Availability and biodegradation of metribuzin in alluvial soils as affected by temperature and soil properties

Herbicide degradation in soils is highly temperature‐dependent. Laboratory incubations and field experiments are usually conducted with soils from the temperate climatic zone. Few data are available for cold conditions and the validation of approaches to correct the degradation rate at low temperatures representative of Nordic environments is scarce. Laboratory incubation studies were conducted at 5, 15 and 28°C to compare the influence of temperature on the dissipation of metribuzin in silt/sandy loam soils in southern and northern Norway and in a sandy loam soil under temperate climate in France. Using ¹⁴C‐labelled metribuzin, sorption and biodegradation were studied over an incubation period of 49 days. Metribuzin mineralisation and total soil organic carbon mineralisation rates showed a positive temperature response in all soils. Metribuzin mineralisation was low, but metabolites were formed and their abundance depended on temperature conditions. The rate of dissipation of ¹⁴C‐metribuzin from soil pore water was strongly dependent on temperature. In Nordic soils with low organic content, metribuzin sorption is rather weak and biodegradation is the most important process controlling its mobility and persistence.     

Biocompost from sugar distillery effluent: effect on metribuzin degradation, sorption and mobility

BACKGROUND: Metribuzin (4-amino-6-tert-butyl-4,5-dihydro-3-methylthio-1,2,4-triazin-5-one) is weakly sorbed in soils and therefore leaches easily to lower soil profiles and results in loss of activity. Soil amendments play an important role in the management of runoff and leaching losses of pesticides from agricultural fields. Therefore, the effect of biocompost from sugarcane distillery effluent on metribuzin degradation and mobility was studied in a sandy loam soil.RESULTS: Metribuzin was more persistent in biocompost-unamended (T-0) flooded soil (t(1/2) - 41.2 days) than in non-flooded (t(1/2) - 33.4 days) soil. Biocompost application at the rate of 2.5 and 5.0% (T-1 and T-2) in non-flooded soils increased metribuzin persistence, but no significant effect was observed on persistence in flooded soils. Freundlich adsorption constants (K(f)) for treatments T-0, T-1 and T-2 were 0.43, 0.64 and 1.13 respectively, suggesting that biocompost application caused increased metribuzin sorption. Leaching studies in packed soil columns indicated that biocompost application affected both metribuzin breakthrough time and maximum concentration in the leachate. Leaching losses of metribuzin were drastically reduced from 93% in control soil (T-0) to 65% (T-1) and 31% (T-2) in biocompost-amended soils.CONCLUSION: Biocompost from sugarcane distillery effluent can be used effectively to reduce downward mobility of metribuzin in low-organic-matter sandy loam soil. Copyright (c) 2008 Society of Chemical Industry.     

Modeling hydrology, metribuzin degradation and metribuzin transport in macroporous tilled and no-till silt loam soil using RZWQM

Due to the complex nature of pesticide transport, process-based models can be difficult to use. For example, pesticide transport can be effected by macropore flow, and can be further complicated by sorption, desorption and degradation occurring at different rates in different soil compartments. We have used the Root Zone Water Quality Model (RZWQM) to investigate these phenomena with field data that included two management conditions (till and no-till) and metribuzin concentrations in percolate, runoff and soil. Metribuzin degradation and transport were simulated using three pesticide sorption models available in RZWQM: (a) instantaneous equilibrium-only (EO); (b) equilibrium-kinetic (EK, includes sites with slow desorption and no degradation); (c) equilibrium-bound (EB, includes irreversibly bound sites with relatively slow degradation). Site-specific RZWQM input included water retention curves from four soil depths, saturated hydraulic conductivity from four soil depths and the metribuzin partition coefficient. The calibrated parameters were macropore radius, surface crust saturated hydraulic conductivity, kinetic parameters, irreversible binding parameters and metribuzin half-life. The results indicate that (1) simulated metribuzin persistence was more accurate using the EK (root mean square error, RMSE = 0.03 kg ha(-1)) and EB (RMSE = 0.03 kg ha(-1)) sorption models compared to the EO (RMSE = 0.08 kg ha(-1)) model because of slowing metribuzin degradation rate with time and (2) simulating macropore flow resulted in prediction of metribuzin transport in percolate over the simulation period within a factor of two of that observed using all three pesticide sorption models. Moreover, little difference in simulated daily transport was observed between the three pesticide sorption models, except that the EB model substantially under-predicted metribuzin transport in runoff and percolate >30 days after application when transported concentrations were relatively low. This suggests that when macropore flow and hydrology are accurately simulated, metribuzin transport in the field may be adequately simulated using a relatively simple, equilibrium-only pesticide model.     

