Adsorption-desorption behaviour of flufenacet in five different soils of India

Adsorption-desorption of the herbicide flufenacet (FOE 5043) has been studied in five soils from different locations in India (Delhi, Ranchi, Nagpur, Kerala and Assam) varying in their physicochemical properties. The organic matter (OM) content varied from 0.072 to 0.864%, clay content from 2.5 to 43.7% and pH from 4.45 to 8.35. The adsorption studies were carried out using a batch equilibration technique. Ten grams of soil were equilibrated with 20 ml of aqueous 0.01 M CaCl2 solution containing different concentrations (0-30 mg litre-1) of flufenacet. After equilibration, an aliquot of supernatant was taken out for analysis. During desorption, the amount withdrawn for analysis was replenished with fresh 0.01 M CaCl2 solution and further equilibrated. Desorption studies were carried out with the 30 mg litre-1 concentration of flufenacet only. The adsorption studies revealed that there was moderate to high adsorption of flufenacet considering the comparatively low organic carbon content in the five test soils. Average Kd values ranged from 0.77 to 4.52 and Freundlich KF values from 0.76 to 4.39. The highest adsorption was observed in Kerala soil (OM 0.786%; clay 25%; pH 4.45) followed by Ranchi, Nagpur and Delhi soils, and the lowest in Assam soil (OM 0.553%; clay 2.5%; pH 6.87). The trend in adsorption could be attributed to the chemical nature of flufenacet and the physicochemical properties of the soil such as pH, OM and clay contents. OM and clay contents were positively correlated whereas pH was negatively correlated. Soils having low pH, high OM and high clay contents showed higher adsorption. Desorption studies revealed that there was a hysteresis effect in all the soils. Hysteresis coefficient values (ratio of n(ad) and n(des)) varied from 0.09 to 0.45. The study implies that, because of its moderate to high adsorption, flufenacet is likely to persist in soil for some time. However, the possibility of its movement by leaching or surface run off is less.     

Interactions between organophosphorus compounds and soil materials I. Adsorption of ethyl methylphosphonofluoridate by clay and organic matter preparations and by soils

Data for the adsorption of ethyl methylphosphonofluoridate from aqueous and the vapour phases onto montmorillonite and kaolinite clays, onto soil organic matter preparations, and onto a limited number of soils are reported. These show that the phosphonofluoridate was absorbed from the vapour phase onto the dry clay preparations by physical-chemical forces but was not adsorbed by the organic soil materials. In a general way adsorption onto dry soils could be related to their clay contents when the organic matter contents were low. Water was found to compete effectively with the phosphonofluoridate for adsorption sites, and it is concluded that this molecule will be most effectively retained by dry soils low in organic matter and rich in clay. Mechanisms for its adsorption onto clays are discussed.     

OBSERVATIONS ON THE RELATIONSHIP BETWEEN THE ADSORPTION OF DIURON AND THE NATURE OF THE ADSORBENT

Summary. A series of adsorption experiments was carried out in order to determine if there was significant competition for adsorption sites between diuron and water. Adsorption of diuron was much lower on hydrophilic materials such as cellulose, chitin, aluminium oxide and a soil mineral fraction than on the less hydrophilic ion exchange resins, lignin, carbon and a soil organic fraction. Methylation with methanolic HCL or diazomethane increased adsorption by the soil organic material, but methylation with dimethyl sulphate did not.
The soil mineral fraction adsorbed considerably more diuron from petroleum spirit solution than from aqueous solution, but the organic matter preparation adsorbed more from aqueous than from petroleum solution.
It was concluded that there is competition between water and diuron for adsorption sites and that diuron is a more effective competitor at soil organic matter surfaces than at soil mineral matter surfaces.
Observations sur la relation entre l'adsorption du diuron el la nature de l'adsorbant     

施用7%草甘膦水剂对土壤盐化和碱化的影响

通过室内盆栽模拟实验,研究了5种浓度的7%草甘膦水剂对土壤盐化和碱化的影响。结果表明,施药后土壤盐度(用电导率表示)、钠碱化度(ESP)、钠吸附比(SAR)、总碱度及pH值都明显增大,且随施药次数的增加,上述各项盐化和碱化指标不断增大;每次施药后,土壤的各项盐化和碱化指标都随施药浓度的升高呈增大趋势。6次施用0.352 g/L的7%草甘膦水剂后,土壤的电导率由施药前的1 010增加为2 460 μS/cm,ESP由2.247％增加为7.983％,SAR由1.576增加为4.305,总碱度由1.443 mmol/L增加为4.485 mmol/L,pH值由6.92变为7.89。虽然土壤各项盐化和碱化指标的变化都还在非盐化和非碱化土范围内,但有盐化和碱化的趋势。     

