Enhanced degradation of some soil-applied herbicides

In a field experiment involving repeated herbicide application, persistence of simazine was not affected by up to three previous doses of the herbicide. With propyzamide, there was a trend to more rapid rates of degradation with increasing number of previous treatments. Persistence of linuron and alachlor was affected only slightly by prior applications. In a laboratory incubation with soil from the field that had received four doses of the appropriate herbicide over a 12–month period, there was again no effect from simazine pretreatments on rates of loss. However, propyzamide, linuron and alachlor all degraded more rapidly in the previously treated than in similar untreated soil samples. Propyzamide, linuron, alachlor and napropamide degradation rates were all enhanced by a single pretreatment of soil in laboratory incubations, whereas degradation rates of isoproturon, metazachlor, atrazine and simazine were the same in pretreated and control soil samples.     

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.     

Spatial variability in 14C-herbicide degradation in surface and subsurface soils

The spatial variability in mineralization of atrazine, isoproturon and metamitron in soil and subsoil samples taken from a 135-ha catchment in north France was studied. Fifty-one samples from the top layer were taken to represent exhaustively the 31 agricultural fields and 21 soil types of the catchment. Sixteen additional samples were collected between depths of 0.7 and 10 m to represent the major geological materials encountered in the vadose zone of the catchment. All these samples were incubated with 14C-labelled atrazine under laboratory conditions at 28 degrees C. Fourteen selected surface samples which exhibited distinctly different behaviour for atrazine dissipation (including sorption and mineralization) were incubated with 14C-isoproturon and 14C-metamitron. Overall soil microbial activity and specific herbicide degradation activities were monitored during the incubations through measurements of total carbon dioxide and 14C-carbon dioxide respectively. At the end of the incubations, extractable and non-extractable (bound) residues remaining in soils were measured. Variability of herbicide dissipation half-life in soil surface samples was lower for atrazine and metamitron (CV < 12%) than for isoproturon (CV = 46%). The main contributor to the isoproturon dissipation variability was the variability of the extractable residues. For the other herbicides, spatial variability was mainly related to the variability of their mineralization. In all cases, herbicide mineralization half-lives showed higher variability than those of dissipation. Sorption or physicochemical soil properties could not explain atrazine and isoproturon degradation, whose main factors were probably directly related to the dynamics of the specific microbial degradation activity. In contrast, variability of metamitron degradation was significantly correlated to sorption coefficient (K(d)) through correlation with the sorptive soil components, organic matter and clay. Herbicide degradation decreased with depth as did the overall microbial activity. Atrazine mineralization activity was found down to a depth of 2.5 m; beyond that, it was negligible.     

Accelerated degradation of thiocarbamate herbicides in Israeli soils following repeated use of vernolate

Accelerated degradation of vernolate, EPTC and butylate but not of cycloate was detected in soils from three locations in Israel which were treated annually with vernolate. Repeated application of EPTC to soils with and without a history of vernolate application, under laboratory conditions, resulted in a progressive increase in its rate of dissipation with each application. Accelerated degradation of EPTC was also rapidly induced by mixing small amounts (5%) of soil with a history of vernolate treatment with soil that had never received vernolate. Liberation of ¹⁴CO₂ from [¹⁴C]EPTC was more rapid in vernolate-treated soils than in untreated soils, indicating a development of microbial populations in soil capable of rapidly degrading the EPTC. Degradation of [¹⁴C]EPTC was faster in soil previously cropped with maize than in non-cropped soil, but slower in soils cropped with cotton or peanuts.     

Persistence and management of enhanced carbetamide biodegradation in soil

The extent of enhanced degradation of the herbicide carbetamide declined over time after herbicide application was discontinued. The kinetics of carbetamide degradation were determined in the same soil for three consecutive years (1994–96) after single annual applications from 1989 to 1992. The DT₅₀ of carbetamide increased from 5.4 d in 1994 to 10.2 d in 1996. However, this was still less than the DT₅₀ in previously untreated soil (23–44 d). A most probable number (MPN) assay demonstrated a link between carbetamide degradation rate and the numbers of micro-organisms capable of carbetamide mineralization. Degradation of six other herbicides was assayed in the carbetamide-pretreated and the previously untreated soils. Propham was the only herbicide which degraded more rapidly in the soil with a history of carbetamide application. Rapid degradation of chlorpropham, a herbicide structurally similar to carbetamide and propham, and propyzamide, a herbicide with similar mode of action and weed control spectrum, was not observed. The results suggest that enhanced biodegradation of carbetamide can be managed by less frequent carbetamide application as a part of a herbicide rotation involving compounds which are structurally dissimilar.     

