Adsorption of chloroacetanilide herbicides on homoionic montmorillonite, soil humic acid, and their mixtures was studied by coupling batch equilibration and FT IR analysis. Adsorption isotherms of acetochlor, alachlo...Adsorption of chloroacetanilide herbicides on homoionic montmorillonite, soil humic acid, and their mixtures was studied by coupling batch equilibration and FT IR analysis. Adsorption isotherms of acetochlor, alachlor, metolachlor and propachlor on Ca 2+ \|, Mg 2+ \|, Al 3+ \| and Fe 3+ \| saturated clays were well described by the Freundlich equation. Regardless of the type of exchange cations, K f decreased in the order of metolachlor > acetolachlor > alachlor > propachlor on the same clay. FT IR spectra showed that the carbonyl group of the herbicide molecule was involved in binding, probably via H bond with water molecules in the clay interlayer. The type and position of substitutions around the carbonyl group may have affected the electronegativity of oxygen, thus influencing the relative adsorption of these herbicides. For the same herbicide, adsorption on clay increased in the order of Mg 2+ <Ca 2+ <Al 3+ ≤Fe 3+ which coincided with the increasing acidity of homoionic clays. Acidity of cations may have affected the protonation of water, and thus the strength of H bond between the clay water and herbicide. Complexation of clay and humic acid resulted in less adsorption than that expected from independent adsorption by the individual constituents. The effect varied with herbicides, but the greatest decrease in adsorption occurred at a 60:40 clay to humic acid ratio for all the herbicides. Causes for the decreased adsorption need to be characterized to better understand adsorption mechanisms and predict adsorption from soil compositions.展开更多
Adsorption of chloroacetanilide herbicide acetochlor, alachlor, metolachlor and propachlor on soils and soil components was determined, and the structural differences of these herbicides were used to explain the order...Adsorption of chloroacetanilide herbicide acetochlor, alachlor, metolachlor and propachlor on soils and soil components was determined, and the structural differences of these herbicides were used to explain the order of sorptivity. Adsorption isotherms for all herbicide-soil combinations conformed to the Freundlich equation, and Kf increased with increasing soil organic carbon content. Kd on soil humic acid was greater than that on clay, but association of humic acid with clay reduced the overall adsorption. On all soils and soil humic acids, herbicide adsorption decreased in the order: metolachlor > acetochlor > propachlor > alachlor. On Ca2+ - montmorrilonite, the order changed to metolachlor > acetochlor > alachlor > propachlor. FT-IR spectra of herbicide-clay or herbicide-humic acid-clay mixtures showed that H-bonding and charge transfer were the primary interaction pathways between these compounds and the surface of clay or humic acids. The different moieties attached to 2-chloro-acetanilide and their unique arrangement may have influenced the binding mechanisms and thus the sorptivity of these herbicides. This study indicates that the structural difference of pesticides in the same classes may be used as a molecular probe to obtain a better understanding of sorption mechanisms of pesticides on soil.展开更多
The soil dissipation of the widely used herbicides S-metolachlor(SM)and butachlor(BUT)was evaluated in laboratory microcosms at two environmentally relevant doses(15 and 150μg/g)and for two agricultural soils(crop an...The soil dissipation of the widely used herbicides S-metolachlor(SM)and butachlor(BUT)was evaluated in laboratory microcosms at two environmentally relevant doses(15 and 150μg/g)and for two agricultural soils(crop and paddy).Over 80%of SM and BUT were dissipated within 60 and 30 days,respectively,except in experiments with crop soil at 150μg/g.Based on compound-specific isotope analysis(CSIA)and observed dissipation,biodegradation was the main process responsible for the observed decrease of SM and BUT in the paddy soil.For SM,biodegradation dominated over other dissipation processes,with changes of carbon isotope ratios(Δδ13C)of up to 6.5‰after 60 days,and concomitant production of ethane sulfonic acid(ESA)and oxanilic acid(OXA)transformation products.In crop soil experiments,biodegradation of SM occurred to a lesser extent than in paddy soil,and sorption was the main driver of apparent BUT dissipation.Sequencing of the 16 S rRNA gene showed that soil type and duration of herbicide exposure were the main determinants of bacterial community variation.In contrast,herbicide identity and spiking dose had no significant effect.In paddy soil experiments,a high(4:1,V/V)ESA to OXA ratio for SM was observed,and phylotypes assigned to anaerobic Clostridiales and sulfur reducers such as Desulfuromonadales and Syntrophobacterales were dominant for both herbicides.Crop soil microcosms,in contrast,were associated with a reverse,low(1:3,V/V)ratio of ESA to OXA for SM,and Alphaproteobacteria,Actinobacteria,and Bacillales dominated regardless of the herbicide.Our results emphasize the variability in the extent and modes of SM and BUT dissipation in agricultural soils,and in associated changes in bacterial communities.展开更多