施用10％草甘膦水剂对土壤环境的影响

本文通过三地田间试验,研究了长期施用草甘膦水剂对土壤性质的影响。结果表明,湖北罗田、潜江和广水三地土壤的电导率、钠碱化度、钠吸附比、pH值和总碱度均呈现增加的现象,虽然根据国内对盐碱土的分类标准指标三地均属于非盐化和碱化土,但有盐化和碱化的趋势。     

Uptake of pesticides from water and soil by earthworms

The uptake of pesticides by earthworms from aqueous solutions was examined and shown to be a reversible physical process. Measurements of distributions of pesticides between aqueous solutions and worm solids showed that adsorption coefficients were related to octanol-water distribution coefficients, as are soil-water distributions. From these relationships it was calculated that concentration factors of stable chemicals in earthworms from soil should be similar, except for polar substances which penetrate poorly, and be determined mainly by the soil organic matter content. Examination of uptake from soils indicated that the calculated concentration factors are unlikely to be achieved because of slow diffusion of chemicals in soils and because of metabolism in the soil or the worm.     

Co‐solvent effects on the adsorption of carbofuran by two Indian soils

The adsorption of carbofuran on soils from water‐methanol mixtures has been evaluated by batch shake testing. Two uncontaminated soils having different physicochemical properties were used in these experiments. The volume fraction of methanol in the liquid phase (f_s) was varied from 0.25 to 1.0. Higher adsorption of carbofuran was observed in medium black (silt loam) soil than in alluvial (sandy loam) soil; calculated values of the Freundlich constant (K^m) and distribution coefficient (K_d) showed that adsorption of carbofuran in both soils decreased with increase in f_S values. The decreased carbofuran adsorption in methanol–water mixtures meant a greater potential of ground‐water contamination through leaching from potential sites. The data have been used to evaluate the co‐solvent theory for describing adsorption of carbofuran in methanol–water mixtures. The aqueous phase partition coefficient K_dw (mol g⁻¹) normalized with respect to f_oc and the aqueous phase adsorption constant K_w for carbofuran were evaluated by extrapolating to f_S = 0. © 2000 Society of Chemical Industry     

The adsorption and degradation of glyphosate in five Hawaiian sugarcane soils*

The rate of aerobic evolution of ¹⁴CO₂ from ¹⁴C-glyphosate labelled in the methylphosphonyl carbon, varied 100-fold within a group of five Hawaiian sugarcane soils. The rate depended inversely on the degree of soil binding, probably associated with the phosphonic acid moiety, and to a less certain extent on soil pH and soil organic matter. After an initial rapid degradation, the rate of ¹⁴CO₂ evolution in three soils reached a constant at 16–21 days which continued to the 60-day termination. The other two soils showed a continually decreasing rate throughout. Two soils released over 50% of the labelled carbon in 60 days, a third released 35%, while the remaining soils released 1.2 and 0.8% respectively. Labelled carbon in the soils after 60 days consisted of glyphosate and one metabolite, aminomethyl-phosphonic acid, with glyphosate predominating in high fixing soils. The ¹⁴C could be extracted almost completely with NaOH solution, and remained mainly in solution after acidification.     

High pressure liquid chromatography of benzimidazolcs

A laboratory-assembled high pressure liquid chromatograph with variable wavelength ultraviolet detector is described. The chromatography of the systemic fungicides benomyl, thiabendazole, thiophanate, related fungicides and benzimidazoles (13 compounds in all) is described using reverse phase and adsorption systems. Temperature affects reverse phase systems but not adsorption systems. Use of a variable wavelength detector increases sensitivity and selectivity. High pressure liquid chromatography (h.p.l.c.) has been applied to measurements of the solubility of benomyl and carbendazim in water and the degradation of benomyl in solution. Use of h.p.l.c. to measure benzimidazole residues awaits the development of methods of avoiding interference by substances extracted from crops and soils.     