Retention and degradation of metribuzin in sandy loam and clay soils of Lebanon

The retention and degradation of metribuzin herbicide were studied under two environmental conditions. Field studies were carried out on two soils, a sandy loam soil (soil A) and a clay soil (soil B). Metribuzin was applied with a jet sprayer at 1060 g a.i. ha^?1 and 1960 g a.i. ha^?1 on soils A and B respectively. Reconstituted soil columns were used to study the herbicide movement and metabolism in the two soils. Analyses of metribuzin and its metabolites were carried out using standardized methods. The results indicated a very weak capacity of adsorption of metribuzin in the two soils, and the weak adsorbed fraction is easily desorbed. Degradation and mobility of metribuzin in the field and laboratory soil columns were very intense and rapid. Soil A favoured reductive deamination whereas soil B favoured oxidative desulphuration and the respective metabolites deaminometribuzin and diketometribuzin yield the same product deaminodiketometribuzin. Both leaching by rainfall and degradation were important in the disappearance of metribuzin from the soils.     

Evidence for the enhanced biodegradation of napropamide in soil

In laboratory incubations, the time to 50% loss of napropamide was approximately 60; 21 and 8 days in soil treated for the first, second and third time respectively. In a survey of soils from commercial fields, there was evidence that enhanced biodegradation of the compound had been induced by normal field applications—in some soils by a single previous treatment. Confirmation of the observations of rapid rates of loss in pre-treated soil was obtained in experiments with three formulations of napropamide. The rate of degradation in enhanced soils was unaffected by treatment of the soils with the antifungal antibiotic cycloheximide, but was inhibited by the antibacterial antibiotic chloramphenicol. Mixed bacterial cultures able to degrade the herbicide were obtained from three rapid-degrading soils by enrichment culture. Isolates from two of them were able to degrade the herbicide in pure culture. These bacteria have, as yet, not been characterised.     

Induction and Transfer of Enhanced Biodegradation of the Herbicide Napropamide in Soils

In laboratory incubations, the times to 50% loss (DT₅₀) of a first application of napropamide were approximately 25, 45 and 75 days in soil incubated at 25, 15 and 5°C respectively. When treated for a second time, the DT₅₀ values were 4, 7 and 15 days at the same temperatures, irrespective of the temperature of the first incubation. This indicates that enhanced degradation of napropamide in soil can be both induced and expressed at low temperature. A mixed microbial culture able to degrade the herbicide to a single degradation product, identified by HPLC retention time as naphthoxypropionic acid, was obtained from a soil capable of rapid degradation. Addition of a sub-sample of this mixed culture to a previously untreated soil introduced rapid degrading ability. When small amounts of soil capable of rapid degradation were added to previously untreated soil, in both the laboratory and the field, the degradation rate of napropamide increased compared with that in unamended soils.     

Degradation of atrazine and isoproturon in surface and sub-surface soil materials undergoing different moisture and aeration conditions

The influence of different moisture and aeration conditions on the degradation of atrazine and isoproturon was investigated in environmental samples aseptically collected from surface and sub-surface zones of agricultural land. The materials were maintained at two moisture contents corresponding to just above field capacity or 90% of field capacity. Another two groups of samples were adjusted with water to above field capacity, and, at zero time, exposed to drying-rewetting cycles. Atrazine was more persistent (t(1/2) = 22-35 days) than isoproturon (t(1/2) = 5-17 days) in samples maintained at constant moisture conditions. The rate of degradation for both herbicides was higher in samples maintained at a moisture content of 90% of field capacity than in samples with higher moisture contents. The reduction in moisture content in samples undergoing desiccation from above field capacity to much lower than field capacity enhanced the degradation of isoproturon (t(1/2) = 9-12 days) but reduced the rate of atrazine degradation (t(1/2) = 23-35 days). This demonstrates the variability between different micro-organisms in their susceptibility to desiccation. Under anaerobic conditions generated in anaerobic jars, atrazine degraded much more rapidly than isoproturon in materials taken from three soil profiles (0-250 cm depth). It is suggested that some specific micro-organisms are able to survive and degrade herbicide under severe conditions of desiccation.     

