Aerobic soil metabolism of metsulfuron-methyl

A laboratory study was conducted to determine the degradation rates and identify major metabolites of the herbicide metsulfuron-methyl in sterile and non-sterile aerobic soils in the dark at 20°C. Both [phenyl-U-¹⁴C]- and [triazine-2-¹⁴C]metsulfuron-methyl were used. The soil was treated with [¹⁴C]metsulfuron-methyl (0.1 mg kg⁻¹) and incubated in flow-through systems for one year. The degradation rate constants, DT₅₀, and DT₉₀ were obtained based on the first-order and biphasic models. The DT₅₀ (time required for 50% of applied chemical to degrade) for metsulfuron-methyl, estimated using a biphasic model, was approximately 10 days (9–11 days, 95% confidence limits) in the non-sterile soil and 20 days (12–32 days, 95% confidence limits) in the sterile soil. One-year cumulative carbon dioxide accounted for approximately 48% and 23% of the applied radioactivity in the [phenyl-U-¹⁴C] and [triazine-2-¹⁴C]metsulfuron-methyl systems, respectively. Seven metabolites were identified by HPLC or LC/MS with synthetic standards. The degradation pathways included O-demethylation, cleavage of the sulfonylurea bridge, and triazine ring opening. The triazine ring-opened products were methyl 2-[[[[[[[(acetylamino)carbohyl]amino]carbonyl]amino] carbonyl]-amino]sulfonyl]benzoate in the sterile soil and methyl 2-[[[[[amino[(aminocarbonyl)imino]methyl] amino]carbonyl]amino]sulfonyl]benzoate in the non-sterile soil, indicating that different pathways were operable. © 1999 Society of Chemical Industry     

Degradation of primisulfuron-methyl and metsulfuron-methyl in soil

A newly developed chemical assay was used to determine the degradation in soil of two sulfonylurea herbicides, primisulfuron-methyl and metsulfuron-methyl, under both controlled and field conditions. The results from the chemical assay were compared with those from traditional bio-assays for determination of persistence in the field. Phytotoxic effects of these herbicides were not observed after 6 weeks following application to an acidic (pH 5.7) soil with high organic matter content (7.3% o.c). Half-lives of 13 to 29 days were measured for primisulfuron-methyl at different soil-water contents and temperatures while those for metsulfuron-methyl ranged from 8 to 36 days. The rate of degradation of metsulfuron-methyl was more sensitive to temperature than that of primisulfuron-methyl. Persistence in the field was shorter than expected considering the results from the controlled environment studies. However, determination of the persistence by both chemical assay and bioassay methods produced very similar results.     

The relative movement and persistence in soil of chlorsulfuron, metsulfuron-methyl and triasulfuron

Summary. Adsorption and degradation rates of triasulfuron in 8 different soils were negatively correlated with soil pH and were generally lower in subsoils than in soils from the plough layer. The half-life at 20°C varied from 33 days in a top soil at pH 5·8 to 120 days in a subsoil at pH 7·4. Adsorption distribution coefficients in these two soils were 0·55 and 0·19, respectively. Movement and persistence of residues of chlorsulfuron, triasulfuron and metsulfuron-methyl were compared in a field experiment prepared in spring 1987. Triasulfuron was less mobile in the soil than the other two compounds. Residues of all three herbicides were largely confined to the upper 40–50 cm soil 148 days after application. With an initial dose of 32 g ha⁻¹, residues in the surface soil layers were sufficient to affect growth of lettuce and sugar-beet sown approximately one year after application. Laboratory adsorption and degradation data were used with appropriate weather data in a computer model of herbicide transport in soil. The model gave good predictions of total soil residues during the first five months following application, and also predicted successfully the maximum depth of penetration of the herbicides into the soil during this period. However, more herbicide was retained close to the soil surface than was predicted by the model. The model predicted extensive movement of the herbicides in the soil during winter but did not predict that residues sufficient to affect crop growth could be present in the upper 15–20 cm soil after one year.     

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.     

