The degradation of aldicarb and oxamyl in soil

The breakdown of oxamyl was studied in three downland chalk soils, a peat loam, a sandy loam, and the same sandy loam modified by adding peat. The kinetics of aldicarb degradation via its sulphoxide and aldoxycarb (aldicarb sulphone) were also studied in these two sandy loam soils. All the reactions followed first-order kinetics, the reaction being faster in the original than in the modified sandy loam. Rates of reaction were slower at low moisture contents, and decreased markedly when the temperature was reduced from 10 to 5°C though less so than from 15 to 10°C.     

Potential enhancement of degradation of the nematicides aldicarb,oxamyl and fosthiazate in UK agricultural soils through repeated applications

BACKGROUND: The potential for enhanced degradation of the carbamoyloxime nematicides aldicarb and oxamyl and the organophosphate fosthiazate was investigated in 35 UK agricultural soils. Under laboratory conditions, soil samples received three successive applications of nematicide at 25 day intervals. RESULTS: The second and third applications of aldicarb were degraded at a faster rate than the first application in six of the 15 aldicarb‐treated soils, and a further three soils demonstrated rapid degradation of all three applications. High organic matter content and low pH had an inhibitory effect on the rate of aldicarb degradation. Rapid degradation was observed in nine out of the ten soils treated with oxamyl. In contrast, none of the fosthiazate‐treated soils demonstrated enhanced degradation. CONCLUSION: The potential for enhanced degradation of aldicarb and oxamyl was demonstrated in nine out of 15 and nine out of ten soils respectively that had previously been treated with these active substances. Degradation of fosthiazate occurred at a much slower rate, with no evidence of enhanced degradation. Fosthiazate may provide a useful alternative in cases where the efficacy of aldicarb and oxamyl has been reduced as a result of enhanced degradation. Copyright © 2009 Society of Chemical Industry     

Measured and simulated behaviour of oxamyl in fallow soils

The movement and breakdown of the insecticide and nematicide oxamyl was monitored in fallow sandy loam soils under field conditions. Using measurements of rainfall and evaporation from a water surface, the water flow in soil was simulated by a computer model, and the results were compared with the measured soil-moisture profiles. The model was extended to simulate the behaviour of oxamyl, using laboratory data for adsorption and rates of degradation in soil. The model generally underestimated oxamyl movement in the first month, whereas it tended to overestimate later movement. The rate of breakdown of oxamyl, as affected by soil type, temperature and soil-moisture content, was fairly well described. After about 2 months only small amounts of oxamyl remained. Accumulation of oxamyl near the soil surface in dry periods was overestimated, indicating deficiencies in the modelling procedure under these conditions.     

Leaching of aldicarb and thiofanox,and their uptake in soils by sugarbeet plants

The leaching of aldicarb and thiofanox in soils (sandy loam, silt loam and sandy clay loam), and their uptake by sugarbeet plants were studied. Three irrigation levels were maintained: half, normal and double dose. The residues were determined as the sum of the insecticidal metabolites (parent compound + sulphoxide+ sulphone) for both pesticides. Leaching was greatly influenced by the amount of water added and the soil type. Under normal conditions, leaching seemed to proceed very slowly, keeping the chemicals available for uptake by the root systems for a long time. The concentration of insecticide in the leaves was highest in beets grown on sandy loam and lowest in those grown on sandy clay loam. The quantity of irrigation did not influence the residue concentration in the leaves greatly, although its influence was obvious on the total residue present (μg per plant). Increasing the water dose always resulted in a higher total residue, and a greater plant weight. The breakdown in the soils was directly related to the water dose. The experiments show that thiofanox was more stable than aldicarb and was taken up by sugarbeet to a greater extent.     

The degradation of simazine, linuron and propyzamide in different soils

Simazine, linuron and propyzamide were incubated in 18 different soils at 25°C and field capacity soil moisture content. The degradation of each herbicide followed first-order kinetics. The half-life of simazine varied from 20 to 44 days, that of linuron from 22 to 86 days and that of propyzamide from 10 to 32 days. The rate of linuron degradation was highly significantly correlated with soil organic matter content, clay content, soil respiration and the extent of herbicide adsorption by the soil. The rate of simazine degradation was significantly and negatively correlated with soil pH, but the rate of propyzamide degradation was not related with any of the soil factors examined.     

Measured and simulated behaviour of aldicarb and its oxidation products in fallow soils

Aldicarb and its oxidation product aldoxycarb (aldicarb sulphone) were applied separately to columns of fallow, sandy loam soils under field conditions. The breakdown and movement of these compounds were monitored, as was the behaviour of aldicarb sulphoxide and aldoxycarb formed by oxidation of the applied aldicarb. The behaviour of these compounds was simulated by a computer model using laboratory data for adsorption and rates of degradation in soil. The model simulated the observed behaviour reasonably well, although redistribution of chemicals was often more rapid than predicted. Production of aldoxycarb from the sulphoxide was less in the field than was expected from the laboratory incubations. Accumulation of chemicals near the soil surface in dry periods was overestimated, indicating that the processes occurring under these conditions are not well described by the model. About 4 months after application, only aldoxycarb, in small amounts, remained in the soils.     

