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     

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.     

Resistance to inhibitors of sterol biosynthesis in field isolates or laboratory strains of the eyespot pathogen Pseudocercosporella herpotrichoides

Strains of Pseudocercosporella herpotrichoides collected in France on winter wheat give either fast-growing mycelial colonies with regular margins or slow-growing mycelial colonies with irregular margins. Most of the fastgrowing isolates were sensitive to triadimenol (EC₅₀ below 2mg litre^?1), but some of them were resistant to this inhibitor of sterol C-14 demethylation. In contrast, all the slow-growing strains were highly resistant to triadimenol (EC₅₀ greater than 100 mg litre^?1). This resistance was also expressed in inhibition of germ-tube elongation. Positive cross-resistance was observed between most of the inhibitors of sterol C-14 demethylation, with the exception of some imidazole derivatives (clotrimazole, prochloraz). All the fast-growing strains were tolerant to fenpropimorph and fenpropidin whereas the slow-growing ones were susceptible; the reverse was true with piperalin and tridemorph. All the field isolates were inhibited to the same extent by the inhibitors of squalene-epoxidase, nafifine and terbinafine. Two types of mutant resistant to triadimenol have been induced under laboratory conditions from sensitive fast-growing strains. The most common mutants were resistant to all the inhibitors of sterol C–14 demethylation and also in some conditions to fenpropimorph, tridemorph and the inhibitors of squalene-epoxidase. The other mutants were characterised by a reduced spectrum of cross-resistance between triadimenol and the other inhibitors of sterol biosynthesis. The field isolates and laboratory mutants resistant to triadimenol and propiconazole were also resistant to each of the four enantiomers of these two fungicides.     

Effect of propiconazole on substrate amended soil respiration following laboratory and field application

The effect of the fungicide propiconazole (‘Tilt’^TM 250 EC) on substrate-amended soil respiration has been studied in dose-response experiments, following application of the compound in the field and in the laboratory. The field study was supplemented with spray-deposition measurements showing a throughfall at the soil surface of 15-45%, depending on the time of fungicide application. When propiconazole was amended to the soil in low dosages in laboratory conditions, the soil respiration was stimulated. Even at the very high and agriculturally unrealistic dosages in the laboratory experiment, the mean, daily soil respiration almost recovered within the incubation period of 30 days. Given the present conditions, the results did, however, also show that side-effects of the application of the fungicide were provoked at lower dosages in the field, and that they lasted for a considerably longer time than in the laboratory, indicating the importance of indirect effects of fungicide application in field conditions. Possible reasons for the dose-response relationship in the field being different from the one found in the laboratory are discussed.     

Degradation of the herbicide benzoylprop-ethyl in soil

The degradation of [¹⁴C] benzoyl prop ethyl (SUFFIX,^a ethyl N-benzoyl-N-(3,4-dichlorophenyl)-2-aminopropionate) in four soils has been studied under laboratory conditions. The major degradation product of benzoylprop ethyl at up to 4 months after treatment was its corresponding carboxylic acid (II). On further storage this compound became firmly bound to soil before it underwent a slow debenzoylation process which led to the formation of a number of products including N-3,4-dichlorophenylalanine (IV), benzoic acid, 3,4-dichloroaniline (DCA), which was mainly present complexed with humic acids, and other polar products. Although these polar products were not identified, they were probably degradation products of DCA, since they were also formed when DCA was added to soil. No 3,3′,4,4′-tetrachloroazobenzene (TCAB) was detected in any of the soils at limits of detectability ranging from 0.01-0.001 parts/million. Since N-3,4-dichlorophenylalanine (IV) and 3,4-dichloroaniline were transient degradation products of benzoylprop ethyl, the metabolism in soil of radiolabelled samples of these compounds was also studied. In these laboratory experiments the persistence of the herbicide increased as the organic matter content of the soil increased and the time for depletion of half of the applied benzoylprop ethyl varied from 1 week in sandy loam and clay loam soils to 12 weeks in a peat soil.     

