contrast, the residues from CF along the complete soil column were only 20.4%. From the results of bioassays, MEFs showed a higher efficacy than CF at 30 days after the treatment. The use of ME formulations could provide an advantage in minimizing the risk of groundwater contamination by alachlor and reducing the application rates, as a result of maintaining the desired concentration of the herbicide in the top soil layer, obtaining longer periods of weed control.     

纳米粘土矿物对阿特拉津的吸附-解吸特性研究

采用批量平衡实验,研究了纳米粘土矿物与原粘土矿物对除草剂阿特拉津的吸附解吸特陛。结果表明,粘土矿物对阿特拉津的吸附-解吸均能用Freundlich方程很好地拟合。随着溶液中阿特拉津浓度的增加,粘土矿物对阿特拉津的吸附量增加;粘土矿物粒径越小,吸附量越大,纳米粘土矿物的吸附量显著大于原粘土矿物。粘土矿物对阿特拉津吸附量大小顺序为：纳米SiO2）纳米蒙脱石〉凹凸棒石〉蒙脱石〉SiO2。粘土矿物对阿特拉津的解吸表现出一定的滞后效应,即粘土矿物吸附的阿特拉津越多,解吸的越少。粘土矿物对阿特拉津的解吸率大小顺序为：SiO2〉凹凸棒石〉纳米蒙脱石〉纳米SiO2〉蒙脱石。     

Herbicide solubilization in micelle-clay composites as a basis for controlled release sulfentrazone and metolachlor formulations

Sulfentrazone and metolachlor have been detected in groundwater due to extensive leaching. To reduce herbicide leaching and increase weed control, we have developed, designed, and tested controlled release formulations (CRFs) for both herbicides based on their solubilizion in cationic micelles and adsorption of the mixed micelles (surfactant and herbicide) on a clay mineral, montmorillonite. A better understanding of solubilizing anionic (sulfentrazone) and nonionic (metolachlor) organic molecules in cationic micelles was reached. The percent of active ingredient in the formulations was much higher than previously designed CRFs due to the enhanced solubilization of the herbicides in the micelles and due to their adsorption on the clay. Both CRFs demonstrated controlled release (compared to the commercial formulations) when applied to a thin soil layer. A bioassay in soil columns determined that the new sulfentrazone and metolachlor CRFs significantly improve weed control and reduce leaching (for the latter) in comparison with the commercial formulations.     

Interference with soil phosphatase activity by maize herbicidal treatment and incorporation of maize residues

Summary This study is concerned with the way alachlor, atrazine and metolachlor interfered with phosphatase activity in a clay loam soil unenriched and enriched with maize residues. Enrichment caused an increase in all phosphatase activities (acid and alkaline phosphomonoesterase, phosphodiesterase, phosphotriesterase) tested. Interference with phosphatase activity following herbicidal treatment was found in both unenriched and enriched soil samples. Statistically significant interference was dependent on soil enrichment, the type of herbicide and its rate of application and the time elapsed since the herbicidal treatment. The observed changes in phosphatase activities are attributed to herbicidal action on phosphatase-producing microorganisms. Among the herbicides tested, the acetanilide derivatives exerted a lesser inhibiting effect than atrazine. Nevertheless, all the altered phosphatase activities showed a tendency, more or less rapid, to reach the levels in the corresponding untreated soil samples.     

Slow-release formulations of sulfometuron incorporated in micelles adsorbed on montmorillonite

The design and tests of slow-release formulations of sulfometuron (SFM), an anionic sulfonylurea herbicide, are described. The formulations are based on incorporation of the herbicide in octadecyltrimethylammonium (ODTMA) micelles, which adsorb on a clay mineral, montmorillonite. An optimization of herbicide/micelle clay ratios yielded high adsorption of SFM (95%), and at a 1% (w/w) water suspension only 0.5% of the adsorbed SFM was released at times varying from hours to 9 days. An analytical test in Seville soil showed that under excessive irrigation (400 mm) 100% of the commercial formulation leached, whereas the micelle-clay formulations showed only 50-65% elution. A plant bioassay in Rehovot soil showed that the commercial dispersible granule formulation (Oust, 75% ai sulfometuron methyl) yielded only 23% root elongation inhibition at the top 5 cm of the soil, whereas complete inhibition was achieved with the micelle-clay formulation. The detected concentration of SFM for the micelle-clay formulation at a depth of 15-20 cm was half of that detected for the commercial one, indicating a reduction in leaching when applying the micelle-clay formulation. A 10-fold reduction in the applied dose of SFM in the micelle-clay formulations resulted in good herbicidal activity of 60-87% inhibition. These characteristics make the new formulation promising from the environmental and economic points of view.     

