Degradation of Kresoxim-Methyl in Water: Impact of Varying pH, Temperature, Light and Atmospheric CO2 Level.

In the present investigation, persistence of kresoxim-methyl (a broad spectrum strobilurin fungicide) was studied in water. Results revealed that kresoxim-methyl readily form acid metabolite. Therefore, residues of kresoxim-methyl were quantified on the basis of parent molecule alone and sum total of kresoxim-methyl and its acid metabolite. In water, influence of various abiotic factors like pH, temperature, light and atmospheric carbon dioxide level on dissipation of kresoxim-methyl was studied. The half life value for kresoxim-methyl and total residue varied from 1 to 26.1 and 6.1 to 94.0 days under different conditions. Statistical analysis revealed the significant effect of abiotic factors on the dissipation of kresoxim-methyl from water.

Residue behavior of combination formulations of insecticides in/on cabbage and their efficacy against aphids and diamondback moth.

Persistence behavior of insecticides chlorpyriphos, profenofos, triazophos, cypermethrin, and deltamethrin following the use of three combination formulations Action 505 (chlorpyriphos + cypermethrin), Roket 44EC (profenofos + cypermethrin), and Anaconda Plus (triazophos + deltamethrin) was studied in cabbage following the spray application at the recommended and double doses. Bio-efficacy of these formulations was also evaluated against mustard aphids (Lipaphis erysimi Kaltenbach) and diamondback moth (Plutella xylostella L.). The residues of different insecticides persisted for 5-8 days at low dose and 8-12 days at high dose. The residues dissipated with time and 87-100% dissipation was recorded on the 8th day. The half-life values varied from 0.4 to 1.6 days. Based on the acceptable daily intake (ADI) values, a safe waiting period of 1 day has been suggested for the formulations Action 505 and Roket 44EC and 3 days for Anaconda Plus at the recommended dose of application. Action (1.6 L/ha) treatment was found to be the best as it significantly reduced the diamondback moth (DBM) (~60%) and aphid population (~70%) besides giving the highest yield (170% increase over control).

Degradation of kresoxim-methyl in soil: impact of varying moisture, organic matter, soil sterilization, soil type, light and atmospheric CO2 level.

In the present investigation, persistence of kresoxim-methyl (a broad spectrum strobilurin fungicide) was studied in two different soil types of India namely Inceptisol and Ultisol. Results revealed that kresoxim-methyl readily form acid metabolite in soil. Therefore, residues of kresoxim-methyl were quantified on the basis of parent molecule alone and sum total of kresoxim-methyl and its acid metabolite. Among the two soil types, kresoxim-methyl and total residues dissipated at a faster rate in Inceptisol (T1/2 0.9 and 33.8d) than in Ultisol (T1/2 1.5 and 43.6d). Faster dissipation of kresoxim-methyl and total residues was observed in submerged soil conditions (T1/2 0.5 and 5.2d) followed by field capacity (T1/2 0.9 and 33.8d) and air dry (T1/2 2.3 and 51.0d) conditions. Residues also dissipated faster in 5% sludge amended soil (T1/2 0.7 and 21.1d) and on Xenon-light exposure (T1/2 0.5 and 8.0d). Total residues of kresoxim-methyl dissipated at a faster rate under elevated CO2 condition (∼550µLL(-)(1)) than ambient condition (∼385µLL(-)(1)). The study suggests that kresoxim-methyl alone has low persistence in soil. Because of the slow dissipation of acid metabolite, the total residues (kresoxim-methyl+acid metabolite) persist for a longer period in soil. Statistical analysis using SAS 9.3 software and Duncan's Multiple Range Test (DMRT) revealed the significant effect of moisture regime, organic matter, microbial population, soil type, light exposure and atmospheric CO2 level on the dissipation of kresoxim-methyl from soil (at 95% confidence level p<0.0001).

Adsorption-desorption and leaching of pyraclostrobin in Indian soils.