Investigations on the metabolic fate of prochloraz in soil under field and laboratory conditions

The degradation of prochloraz in different soils was investigated in field and laboratory experiments. In laboratory degradation experiments in the dark, initial prochloraz concentrations decreased to 30–64% within 56 days, depending on temperature and soil pH. In neutral to basic soils, formation of up to 3.7% of the metabolite prochloraz-urea was observed. The rate of mineralization was strongly pH-dependent, not exceeding 3.2% in the acidic and 18.3% in the neutral to basic soils. Amounts of non-extractable residues ranged from 14 to 31%. Under field conditions, prochloraz disappeared much more rapidly with DT₅₀ values of 11–43 days. The metabolites prochloraz-formylurea and prochloraz-urea were found in significant concentrations. Laboratory experiments with fresh and sterilized soils under UV irradiation confirmed the enhancing effect of light on the formation of the primary metabolite, prochloraz-formylurea. The latter is hydrolysed to prochloraz-urea predominantly by microbial degradation. © 1999 Society of Chemical Industry     

Chemistry and biology of novel amine fungicides: Attempts to improve the antifungal activity of fenpropimorph

In spite of considerable efforts by many workers, there has been a lack of progress in the area of amine fungicides since fenpropimorph. Random synthesis of a large variety of different amine compounds, as well as intelligent structural modification of the lead structure fenpropimorph (well over 15 000 amines have been screened at BASF alone) have not led to a new market product so far. Further work has been focused on the reported mode of action of fenpropimorph, notably on the inhibition of the sterol Δ¹⁴-reductase. Although some doubt has to be cast on the hypothesis that fenpropimorph behaves as a sterol mimic, the concept of ‘high energy intermediate’ inhibitors has been employed successfully. Rational drug design of azasterol mimics has led to a number of very potent inhibitors of the sterol Δ¹⁴-reductase which also displayed high fungicidal activity in the greenhouse. Although many of these compounds are more powerful reductase inhibitors than fenpropimorph, under field conditions none showed significant advantages over this established fungicide. Most likely, fenpropimorph already exhibits the maximum fungicidal activity which can be attained by blocking the sterol Δ¹⁴-reductase. This would mean that, with the development of the ‘second generation’ amine fungicide fenpropimorph, this class of compounds has already virtually been optimized.     

Phytotoxic activity of clomeprop in soil and concentration of its hydrolysed metabolite DMPA in soil water

The relationship between the fate of clomeprop in soil and its phytotoxic activity on the growth of radish (Raphanus sativus) seedlings was investigated in the laboratory. The phytotoxic activity of clomeprop in sea sand was much higher than in non-autoclaved soil, and the phytotoxic activity in non-autoclaved soil was higher than in autoclaved soil. The phytotoxic activity of 2-(2,4-dichloro-3-methylphenoxy)propionic acid (DMPA), a hydrolysed metabolite of clomeprop, was higher than that of the latter under both soil conditions. Clomeprop was adsorbed on soil to a greater extent than DMPA. The concentration of clomeprop in soil water of non-autoclaved soil decreased with increase of the DMPA concentration in the soil water in a time-dependent manner. It is suggested that the phytotoxic activity of clomeprop applied to soil is induced mostly by the DMPA concentration in soil water after hydrolytic degradation by soil microbes. © 1999 Society of Chemical Industry     

Mechanism of inhibition of sterol biosynthesis enzymes by N-substituted morpholines

Tridemorph, fenpropimorph and derivatives have been tested in vitro on Δ⁸→Δ⁷-sterol isomerase (SI) from maize seedlings. The results show that these N-substituted morpholines strongly inhibit this enzyme (I₅₀: 0.4 μM for fenpropimorph, 0.6 μM for tridemorph). In fenpropimorph, where a chiral centre is present at C-2 of the alkyl chain, good enantioselectivity was observed for enzyme inhibition. Inhibition of SI and of the cycloeucalenol-obtusifoliol isomerase (COI), another enzyme of plant sterol biosynthesis, is probably due to protonation of the N-substituted morpholines, giving a positively charged nitrogen atom, at the pH (7.4) of the enzyme assays. In order to test this hypothesis, the pH dependence of the inhibition constants has been measured. Fenpropimorph, (pK_a 7.5) which can be protonated to give a morpholinium cation and N-methylfenpropimorph, the corresponding quaternary ammonium derivative, have been tested as inhibitors in a pH range from 6 to 8.5. The I₅₀ value of fenpropimorph toward the SI increased 20 times as the pH increased from 6 to 8.5. In contrast the I₅₀ value of fenpropimorph for COI did not change significantly in this pH range. While the I₅₀ value of N-methyl fenpropimorph towards COI decreased more than 50 times as the pH increased from 6 to 8.5, its I₅₀ value for SI only varied slightly in this pH range. Taken together, these results suggest the existence of an interaction of the morpholinium cations with one or several enzyme amino acid residues of a much higher pK_a in the case of COI than SI. Moreover for maize COI, the pK_a of the amino acid residue(s) interacting with these morpholines derivatives is probably close to that of these molecules.     