毒死蜱和氰戊菊酯在土壤中的吸附与迁移

为评估被用作白蚁预防药剂的毒死蜱和氰戊菊酯在土壤中的移动性,采用平衡吸附法和薄层层析法分别测定了两种农药在浙江宁波地区的东钱湖土(粉砂质壤土)、青岭土(粉砂质壤土)和象山土(粉砂质黏壤土)3种土壤中的吸附常数(Kd)和迁移率(Rf)。结果表明,两种供试药剂在东钱湖土中的吸附等温线线性化程度均较高,而在青岭土和象山土中的吸附等温线均近似于 "L"型。从Kd和有机质吸附常数Koc的数值看,氰戊菊酯在土壤中的吸附作用主要受土壤有机质因素影响,而毒死蜱的吸附并非只受土壤有机质因素的影响。毒死蜱在3种供试土壤中的Kd和Rf值均高于氰戊菊酯。这表明由Kd值推测不同农药在土壤中的相对移动性可能会存在一定偏差。毒死蜱和氰戊菊酯在3种土壤中的Rf值由大到小的顺序为:东钱湖土>青岭土>象山土;而Kd值由大到小顺序为象山土>青岭土>东钱湖土。对Kd和Rf值与土壤理化性质的多元线性回归分析表明:1)土壤有机质含量和阳离子代换量在决定Kd和Rf值中所起的作用相互重叠;2)土壤有机质含量(或土壤阳离子代换量)和土壤黏粒含量是影响Kd和Rf值的关键因素,而土壤pH值对于Kd和Rf值无决定性影响。     

Fate of chlorsulfuron in the environment. 1. Laboratory evaluations

The behaviour and fate of chlorsulfuron in aqueous and soil systems were examined in laboratory studies. Aqueous hydrolysis was pH-dependent and followed pseudo-first-order degradation kinetics at 25°C, with faster hydrolysis occurring at pH 5 (half-life 24 days) than at either pH 7 or 9 (half-lives >365 days). Degradation occurred primarily by cleavage of the sulfonylurea bridge to form the major metabolites chlorobenzenesulfonamide (2-chlorobenzenesulfonamide) and triazine amine (4-methoxy-6-methyl-1,3,5-triazin-2-amine). This route is a major degradation pathway in water and soil systems. Aqueous photolysis (corrected for hydrolysis) proceeded much more slowly (half-life 198 days) than aqueous hydrolysis and is not expected to contribute significantly to overall degradation. Hydrolysis in soil thin-layer plates exposed to light (half-life 80 days), however, progressed at a much faster rate than in dark controls (half life 130 days), which suggests that a mechanism other than direct photolysis may have been operative. An aerobic soil metabolism study (25°C) in a Keyport silt loam soil (pH 6·4, 2·8% OM) showed that degradation was rapid (half-life 20 days). Dissipation in an anaerobic sediment/water system (initial pH of water phase 6·7, final pH 7·4) progressed much more slowly (half-life >365 days) than in aerobic soil systems. Major degradation products in aerobic soil included the chlorobenzenesulfonamide and triazine amine as in the aqueous hydrolysis study. Neither of these degradation products exhibited phytotoxicity to a variety of crop and weed species in a glasshouse experiment, and both exhibited an acute toxicological profile similar to that of chlorsulfuron in a battery of standard tests. Demethylation of the 4-methoxy group on the triazine moiety and subsequent cleavage of the triazine ring is another pathway found in both aqueous solution and soils, though different bonds on the triazine amine appear to be cleaved in the two systems. Hydroxylation of the benzenesulfonamide moiety is a minor degradation pathway found in soils. Two soils amended with 0·1 and 1·0 mg kg^-1 chlorsulfuron showed slight stimulation of nitrification. The 1·0 mg kg^-1 concentration of chlorsulfuron resulted in minor stimulation and inhibition of ¹⁴C-cellulose and ¹⁴C-protein degradation, respectively, in the same soils. Batch equilibrium adsorption studies conducted on four soils showed that adsorption was low in this system (K_oc 13–54). Soil thin-layer chromatography of chlorsulfuron (R_f=0·55–0·86) and its major degradation products demonstrated that the chlorobenzenesulfonamide (R_f=0·34–0·68) had slightly less mobility and that the triazine amine (R_f=0·035–0·40) was much less mobile than chlorsulfuron. In an aged column leaching study, subsamples of a Fallsington sandy loam (pH_water 5·6, OM 1·4%) or a Flanagan silt loam (pH_water 6·4, OM 4·0%) were treated with chlorsulfuron, aged moist for 30 days in a glasshouse and then placed upon a prewet column of the same soil type prior to initiation of leaching. This treatment resulted in the retention of much more total radioactivity (including degradation products) than by a prewet column, where initiation of leaching began immediately after chlorsulfuron application, without aging (primarily chlorsulfuron parent). © 1998 SCI     

