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     

Mode of action of famoxadone

Famoxadone is a preventative and curative fungicide recently developed for plant disease control. The molecule and its oxazolidinone analogs (OADs) are potent inhibitors of mitochondrial electron transport, specifically inhibiting the function of the enzyme ubiquinol:cytochrome c oxidoreductase (cytochrome bc₁). Visible absorbance spectral studies on the purified enzyme suggested that famoxadone bound close to the low potential heme of cytochrome b. This binding mode was confirmed in competitive binding experiments by studying the displacement of a radiolabelled OAD from submitochondria. EPR studies on the binding of famoxadone to submitochondria and purified bc₁ suggested its binding mode was more like that of myxothiazol than that of stigmatellin (ligands known to bind near the low potential heme). Zoospores of Phytophthora infestans, when given low concentrations of famoxadone and other OADs, were observed to cease oxygen consumption and motility within seconds and later the cells disintegrated, releasing the cellular contents. Famoxadone was a potent inhibitor of the growth of Saccharomyces cerevisiae when grown on non-fermentable carbon sources and it was an approximately 50-fold less potent inhibitor of growth when the yeast was grown on a fermentable carbon source, glucose. Such physiological observations are consistent with the loss of mitochondrial function imposed by famoxadone and OADs. Single amino acid changes in the apocytochrome b of baker's yeast cytochrome b located near the low potential heme altered the inhibition constants for the inhibitors famoxadone, myxothiazol, azoxystrobin and kresoxim-methyl differentially, thus strongly suggesting different binding interactions of the protein with the inhibitors. © 1999 Society of Chemical Industry     

Comparative metabolism of famoxadone in fish,plants and animals

The fate and comparative metabolism of famoxadone in fish, plants and animals were evaluated. Famoxadone residues were retained by the fish after exposure (BCF 2800), mainly in the viscera; however, rapid and complete elimination/depuration of the absorbed residues occurred within seven days after the exposed fish were placed in untreated water. Minimal absorption, translocation, and metabolism of famoxadone were observed in grape and potato plants after foliar treatment. Metabolism of famoxadone in the wheat plants, rats, goats, and poultry was extensive. Transfer of ¹⁴C-residues to the wheat grain, milk, eggs, organs and tissues was minimal. Common metabolic reactions of famoxadone in plants and animals include aryl hydroxylation, cleavage of the anilino-oxazolidinedione and phenoxy-phenyl ether linkages, opening of the oxazolidinedione ring and conjugation.     

Hydrolysis and photolysis of flumioxazin in aqueous buffer solutions

To determine the degradation rates and degradation products of the herbicide flumioxazin in aqueous buffer solutions (pH 5, 7 and 9), its hydrolysis and photolysis were investigated at 30 degrees C in the dark, and in a growth chamber fitted with fluorescent lamps simulating the UV output of sunlight. The rate of hydrolysis of flumioxazin was accelerated by increasing pH. The t(1/2) values at pH 5, 7 and 9 were 16.4, 9.1 and 0.25 h, respectively. Two degradation products were detected and their structural assignments were made on the basis of LC-MS data. Degradation product I was detected in all buffer solutions while degradation product II was detected in acidic buffer only. Both degradation products appeared to be stable to further hydrolysis. After correcting for the effects of hydrolysis, the photolytic degradation rate also increased as a function of pH and was approximately 10 times higher at pH 7 than that at pH 5, showing t(1/2) values of 4.9 and 41.5 h, respectively. Degradation products formed by photolysis were the same as those formed by hydrolysis. Flumioxazin was degraded more extensively at high pH and should degrade in surface water.     

Behaviour of famoxadone deposits on grape leaves

Famoxadone is a new fungicide developed for the control of crop diseases, including grape downy mildew (Plasmopara viticola). The majority (>90%) of the spray deposit from a famoxadone 500 g kg⁻¹ water‐dispersible granule formation on a grape leaf were found on the leaf surface or associated with epicuticular waxes. A significant fraction of this deposit could not be removed by a water wash, suggesting strong binding to the waxes. Nearly 100% of the spray deposit was still recovered after 12 days of exposure to a dry environment, confirming the good residual properties of the substance. Thirty per cent of the applied active ingredient was lost after exposure to a wet environment, probably via hydrolysis or wash‐off. Studies with radiolabelled famoxadone formulated as a suspension concentrate indicated that redistribution occurred both in dry conditions, via diffusion in the cuticular waxes, and in wet conditions via dissolution in water followed by re‐deposition. No systemic movement of famoxadone was observed within the treated plant. Grape plants treated with famoxadone alone or in mixture with cymoxanil and subjected to up to 50 mm of artificial rain remained well protected against downy mildew infections. Good rain‐fastness was observed even 2 h after fungicide application. Despite low water solubility, famoxadone spray residues on grape leaves were reactivated in surface water sufficiently quickly to prevent infection by P viticola. © 2000 Society of Chemical Industry     

