Degradation of the dicarboximide fungicides iprodione,vinclozolin and procymidone in Patumahoe clay loam soil,New Zealand

An enhanced rate of degradation of the dicarboximide fungicides iprodione and vinclozolin was induced in the laboratory in Patumahoe clay loam soil by adding three successive applications of fungicide. Enhanced degradation of the dicarboximide fungicide procymidone could not be induced. Following the first fungicide treatment, the time to 50% loss of iprodione was greater than 35 days; for vinclozolin the time to 50% loss was 22 days. The rate of degradation accelerated with successive applications until, after a third successive application of fungicide, the time to 50% loss of iprodione was only two days and none was detectable at seven days. For vinclozolin, after the third successive application of fungicide, 50% loss occurred after 35 days. By comparison, minimal loss of procymidone was detected after 35 days following each of two successive soil treatments. The induction of enhanced degradation of iprodione and vinclozolin in this soil in the laboratory may explain the observed loss of field control of onion white rot disease. Degradation of iprodione occurred in non-sterile soil but not in sterile soil, indicating that microbial involvement may be responsible for the degradation of iprodione and vinclozolin in soil.     

Field effectiveness and biodegradation of cyclic imides in lettuce field soils

When 42 field trials, carried out from 1975 to 1989 in the Perpignan region (France) for control of lettuce drop caused by Sclerotinia minor, were compared, a decrease in the field effectiveness of cyclic imides was perceptible, beginning approximately in 1985. Moreover, in 15 out of 46 commercial lettuce fields surveyed in 1988 and 1989, the effectiveness of iprodione was less than 80%, the level of acceptability for the growers. In these fields, fungicide degradation, estimated by 3,5-dichloroaniline formation, was faster than in soils in which S. minor was adequately controlled. Statistical analyses showed that the iprodione degradation index was strongly linked to the history of fungicide treatment and was weakly correlated to soil pH or clay content. All the fields characterized by low iprodione effectiveness were associated with high levels of fungicide treatment and high degradation index. Moreover, we observed that soil from a field which had received iprodione for more than ten years did not degrade vinclozolin quickly, while soil from another part of the same field which had been treated with vinclozolin for eight years degraded vinclozolin faster than iprodione.     

Enhanced degradation of iprodione and vinclozolin in soil

Residues of iprodione and vinclozolin were measured following repeated application of the fungicides to a sandy loam soil in the laboratory. There was a progressive increase in rates of degradation with successive treatments. With iprodione, for example, the times for 50% loss of the first and second applications were about 23 and 5 days respectively. When treated for the third time, less than 10% of the applied dose remained in the soil after just 2 days. Similar results were obtained with vinclozolin in the same soil, and with both compounds in a second soil. In a third soil, which had relatively low pH, degradation of both compounds occurred only slowly and the rate of degradation of a second application was the same as that of the first. Degradation rates in this soil were increased by addition of 100 g kg^?1 of a soil in which degradation occurred more readily, and they were markedly increased by addition of 100 g kg^?1 of a soil in which enhanced degradation had been previously induced. Residues of both fungicides were also measured following repeated application in the field. When iprodione was applied to previously untreated plots, about 3% of the initial dose remained in the soil after 77 days. When applied to plots treated once before, less than 1% remained after 18 days, and when applied to plots treated twice previously less than 1% remained after 10 days. Similar results were obtained with vinclozolin. Enhanced degradation of subsequent soil treatments was also observed following a sequence of low-dosage sprays in the field.     

Rapid Onset of the Accelerated Degradation of Dicarboximide Fungicides in a UK Soil with a Long History of Agrochemical Exclusion

In field and laboratory experiments, enhanced degradation of the dicarboximide fungicides, iprodione and vinclozolin, was stimulated by only one application of the fungicides in a soil with no previous history of any pesticide input. Field and laboratory studies demonstrated the ease of stimulation by pre-treatment with even very low concentrations of the fungicides (0·5 μg g⁻¹ soil) and at a range of temperatures and soil moisture conditions. Soils that had acquired full enhanced degradation could rapidly degrade fungicide applied at 30 times the recommended field rate. Cross-enhancement of degradation was noted with both fungicides, but not with their common metabolite, 3,5-dichloroaniline. Application of the antibiotics chloramphenicol or rifampicin to soil reduced enhanced degradation to control levels; cycloheximide had no effect. This, together with the inhibitory action of azide, mercuric chloride and repetitive microwaving, indicated that the agent(s) of enhanced degradation was probably bacterial.     