Adsorption,decomposition and movement of oxamyl in soil

A study was conducted of the behaviour of oxamyl in Israeli soils of varying clay and organic matter contents. The adsorption isotherms for oxamyl were linear, and the adsorption coefficient (K_d) could be correlated to the clay content of the soils, as well as to the organic matter content of the soil. Oxamyl adsorption was underestimated by using published correlations between the adsorption and the chemical properties of pesticides, such as their solubility or octan-1-ol-water partition coefficient. The decomposition of oxamyl in soils followed first-order kinetics. The half-life ranged from 4 to 33 days in a Bet Dagan soil. The reaction rate increased with increasing moisture content of the soil until field capacity was reached, at which point it levelled off. The Arrhenius relationship was followed, with degradation proceeding more rapidly at higher temperatures. In several soils of varying composition, which were kept at field capacity, no difference in the degradation rates was observed. Oxamyl was applied to a Bet Dagan soil from a point source in a single pulse, as a split application, and on a continuous basis. The distribution patterns of oxamyl under the various treatments differed significantly. After the single-pulse application, oxamyl was leached out of the emitter zone. While the split application decreased the oxamyl-free zone, the best results were obtained by continuous application, which gave a nearly uniform distribution of oxamyl in the soil.     

Conversion rates of aldicarb and its oxidation products in soils. III. Aldicarb

Aldicarb was incubated in seven soils at 15°C and its loss was well described by first-order kinetics. Rate constants varied between 0.078 day^?1 in a peaty sand to 0.35 day^?1 in a clay loam. The concentration-time relationships for aldicarb, its sulphoxide and its sulphone were approximated by a computation model which was used to analyse the importance of the various consecutive and simultaneous reactions. It was computed that 91 to 100% of the aldicarb would be oxidised to its sulphoxide.     

Conversion rates of aldicarb and its oxidation products in soils. I. Aldicarb sulphone

The rate of loss of aldicarb sulphone was studied in incubation experiments on soils from four plough layers and two deeper layers. In all instances the loss could be described by first-order kinetics in the first period of two to three times half-life. However, in a clay loam soil and a greenhouse soil a faster degradation rate was observed after the first 56 and 112 days of incubation respectively. The half-lives of sulphone in plough layer soils at 15°C ranged from 18 days in a clay loam to 154 days in a peaty sand. Conversion in deeper layers was considerably slower than in the corresponding top layers of the soil profile. In a silty layer at 70 to 90 cm depth the half-life at 15°C was 46 days, whereas in a sand layer at 90–110 cm no clear loss was found during the 294 days of incubation.     

The metabolic fate of methomyl in the cabbage looper

Methomyl, S-methyl N-[(methylcarbamoyl)oxy] thioacetimidate, is metabolized primarily to water-soluble products by susceptible, DDT-resistant, and parathion-resistant strains of the cabbage looper, Trichoplusia ni (Hübner). However, the rate of injected methomyl metabolized varies with the strain to give respective half-lives of 60, 44, and 15 min. In each strain, maximum methomyl-metabolizing activity is present in the last larval stage and prepupal forms, particularly in the fat body. Metabolism by fat body homogenates is dependent on oxygen and NADPH and is inhibited by carbon monoxide and methylenedioxyphenyl synergists. The water-soluble metabolites could not be converted to organosoluble materials by acid or enzymatic treatment. Methomyl sulfoxidation products or oxime derivatives do not appear to be terminal metabolites in the cabbage looper.     

Conversion rates of aldicarb and its oxidation products in soils. II. Aldicarb sulphoxide

The loss of aldicarb sulphoxide was studied in incubation experiments with soil from four plough layers and two deeper layers. The loss during the 111 days of the experiment could be described by first-order kinetics. The half-lives at 15°C ranged from 20 days in a clay loam to 46 days in a peaty sand. The loss of sulphoxide in deeper layers was considerably slower than in the corresponding top layers of a soil profile. In soil from a silty layer at 70–90 cm depth the half-life was about 53 days. In soil from a sand layer at 90–110 cm depth a loss of only about 15% was measured after 111 days of incubation. First-order rate constants for sulphoxide conversion in a clay loam at 6, 15 and 25°C were found to be 0.009, 0.033, and 0.05 day^?1 respectively; in a greenhouse soil these rate constants were 0.0052, 0.019 and 0.04 day^?1 respectively. The fractions of aldicarb sulphoxide that were oxidised to sulphone at 15°C in soil from plough layers were computed to range from 0.52 to 0.76.     

The fate of the herbicide chlortoluron and its possible degradation products in soils

Chlortoluron hadàhalf-tire in soil of 4–6 weeks. The only metabolite identified was monomethyl chlortoluron, half-life 8 weeks. 3-Chloro-4-methylphenylurea hadàsimilar half-life but was not detected in soils treated with chlortoluron or monomethyl chlortoluron suggesting that 3-chloro-4-methylaniline was formed directly from monomethyl chlortoluron. This aniline hadàhalf-life of 1–2 days in soil, initial concentrations above 5 ppm yielding dimers and trimers predominantly C — N linked. Neither the aniline nor polymeric products were detected in chlortoluron treated soils, presumably because slow formation of the aniline was followed by rapid degradation which kept concentration low.     