Spatial variability in the degradation rates of isoproturon and chlorotoluron in a clay soil

Thirty separate soil samples were taken from different locations at the Brimstone farm experimental site, Oxfordshire, UK. Incubations of isoproturon under standard conditions (15 °C; ?33 kPa soil water potential) indicated considerable variation in degradation rate in the soil, with the time to 50% loss (DT₅₀) varying from 6 to 30 days. These differences were confirmed in a second comparative experiment in which degradation rates were assessed in 11 samples of the same soil in two separate laboratories using an identical protocol. There was a significant negative linear relationship (r²= 0.746) between the DT₅₀ values and soil pH in this group of soils. In a third experiment, degradation rates of the related compound chlorotoluron were compared with those of isoproturon in 12 separate soil samples, six of which had been stored for several months, and six of which were freshly collected from the field. Degradation of both herbicides occurred more slowly in the stored samples than in the fresh samples but, in all of them, chlorotoluron degraded more slowly than isoproturon, and there was a highly significant linear relationship (r²=0.916) between the respective DT₅₀ values.     

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.     

Effect of long‐term field application of pendimethalin: enhanced degradation in soil

The effect of long‐term application of pendimethalin in a maize–wheat rotation on herbicide persistence was investigated. Pendimethalin was applied at 1.5 kg AI ha⁻¹ separately as one or two annual applications for five consecutive years in the same plots. Residues of pendimethalin were determined by gas chromatography. Harvest‐time residues of the herbicide decreased gradually over the years and at the end of five years less than 3% of applied pendimethalin was recovered from soil as against 18% in the first year. Residues were found distributed in the soil profile up to 90 cm depth at the end of the experiment with peak distribution of 0.03 µg g⁻¹ in the surface layer of soil treated with 10 herbicide applications. The minimum distribution was, however, in the deepest soil (75–90 cm) profile. Some of the metabolites of pendimethalin ie dealkylated pendimethalin derivative, partially reduced derivative and cyclized product were also traced in surface and sub‐surface soils up to 90 cm. A study of the rate of degradation of pendimethalin in field‐treated soils under laboratory conditions revealed faster degradation compared to control soils. Only the surface soil (0–15 cm) showed this enhanced degradation of the herbicide, which could be due to the adaptability of the aerobic micro‐organisms to degrade pendimethalin. Microbes capable of degrading herbicide were isolated, identified and pendimethalin degradation was confirmed in nutrient broth. © 2000 Society of Chemical Industry     

Degradation of the herbicide flamprop-methyl in soil

The degradation of the wild oat herbicide flamprop-methyl [methyl DL -N-benzoyl-N-(3-chloro-4-fluorophenyl)alaninate] in four soils has been studied under laboratory conditions using ¹⁴C-1abelled samples. The flamprop-methyl underwent degradation more rapidly than its analogue flamprop-isopropyl. However, similar degradation products were formed, namely the corresponding carboxylic acid and 3-chloro-4-fluoroaniline. The latter compound occurred mainly as ‘bound’ forms although evidence was obtained of limited ring-opening to give [¹⁴C]carbon dioxide. The time for depletion of 50% of the applied herbicide was approximately 1-2 weeks in sandy loam, clay and medium loam soils and 2-3 weeks in a peat soil.     