Persistence and biodegradation of vinclozolin in tropical rice soils

The persistence of vinclozolin in three tropical rice soils, widely varying in their physicochemical characteristics, was compared under both non-flooded and flooded conditions. Degradation of the fungicide was more rapid in all the soils under flooded conditions than under non-flooded conditions. Kinetic analysis indicated that the degradation of the fungicide followed a first-order reaction irrespective of soil or water regime. Soil acidity and salinity significantly affected the persistence of the fungicide under non-flooded conditions. The degradation of the dicarboxymide fungicide was enhanced following repeated applications to an alluvial soil under both water regimes, with the enhancement being more marked under flooded conditions. Faster degradation of vinclozolin in mineral salts medium inoculated with non-sterile suspension from retreated alluvial soil indicates the involvement of micro-organisms. 3,5-Dichloroaniline was detected as a metabolite in the degradation of the fungicide in both soil and mineral salts medium. © 1999 Society of Chemical Industry     

Laboratory studies on formation of bound residues and degradation of propiconazole in soils

Laboratory studies on the formation of bound residues and on the degradation of the triazole fungicide propiconazole were conducted in two different soils. Soils treated with 14C-propiconazole were incubated at 22 degrees C and extracted exhaustively with a solvent at each sampling date until no further propiconazole was extracted. The solvent-extractable residues were used to measure propiconazole remaining in the soil, and the extracted soils were used to investigate bound residues of propiconazole. Mineralization of propiconazole was investigated by measuring [14C]carbon dioxide evolved from the soil samples. Formation of bound residues of propiconazole was higher in silty clay loam soil than in sandy loam soil, giving approximately 38 and 23% of the applied 14C, respectively. In contrast, the rates of degradation and mineralization of propiconazole were lower in silty clay loam soil than in sandy loam soil. Decreased extractability of the 14C residues with incubation time was observed with increased formation of bound residues. When the propiconazole remaining in the solvent-extractable residues was quantitatively measured by high-pressure liquid chromatographic analysis, the half-life value in sandy loam soil was about 315 days, while the half-life in silty clay loam soil exceeded the duration of the 1 year experimental period. Increased formation of bound residues was observed as propiconazole degraded with incubation time, suggesting that degradation products are involved in the formation of bound residues. Our study suggests that the formation of bound residues of propiconazole contributes to the persistence of this fungicide in soil.     

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

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

Enhanced Degradation of the Fungicide Vinclozolin: Isolation and Characterisation of a Responsible Organism

Enhanced degradation of the fungicide vinclozolin was stimulated by multiple successive applications to a soil without any history of previous pesticide input. A vinclozolin-degrading bacterium isolated from this soil was identified as a strain of Pseudomonas putida. This organism metabolised vinclozolin as a source of carbon, but it would neither grow with nor transform any other closely related dicarboximide fungicides nor the degradation product, 3,5-DCA. The degradation of vinclozolin by cultures of P. putida St-1 was investigated under various culture conditions; biodegradation was optimal at 23°C, pH 6·5 and inoculum densities of 10⁷ cells ml⁻¹ but cultures would grow from as little as 100 cells ml⁻¹. Amendments of the vinclozolin-degrading isolate to soil previously untreated with the fungicide caused rapid degradation of applied vinclozolin, whereas amendments of boiled cells, or viable cells grown in the absence of vinclozolin, produced no discernible effect on the rate of vinclozolin degradation.     

Persistence of imazamethabenz-methyl in soils after autumn and spring applications to wheat

Imazathabenz-methyl dissipated rapidly in sandy and sandy loam field soils in Nova Scotia. Canada, seeded to wheat ( Triticum aestivam L.).The time to 50% loss of herbicide residues in the 0-10 cm soil zone was about 3-4 weeks after October applications and about 2.5 weeks after June ones. After October applications, there was further loss of >60% of the remaining parent herbicide during the winter and early spring despite periods of prolonged snow cover and freezing, or near freezing, soil temperatures. After October applications, imazamethabenz-methyl residues in May-collected samples from the 10-20 and 20-30 cm soil zones ranged from 40% to 80% and from 15% to 40%, respectively of those extracted from the 0-10 cm zone over four sites. Precipitation in the month after October applications ranged from 105 to 180 mm. which suggests leaching may play an important role in dissipation at times of the year when precipitation greatly exceeds evapotranspiration. Levels of the phytoioxic free acid ranged from 15% to 35% of the parent herbicide in selected samples. These residues had no effect on spring wheat replacement crops. The effect of the herbicide on replacement crops may also be influenced by the soil pH. A laboratory study demonstrated that as soil pH increased from 4.1 to 6.5. degradation of imazamethabenz-methyl increased with a corresponding increase in free acid formation.     