Sulfosulfuron incorporated in micelles adsorbed on montmorillonite for slow release formulations

Slow release formulations of the anionic herbicide sulfosulfuron (SFS) were prepared by incorporating it in micelles of an organic cation octadecyltrimethylammonium, which adsorb on the clay-mineral montmorillonite. The fraction of SFS adsorbed on the micelle-clay complex reached 98%, whereas for monomer-clay complexes, its adsorption was insignificant. Fluorescence studies showed surface contact between the micelles and the clay surface. The rate of SFS release from the micelle-clay formulations in aqueous suspensions was slow (<1%, 72 h). Spraying SFS formulations on a thin soil layer in a funnel, followed by irrigations (50 mm), resulted in complete elution of SFS from the commercial formulation (dispersible granular) versus 4% from the micelle-clay formulation. A plant bioassay in Rehovot soil showed that these respective formulations yielded 23 and 65% of shoot growth inhibition of foxtail. Consequently, the slow release micelle-clay formulations of SFS yield significantly reduced leaching and enhanced biological activity, thus providing environmental and agricultural advantages.     

Structural influences in relative sorptivity of chloroacetanilide herbicides on soil

Adsorption of the chloroacetanilide herbicides acetochlor, alachlor, metolachlor, and propachlor was determined on soils and soil components, and their structural differences were used to explain their sorptivity orders. On all soils and soil humic acids, adsorption decreased in the order: metolachlor > acetochlor > propachlor > alachlor. On Ca(2+)-saturated montmorillonite, the order changed to metolachlor > acetochlor > alachlor > propachlor. FT-IR differential spectra of herbicide-clay or herbicide-humic acid-clay showed possible formation of hydrogen bonds and charge-transfer bonds between herbicides and adsorbents. The different substitutions and their spatial arrangement in the herbicide molecule were found to affect the relative sorptivity of these herbicides by influencing the reactivity of functional groups participating in these bond interactions. It was further suggested that structural characteristics of pesticides from the same class could be used to improve prediction of pesticide adsorption on soil.     

Inorganic and organic clays as carriers for controlled release of the herbicide hexazinone

The risk of ground water contamination resulting from rapid leaching of highly soluble pesticides can be minimized through the application of the pesticide adsorbed on a matrix or carrier, which limits the amount of pesticide immediately available for undesirable losses. The use of natural materials for this purpose is of special interest in terms of economy and sustainability. In this work the adsorption of the herbicide hexazinone by two montmorillonites saturated with various inorganic and organic cations was determined and the ability of the two clays displaying the highest adsorption capacities [Fe(3+)-saturated Wyoming montmorillonite, (Fe-SW) and hexadecyltrimethylammonium-saturated Arizona montmorillonite (HDTMA-SA)] to act as carriers for slow release of hexazinone and to reduce herbicide leaching losses was evaluated. Hexazinone formulations based on Fe-SW and HDTMA-SA displayed slow release properties in water and soil/water suspensions, reduced herbicide leaching in soil columns, and maintained herbicidal activity, as compared with the currently available commercial hexazinone formulation (wettable powder). Loosely bound hexazinone-HDTMASA formulations, which led to the slowest breakthrough of hexazinone in soil columns along with the greatest amounts of herbicide released from the clay particles, displayed the most interesting characteristics for their use as slow release formulations and to prevent ground water contamination.     

Sulfometuron incorporation in cationic micelles adsorbed on montmorillonite

The aim of this study was to understand the interactions between alkylammonium cations present as monomers and micelles and a clay mineral, montmorillonite, to develop slow release formulations of anionic herbicides, such as sulfometuron (SFM) whose leaching in soils is an environmental and economic problem. In the proposed formulation the herbicide is incorporated in positively charged micelles of quaternary amine cations, which in turn adsorb on the negatively charged clay. The adsorption of hexadecyltrimethylammonium (HDTMA) and octadecyltrimethylammonium (ODTMA) on montmorillonite was studied above and below their critical micelle concentrations (CMC). At concentrations above the CMC, the loading exceeded the clay's cation exchange capacity (CEC) and indicated higher affinity of the cation with the longer alkyl chain. An adsorption model could adequately simulate adsorption at concentrations below the CMC, and yield fair predictions for the effect of ionic strength. The model indicated that above the CMC adsorbed micelles contributed significantly to the amount of ODTMA adsorbed. Evidence for adsorption of ODTMA micelles on montmorillonite was provided by X-ray diffraction, freeze-fracture electron microscopy, and dialysis bag measurements. SFM was not adsorbed directly on the clay mineral, and adsorbed at low levels, when the organic cation was adsorbed as monomers. In contrast, a large fraction of SFM adsorbed on the clay mineral when incorporated in micelles that adsorbed on the clay.     