Adsorption of isoproturon,diuron and metsulfuron-methyl in two soils at high soil:solution ratios

Rates of degradation of isoproturon, diuron and metsulfuron-methyl were measured in two soils incubated at two temperatures (5 and 25 °C) with soil moisture at a matric potential of ?5 kPa. Rates of change in soil solution concentration were also measured after extraction of water from the soil using a centrifugation technique. The data, in general, indicated a more rapid rate of decline in aqueous-phase concentrations of herbicide than in total soil concentrations, and hence a progressive increase in partition coefficient in favour of the adsorbed phase^. In all of the incubations, however, adsorption of the herbicide was initially less than that measured using standard equilibration techniques that involved shaking with large volumes of solution relative to weights of soil. This may be explained by the ready availability of more adsorption sites in the shaken systems. With isoproturon and diuron, the changes in adsorption with time were similar at the two incubation temperatures. This indicates that the apparent changes in adsorption with these two compounds were not caused by preferential degradation in the soil solution, but by a slow equilibration with adsorption sites. The results with the weakly adsorbed compound metsulfuron-methyl, however, suggested the possibility of preferential degradation in the solution phase because, when degradation was slow, the absolute amounts adsorbed remained constant or increased slightly, even although solution concentrations declined. Implications of the results for pesticide behaviour in soils in the field are discussed.     

THE ADSORPTIVE BEHAVIOUR OF ACID AND ESTER FORMS OF 2,4-D ON SOILS

Summary. The adsorption of acid, n-butyl, and iso-octyl ester forms of 2,4-D (2,4- dichloiophenoxyacetic acid) was studied for several Canadian prairie soils. The k values for the acid ranged from 0·09 to 1·30 and were correlated to the soil organic matter and not to the clay content. The Q , values (μg adsorbed/g of organic matter) for the acid were 7–2±l. The n-butyl and the iso-octyl esters hydrolysed to the acid form in the aqueous medium and this process was accelerated in the presence of the moist soil. Consequently, the k values for the esters, using slurry type adsorption experiments, or their distribution coefficients, using leaching columns, could not be determined. It was concluded that the adsorptive behavior of the two esters in moist soil was similar to that of the acid form.
Comportement des formes actde, et ester du 2,4-D quant à leur adsorption dans tes sols     

Adsorption,desorption and dissipation of metolachlor in surface and subsurface soils

BACKGROUND: Variations in soil properties with depth influence retention and degradation of pesticides. Understanding how soil properties within a profile affect pesticide retention and degradation will result in more accurate prediction by simulation models of pesticide fate and potential groundwater contamination. Metolachlor is more persistent than other acetanilide herbicides in the soil environment and has the potential to leach into groundwater. Reasonably, information is needed about the dissipation and eventual fate of metolachlor in subsoils. The objectives were to evaluate the adsorption and desorption characteristics and to determine the dissipation rates of metolachlor in both surface and subsurface soil samples. RESULTS: Adsorption of metolachlor was greater in the high‐organic‐matter surface soil than in subsoils. Lower adsorption distribution coefficient (K_ads) values with increasing depth indicated less adsorption at lower depths and greater leaching potential of metolachlor after passage through the surface horizon. Desorption of metolachlor showed hysteresis, indicated by the higher adsorption slope (1/n_ads) compared with the desorption slope (1/n_des). Soils that adsorbed more metolachlor also desorbed less metolachlor. Metolachlor dissipation rates generally decreased with increasing soil depth. The first‐order dissipation rate was highest at the 0–50 cm depth (0.140 week^?1) and lowest at the 350–425 cm depth (0.005 week^?1). Degradation of the herbicide was significantly correlated with microbial activity in soils. CONCLUSION: Metolachlor that has escaped degradation or binding to organic matter at the soil surface might leach into the subsurface soil where it will dissipate slowly and be subject to transport to groundwater. Copyright © 2009 Society of Chemical Industry     