Desorption of diuron and isoproturon from undispersed clay loam soil

Studies were conducted to investigate the desorption of diuron and isoproturon adsorbed on undispersed clay loam soil, and the influence of residence time in soil on desorption. The soil was treated at 0·6 or 3 mg kg^-1, at 70% moisture content and in the presence of sodium azide to prevent degradation. Measurement of herbicide concentrations in soil solution sampled by means of glass microfibre filters showed that adsorption mainly occurred for one day but long-term sorption proceeded for >two weeks. After a one-day or three-week residence time, soil solution was partly replaced (28%). Measurement of concentrations in solution showed rapid desorption, with equilibria being achieved within 1 h (diuron) or a few hours (isoproturon). After 16 successive desorptions done at 30-min or 12-h intervals, equilibration times tended to be longer. For the short residence time, desorption and long-term sorption could occur simultaneously and equilibration might be faster. Residence time had no significant effect on desorption kinetics nor on the small hysteresis observed for diuron. The aging effect, involving long-term sorption only, decreased the proportion of diuron removed from the soil by successive desorptions but, for isoproturon, desorption frequency and desorption kinetics were more important. © 1997 SCI     

Field degradation of the herbicide metribuzin and its degradation products in a Manitoba sandy loam soil*

The degradation of the herbicide metribuzin (4-amino-6 r-butyl-3-(methylthio)-1, 2, 4-tnazin-5-(4H)one) applied at 1 and 2 kg/ha at times equivalent to pre-emergence (12 June), post-emergence (5 July), and pre-harvest (15 August), has been investigated in Almasippi very line sandy loam at Carman, Manitoba. Gas-liquid chromatographic analytical results showed that metribuzin degraded during the growing season, and that residue levels immediately prior to freeze-up (25 October) were in general less than 10% of applied metribuzin independent of application date, and were largely unchanged the following spring. The metabolites and photoproduct of metribuzin were present in maximum amounts near 13 July for the first two treatment dates, a time closely following maximum soil temperature readings, and these compounds in turn degraded almost completely by freeze-up. The following spring only very low levels were detected. Under the conditions described, metribuzin and its degradation products degraded to low levels and should not provide a carryover problem the next growing season.     

psbA Mutation (valine219 to isoleucine) in Poa annua resistant to metribuzin and diuron

The herbicide‐binding region of the chloroplast psbA gene from a total of 20 biotypes of Poa annua L resistant and susceptible to metribuzin and diuron was selectively amplified using PCR. Sequence analysis of the fragment from six herbicide‐resistant biotypes of P annua exhibited a substitution from valine to isoleucine at position 219 of the D1 protein encoded by the psbA gene. This is the same mutation as reported for Chlamydomonas and Synechococcus through site‐directed mutagenesis and in cell cultures of Chenopodium rubrum L. To our knowledge this is the first report of a higher plant exhibiting resistance in the field to photosystem II inhibitors due to a psbA mutation other than at position 264. The existence of additional biotypes of P annua resistant to diuron or metribuzin but lacking mutation in the herbicide‐binding region indicates that resistance to these herbicides can also be attained by other mechanisms. © 2000 Society of Chemical Industry     

Inheritance of tolerance to metribuzin in durum wheat

The inheritance of tolerance to the herbicide metribuzin was studied in two durum wheat cultivars, one of which, 'Anton', is resistant and one, 'Nita', susceptible. Parents, F₁, F₂ and F₃ of the crosses 'Anton' × 'Nita' and 'Nita' × 'Anton' were tested for herbicide response. The character evaluated was the increase in weight of plants treated with the herbicide. As there were no significant differences between progenies of reciprocal crosses, cytoplasm was not involved in tolerance. Tolerance was semi-dominant with means values of F₁, F₂ and F₃ progenies in the range of mid-parent. The heritability of this trait estimated by regression of the average of progeny F₃ in their parent F₂ had a value of 0.23 ± 0.063 and a value of 0.52 ± 0.150 estimated by the relation V _G/ V _P for full-sib F₂ families.     