Adsorption mechanisms of thiazafluron in mineral soil clay components

The adsorption of the herbicide thiazafluron, 1,3-dimethyl-1-(5-trifluoromethyl-1,3,4-thiadiazol-2-yl)urea, by three smectites, illite, kaolinite, ferrihydrite and the clay fraction of an illitic soil (54.9% illite, 17.0% montmorillonite and 24.9% kaolinite) and a montmorillonitic soil (33.9% illite, 55.0% montmorillonite and 11.1% kaolinite) has been determined. Thiazafluron adsorbed on neither kaolinite nor iron oxide. The adsorption isotherms on smectites and illite conformed to the Freundlich equation. Values of K_f-obtained for smectites were larger than for the illite and increased as the layer charge of the smectite decreased. Desorption of thiazafluron on smectites was shown to be highly irreversible. Adsorption isotherms of thiazafluron on different homoionic montmorillonite samples suggest an important role of the exchangeable cations in the adsorption. Infrared spectra and X-ray diffraction analysis of the complexes of thiazafluron with homoionic montmorillonites indicated that thiazafluron adsorbs in the interlamellar space of the smectites, mainly by substitution of water molecules associated with the exchangeable cations through the carbonyl-amide group and formation of H-bonds or waterbridge between the NH group of the amide and the basal oxygens of the montmorillonite. The illitic soil clay adsorbed more of the herbicide than the montmorillonitic one did, suggesting that illite and montmorillonite may be present in soils in altered forms giving rise to different adsorption capacities from those of the pure minerals.     

Use of activated bentonites in controlled-release formulations of atrazine

The herbicide atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine) was incorporated in alginate-based granules to obtain controlled-release (CR) properties. The basic formulation [sodium alginate (1.40%)-atrazine (0.60%)-water] was modified by the addition of sorbents. The effect on atrazine release rate caused by the incorporation of acid-treated bentonite (0.5 and 2.5 M H2SO4) in alginate formulation was studied by immersion of the granules in water under static conditions. The water uptake, sorption capacity of the sorbent, permeability, and time taken for 50% of the active ingredient to be released into water, t50, were calculated for the comparison of the preparations. t50 values were longer for those formulations containing acid-treated bentonite (36.78 and 29.01 days for 0.5 and 2.5 M H2SO4 treatments, respectively) than for the preparation without bentonite (9.69 days). On the basis of a parameter of an empirical equation used to fit the herbicide release data, it appears that the release of atrazine from the various formulations into water is controlled by diffusion mechanism. The sorption capacity of the sorbents and the permeability of the formulations (ranging from 4.99 to 20.83 mg day(-1) mm(-1)) were the most important factors affecting herbicide release.     

Occurrence of active and inactive herbicide ingredients at selected sites in Iowa

The objective of this study was to investigate the occurrence of herbicide active and inactive ingredients (primarily volatile organic compounds) at four selected sites in Iowa representing drain tiles, observation wells, or lysimeters. Water samples were collected monthly and bi-monthly before and after herbicide applications in 1991, respectively. They were analyzed for seven herbicides and 32 volatile organic compounds using methods recommended by the U.S. Environmental Protection Agency. Commercially available herbicide formulations also were obtained and analyzed for volatile organic compounds. Herbicides were detected in 50% of water samples, ranging from 78% of water samples from the Ames site to 25% from the Walnut Creek site. Among herbicides detected, listed in decreasing order of frequency, were atrazine > alachlor > cyanazine > metolachlor > metribuzin. Volatile organic compounds were detected in 11% of water samples. Among the compounds detected, listed in decreasing order of frequency, were xylene > toluene > acetone. One sample contained a detectable amount of aliphatic compound(s), with the empirical formula of C₈H₁₈. Results from the Deer Creek site showed that herbicides were detected primarily in the top layer (1.2 m), whereas xylene and other alkylbenzenes were detected at 2.1 m or deeper. Apparently, physico-chemical and other factors are separating herbicides and volatile organic compounds in the shallow unsaturated zone.     

阿特拉津在土壤, 矿物质及堆肥中的吸附, 运输和转化

Atrazine is a widely used herbicide for controlling weeds on both agricultural and nonagricultural land,which is equally detected in water supplies beyond safe concentrations.Although the presence of atrazine metabolites is an indication of herbicide degradation,some of them still exhibit toxicity,greater water solubility and weaker interaction with soil components than atrazine.Hence,studies with atrazine in the environment are of interest because of its potential to contaminate drinking water sources.Data on atrazine availability for transport,plant uptake,and microbial degradation and mineralization are therefore required to perform more comprehensive and realistic environmental risk assessments of its environmental fate.This review presents an account of the sorption-desorption phenomenon of atrazine on soil and other sorbents by revisiting the several mechanisms of atrazine-sorbent binding reported in the literature.The retention and transport of atrazine in soils;the influence of organic matter on atrazine sorption;the interactions of atrazine with humic substances,atrazine uptake by plants,atrazine bioccumulation and microbial degradation;atrazine transformation in composting environments;and finally atrazine removal by biosorption are discussed.