Pyraclostrobin is a new broad-spectrum foliar applied and seed protectant fungicide of the strobilurin group. In this paper, adsorption-desorption of pyraclostrobin has been investigated in three different soils viz. Inceptisol (sandy loam, Delhi), Vertisol (sandy clay, Hyderabad) and Ultisol (sandy clay loam, Thrissur). Effect of organic matter and clay content on sorption was also studied in Inceptisol of Delhi. Leaching potential of pyraclostrobin as influenced by rainfall was studied in intact soil columns to confirm the results of adsorption-desorption studies. The adsorption studies were carried out at initial concentrations of 0.05, 0.1, 0.5, 1 and 1.5 µg mL(-1). The distribution coefficient (Kd) values in three test soils ranged from 4.91 to 18.26 indicating moderate to high adsorption. Among the three test soils, adsorption was the highest in Ultisol (Kd 18.26), followed by Vertisol (Kd 9.87) and Inceptisol (Kd 4.91). KF value was also highest for Ultisol soil (66.21), followed by Vertisol (40.88) and Inceptisol (8.59). S-type adsorption isotherms were observed in all the three test soils. Kd values in organic carbon-removed soil and clay-removed soil were 3.57 and 2.83 respectively, indicating lower adsorption than normal Inceptisol. Desorption studies were carried out at initial concentrations of 0.5, 1 and 1.5 µg mL(-1). Desorption was the greatest in Inceptisol, followed by Vertisol and Ultisol. Amounts of pyraclostrobin desorbed in three desorption cycles for different concentrations were 23.1-25.3%, 9.4-20.7% and 8.1-13.6% in Inceptisol, Vertisol and Ultisol respectively. Desorption was higher in clay fraction-removed and organic carbonremoved soils than normal Inceptisol. Desorption was slower than adsorption in all the test soils, indicating hysteresis effect (with hysteresis coefficient values varying from 0.05 to 0.20). Low values of hysteresis coefficient suggest high hysteresis effect indicating easy and strong adsorption, and slow desorption, of pyraclostrobin in soils. Higher hysteresis coefficient values in organic carbon removed soil (0.25-0.30) and clay fraction removed soil (0.28-0.36) as compared to normal Inceptisol soil suggest relatively weak adsorption and easy desorption of pyraclostrobin. Results of regression analysis suggest that the organic matter and pH of the soil play a major role in adsorption of pyraclostrobin. Leaching studies were carried out in intact soil columns in Inceptisol. The columns were leached with different amounts of water simulating different amounts of rainfall. The results suggest that most of the pyraclostrobin residues will remain present in the top soil layers even under high rainfall conditions and chances of pyraclostrobin moving to lower soil depth are almost negligible.

Effect of moisture, organic matter, microbial population and fortification level on dissipation of pyraclostrobin in soils.

The dissipation of pyraclostrobin, a strobilurin fungicide, in soil was found to be influenced by soil moisture, organic matter content and microbial population. Among the different moisture regimes, dissipation was faster under submerged condition (T1/2 10 days) followed by field capacity (T1/2 28.7 days) and in dry soil (T1/2 41.8 days). Use of sludge at 5 % level to Inceptisol favoured a faster dissipation of pyraclostrobin, whereas a slower rate of dissipation was observed in partial organic matter removed soil as compared to normal soil. Slower rate of dissipation was also observed in sterile soil (T1/2 47 days) compared to normal soil. Pyraclostrobin dissipated faster in Vertisol (T1/2 21.8 days) than in Inceptisol (T1/2 28.7 days). No significant difference in the dissipation rate was observed at 1 and 10 µg g(-1) fortification levels.

Residue behavior of combination mix formulations in/on bittergourd and their efficacy against melon fruitfly.

Persistence behavior of three combination mix formulations of insecticides viz. chlorpyriphos + cypermethrin (Action-505), profenofos + cypermethrin (Roket 44EC) and triazophos + deltamethrin (Anaconda) and their bioefficacy against melon fruitfly were studied in bittergourd fruits following spray application. Half-life values of the constituent insecticides calculated from first order dissipation kinetics were ~2-3 days. Based on acceptable daily intake values, safe waiting period of 3-days is suggested for all the three combination mix formulations at recommended dose of application. Anaconda (1 L/ha) was found to be most effective against Melon fruitfly as it gave 11.72 % (number/number) and 10.93 % (weight/weight) damage as compared to control 41.13 % and 41.16 %, respectively. Anaconda at lower and higher dose (1 and 2 L/ha) was not significantly different. Rocket (2 L/ha) and Action 505 (2 L/ha) were also found effective.

A liquid chromatography method for determination of selected amino acids, coenzymes, growth regulators, and vitamins from Cicer arietinum (L.) and Solanum lycopersicum (L.).