Gross nitrogen transformations and N_2O emission sources in sandy loam and silt loam soils

The soil type is a key factor influencing N(nitrogen) cycling in soil; however, gross N transformations and N_2O emission sources are still poorly understood. In this study, a laboratory ~(15)N tracing experiment was carried out at 60% WHC(water holding capacity) and 25℃ to evaluate the gross N transformation rates and N_2O emission pathways in sandy loam and silt loam soils in a semi-arid region of Heilongjiang Province, China. The results showed that the gross rates of N mineralization, immobilization, and nitrification were 3.60, 1.90, and 5.63 mg N/(kg·d) in silt loam soil, respectively, which were 3.62, 4.26, and 3.13 times those in sandy loam soil, respectively. The ratios of the gross nitrification rate to the ammonium immobilization rate(n/ia) in sandy loam soil and silt loam soil were all higher than 1.00, whereas the n/ia in sandy loam soil(4.36) was significantly higher than that in silt loam soil(3.08). This result indicated that the ability of sandy loam soil to release and conserve the available N was relatively poor in comparison with silt loam soil, and the relatively strong nitrification rate compared to the immobilization rate may lead to N loss through NO_3~– leaching. Under aerobic conditions, both nitrification and denitrification made contributions to N_2O emissions. Nitrification was the dominant pathway leading to N_2O production in soils and was responsible for 82.0% of the total emitted N_2O in sandy loam soil, which was significantly higher than that in silt loam soil(71.7%). However, the average contribution of denitrification to total N_2O production in sandy loam soil was 17.9%, which was significantly lower than that in silt loam soil(28.3%). These results are valuable for developing reasonable fertilization management and proposing effective greenhouse gas mitigation strategies in different soil types in semiarid regions.     

Effect of recent cropping history and herbicide use on the degradation rates of isoproturon in soils

Five soil samples were taken from each of five fields with different crop management histories. Three of the fields were in an arable rotation, the fourth field was temporary grassland, and the final field was under permanent grass. Of the three arable fields, two had been cropped with winter wheat in three of the preceding 6 years, and the third had last been cropped with winter wheat once only, 6 years previously. With one exception, the winter wheat had been sprayed with the herbicide isoproturon. The rate of isoproturon degradation in laboratory incubations was strongly related to the previous management practices. In the five soils from the field that had been treated most regularly with isoproturon in recent years, <2.5% of the initial dose remained after 14 days, indicating considerable enhancement of degradation. In the soils from the field with two applications of the herbicide in the past 6 years, residues after 27 days varied from 5% to 37% of the amount applied. In soils from the other three sites, residue levels were less variable, and were inversely related to microbial biomass. In studies with selected soils from the field that had received three applications of isoproturon in the previous 6 years, kinetics of degradation were not first‐order but were indicative of microbial adaptation, and the average time to 50% loss of the herbicide (DT₅₀) was 7.5 days. In selected soils from the field that had received just one application of isoproturon, degradation followed first‐order kinetics, indicative of cometabolism. Pre‐incubation of isoproturon in soil from the five fields led to significant enhancement of degradation only in the samples from the two fields that had a recent history of isoproturon application.     