文摘Adsorption of chloroacetanilide herbicides on homoionic montmorillonite, soil humic acid, and their mixtures was studied by coupling batch equilibration and FT IR analysis. Adsorption isotherms of acetochlor, alachlor, metolachlor and propachlor on Ca 2+ \|, Mg 2+ \|, Al 3+ \| and Fe 3+ \| saturated clays were well described by the Freundlich equation. Regardless of the type of exchange cations, K f decreased in the order of metolachlor > acetolachlor > alachlor > propachlor on the same clay. FT IR spectra showed that the carbonyl group of the herbicide molecule was involved in binding, probably via H bond with water molecules in the clay interlayer. The type and position of substitutions around the carbonyl group may have affected the electronegativity of oxygen, thus influencing the relative adsorption of these herbicides. For the same herbicide, adsorption on clay increased in the order of Mg 2+ <Ca 2+ <Al 3+ ≤Fe 3+ which coincided with the increasing acidity of homoionic clays. Acidity of cations may have affected the protonation of water, and thus the strength of H bond between the clay water and herbicide. Complexation of clay and humic acid resulted in less adsorption than that expected from independent adsorption by the individual constituents. The effect varied with herbicides, but the greatest decrease in adsorption occurred at a 60:40 clay to humic acid ratio for all the herbicides. Causes for the decreased adsorption need to be characterized to better understand adsorption mechanisms and predict adsorption from soil compositions.
文摘Adsorption of chloroacetanilide herbicide acetochlor, alachlor, metolachlor and propachlor on soils and soil components was determined, and the structural differences of these herbicides were used to explain the order of sorptivity. Adsorption isotherms for all herbicide-soil combinations conformed to the Freundlich equation, and Kf increased with increasing soil organic carbon content. Kd on soil humic acid was greater than that on clay, but association of humic acid with clay reduced the overall adsorption. On all soils and soil humic acids, herbicide adsorption decreased in the order: metolachlor > acetochlor > propachlor > alachlor. On Ca2+ - montmorrilonite, the order changed to metolachlor > acetochlor > alachlor > propachlor. FT-IR spectra of herbicide-clay or herbicide-humic acid-clay mixtures showed that H-bonding and charge transfer were the primary interaction pathways between these compounds and the surface of clay or humic acids. The different moieties attached to 2-chloro-acetanilide and their unique arrangement may have influenced the binding mechanisms and thus the sorptivity of these herbicides. This study indicates that the structural difference of pesticides in the same classes may be used as a molecular probe to obtain a better understanding of sorption mechanisms of pesticides on soil.
基金supported by scholarship 42/1/0052688 from the Ministry of Science,Research and Technology(MSRT)of Iranthe project PACOV(The Alsacian Platform of Copper in Vineyards)funded by the Rhine-Meuse Water Agency(AERM),Francefunded by the French National research Agency ANR through grant ANR-18-CE040004-01,project DECISIVE。
文摘The soil dissipation of the widely used herbicides S-metolachlor(SM)and butachlor(BUT)was evaluated in laboratory microcosms at two environmentally relevant doses(15 and 150μg/g)and for two agricultural soils(crop and paddy).Over 80%of SM and BUT were dissipated within 60 and 30 days,respectively,except in experiments with crop soil at 150μg/g.Based on compound-specific isotope analysis(CSIA)and observed dissipation,biodegradation was the main process responsible for the observed decrease of SM and BUT in the paddy soil.For SM,biodegradation dominated over other dissipation processes,with changes of carbon isotope ratios(Δδ13C)of up to 6.5‰after 60 days,and concomitant production of ethane sulfonic acid(ESA)and oxanilic acid(OXA)transformation products.In crop soil experiments,biodegradation of SM occurred to a lesser extent than in paddy soil,and sorption was the main driver of apparent BUT dissipation.Sequencing of the 16 S rRNA gene showed that soil type and duration of herbicide exposure were the main determinants of bacterial community variation.In contrast,herbicide identity and spiking dose had no significant effect.In paddy soil experiments,a high(4:1,V/V)ESA to OXA ratio for SM was observed,and phylotypes assigned to anaerobic Clostridiales and sulfur reducers such as Desulfuromonadales and Syntrophobacterales were dominant for both herbicides.Crop soil microcosms,in contrast,were associated with a reverse,low(1:3,V/V)ratio of ESA to OXA for SM,and Alphaproteobacteria,Actinobacteria,and Bacillales dominated regardless of the herbicide.Our results emphasize the variability in the extent and modes of SM and BUT dissipation in agricultural soils,and in associated changes in bacterial communities.