Degradation of dicarboximidic fungicides in wine

The degradation of some dicarboximidic fungicides (chlozolinate, iprodione, procymidone and vinclozolin) has been studied in wine at pH values of 3.0 and 4.0, at 30°. The kinetic data obtained by observing the disappearance of the active ingredient (3.0 mg kg^?1) showed the pseudo first-order rate constants to be higher at pH 4.0 than at 3.0, with a trend for the values to be in the order: chlozolinate > vinclozolin > procymidone > iprodione. 3, 5-Dichloroaniline was not detected as a degradation product of any of the compounds. Chlozolinate and vinclozolin in wine each yielded a major metabolite, the structures of which are proposed.     

Evidence for the Accelerated Degradation of Isoproturon in Soils

The herbicide isoproturon was degraded rapidly in a sandy loam soil under laboratory conditions (incubation temperature, 15°C; soil moisture potential, -33 kPa). Degradation was inhibited following treatment of the soil with the antibiotic chloramphenicol, but unaffected by treatment with cycloheximide, thus indicating an involvement of soil bacteria. Rapid degradation was not observed with other phenylurea herbicides, such as diuron, linuron, monuron or metoxuron incubated in the same soil under the same experimental conditions. Three successive applications of isoproturon to ten soils differing in their physicochemical properties and previous cropping history induced rapid degradation of the herbicide in most of them under laboratory conditions. There were, however, no apparent differences in ease of induction of rapid degradation between soils which had been treated with isoproturon for the last five years in the field and those with no pre-treatment history. A mixed bacterial culture able to degrade isoproturon in liquid culture was isolated from a soil in which the herbicide degraded rapidly.     

Effect of pH on the degradation of atrazine,dichlorprop, linuron and propyzamide in soil

The rates of disappearance of atrazine, dichlorprop, linuron and propyzamide were measured in two soils incubated at 22°C and 80% water holding capacity. Observations were made at four pH levels in each soil. Atrazine degradation was relatively insensitive to pH; it increased slightly with increasing pH in one soil and decreased in the other. The other compounds all degraded more slowly at low pH in both soils although dichlorprop had essentially disappeared in 14 days under all conditions, so that the effect of pH is not unlikely to be of practical interest. The ratios of the degradation rates of atrazine, linuron, and propyzamide varied with the soil and the pH.     

Degradation of guanidated amine acetates

The active ingredient of the fungicide ‘Panoctine’ is a standardised mixture of guanidated amine acetates (GTA). This mixture was degraded in German standard soils with half-lives of 400–600 days. GTA dressed on to wheat seed at 0.75 g kg^? had a half-life of 20 days when seed was incubated in Petri dishes at 25°C and of 80 days on seed sown in pots of soil stored outside. These results demonstrate a substantial influence of the test system on the degradation times of guanidated amine acetates.     

Characterization of a dicarboximide-fungicide-resistant laboratory isolate ofMonilinia laxa

Monilinia laxa, the incitant of blossom blight in stone fruits in Israel, is sensitive to 5μg/ml of the dicarboximide fungicides vinclozolin and iprodione in the growth medium. When a large number of spores, from an isolate never exposed to these fungicides, was seeded on a medium containing 15 μg/ml iprodione, spontaneous resistant mutants appeared at 10^-5 frequency. These mutants showed cross resistance to the dicarboximide fungicides vinclozolin, procymidone, l-(3,5-dichloro-phenyl)-3-propen(2)-pyrrolidin-2,5-dion (Co 4462), l-(3,5-dichlorophenyl)-3-methoxymethyl-pyrrolidin-2,5-dion (Co 6054), and to dicloran. Growth rate on fungicide-free medium was similar to that of the parental sensitive strain but sporulation was much reduced. Growth rate on media supplemented with dicarboximide fungicides decreased gradually with increasing fungicide concentrations. The resistance has been stable for more than one year in the absence of fungicides. Artificial inoculation of cherry, apricot and plum fruits previously treated with 500 μg/ml vinclozolin, iprodione, procymidone or Co 6054, with a resistant strain, resulted in brown rot; similar treatments provided full protection of the fruits against the sensitive strain.     

Influence of soil pH and contents of organic carbon and clay on the volatilization of [14C]fenpropimorph after application to bare soil

The behaviour of the morpholine fungicide fenpropimorph applied to soil was investigated in a laboratory chamber. The volatility and metabolism of a ¹⁴C-labelled fenpropimorph formulation (Corbel^®) was studied after application to three soils (sandy loam, loamy clay and loamy sand), simulating a four-day weather scenario in the volatilization chamber. Additional experiments were conducted under standard climatic conditions over a period of 24 h using sandy soils with different pH values. The results of the first experiments showed that most of the radioactivity applied remained in the soils as unchanged fenpropimorph four days after application. In the experiments with the sandy loam and loamy clay, less than 5% of the applied radioactivity was removed by volatilization whereas 11·4% volatilized from the surface of the loamy sand. The comparatively higher volatilization of the fungicide from the loamy sand was confirmed by the later experiments indicating that higher soil pH favoured volatilization of [¹⁴C]fenpropimorph from sandy soils. Thus 5·6% (pH 5·0), 18·9% (pH 5·8) and 28·3% (pH 6·6) of the radioactivity applied volatilized within one day after application. The overall recoveries were between 93·8% and 111·3% in these experiments. © 1998 SCI     