Photolysis of chlorsulfuron and metsulfuron-methyl in methanol

Photolysis of chlorsulfuron and metsulfuron-methyl was studied in methanol under UV light. Their rates of primary photolysis followed first-order kinetics. The main photoproducts were identified as 2-methoxy-4-methyl-1,3,5-triazin-6-amine, 2-chloro-benzenesulfonamide and methyl 2-(aminosulfonyl)benzoate, which entailed the cleavage of the two N–C ureic bonds. Further photolysis of benzenesulfonamide derivatives involved oxidation of −NH₂, cyclisation with loss of CH₃OH, and scission of the C–S bond A trace of methyl o-mercaptobenzoate was also detected. The corresponding photolysis pathways of chlorsulfuron and metsulfuron-methyl were tentatively proposed. © 1999 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     

Kinetics and hydrolysis mechanism of chlorsulfuron and metsulfuron-methyl

In acidic media, hydrolysis of chlorsulfuron and metsulfuron-methyl occurs via two consecutive reactions which were followed by ultraviolet spectrophotometry. For these two reactions, the pseudo-first-order rate constants increase proportionally to the concentration of hydronium ion in the more acidic media and to the square of this concentration at higher pH values. A kinetic study by HPLC shows that the first reaction leads to the formation of 4-methoxy-6-methyl-1,3,5-triazin-2-amine and (o-chlorophenylsulfonyl) carbamic acid for chlorsulfuron or (o-methoxycarbonylphenylsulfonyl) carbamic acid for metsulfuronmethyl. The second reaction is the conversion of these sulfonylcarbamic acids to sulfonamides and carbon dioxide. The complete lack of saccharin and of o-sulfamoyl benzoic acid proves that the ester function of the methoxycarbonyl group is stable. The lack of general acid-base catalysis and a solvent deuterium isotope effect less than unity are consistent with a rate-determining cleavage of the protonated substrate. In the basic pH range (10–14) a single reaction occurs, the nucleophilic substitution of the methoxy group on the triazine by a hydroxide group.     

Synergistic joint action of MCPA ester and metsulfuron-methyl

MCPA is antagonistic to a range of herbicides but there is limited research on its compatibility with other broad-leaved weed herbicides. In this study we assessed the joint action of MCPA ester and metsulfuron-methyl on Brassica napus L. using the additive dose model (ADM). The fresh weight responses for selected ratios of the mixture were plotted on the ADM and compared to the predicted mixture response at three assessment levels - 50, 75 and 90% control. The mixture demonstrated increasing synergism as the response level increased from 50 to 90%. This result for MCPA ester is in marked contrast to that of the MCPA amine formulation, which was shown in previous studies to be antagonistic towards sulfonylurea herbicides. Formulation is the major deciding factor in determining the compatability of phenoxy herbicides with other herbicides.     

Determination of the sulfonylurea herbicides chlorsulfuron and metsulfuron-methyl in soil,water and plant material by gas chromatography of their pentafluorobenzyl derivatives

The measurement of the sulfonyl urea herbicides, chlorsulfuron and metsulfuron-methyl as pentafluorobenzyl derivatives has been investigated and the kinetics of reaction optimised. The reaction product was identified by mass spectroscopy as N,N-bis(pentafluorobenzyl)-2-chlorobenzenesulfonamide. Amounts of herbicide derivative as low as 0·1 pg per injection can be detected. Suitable conditions for both packed and capillary chromatography are given. Application of the method to residue determination is discussed and the method is shown to be suitable for residues in soil and water but less so for plant material.     

Response of Brassica napus in tissue culture to metsulfuron-methyl and chlorsulfuron

A herbicide bioassay based on tissue cultures of Brassica napus L. was evaluated with selected sulfonylurea herbicides. Data were analysed by fitting the results to a log-logistic dose–response model. Within an experiment, the non-linear regression models were fitted simultaneously to the individual dose–response curves. The results obtained showed good response to even low concentrations of herbicide, with detection limits in the range 0.008–0.69 nmol L^?1 for chlorsulfuron and 0.02–0.13 nmol L^?1 for metsulfuron. The reproducibility of the assays, on the basis of coefficient of variation of the ED₅₀ values, was found to be 44% for chlorsulfuron and 48% for metsulfuron measurements. Assay of herbicide dissolved in aqueous soil extract showed significant interference from this matrix on the response, requiring a five times dilution of the extract to overcome this matrix effect.     

Adsorption and degradation of chlorsulfuron and metsulfuron-methyl in soils from different depths

Adsorption and degradation rates of chlorsulfuron and metsulfuron-methyl were measured in soil taken from depths of 0–20, 20–40 and 40–60 cm at eight sites. Adsorption of both herbicides was negatively correlated with soil pH, and positively correlated with soil organic matter content. When two soils with very high organic matter were excluded from the calculations, the correlations with organic matter content were no longer statistically significant but those with soil pH were affected only slightly. Degradation rates of both herbicides generally decreased with increasing depth in the soil and were positively correlated with microbial biomass and negatively correlated with soil pH. The possible significance of the results to persistence of the herbicides in the field is discussed.     