A bottleneck in crosstalk and QC research has been the quantification of diverse chemotypes in small amounts of tissue. An LC-UV method for estimating 28 selected metabolites of the regulatory network underlying growth, development, maintenance, vital functions, defense reactions, and food quality is reported. The method was based on binary gradient resolutions of the analytes in an RP C18 column. The mobile phase comprised solvent A [water+0.1% trifluoroacetic acid (TFA)] and B (acetonitrile + 0.085% TFA at a flow rate of 1 ml/min. Twenty-three metabolites (selected amino acids, coenzymes, growth regulators, phenolic antioxidant, and water-soluble vitamins) were detected at 254 nm, and four fat-soluble vitamins at 280 nm. Jasmonic acid was quantified at 210 nm. The RSDs of peak area and retention time for each metabolite were <5.8%. The calibration graphs were linear with R2 values ranging from 0.98 to 0.99. The LODs (microg/mL) were about 0.01-1.0 for 23 metabolites quantified at 254 nm, 0.1-0.2 for fat-soluble vitamins, and 0.1 for jasmonic acid. The recoveries ranged from 80 to 105%, with RSDs of 2.8 to 11.2%. The method has been satisfactorily applied for determination of 28 metabolites from Cicer arietinum (L.) and Solanum lycopersicum (L.). It could be an alternative and competitive method of choice that can cheaply and easily perform routine analysis for food quality and targeted metabolomics of chickpea and tomato in response to stressors.

A GC-ECD method for estimation of free and bound amino acids, gamma-aminobutyric acid, salicylic acid, and acetyl salicylic acid from Solanum lycopersicum (L.).

A gas chromatograph with electron capture detection method for estimation of selected metabolites--amino acids (free and bound), gamma-aminobutyric acid (GABA), salicylic acid (SA), and acetyl salicylic acid (ASA) from tomato--is reported. The method is based on nitrophenylation of the metabolites by 1-fluoro-2, 4-dinitrobenzene under aqueous alkaline conditions to form dinitophenyl derivatives. The derivatives were stable under the operating conditions of GC. Analysis of bound amino acids comprised perchloric acid precipitation of protein, alkylation (carboxymethylation) with iodoacetic acid, vapor-phase hydrolysis, and derivatization with 1-fluoro-2,4-dinitrobenzene in that order. The metabolites were resolved in 35 min, using a temperature-programmed run. The method is rapid, sensitive, and precise. It easily measured the typical amino acids (aspartate, asparagine, glutamate, glutamine, alanine, leucine, lysine, and phenylalanine) used for identification and quantification of a protein, resolved amino acids of the same mass (leucine and isoleucine), satisfactorily measured sulfur amino acid (methionine, cystine, and cysteine), and quantified GABA, SA, and ASA, as well. The developed method was validated for specificity, linearity, and precision. It has been applied and recommended for estimation of 25 metabolites from Solanum lycopersicum (L.).

Dissipation of cypermethrin, chlorpyriphos, and profenofos in tomato fruits and soil following application of pre-mix formulations.

Persistence of cypermethrin, chlorpyriphos, and profenofos in tomato and soil were studied following application of two pre-mix formulations of insecticides viz. Roket 44EC (profenofos 40% + cypermethrin 5%) and Action-505EC (chlorpyriphos 50% + cypermethrin 5%) at recommended (0.8-1.0 L ha(-1)) and double dosage (1.6-2.0 L ha(-1)). In all the treatments residues persisted beyond 7 days in tomato fruits. Half-life values were calculated from first-order dissipation kinetics. In the case of Roket 44EC, residues of cypermethrin on fruits dissipated with half-life of 2.0-3.6 days, whereas residues of profenophos dissipated with the half-life of 2.2-5.4 days. In the case of Action-505EC, residues of chlorpyriphos and cypermethrin dissipated from fruits with the half-life values of 2.9-3.3 and 2.5-4.8 days, respectively. In soil, residues of profenofos persisted for 7-15 days, whereas residues of chlorpyrophos and cypermethrin persisted for 0-7 days only.

Metabolism of 14C-azoxystrobin in water at different pH.

Metabolism of (14)C-azoxystrobin was studied in water at pH 4, 7 and 9. The study suggested that volatilization losses of azoxystrobin were very low (3%) during 130 days of incubation. Only 2.5-4.2% of azoxystrobin was mineralised to CO(2) and pH of water did not have much effect on rate of mineralisation. The dissipation of azoxystrobin in water of all the three pHs followed first order kinetic with half-life values ranging from 143 to 158 d; degradation was the fastest at pH 9. Azoxystrobin acid, a major metabolite, was detected 4-7 day onwards and its concentration increased up to 130 days. The formation of azoxystrobin acid was more and faster under alkaline (pH 9) condition than neutral (pH 7) or acidic (pH 4) conditions.

Persistence and nematicidal efficacy of carbosulfan, cadusafos, phorate, and triazophos in soil and uptake by chickpea and tomato crops under tropical conditions.