Behaviour of metamitron and hydroxy-chlorothalonil in low-humic sandy soils

The behaviour of the herbicide metamitron and of the main transformation product, hydroxy-chlorothalonil (HTI), of the fungicide chlorothalonil was studied to assess the risk of leaching from low-humic sandy soil. The adsorption of metamitron corresponded to a K_om value of about 60 dm³ kg⁻¹ (moderate adsorption). The half-life of metamitron in soil at 15 °C was only three days, presumably due to adaptation of the micro-organisms. In the autumn, the residue of metamitron in the soil profiles corresponded to less than 1% of the cumulative dosage. The half-life of chlorothalonil at 15 °C was about 12 days and about 45% of it was transformed to HTI. The adsorption of HTI to the soils corresponded to a K_om value of 260 dm³ kg⁻¹. The incubation study (15 °C) showed the transformation of HTI in the soils to be very slow. The amounts of HTI remaining in the soil profiles in the autumn corresponded to 4 and 16% of the cumulative dosage of chlorothalonil. In winter, the HTI residue decreased by 40% relative to the autumn level. Occasionally, HTI could be detected in the upper ground-water level (at a depth of about 1 m), at an average concentration of 0.1 to 0.2 µg dm⁻³. © 1999 Society of Chemical Industry     

微生物降解二苯醚类除草剂的研究进展

本文概述了降解二苯醚类除草剂的微生物种类、降解机理及影响微生物降解二苯醚类除草剂的因素,指出利用微生物修复土壤中二苯醚类除草剂残留是一个有效的手段; 同时指出二苯醚类除草剂微生物降解过程中起关键作用的酶及基因有待于进一步研究。     

Sorption and leaching potential of herbicides on Brazilian soils

Sorption of the herbicides alachlor, atrazine, dicamba, hexazinone, imazethapyr, metsulfuron-methyl, nicosulfuron, simazine and sulfometuron-methyl was characterized on six Brazilian soils, using the batch equilibration method. In general, weak acid herbicides (dicamba, imazethapyr, metsulfuron-methyl, nicosulfuron and sulfometuron-methyl) were the least sorbed, whereas weak bases such as triazines and nonionic herbicides (alachlor) were the most sorbed. The Kd values found showed a significant correlation with soil organic carbon content (OC) for all herbicides except imazethapyr and nicosulfuron. Koc values showed a smaller variation among soils than Kd . To estimate the leaching potential, Koc and the ground-water ubiquity score (GUS) were used to calculate half-lives ( t_1/2 ) that would rank these herbicides as leachers or non-leachers. Comparison of calculated values to published values for t_1/2 demonstrated that sulfonylureas and hexazinone are leachers in all soils, alachlor is transitional, and atrazine, simazine and dicamba are leachers or transitional, depending on soil type. Results discussed in this paper provide background to prioritize herbicides or chemical groups that should be evaluated in field conditions with regard to their leaching potential to ground-water in tropical soils.     

咪唑啉酮类除草剂的应用及降解

咪唑啉酮类除草剂虽具有高效广谱的特点,但有较长的残留活性,长期使用会造成作物药害,并且会制约正常的作物轮作。因此,如何解决其残留问题已成为目前的重要课题。本文介绍了咪唑啉酮类除草剂的种类和特性,阐述了此类除草剂在杂草体内的作用方式、代谢机制、应用情况及其在土壤中的降解途径,并对该类除草剂的应用与降解研究进行了展望。     

Sorption of atrazine and dicamba in Delaware coastal plain soils: a comparison of soil thin layer and batch equilibrium results