云南元谋干热河谷区旱坡地不同生态农业模式土壤水分差异性分析

对干热河谷旱坡地Ⅰ(罗望子+木豆),Ⅱ(罗望子+木豆+柱花草),Ⅲ(罗望子+象草),Ⅳ(罗望子+自然草被)等4种复合生态农业模式0～40 cm土层水分进行监测和分析的结果表明:4种模式的土壤含水量主要受自然降水的影响,雨季和旱季差异显著;不同模式对土壤含水量的影响存在差异,其中,模式Ⅱ和模式Ⅳ有较强的保水持水能力;在雨水补给不足时,模式Ⅲ对土壤水分的利用效率最高,模式Ⅳ最低;土壤水分季节波动模式Ⅳ最小,模式Ⅲ波动最剧烈;雨季,4种模式具良好的层间补水能力,旱季,模式Ⅰ和Ⅱ土层间补水能力最强.总体上看,4种模式对干热河谷旱坡地的土壤水分均有一定的保持能力,但模式Ⅱ的保水持水能力最强,综合效益最好,更利于干热河谷旱坡地生态农业的可持续发展.     

Variability of retention process of isoxaflutole and its diketonitrile metabolite in soil under conventional and conservation tillage

BACKGROUND: Sorption largely controls pesticide fate in soils because it influences its availability for biodegradation or transport in the soil water. In this study, variability of sorption and desorption of isoxaflutole (IFT) and its active metabolite diketonitrile (DKN) was investigated under conventional and conservation tillage. RESULTS: According to soil samples, IFT K_D values ranged from 1.4 to 3.2 L kg^?1 and DKN K_D values ranged from 0.02 to 0.17 L kg^?1. Positive correlations were found between organic carbon content and IFT and DKN sorption. IFT and DKN sorption was higher under conservation than under conventional tillage owing to higher organic carbon content. Under conservation tillage, measurements on maize and oat residues collected from the soil surface showed a greater sorption of IFT on plant residues than on soil samples, with the highest sorbed quantities measured on maize residues (K_D ≈ 45 L kg^?1). Desorption of IFT was hysteretic, and, after five consecutive desorptions, between 72 and 89% of the sorbed IFT was desorbed from soil samples. For maize residues, desorption was weak (<50% of the sorbed IFT), but, after two complementary desorptions allowing for IFT hydrolysis, DKN was released from maize residues. CONCLUSION: Owing to an increase in organic carbon in topsoil layers, sorption of IFT and DKN was enhanced under conservation tillage. Greater sorption capacities under conservation tillage could help in decreasing DKN leaching to groundwater. Copyright © 2012 Society of Chemical Industry     

Modelling approaches to compare sorption and degradation of metsulfuron-methyl in laboratory micro-lysimeter and batch experiments

Results of laboratory batch studies often differ from those of outdoor lysimeter or field plot experiments--with respect to degradation as well as sorption. Laboratory micro-lysimeters are a useful device for closing the gap between laboratory and field by both including relevant transport processes in undisturbed soil columns and allowing controlled boundary conditions. In this study, sorption and degradation of the herbicide metsulfuron-methyl in a loamy silt soil were investigated by applying inverse modelling techniques to data sets from different experimental approaches under laboratory conditions at a temperature of 10 degrees C: first, batch-degradation studies and, second, column experiments with undisturbed soil cores (28 cm length x 21 cm diameter). The column experiments included leachate and soil profile analysis at two different run times. A sequential extraction method was applied in both study parts in order to determine different binding states of the test item within the soil. Data were modelled using ModelMaker and Hydrus-1D/2D. Metsulfuron-methyl half-life in the batch-experiments (t1/2 = 66 days) was shown to be about four times higher than in the micro-lysimeter studies (t1/2 about 17 days). Kinetic sorption was found to be a significant process both in batch and column experiments. Applying the one-rate-two-site kinetic sorption model to the sequential extraction data, it was possible to associate the stronger bonded fraction of metsulfuron-methyl with its kinetically sorbed fraction in the model. Although the columns exhibited strong significance of multi-domain flow (soil heterogeneity), the comparison between bromide and metsulfuron-methyl leaching and profile data showed clear evidence for kinetic sorption effects. The use of soil profile data had significant impact on parameter estimates concerning sorption and degradation. The simulated leaching of metsulfuron-methyl as it resulted from parameter estimation was shown to decrease when soil profile data were considered in the parameter estimation procedure. Moreover, it was shown that the significance of kinetic sorption can only be demonstrated by the additional use of soil profile data in parameter estimation. Thus, the exclusive use of efflux data from leaching experiments at any scale can lead to fundamental misunderstandings of the underlying processes.     