Fate of metsulfuron-methyl in soils in relation to pedo-climatic conditions

The dependence of the behaviour of metsulfuron-methyl on soil pH was confirmed during incubations under controlled laboratory conditions with two French soils used for wheat cropping. The fate of [¹⁴C] residues from [triazine-¹⁴C]metsulfuron-methyl was studied by combining different experimen-tal conditions: soil pH (8·1 and 5·2), temperature (28 and 10°C), soil moisture (90 and 50% of soil water holding capacity) and microbial activity (sterile and non-sterile conditions). Metsulfuron-methyl degradation was mainly influenced by soil pH and temperature. The metsulfuron-methyl half-life varied from five days in the acidic soil to 69 days in the alkaline soil. Under sterile conditions, the half-life increased in alkaline soil to 139 days but was not changed in the acidic soil. Metsulfuron-methyl degradation mainly resulted in the formation of the amino-triazine. In the acidic soil, degradation was characterised by rapid hydrolysis giving two specific unidentified metabolites, not detected during incubations in the alkaline soil. Bound residues formation and metsulfuron-methyl mineralisation were highly correlated. The extent of bound residue formation increased when soil water content decreased and was maximal [48 (±4)% of the applied metsulfuron-methyl after 98 incubation days] in the acidic soil at 50% of the water holding capacity and 28°C. Otherwise, bound residues represented between 13 and 32% of the initial radioactivity. © 1998 SCI     

噻呋酰胺的光解和水解特性研究

为了明确噻呋酰胺的环境行为规律,采用室内模拟试验方法,研究了噻呋酰胺在不同条件下的光解和水解特性。结果表明:紫外灯照射下,噻呋酰胺在碱性条件下光解速率大于中性和酸性条件下的;不同溶剂中,噻呋酰胺的光降解速率依次为正己烷 >乙腈 >甲醇 >乙酸乙酯 >超纯水;三价铁离子、二价铁离子以及腐殖酸均能抑制噻呋酰胺的光降解。中性条件下,噻呋酰胺水解速率最快,同时,噻呋酰胺的水解受温度影响,温度越高,水解速率越快,平均温度效应系数1.39～2.23;表面活性剂十六烷基三甲基溴化铵（CTAB）和十二烷基磺酸钠（SDS）均可抑制噻呋酰胺在水中的降解。     

丙炔氟草胺的水解及光解特性研究

为深入了解丙炔氟草胺的环境化学行为,通过室内模拟试验研究了其在不同条件下的水解和光解特性。结果表明:15℃下,初始质量浓度为2 mg/L的丙炔氟草胺在pH值为5、7和9的缓冲溶液中的水解半衰期分别为63.00、33.00和28.50 h,即其在碱性条件下水解最快;中性(pH 7)条件下,丙炔氟草胺在15、25和35℃下的水解半衰期分别为33.00、23.10和8.88 h,表明其水解受温度影响,温度越高,水解速率越快;丙炔氟草胺在河水中的水解速率高于在自来水和蒸馏水中的水解速率,3种条件下的半衰期分别为2.70、6.03和19.80 h。300 W汞灯照射下,丙炔氟草胺在碱性条件下的光解速率大于在酸性和中性条件下,半衰期分别为0.03、0.45和0.44 h;此外,丙炔氟草胺在不同有机溶剂中的光解速率顺序依次为甲醇 > 乙酸乙酯 > 正己烷 > 乙腈 > 丙酮;其在不同光源下的光解速率依次为500 W汞灯 > 300 W汞灯 > 氙灯。研究结果可为丙炔氟草胺的环境风险评价提供参考。     