The mobility and retention of atrazine and dicamba in six Atlantic Coastal Plain soils were estimated by soil thin-layer chromatography (soil-TLC). The soils studied were representative of the major agricultural regions in Delaware and were sampled, by horizon, to the water table. Four horizons from each profile were leached simultaneously with distilled water on one soil-TLC plate. Two values were obtained from each plate: the ratio of the distance traveled by the herbicide center of mass over that traveled by the solvent front (R_m), and a sorption distribution coefficient (K_d). The R_m values ranged from 0·06 to 0·94 for atrazine and from 0·80 to 0·94 for dicamba. Herbicide mobility was found to be greatest in coarse-textured soil horizons that contained low levels of organic matter, clay, and Fe and Al oxides. Correlation analysis indicated that effective cation exchange capacity, exchangeable acidity, exchangeable aluminum, and clay were useful predictive variables or both atrazine mobility and sorption. Organic matter was not useful for predicting soil-TLC derived sorption estimates; however, it was correlated to K_d-batch estimates. Distribution coefficients calculated from soil-TLC data were found to be in general agreement with K_d values obtained for the same soils by batch equilibrium techniques. The average K_d-soil-TLC values for atrazine and dicamba were 2·09(±2·24) and 0·03(±0·02), respectively. The ratio of the batch K_d to the soil-TLC K_d ranged from 0·1 to 19 (x̄=1·6, SD=3·8) for atrazine and from 2·9 to 38 (x̄=12·6, SD=8·7) for dicamba. Thus, although for some horizons agreement between the two methods was good, for other horizons significant discrepancies existed. It is suggested that the soil-TLC gives results under non-equilibrium conditions, whereas the batch procedure is, by definition, at quasi-equilibrium. These fundamental differences may account for the observed differences between the two methods. It is also suggested that, due to this difference, the soil-TLC procedure can provide additional information relevant to herbicide partitioning in the field environment that is not provided by traditional batch equilibrium techniques. © 1998 Society of Chemical Industry     

Rate of transformation of atrazine and bentazone in water-saturated sandy subsoils

When pesticides leach through the soil to the upper groundwater zone, it is important to know whether further transformation occurs before the pumping wells for drinking water are reached. Atrazine and bentazone were incubated (at 10°C) in five water-saturated sandy subsoils (collected at depths between 1·5 and 3·5 m), simulating the conditions in the field. In three subsoils with comparatively low pH and intermediate to high redox potential, atrazine was transformed gradually, to leave 1·9%, 6·2% and 17·5% of the dose after about five years. In one of these subsoils, hydroxy-atrazine was detected; the amount corresponded to half of the dose of atrazine. In one anaerobic subsoil with high pH, the transformation of atrazine was comparatively fast (half-life about 0·15 year). Another anaerobic subsoil, with similar pH and a somewhat higher redox potential, however, showed hardly any transformation. Sterilization of the first anaerobic subsoil had no effect on the rate of transformation. In the course of about five years, bentazone in the first three subsoils was transformed gradually to leave <0·25%, 11% and 25% of the dose. Bentazone transformation in the two subsoils with high pH and low redox potential was very slow, but the presence of oxygen in one of these subsoils speeded up the transformation. © 1998 SCI     

鱼藤酮在3种土壤中的吸附-解吸附特性

为了综合评价鱼藤酮在土壤环境中的吸附-解吸附特性,采用批量平衡法,系统研究了鱼藤酮在砂壤土、黏壤土及壤土3种农业土壤中的吸附-解吸附行为。结果表明,鱼藤酮在3种土壤中的吸附-解吸附行为符合Freundlich模型 (R2≥0.946 8),吸附常数 (K_f-ads) 在1.52~11.39之间,吸附能力为:黏壤土 > 砂壤土 > 壤土;而解吸附常数 (K_f-des) 在1.02~4.55之间,解吸附强弱次序为壤土 > 黏壤土 > 砂壤土。鱼藤酮在砂壤土、黏壤土和壤土3种土壤中有机碳吸附常数 (K_OC) 分别为982、101 7和219,而滞后系数 (H) 分别为0.687 3、0.556 9和0.892 3,表明鱼藤酮在黏壤土及砂壤土中移动性较弱,有正迟滞作用,而在壤土中移动性较强,无迟滞作用。该研究将对鱼藤酮的环境风险评估具有一定的理论指导意义。     

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.     

The phytotoxicity of various herbicides in two sandy loam soils and the effect of liming

The phytotoxicity of five soil-acting herbicides was investigated in two sandy loam soils and that of a further five herbicides in one of these soils. The effect of liming on phytotoxicity was also examined. Metoxuron, fenuron, metribuzin and fluometuron were more active in Boddington Barn soil than in Bledington soil. Prometryne was similar in effect in both soils. Liming significantly increased the effect of metoxuron in Boddington Barn soil and metoxuron, atraton, difenoxuron and metribuzin in Bledington soil. Monolinuron was less toxic in limed Bledington soil. Reasons for these differences have not been determined.