Rapid mineralisation of the herbicide isoproturon in soil from a previously treated Danish agricultural field

Mineralisation of the phenylurea herbicide isoproturon (3-(4-isopropylphenyl)-1,1-dimethylurea) and two of its known metabolites, 3-(4-isopropylphenyl)-1-methylurea (monodesmethyl-isoproturon) and 4-isopropylaniline, was studied in Danish agricultural soils with or without previous exposure to isoproturon. A potential for rapid mineralisation of isoproturon and the two metabolites was present in soils sampled from three plots within an agricultural field previously treated regularly with the herbicide, with 34-45%, 51-58% and 33-36% of the added [phenyl-U-14C]isoproturon, [phenyl-U-14C]monodesmethyl-isoproturon and [phenyl-U-14C]4-isopropylaniline metabolised to [14C]carbon dioxide within 30 days at 20 degrees C. In contrast, such extensive mineralisation of these three compounds was not observed within this period in soils sampled from two other agricultural fields without previous treatment with isoproturon. The mineralisation patterns indicated growth-linked metabolism of the three compounds in the previously exposed soils, and doubling times for [14C]carbon dioxide production ranged from 1.6 to 3.2, 1.0 to 2.1 and 1.3 to 1.7 days for isoproturon, monodesmethyl-isoproturon and 4-isopropylaniline, respectively. The ability to mineralise [phenyl-U-14C]isoproturon to [14C]carbon dioxide was successfully sub-cultured to a fresh mineral medium which provided isoproturon as sole source of carbon and nitrogen. One of the soils sampled from an agricultural field not previously treated with isoproturon showed accelerated mineralisation of [phenyl-U-14C]4-isopropylaniline toward the end of the experiment, with a doubling time for [14C]carbon dioxide production of 7.4days. This study indicates that the occurrence of rapid mineralisation of the phenyl ring of isoproturon to carbon dioxide is related to previous exposure to the herbicide, which suggests that microbial adaptation upon repeated isoproturon use may occur within agricultural fields.     

Further observations on the enhanced degradation of iprodione and vinclozolin in soil

The effects of soil pH on rates of degradation of iprodione and vinclozolin were measured in a silty clay loam soil. Little degradation of either fungicide occurred at pH 4.3 or 5.0, and degradation at pH 5.7 was slower than at pH 6.5. In both of the higher-pH soils, the rate of loss of a second application of either fungicide was faster than that of the first, and a third application degraded even more quickly. In soil with pH 6.5, for example, the times for 50% degradation of iprodione following the first, second and third applications were about 30, 12 and 4 days, and for vinclozolin were 30, 22 and 7 days respectively. Iprodione degraded very rapidly in a sandy loam that had been treated three times previously with this fungicide and also degraded rapidly in the same soil pretreated three times with vinclozolin. Vinclozolin degraded rapidly in the vinclozolin pre-treated soil, but its rate of loss in the iprodione pre-treated soil was only slightly faster than in the previously untreated control. Studies of iprodione degradation in 33 soils from commercial fields demonstrated a clear trend towards faster rates of loss in soils with an extensive history of iprodione use. The time for 90% loss from previously untreated soils varied from 22 to 93 days. It varied from 16 to 28 days in soils treated once previously and from 5.2 to 23 days in soils treated twice previously. In soils that had received three or more previous doses, the time to 90% degradation varied from 3.8 to 15 days.     

Spatial variability in herbicide degradation in the subsurface environment of a groundwater protection zone

The aim of this study was to investigate the spatial variability in degradation and mineralization of atrazine and isoproturon in subsurface samples taken from sandy loam soils overlying gravel terraces which form part of a groundwater protection zone. Percussion drilling was used to obtain samples from 11 boreholes (maximum depth 3 m). Unlabelled atrazine or isoproturon, and ring-14C-labelled atrazine or isoproturon were added to samples, incubated at 25 degrees C for up to 16 weeks, and analyzed for the residual herbicide or [14C]carbon dioxide. All samples showed the potential to degrade these herbicides, although the percentage degradation decreased by a factor of 2-3 from the surface soil to a depth of 3 m. This was associated with a decrease in organic matter content, but there was no change in the potential to mineralize acetate, indicating that specific changes in the catabolic ability of the microbial population occurred with depth. The capacity of samples to mineralize atrazine and isoproturon to carbon dioxide decreased markedly with depth, with no mineralization potential observed at a depth of 80 cm.     