Accumulation patterns and fungicidal effect of carbendazim and thiabendazole in peanut plants after soil injection

Carbendazim and thiabendazole applied to the rhizosphere of peanut plants by injection into the soil at doses of 0.1, 0.5 and 2.5 g per 1 m row, accumulated in the leaves during the first week after treatment, the concentrations being related to the doses applied. Two weeks after treatment the concentrations of both fungicides dropped sharply. During the rest of the season, whilst the concentration of carbendazim in the high-dose treatment was 0.1 mg/kg fresh weight, the concentration of thiabendazole increased from 0.1 to 2.0 mg/kg and remained at this level until harvest. At the end of the growing season treated plants were less infected with Cercospora leaf spot (Cercospora per sonata) than the untreated control, thiabendazole affording better protection than carbendazim. Plants treated with the highest dose of thiabendazole were the only ones that did not wilt, even though infected. Laboratory studies of the adsorption of these fungicides on soil revealed that carbendazim is less adsorbed and also less persistent than thiabendazole.     

An analytical procedure for bromoxynil and its octanoate in soils; persistence studies with bromoxynil octanoate in combination with other herbicides in soil

A method is described for the analysis of the herbicide bromoxynil and its octanoate in soils. Following extraction with aqueous acidic acetonitrile, the octanoate was separated from the phenolic bromoxynil by solvent partitioning. The ester and the phenol were assayed by gas-liquid chromatography without further modification or preparation of a derivative. Recoveries in excess of 93% were obtained from soils treated with the phenol and the ester at levels of 0.5 or 0.1 μg g^?1. The persistence of bromoxynil octanoate applied at a rate of 3 μg g^?1 was studied in the laboratory on a heavy clay and a sandy loam at 85% of field capacity moisture and 20°1°C, both alone and in the presence of 2,4-D (2 μg g^?1); MCPA (2 μg g^?1); MCPA+asulam (both at 2 μg g^?1); and MCPA+difenzoquat (both at 2 μg g^?1). In each soil there was a rapid conversion of bromoxynil octanoate to the free phenol, which then underwent a rapid degradation, so that after 7 days, over 90% of the original treatment had disappeared. There appeared to be no effect on bromoxynil breakdown by any of the herbicides added in combination. Small field plots were treated, in early May 1977 and 1978 at two locations in Saskatchewan, with a combination of commercial formulations containing asulam, bromoxynil octanoate, and MCPA at rates of 1 kg ha^?1 each. After 10 weeks the plots were sampled and analysis showed that in all cases, no asulam, bromoxynil, or bromoxynil octanoate could be extracted from the top 10 cm of soil.     

Adsorption, transport and degradation of fipronil termiticide in three Hawaii soils

BACKGROUND: The behavior of the termiticide fipronil in soils was studied to assess its potential to contaminate ground and surface water. This study characterizes (1) adsorption of fipronil in three different soils, (2) transport of fipronil through leaching and runoff under simulated rainfall in these soils and (3) degradation of fipronil to fipronil sulfide and fipronil sulfone in these soils. RESULTS: The adsorption experiments showed a Freundlich isotherm for fipronil with K_oc equal to 1184 L kg^?1. In the leaching experiments, the concentration of fipronil and its metabolites in leachate and runoff decreased asymptotically with time. The concentration of fipronil in the leachate from the three soils correlated inversely with soil organic carbon content. The degradation experiment showed that the half‐life of fipronil in the soils ranged from 28 to 34 days when soil moisture content was 75% of field capacities, and that 10.7–23.5% of the degraded fipronil was transformed into the two metabolites (fipronil sulfide and fipronil sulfone). CONCLUSION: Fipronil showed large losses through leaching but small losses via runoff owing to low volumes of runoff water generated and/or negligible particle‐facilitated transport of fipronil. The half‐life values of fipronil in all three soils were similar. Copyright © 2011 Society of Chemical Industry     

A new extraction method for benomyl residues in soil and its application in movement and persistence studies