Limited survival of Ralstonia solanacearum Race 3 in bulk soils and composts from Egypt

Survival of Ralstonia solanacearum race 3 biovar 2 (phylotype II sequevar 1) in Egyptian soils and compost was studied under laboratory and field conditions. Survival of the pathogen under laboratory conditions varied with temperature, water potential and soil type, with temperature being the major determinant of survival of the pathogen. The effects of temperature and moisture content were variable between different experiments, but survival was generally longer at 15°C than at 4, 28 and 35°C respectively. Survival was also longer when moisture levels were constant compared with varying moisture levels at all temperatures. In experiments to compare the effects of progressive drying in sandy and clay soils there was a difference in survival times between the two soil types. In sandy soils, the pathogen died out more rapidly when soil was allowed to dry out than in controls where the soil was kept at constant water potential. In clay soils there was little difference between the two treatments, possibly due to the formation of a hard impermeable outer layer during the drying process, which retarded water loss from within. Survival in mature composts at 15°C was of the same order of magnitude as in soils but shorter at 28°C, possibly owing to increased biological activity at this temperature, or a resumption of the composting process, with concomitant higher temperatures within the compost itself. The maximum survival time recorded over all soil types and conditions during in vitro studies was around 200 days. In field studies, the maximum survival time in both bare sand and clay was around 85 days at depths up to 50 cm. The survival time was reduced in field experiments carried out in summer to less than 40 days and in one study when the ground was flooded for rice cultivation, the bacterium could not be detected 14 days after flooding. The maximum survival time of R. solanacearum in infected plant material or in infested soil samples incorporated into compost heaps was less than 2 weeks. At the culmination of field soil and compost experiments, no infection was detected in tomato seedlings up to 10 weeks after transplanting into the same soils or composts under glasshouse conditions at a temperature of 25°C.     

Persistence of pyrazosulfuron in rice-field and laboratory soil under Indian tropical conditions

BACKGROUND: Pyrazosulfuron ethyl, a new rice herbicide belonging to the sulfonylurea group, has recently been registered in India for weed control in rice crops. Many field experiments revealed the bioefficacy of this herbicide; however, no information is available on the persistence of this herbicide in paddy soil under Indian tropical conditions. Therefore, a field experiment was undertaken to investigate the fate of pyrazosulfuron ethyl in soil and water of rice fields. Persistence studies were also carried out under laboratory conditions in sterile and non‐sterile soil to evaluate the microbial contribution to degradation. RESULTS: High‐performance liquid chromatography (HPLC) of pyrazosulfuron ethyl gave a single sharp peak at 3.41 min. The instrument detection limit (IDL) for pyrazosulfuron ethyl by HPLC was 0.1 µg mL^?1, with a sensitivity of 2 ng. The estimated method detection limit (EMDL) was 0.001 µg mL^?1 and 0.002 µg g^?1 for water and soil respectively. Two applications at an interval of 10 days gave good weed control. The herbicide residues dissipated faster in water than in soil. In the present study, with a field‐soil pH of 8.2 and an organic matter content of 0.5%, the pyrazosulfuron ethyl residues dissipated with a half‐life of 5.4 and 0.9 days in soil and water respectively. Dissipation followed first‐order kinetics. Under laboratory conditions, degradation of pyrazosulfuron ethyl was faster in non‐sterile soil (t_1/2 = 9.7 days) than in sterile soil (t_1/2 = 16.9 days). CONCLUSION: Pyrazosulfuron ethyl is a short‐lived molecule, and it dissipated rapidly in field soil and water. The faster degradation of pyrazosulfuron in non‐sterile soil than in sterile soil indicated microbial degradation of this herbicide. Copyright © 2012 Society of Chemical Industry     

Metabolism of the insecticide SD 8280, 2-chloro-1-(2,4-dichlorophenyl)vinyl dimethyl phosphate,following its application to rice