氟虫腈在三种土壤中的降解特性研究

实验室条件下,研究了氟虫腈在东北黑土、江西红壤和太湖水稻土中的降解特性。结果表明,氟虫腈在土壤中降解较慢,其在好气条件下的东北黑土、江西红壤和太湖水稻土中的降解半衰期分别为165、267和42 d,在渍水条件下的3种土壤中的降解半衰期分别为31、173和32 d。氟虫腈在pH 偏中性的太湖水稻土中降解最快;微生物对氟虫腈在土壤中的降解起主要作用;渍水条件有利于氟虫腈的降解,推测降解氟虫腈的微生物主要是厌氧菌属。     

Behaviour of sulcotrione and mesotrione in two soils

The behaviour of sulcotrione, a recently introduced triketone herbicide, in various soil types was studied under laboratory conditions. In particular, degradation and sorption processes were examined on Ghent and Perpignan soils. Kinetics showed that the degradation of sulcotrione was influenced by biotic and/or abiotic factors. Half-lives ranged between 45 and 65 days. Among the degradation compounds identified were 1,3-cyclohexanedione (CHD) and 2-chloro-4-mesyl benzoic acid (CMBA), previously described as hydrolysis products, and, under special conditions, a derivative of phenylheptanoic acid (PHD). This new degradation product suggested that sulcotrione could follow two possible pathways in the soil, as in water. During the sorption study, a moderate retention of sulcotrione and CMBA relative to CHD and PHD, which were highly adsorbed whatever the soil type, was reported. Experiments carried out under the same conditions for sulcotrione and mesotrione, another triketone herbicide recommended in maize culture, made it possible to compare the two triketones and to conclude that they exhibited relatively similar behaviour in the soil, i.e. that their leaching potential needs to be properly addressed and risks evaluated. Copyright (c) 2007 Society of Chemical Industry.     

Degradation of the herbicide flamprop-isopropyl in soil under laboratory conditions

The degradation of the wild-oat herbicide flamprop-isopropyl, [isopropyl (±)-N-benzoyl-N-(3-chloro-4-fluorophenyl)alaninate], in four soils has been examined under laboratory conditions with sampling times of up to 45 weeks after treatment. The major degradation product of [¹⁴C]flamprop-isopropyl in all soils at up to 10 weeks after treatment was the carboxylic acid (±)-N-benzoyl-N-(3-chloro-4-fluorophenyl)alanine. This compound in turn underwent degradation by loss of the benzoyl group and the propionic acid moiety, with evolution of [¹⁴C]carbon dioxide to form 3-chloro-4-fluoroaniline (CFA). The CFA was formed slowly in soil and occurred mainly as a bound form. There was evidence to show that the CFA was subsequently converted into other polar products. The time for depletion of 50% of the applied herbicide was approximately 10 weeks in sandy loam and medium loam soils, 11 weeks in a clay loam soil and 23 weeks in a peat soil.     

Dissipation of imazapyr, flumetsulam and thifensulfuron in soil

The degradation of imazapyr, flumetsulam and thifensulfuron applied at 500.40 and 30 g active ingredient (a.i.) ha^-1, respectively, to silt loam soil was studied under laboratory and field conditions. Herbicide residues were analysed by a lentil ( Lens culinarits L.) bioassay. Results showed that temperature had a significant effect on herbicide degradation, whereas the impact of soil organic matter ami pH were less well defined. Half-lives for imazapyr, flumetsulam and thifensulfuron in soil samples from the 0-5 cm layer (6.4% organic carbon) at 15 °C were 125, 88 and 5.4 days, respectively, and 69, 30 and 3.9 days at 30°C. In soil sampled from the 15-20 cm layer (3.5% organic carbon) half-lives were 155. 70 and 6.4 days, respectively, at 15 °C and 77, 24 and 4.8 days at 30 °C, A field experiment investigated the degradation and teaching of each herbicide under two precipitation regimes [natural precipitation (208 mm), and natural precipitation plus 75 mm irrigation (283 mm) over 4 months to a soil depth of 25 cm. Thifensulfuron degraded rapidly, whereas residues of flumetsulam and imazapyr leached below 25 cm in both the low-and high-precipitasion treatments after 4 months. Significant imazapyr residues were still present in the soil to 25 cm depth after 3 months, A multi-component model for herbicide dissipation was developed and evaluated using data from the laboratory and field experiments.