A simple and rapid method for extracting benomyl residues from soils was compared with previous methods. Soil was extracted by shaking for 2 h at room temperature with (1:1) acetone/M aqueous ammonium chloride followed by clean-up by solvent partition and ultraviolet absorption estimation of carbendazim. Recoveries were comparable to those obtained by refluxing with methanolic hydrochloric acid for 4 h, hitherto the most efficient method reported, and were much greater than those obtained by extraction with ethyl acetate or chloroform. The new method gave more tractable extracts than those obtained by refluxing with methanolic hydrochloric acid, which form troublesome metal hydroxide precipitates during clean-up. In field experiments with 2-[¹⁴C]-benomyl and 2-[¹⁴C]-carbendazim, no radioactivity was found more than 25 mm from the soil surface during 10 months after surface application of 1 kg/ha. Carbendazim residues in soils from three field experiments indicated that its persistence is very sensitive to soil pH. The time for 50% loss of initial dose ranged from 26 months at pH 5.5 to less than 3 months at pH 7.2. Biological effectiveness in a crop may therefore depend markedly on differences in soil pH.     

Copper and Zinc Competitive Adsorption: Desorption in Calcareous Soils

The behavior in competitive adsorption-desorption reactions of Cu and Zn was studied in four calcareous soils. Cu and Zn were added to the soil by Cu, Zn, and Cu+Zn sulfate solutions in a CaSO4 background. Soil sorption of these cations was described by equilibrium isotherms that fitted either Freundlich- or Langmuir type equations, although Cu desorption data fitted only Freundlich isotherms. Cu and Zn competition was quantified by distribution coefficients, Kd, relating cation distribution between soil and solute and by the competitive Langmuir equation. The competitive Langmuir equation was the better suited to describe the Cu-Zn competitive adsorption in these soils. Distribution coefficients presented lower values when both cations were present, decreasing when the Cu and Zn concentration in solution increased (decreasing soil affinity for these cations), thereby increasing their mobility through the soil. However, the distribution coefficient of specifically adsorbed Cu in equilibrium with cations extracted by a Mg (NO) solution increased with Cu concentration. Cu adsorption was more depres 3 se 2 d by Zn than Zn adsorption by Cu. The different behavior of Cu and Zn seems dependent on the percentage Ca (CO) and, to a lesser degree, on Cu and Zn organic matter complexes, free iro 3 n 2 content, and surface precipitation on oxides and carbonates.     

Determination of extractable and non-extractable radioactivity from prairie soils treated with carboxyl- and ring-labelled [14C]2,4-D

Ring- and carboxyl-labelled [¹⁴C]2,4-D were incubated under laboratory conditions, at the 2 g/g level, in a heavy clay, sandy loam, and clay loam at 85% of field capacity and 20 1C. The soils were extracted at regular intervals for 35 days with aqaeous acidic acetonitrile, and analysed for [¹⁴C]2,4-D and possible radioactive degradation products. Following solvent extraction, a portion of the soil residues were combusted in oxygen to determine unextracted radioactivity as [¹⁴C]carbon dioxide. The remaining soil residues were then treated with aqueous sodium hydroxide, and the radioactivity associated with the fulvic and humic soil components determined. In all soils there was a rapid decrease in the amounts of extractable radioacitivity, with only 5% of that applied being recoverable after 35 days. All recoverable radioactivity was attributable to [¹⁴C]2,4-D, and no [¹⁴C]-containing degradation products were observed. This loss of extractable radioactivity was accompanied by an increase in non-extractable radioactivity. Approximately 15% of the applied radioactivity, derived from carboxyl-labelled [¹⁴C]2,4-D, and 30% from the ring-labelled [¹⁴C]2,4-D was associated with the soil in a non-extractable form, after 35 days of incubation. After 35 days, less than 5% of the radioactivity from the carboxyl-labelled herbicide, and less than 10% of the ringlabelled material, was associated with the fulvic components derived from the three soils. Less than 5% of the applied radioactivities were identifiable with any of the humic acid components. It was considered that during the incubation [¹⁴C]2,4-D did not become bound or conjugated to soil components, and that non-extractable radioactivity associated with the three soil types resulted from incorporation of radioactive degradation products, such as [¹⁴C]carbon dioxide, into soil organic matter.