The metabolism of the insecticide SD 8280 [2-chloro-1-(2,4-dichlorophenyl)vinyl dimethyl phosphate] in rice plants has been examined. When rice seedlings were treated with [¹⁴C]-SD 8280 the major metabolite was 1-(2,4-dichlorophenyl)ethanol which was present mainly conjugated with plant carbohydrates. This compound was also the major metabolite present in grain and straw from rice treated with [¹⁴C]-SD 8280 and grown to maturity under paddy conditions both in the glasshouse and in an outdoor enclosure. Other metabolites detected in the mature plants included 2-chloro-1-(2,4-dichlorophenyl)vinyl methyl hydrogen phosphate and 2,4-dichloro-benzoic acid, both of which occurred in free and conjugated forms. Paddy water was sampled at intervals after the application of [¹⁴C]-SD 8280 and the total residue in the water fell from initial levels of 0.28–1.1 μg/ml (expressed as SD 8280 equivalent) immediately after treatment to <0.01 μg/ml after 2–3 weeks. The total residues in the soil from these experiments were low and did not exceed 0.20 mg/kg (SD 8280 equivalents) through the 0–15 cm profile.     

Aerobic Metabolism of Flupropacil in Sandy Loam Soil

The aerobic soil metabolism of [¹⁴C]flupropacil (isopropyl 2-chloro-5-(1,2,3,6-tetrahydro-3-methyl-2,6-dioxo-4-trifluoromethylpyrimidin-1-yl)benzoate) was determined in microbially active, sieved (2-mm) sandy loam soil with a soil moisture content of 75% at 1/3 bar. The soil was treated with [¹⁴C]flupropacil at 0·5 mg kg⁻¹ (twice the field use rate) and placed in incubation flasks connected to a series of traps (50 g litre⁻¹ NaOH, 0·5M H₂SO₄, ethylene glycol) and incubated at 25(±1)°C. Soil was sampled at 0, 3, 9, 20, 30, 48, 76, 120, 181 and 238 days of aerobic incubation. Volatiles were collected once every two weeks and on the day of soil sampling. Flupropacil metabolized with a half-life of 79 days under aerobic conditions. The major metabolite was flupropacil acid which accounted for up to 69·1% of the initially applied radioactivity at Day 238. Each of the two minor metabolites detected at the end of the study accounted for less than 0·5%. One of the minor metabolites was identified as C4242 acid (2-chloro-5-(1,2,3,6-tetrahydro-2,6-dioxo-4-trifluoromethylpyrimidin-1-yl)benzoic acid). Only a negligible portion (less than 0·3%) of the applied flupropacil was mineralized to [¹⁴C]carbon dioxide. Extractable radioactivity ranged from 78·9% to 95·5%, with bound residues accounting for 3·2%–23·4%. The material balance ranged from 91·6% to 104·4%.     

Effects of isoproturon in the rhizosphere of wheat

In a field experiment, isoproturon (as Arelon) applied to soil at 2·5 kg ai ha^?1 caused variable effects in the rhizosphere of winter wheat. These included transient increases and decreases in the number of bacterial and fungal propagules. No changes in soil levels of NH₄⁺-N, NO₂^?-N, NO₃^?-N or PO₄^3? were detected. Similar results were recorded with wheat grown in pots and in laboratory-incubated soil. Arelon (1–60 μg ai ml^?1) did not affect pure cultures of bacteria but at the highest concentration (approximating to fifty times field rate) inhibited growth of some fungi. The value of laboratory and field experiments for studying effects of pesticides on micro-organisms is discussed. The results suggest that Arelon, in practical use, is unlikely to have harmful effects on the micro-organisms or fertility of soil.     

Effect of application rate on the sensitivity of Erysiphe graminis f.sp. tritici to fenpropimorph

Two sprays of fenpropimorph per season were applied to a winter wheat field trial, at a range of rates, which included the full commercial rate, in order to test the effect of fenpropimorph sprays on the sensitivity of Erysiphe graminis f.sp. tritici. While a reduction in the sensitivity of the mildew isolates was detected after fungicide application, this was not dependent on the rate of fungicide applied. Reduced rates were not found to induce a larger shift towards insensitivity than the full commercial rate. Powdery mildew isolates were collected from 1993 to 1996 and their sensitivity to fenpropimorph determined in order to monitor sensitivity changes in the population. While a decline in sensitivity was noted from season to season, there was no correlation between a lower sensitivity and the rate of fenpropimorph previously used. Isolates collected in Scotland were found to be significantly less sensitive than those sampled in the south of England. ©1997 SCI     