腐霉利的光解及水解特性研究

为研究腐霉利的消解特性,采用乙腈提取,弗罗里硅土柱净化,建立了油菜叶片中腐霉利残留的气相色谱-电子捕获检测器 (GC-ECD) 分析方法;并在室内模拟条件下,研究了腐霉利在油菜叶片表面的光解行为,以及不同初始浓度、不同pH值缓冲液、不同浓度Fe2+、Fe3+ 和NO₃–、NO₂– 对水溶液中腐霉利光解的影响;通过气相色谱-电子轰击电离源质谱仪 (GC-EIMS) 鉴定了其在甲醇、丙酮和乙腈溶液中的光解产物;同时研究了不同pH值缓冲液和阴、阳离子表面活性剂对腐霉利水解特性的影响。结果表明:腐霉利添加水平为0.05、0.2、2及12 mg/kg时,其在油菜叶片中的平均回收率为80%~100%,相对标准偏差为2.3%~7.8%。腐霉利在油菜叶片表面的消解动态符合一级动力学方程,紫外灯下的消解半衰期为1.03 h。腐霉利在水溶液中的光解速率随其初始浓度的升高而减慢;其在酸性条件下稳定,碱性条件下易光解;NO₃–、NO₂–、Fe2+ 及Fe3+均可抑制腐霉利在水溶液中的光解,因此可用作为其光猝灭剂。共鉴定出两种腐霉利在甲醇、丙酮和乙腈溶液中的光解产物,分别为其单脱氯化产物C₁₃H₁₂ClNO₂和其脱甲基化产物C₁₂H₉Cl₂NO₂。腐霉利在碱性条件下易水解,酸性条件下水解较慢;阴离子表面活性剂十二烷基磺酸钠 (SDS) 对其水解无影响,而阳离子表面活性剂十六烷基三甲基溴化铵 (CTAB) 则可促进其水解。研究结果可为腐霉利的合理使用及其环境安全性评价提供参考。     

单嘧磺酯水解及在水中的光解研究

实验室条件下,利用高效液相色谱研究了单嘧磺酯水解和在水中的光解动态特性。结果表明:在pH值分别为5、7和9的缓冲溶液中,25 ℃时单嘧磺酯的水解半衰期分别为13.1、192和347 d,为易水解或较难水解,50 ℃时则分别为19.6 h和4.6、7.1 d,为易水解;其水解速率随着温度的升高而升高,温度效应系数为32.7~48.9;单嘧磺酯在酸性缓冲溶液中水解最快,在碱性条件下水解最慢,其水解活化能和活化熵与缓冲溶液的pH值呈显著正相关关系。在25 ℃、照度为3 620 lx 以及紫外强度为71.1 μW/cm2条件下,单嘧磺酯在水中的光解半衰期为4.9 h,为较易光解。     

Sorption–desorption of 'aged' isoxaflutole and diketonitrile degradate in soil

Isoxaflutole is a relatively new herbicide used for weed control in maize. The objective of this research was to increase the understanding of the behaviour and environmental fate of isoxaflutole and its diketonitrile (DKN) degradate in soil, including determination of the strength of sorption to soil and whether sorption is affected by ageing. In sandy loam (SL) and silty clay (SiCl) soils, ¹⁴C‐isoxaflutole was found to dissipate rapidly after application to soil; recovery ranged from ～42% to 68% at week 0, and recovery had decreased to <10% at week 12. Decreases in ¹⁴C isoxaflutole residues over time in SL and SiCl soils are consistent with hydrolysis of isoxaflutole and formation of bound DKN residues in the soil. DKN recovery from freshly treated SiCl and SL soils was 41% to 52%. After a 12‐week incubation in SL soil at pH 7.1 and 8.0, recoveries were similar, ～40%. However, at week 12 in SL soil pH 5.7, DKN recovery decreased to ～28%. DKN recovery in SiCl soil at week 12 was <10%. Increases in sorption of DKN in SL at pH 5.7 and SiCl soil over time indicate that the DKN degradate is tightly bound to the soil and sorption is affected by soil pH and soil type. Sorption of ¹⁴C‐DKN in the SiCl soil more than doubled with ageing compared with the lower K_d sorption coefficient values of the SL soils. In the SiCl soil at time 0, the K_d was 0.6; at 1 week, K_d increased to 2; and at the end of the 12‐week incubation period, K_d was 4.5. This strong binding of DKN to the soil may be due to chelate formation in the interlayer of the clay.     