FACTORS AFFECTING THE LOSS OF TRI-ALLATE FROM SOILS

Summary. Electron-capture gas chromatography was used to detect tri-allate residues in persistence studies with two soils. At rates equivalent to 0–75, 15 and 3 Ib/ac, 50% of the amount applied was degraded in 8–11 weeks at 25°C in moist Regina heavy clay and Weyburn loam. No loss occurred in sterile soils, indicating that microbial degradation may be a, major factor contributing to tri-allate breakdown.
When aqueous solutions buffered at pH 4–8 were held at 25° G, only 10–15% of the tri-allate was chemically degraded during 24 weeks.
At the normal field rate of 1·25 Ib/ac, tri-allate was not readily leached. From soil columns of Weyburn loam, 5–7% was eluted by 9 in. of water; with clay the corresponding value was 12–13% of the amount applied. When field plots were sprayed with 125 lb/ac in April, tri-allate could still be detected until the soil froze in November.
Facteurs agissant sur la perte de tri-allate dans les sots     

Factors affecting degradation rates of five triazole fungicides in two soil types: 1. Laboratory incubations

Triazole fungicides are now widely used commercially and several are known to be persistent in soil. The degradation rates of five such fungicides were measured in laboratory tests with two soils over 720 days, with analysis of soil extracts by high-pressure liquid chromatography. Behaviour in a sandy loam and a clay loam were similar, and incubation of the compounds either singly or in admixture did not influence loss rates except for those of flutriafol which were lower in the latter. Triadimefon was quite rapidly reduced to triadimenol, though traces of the former were always found, indicating a possible redox equilibrium. Flutriafol, epoxiconazole and triadimenol (derived from triadimefon) were very persistent, breakdown following first-order kinetics with half-lives greater than two years at 10 °C and 80% field capacity. Propiconazole was moderately persistent, with a half-life of about 200 days under these conditions. Degradation rates increased about 3-fold as the temperature was increased from 5 to 18 °C, though decreasing soil moisture to 60% field capacity only slightly slowed degradation. The rate constants obtained are used in a companion paper describing field studies on these two soils to compare laboratory-measured degradation rates with losses in the field following commercial sprays. © 1999 Society of Chemical Industry     

Movement and rate of decomposition of ethoprophos in soil columns under field conditions

The rates of degradation and downward movement of ethoprophos (O-ethyl SS-dipropyl phosphorodithioate) were measured under field conditions in four soils in aluminium columns (40 cm long). A 10% granular formulation was incorporated in the top 10 cm at a rate of 10.0–10.5 kg a.i./ha. Under outdoor conditions during spring and summer, loss of ethoprophos approximated to first order kinetics; the half-life was about 87 days in a humic sand and a peaty sand, with pH values of 4.5 and 4.6, respectively. In a sandy loam and a loam soil with pH values of 7.2 and 7.3, respectively, the half-life ranged between 14 and 28 days. Under experimental conditions with fallow soils and 35.3 cm rainfall, the downward movement of substantial concentrations of ethoprophos by leaching and diffusion was restricted to a few centimetres.     

环境条件和微生物对灭线磷降解的影响

环境条件和微生物影响灭线磷在土壤中的降解。随着土壤含水量和温度的增加,灭线磷的降解速度加快;微生物对灭线磷的降解有显著影响,30℃、含水量为40%条件下,未灭菌土中灭线磷的半衰期为16.6 d,灭菌土中灭线磷的半衰期为31.6 d;有机质对灭线磷的降解也有显著影响,有机质含量高,有利于灭线磷的降解;灭线磷在碱性土壤中的降解快于在酸性土壤中;30℃、含水量为40%条件下,灭线磷在3种土壤中的降解速度为:东北黑土＞广东红土＞山东砂壤土。     

Uptake of iprodione and control of diseases on potato stems

When applied to the roots of potato plants growing in different soils iprodione became systemic in the plants. Although iprodione was adsorbed on the soils tested, sufficient fungicide was present in potato stems to prevent infection by Phoma exigua var. foveata on all plants except those grown in peat soils. The amount of fungicide present in the aerial parts of the plant was related to the soil/water distribution coefficients. Application of iprodione to the sprouts of seed potato tubers prior to planting decreased the incidence and severity of infection by Rhizoctonia solani (stem canker) and Polyscytalum pustulans on stem bases.