Transformation of aldicarb sulfoxide and aldicarb sulfone in four water-saturated sandy subsoils

The transformation of aldicarb sulfoxide and aldicarb sulfone was studied in incubations with water-saturated subsoils under simulated field conditions at 10°C. The subsoils were collected at four locations from beneath the water table at a depth of 2.5 to 3.5 m. In three of the subsoils, the half-life of sulfoxide, incubated at concentrations of 0.14-0.17 mg litre^?1, ranged from 0.7 to 2.8 years. At higher concentrations (8-13 mg litre^?1), its half-life ranged from 3.4 to 6.4 years. At the lower concentration, a large fraction of sulfoxide was transformed into sulfone. The rates of transformation of the sulfone at the lower concentration in the three subsoils corresponded to half-lives of 3.3 to 8.1 years, but in only one subsoil was a significant transformation rate (half-life 6.7 years) measured at the higher concentration during the 2.3-year incubation period. The half-lives at the lower concentrations were more like those in field studies, and perhaps would still underestimate transformation rates under field conditions. After a year, 2.5-15% of the higher sulfoxide and sulfone doses had been trapped as [¹⁴C] carbon dioxide. In the fourth subsoil, with more anaerobic conditions, the half-life of sulfoxide at both concentrations was less than 0.02 year and that of sulfone was about 0.04 year. Four or five radio-labelled transformation products could be traced in this subsoil and about half of the dose of both compounds was trapped as [¹⁴C] carbon dioxide.     

Residues of methomyl in strawberries,tomatoes and cucumbers

An accurate and rapid high performance liquid chromatography method was developed to monitor residues of methomyl in plant extracts. The rate of disappearance of foliage-applied methomyl from strawberries, tomatoes and cucumbers was studied. Residues reached levels of 0.55, 0.2 and 0.6 mg kg^?1 seven days after methomyl had been applied to strawberries, tomatoes and cucumbers, respectively. Results also showed that rinsing treated fruits with tap water removed considerable amounts of methomyl. Samples of strawberries, tomatoes and cucumbers were collected from local markets at Ismailia, and checked for methomyl residues. Residues in 12.5% of tomato and 25% of strawberry samples were above 0.2 mg kg^?1.     

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     

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.     

Determination of methomyl in rape seeds,oils and meals

Methomyl added to rape seeds, oils or meals was detected by a thin-layer chromatographic-enzyme inhibition technique. The limit of detection in the presence of oil or meal extractive was 20 mg or 0.01 mg/kg. The amounts of methomyl recovered from oils and meals fortified at 0.01 to 20 mg/kg were comparable to the standard. When stored at 4 °C, methomyl in oil or meals, or in chloroform extracts, was stable for at least 10 and 21 days, respectively. No degradation was observed when methomyl was heated in ethanol at 72 °C for 2 h. Methomyl and its oxime were also detected with either iodo- or chloroplatinate reagent after t.l.c. The detection limits were approximately 600 mg for methomyl and 190 for the oxime.     

The distribution of aldicarb and its metabolites between Lumbricus terrestris,water and soil

Aldicarb is taken up by earthworms from aqueous solution to give concentrations in the worms comparable to that in the external aqueous solutions. Uptake from waterlogged soils is similar, but much less aldicarb is taken up from drier soils. Aldicarb sulphoxide [2-methyl-2-(methylsulphinylpropionaldehyde O-methylcar-bamoyloxime], aldoxycarb and oxamyl are poorly taken up, giving concentrations in the worm of about 5% of the external aqueous concentration. In worms, aldicarb is rapidly converted to the sulphoxide which has a half-life in worms of 19 h at 15°C, and 50 h at 5°C.     

异噁唑草酮在土壤表面光解及在土壤中的降解和淋溶特性

为合理评估除草剂异唑草酮的环境风险,在实验室模拟条件下,研究了异唑草酮在土壤 (红壤土)表面光解以及在不同质地土壤 (潮土、水稻土和红壤土) 中的降解和淋溶特性。结果表明:异唑草酮在土壤表面的光解遵循一级反应动力学方程c_t = 4.23e–0.008t (r = 0.937),半衰期为82.5 h;其在潮土、水稻土和红壤土中的降解均符合一级动力学方程,好氧条件下,异唑草酮在3种土壤中的降解半衰期分别为10.5、43.3和139 h,厌氧条件下的降解半衰期分别为19.4、18.4和158 h;其在潮土、水稻土和红壤土中的淋溶系数 (R_f) 分别为0.417 0、0.083 3和0.083 3。研究表明:异唑草酮在土壤表面光解速率较慢,而在土壤中好氧及厌氧条件下降解速率均较快,残留期短;其在土壤中淋溶性较弱,不易对周围环境及地下水造成污染风险。