Fate of the insecticide lambda-cyhalothrin in ditch enclosures differing in vegetation density

Use of the insecticide lambda-cyhalothrin in agriculture may result in the contamination of water bodies, for example by spray drift. Therefore, the possible exposure of aquatic organisms to this insecticide needs to be evaluated. The exposure of the organisms may be reduced by the strong sorption of the insecticide to organic materials and its susceptibility to hydrolysis at the high pH values in the natural range. In experiments done in May and August, formulated lambda-cyhalothrin was mixed with the water body of enclosures in experimental ditches containing a bottom layer and macrophytes (at different densities) or phytoplankton. Concentrations of lambda-cyhalothrin in the water body and in the sediment layer, and contents in the plant compartment, were measured by gas-liquid chromatography at various times up to 1 week after application. Various water quality parameters were also measured. Concentrations of lambda-cyhalothrin decreased rapidly in the water column: 1 day after application, 24-40% of the dose remained in the water, and by 3 days it had declined to 1.8-6.5%. At the highest plant density, lambda-cyhalothrin residue in the plant compartment reached a maximum of 50% of the dose after 1 day; at intermediate and low plant densities, this maximum was only 3-11% of the dose (after 1-2 days). The percentage of the insecticide in the ditch sediment was 12% or less of the dose and tended to be lower at higher plant densities. Alkaline hydrolysis in the water near the surface of macrophytes and phytoplankton is considered to be the main dissipation process for lambda-cyhalothrin.     

吡唑醚菌酯·噁唑菌酮30%水分散粒剂高效液相色谱分析

建立了在同一色谱条件下测定混剂中吡唑醚菌酯和噁唑菌酮含量的方法。采用ODS C18、5μm为填料的不锈钢柱和二极管阵列检测器分离,以甲醇+水(体积比为80∶20)为流动相,在254nm波长下,经保留时间定性确证,峰面积外标法进行定量分析。结果表明:吡唑醚菌酯与噁唑菌酮的线性相关系数分别为0.999 5和0.999 6;变异系数分别为0.68%和0.45%;平均加标回收率分别为100.28%和100.32%。     

Studies on photodegradation of chlorimuron-ethyl in soil

Photolysis of chlorimuron-ethyl was studied on a soil surface under sunlight and UV light. Eight photoproducts were isolated and characterised by spectroscopic methods. Major photoproducts are formed by cleavage of the sulfonylurea bridge and minor products are formed via dechlorination, hydrolysis and cyclisation. The rates of photodegradation of chlorimuron-ethyl on different soils followed first-order rate kinetics, with half lives of 22·3 h, 9·4 h, 4·9 h (UV) and 20·7 days, 11·1 days and 11·1 days (sunlight) for alluvial, red and laterite soils, respectively. The differences in rates of photodegradation were dependent upon the soil pH. © 1997 SCI     

Kinetic Study of the Degradation of Ethiofencarb in Aqueous Solutions

A kinetic study of the hydrolysis of ethiofencarb (α-ethylthio-o-tolyl methylcarbamate) in pure water and in aqueous solutions at pH 2, 6, 9 and 12 and at three different temperatures (4, 20 and 50(±1)°C) has been carried out using a gas chromatographic nitrogen-phosphorus detection method. The values of the first-order rate constants (k) for the degradation reaction were calculated. The values for k were found to be dependent on pH and temperature. No acid hydrolysis was observed in any case. Complete degradation of ethiofencarb was observed at pH 12 at all three temperatures; it was practically instantaneous at room temperature. Ethiofencarb was also completely degraded at pH 9 at 20 and 50°C, while in pure water (pH 6) degradation took place at 50°C but not at 20°C. Ethiofencarb was not degraded in pure water at lower temperatures and, due to the reversible nature of the reaction, at equilibrium about 80% of the pesticide remained undegraded at room temperature. © 1997 SCI.     

Fate in the soil of an oil additive of plant origin

The methyl ester of oleic acid, a plant oil derivative, can be used as an additive oil for pesticides. We compared the biodegradability in soil of this oil with that of a mineral oil by means of laboratory experiments using lysimeters of 70 cm height x 20 cm diameter. The migration in soil of the oils and of the metabolites of the plant ester over 120 days was examined by gas chromatography and liquid chromatography. The plant oil and its metabolites were completely degraded within 60 days, whereas degradation of the mineral oil required 90 days. The molecules did not migrate far into the soil and therefore presented no risk of contaminating groundwater.     