Quality control in bioassays used in screening for plant viruses

Test plants are often used for broad screening for plant viruses. Mechanical inoculation of a series of test plants enables generic detection of mechanically transmitted viruses in only 1 assay. Moreover, such an assay is suitable for known as well as unknown viruses and their variants. However, in comparison to serological and molecular methods, quality control in bioassays is almost never addressed. The system of positive and negative controls, blind samples and proficiency tests is applicable, provided that a broader interpretation of positive and negative controls is used. For validation, performance criteria can only be determined for individual viruses. However, results can often be extrapolated. Sensitivity is addressed by dilution and expressed as a relative value. Specificity has to consider the virus species and the plant species to be tested. Selectivity mostly depends on the plant species tested, because some hosts contain components that inhibit transmission. Repeatability and reproducibility, determined for a limited number of samples, appears high, as also substantiated by the authors' experience. This paper details how EPPO Standards on quality control were implemented by the National Plant Protection Organization of the Netherlands (NPPO‐NL). This information will be of use for other laboratories that wish to introduce quality control in bioassays for virus testing.     

Comparison of chlorophyll fluorescence and whole-plant bioassays of isoproturon

Summary The response to aqueous solutions of isoproturon was examined on intact plants of Matricaria perforata , Apera spica-venti and Sinapis alba in greenhouse tests, comparing visual estimates of shoot phytotoxicity at 30 d after application (DAA) with measurements of fast chlorophyll fluorescence induction at 10 DAA on leaves of the same treated plants. The sensitivity was greatest from pre-emergence application to intact plants of M. perforata and A. spica-venti , whereas post-emergence sprays were relatively more active on S. alba . The use of fluorescence induction was investigated further in Petri-dish experiments on excised M. perforata leaf segments. The Petri-dish bioassay enabled detection of isoproturon at concentrations above 9 × 10⁻⁷ M within 96 h after herbicide exposure. The potential for using chlorophyll fluorescence assays for the determination of isoproturon content in soil extracts is discussed.     

A comparison of herbicide bioassays in cell cultures and whole plants

Dose-response curves were established for the herbicides chlorsulfuron, metsulfuron-methyl, ethametsulfuron-methyl, imazamethabenz and glyphosate. The plant species were Daucus carota L. and Triticum aestivum L. in cell culture assays, and D. carota L., T. aestivum L., Stellariamedia L., Chenopodium album L. and Avena sativa L., in whole plant assays. Potency ranking of herbicides were similar in the two assays. Low doses of herbicide stimulated growth in both assays, but stimulation was greater in cell cultures. Image processing measured growth in cell cultures and was more sensitive to small differences in responses than manual counts of cell colonies. Dose-response curves had the same shape in both assays, but cell cultures were more sensitive than were whole plants. Comparaison d'essais biologiques d'herbicides effectués sur cultures de cellules et sur plantes entiéres Des courbes dose-effet ont étéétablies pour les herbicides metsulfuron-methyl, ethametsulfuron-methyl, imazamethabenz et glyphosate. Les espèces végétales étaient Daucus carota L. et Triticum aestivum L. en cultures de cellules, et D. carota L., T. aestivum L., Stellaria media L., Chenopodium album L. et Avena sativa L. dans les essais sur plantes entières. Le classement d'efficacité des herbicides était le meme dans les deux types d'essais. Les faibles doses d'herbicides stimulaient la croissance dans les deux essais mais la stimulation était plus importante en cultures de cellules. La mesure par analyse d'image de la croissance des cultures de cellules était plus sensible à de faibles différences que le comptage manuel des colonies. Les courbes dose-effet avaient la meme forme dans les deux essais mais les cultures de cellules étaient plus sensibles que les plantes entières. Vergleich von Herbizid-Biotests mit Zellkulturen und ganzen Pflanzen Fur die Herbizide Chlorsulfuron, Metsulfuronmethyl, Ethametsulfuron-methyl, Imazamethabenz und Glyphosat wurden Dosis/Wirkungs-Kurven erstellt. Die in den Zellkulturen verwendeten Pflanzenarten waren Daucus carota L. und Triticum aestivum L., und bei den Tests mit ganzen Pflanzen D. carota L., T. aestivum L., Stellaria media L., Chenopodium album L. und Avena sativa L. Die Reihenfolge der Herbizide hinsichtlich ihrer Wirksankeit war in beiden Tests ahnlich. Niedrige Herbiziddosen steigerten in beiden Tests das Wachstum, in den Zellkulturen jedoch deutlicher. Bei den Zellkulturen war die Bildanalyse-Messung fur das Erkennen geringer Unterschiede empfindlicher als das Auszahlen der Zellkolonien. Die Dosis/Wirkungs-Kurven hatten fur beide Testmethoden den gleichen Verlauf, aber auch hier erwiesen sich die Zellkulturen empfindlicher als die ganzen Pflanzen.