Dégradation de l'isoproturon et disponibilité de ses résidus dans le sol

Degradation if isoproturon and availability of residues in soil The availability and degradation of ¹⁴C-ring-labelled isoproturon in soil was investigated over 140 days under controlled laboratory conditions. Degradation of the active ingredient followed and 65 days later only a minor fraction (0.6%) of the parent molecule remained extractable. A demethylated-isoproturon metabolite was detectable in soil from day 15 (2.6%). The amount of ¹⁴CO₂ derived from the ¹⁴C benzene ring label and liberated over time indicated that a total of 13.6% isoproturon was mineralized during the incubation period. In parallel, the amount of ¹⁴C residue extracted from the soil by water followed by methanol or remaining within the soil—analysed by combustion—was also determined at intervals. After 140 days, 72% of the radiolabel added remained in the soil as non-extractable residue. The degradation half-life of extractable isoproturon was an estimated 14 days.     

Isolation and characterization of efficient isoxaben-transforming Microbacterium sp strains from four European soils

Nutrient-agar plates containing isoxaben (500 mg litre(-1)) were used to isolate isoxaben-metabolising bacteria from four European soils incubated with the herbicide under laboratory conditions. In flask experiments, inoculation of a basal salts medium containing nitrogen and [phenyl-U-14C]isoxaben with an isolate (B2b) resulted in 33% recovery of the initial radioactivity as [14C]carbon dioxide after 2 weeks. A major metabolite identified by GC-MS and NMR analysis as 3-(1-ethyl-1-methylpropyl)isoxazol-5-ylamine accumulated both in basal salts and nutrient broth media. 2,6-Dimethoxybenzoic acid, a suspected metabolite of isoxaben, was not detected in either liquid media. However, the capability of the B2b isolate to use 2,6-dimethoxybenzoic acid as a source of carbon was demonstrated. Soil inoculation with the B2b strain resulted in an increase in the recovery of [14C] carbon dioxide from both [phenyl-U-14C] and [isoxazole-5-14C]isoxaben. The metabolite identified as 3-(1-ethyl-1-methylpropyl)isoxazole-5-ylamine only accumulated if the soil was autoclaved before inoculation. This metabolite was rapidly mineralized by the microflora of a natural soil without history of isoxaben treatment. Homology patterns of sequenced 16S rDNA between isoxaben-transforming isolates and reference strains showed that the four isolates identified belonged to the genus Microbacterium.     

Sterol composition of isolates of Erysiphe graminis f.sp. tritici differing in sensitivity to fenpropimorph

Isolates of Erysiphe graminis f.sp. tritici with wild-type or reduced sensitivity to fenpropimorph were similar in sterol composition, viz. ergosta-5,24(28)-dienol (±90%) and episterol (±10%). Following treatment with fenpropimorph, the relative content of episterol increased in conidia of all isolates tested, while that of ergosta-5,24(28)-dienol decreased. These results suggest that fenpropimorph, under the test conditions used, does not inhibit activity of sterol Δ¹⁴-reductase or Δ⁸→Δ⁷-isomerase but probably interferes with the final part of the demethyl sterol synthesis. However, modifications in this part of the pathway are probably not responsible for the decreased sensitivity of the pathogen to the fungicide. © 1998 SCI.     

The metabolism of the herbicide flamprop-methyl in wheat

The metabolism of the wild oat herbicide flamprop-methyl, methyl (±)-2-[N-(3-chloro-4-fluorophenyl)benzamido]propionate, in spring wheat grown to maturity has been studied under glasshouse and outdoor conditions. [¹⁴C]-Flamprop-methyl labelled separately in the halophenyl ring and the carbonyl of the benzoyl group was used. The major metabolite formed in plants was the corresponding carboxylic acid, II, which also occurred as conjugates. Other minor metabolites detected under glasshouse conditions only were the 3- and 4-hydroxybenzoyl analogues of flamprop-methyl and 3′-chloro-4′-fluorobenzanilide. The soil in which the plants were grown contained residues comprising mainly flamprop-methyl and II together with smaller amounts of unidentified polar material.