Abiotic persistence of atrazine and simazine in water

Hydrolysis and photolysis experiments have been undertaken to investigate the abiotic persistence of atrazine and simazine in a variety of waters. Hydrolysis only occurs to a significant extent at pH values at the lower limit of those found in the natural aquatic environment (pH 4.0 or less). Photolysis was initiated by a wide range of wavelengths in waters at pH 4.0, but only by more energetic wavelengths of less than 300 nm at higher pH values (pH 6 to 8). Based on these data, the aquatic half-life of atrazine and simazine in well-lit acidic upland waters will be typically six days. In lowland rivers with higher pH (7 to 8.5), these triazines are likely to exhibit half-lives of months rather than days. In groundwaters, atrazine and simazine will have half-lives in the order of years, due to the exceedingly slow rate of hydrolysis. © 1999 Society of Chemical Industry     

Degradation Studies of the Non-lethal Bird Repellent,Methyl Anthranilate

Methyl anthranilate (MA), a food grade flavor and fragrance additive, has been reported to be an effective non-lethal bird repellent in a variety of situations. Despite the experimental success of MA, field studies have yielded widely differing levels of efficacy. Diminished efficacy in some field trials probably results from the failure of specific formulations to retain or protect the active ingredient under natural conditions. Therefore, a clearer understanding of the physical and chemical factors affecting the stability of MA is needed. We undertook a series of laboratory studies on hydrolysis, photolysis and microbial degradation of MA, the results of which could be useful in the development of appropriate formulation strategies and residue analyses. We found the n-octanol:water partition coefficient, (P) to be 84. MA is not subject to hydrolysis at 25°C in phosphate buffer media at pH 5·0, 7·0 and 9·0. MA slowly photodegrades under simulated UV ‘sunlight’. Forty-four percent of MA is lost after 432 h illuminance at 1·25 mW cm⁻², which is equivalent to approximately 1200 h natural sunlight (40°N, noontime, June). Kinetic data indicate that the initial step of photolysis, subsequent to excitation, is a second-order reaction with respect to MA. A major photodegradation product appeared in an amount of about 10% of the mass balance and was determined to be an oxidized trimer of MA. MA is primarily affected by aerobic microbial degradation. For a 12:12 h light:dark, under laboratory illumination, 12% of water-solubilized material can be lost in the first seven days. Losses were 30% and 42% at 16 and 27 days, respectively. Under conditions of optimal bacterial growth (warmth and darkness) loss of MA was 22% at nine days and 100% by 20 days. The susceptibility of MA to microbial degradation is promising for the prospects of developing formulated, environmentally safe, bird repellents.     

Photolysis and hydrolysis of rimsulfuron

The degradation in the liquid phase of rimsulfuron and its commercial 250 g kg⁻¹ WG formulation (Titus®) was investigated. Photolysis reactions were carried out at 25 °C by a high-pressure mercury arc (Hg-UV) and a solar simulator (Suntest), while the hydrolysis rate was determined by keeping aqueous buffered samples in the dark. The effects of solvent and water pH on reaction kinetics were studied, and the results compared to literature data. Photoreactions of the commercial product in organic solvents were faster than pure rimsulfuron. Under simulated sunlight in water, the half-life for the photolysis reaction ranged from one to nine days at pH 5 and 9, respectively. The hydrolysis rate was as high as the photolysis rate, but decreased on increasing water pH. The main metabolite identified in neutral and alkaline conditions as well as in acetonitrile was N-[(3-ethylsulfonyl)-2-pyridinyl]-4,6-dimethoxy-2-pyridinamine, while N-(4,6-dimethoxy-2-pyrimidinyl)-N-[(3-(ethylsulfonyl)-2-pyridinyl)]urea and minor metabolites prevailed in acidic conditions. © 1999 Society of Chemical Industry     

毒死蜱在灭菌和未灭菌土壤中的降解研究

研究了不同浓度毒死蜱在灭菌和未灭菌土壤中的降解规律。结果表明,不同浓度毒死蜱处理土壤,其降解速率不同。10 mg/kg处理未灭菌土壤时的半衰期为79.2 d,100 mg/kg和1 000 mg/kg处理土壤时,半衰期分别为91.8 d和278 d;而灭菌土壤中毒死蜱的半衰期分别为未灭菌土的3~4倍,1 000 mg/kg药液处理灭菌土时毒死蜱的半衰期长达672.3 d。