The productivity of chickpea, Cicer arietinum (L.), and tomato, Solanum lycopersicum (L.), is adversely affected by root-knot nematode, Meloidogyne species. Nematode-resistant chickpea and tomato are lacking except for a few varieties and therefore grower demand is not met. The available nematicides, namely, carbosulfan, cadusafos, phorate, and triazophos, were, therefore evaluated for their efficacy and persistence in soil and crops to devise nematode management decisions. In alluvial soil, cadusafos was the most persistent nematicide followed by phorate, carbosulfan, and triazophos in that order. The percent dissipation of cadusafos was greater (P < 0.05) in chickpea than in tomato plots, which influenced its half-life in soil. Nematicide residues were differentially taken up by chickpea and tomato plant roots with active absorption continuing for up to 45 days. Cadusafos and triazophos were absorbed to greater extent (P < 0.05) in tomato than in chickpea. The translocation of residues to shoot was highest by day 15 for cadusafos and at day 45 for other nematicides, with carbosulfan residues translocated the most. Nematicide residue concentrations in shoots never exceeded those in roots, with residues in both roots and shoots persisting beyond 90 days. Nematicide residues in green seeds of chickpea and tomato fruits were all below the Codex/German MRLs of 0.02, including the Indian tolerances of 0.1 microg/g in fruits and vegetables. Cadusafos was found to be the most effective nematicide followed by triazophos against Meloidogyne incognita and reniform nematode, Rotylenchulus reniformis . Application of cadusafos (Rugby 10 G) or, alternatively, spray application of triazophos (Hostathion 40 EC) in planting furrows, both at 1.0 kg of active ingredient/ha, followed by light irrigation is recommended for the effective control of M. incognita and R. reniformis infestations on chickpea and tomato.

Virulence development and genetic polymorphism in Meloidogyne incognita (Kofoid & White) Chitwood after prolonged exposure to sublethal concentrations of nematicides and continuous growing of resistant tomato cultivars.

BACKGROUND: The root-knot nematode, Meloidogyne incognita (Kofoid & White) Chitwood, is an important plant pathogen damaging to tomato. Continuous use of resistant tomato cultivars and nematicides for its effective management might lead to resistance break-up or nematicide failure. Genetic variability and virulence in M. incognita on susceptible Pusa Ruby tomato were analysed by bioassay, esterase and DNA polymorphism after a 5 year weekly exposure to carbofuran, carbosulfan, cadusafos and triazophos at 0.0125, 0.0250 and 0.0500 microg g(-1). Virulence in M. incognita after a 5 year multiplication on resistant tomatoes was assessed. RESULTS: The nematicidal treatments resulted in the development of virulent M. incognita populations. Their invasion potential increased significantly after continuous exposure to low concentrations of the nematicides. Also, growing resistant tomato cultivars for ten successive seasons resulted in a 6.6% increase in the invasion potential. These virulent populations exhibited 1-3 additional esterase and DNA bands compared with untreated populations. CONCLUSION: A 5 year exposure of M. incognita to sublethal concentrations of nematicides or resistant tomato cultivars exerted enough selection pressure to cause genomic alterations for virulence development. Isozyme markers can be used for rapid and precise diagnostics of field populations by advisory services, enabling judicious remedial management decisions.

Adsorption-desorption, persistence and leaching behavior of thifluzamide in alluvial soil.

Investigations were undertaken to study the adsorption-desorption, persistence and leaching of thifluzamide (2',6'-dibromo-2-methyl-4'-trifluoromethoxy-4-trifluoro methyl-1,3-thiazole-5-carboxanilide) in an alluvial soil under laboratory conditions. The adsorption-desorption studies were carried out using batch equilibration technique. The results revealed high but weak adsorption of thifluzamide in alluvial soil with K(F) value of 9.62 and 'n' value of 0.63. About 47-62% of the adsorbed amount got desorbed in four desorption cycles, which further substantiate the hypothesis of weak binding. The hysteresis coefficient varied from 0.19 to 0.40. Persistence studies carried out at three concentration levels (0.1, 1.0 and 10.0 microgg(-1)) and under three moisture conditions (air-dry, field capacity moisture and submerged) revealed that thifluzamide is a persistent chemical and only 19.5-54.0% dissipation was recorded on 90th day. However, it appears that aerobic microbes are more efficient in degrading thifluzamide than anaerobic microbes. The preliminary leaching studies carried out in the laboratory revealed that thifluzamide was moderately mobile in alluvial soil. Only small amounts (<1%) were recovered from leachate fractions whereas major portion remained in 0-15 cm soil depth.

Persistence and leaching of beta-cyfluthrin in alluvial soil of India.

Persistence as affected by rate of application and moisture regimes and leaching of beta-cyfluthrin was studied in alluvial soil under laboratory conditions. The effects of rate of application and moisture regimes on persistence were studied by incubating fortified soil at 0.1, 1.0 and 10.0 mg kg(-1) under air-dry, field capacity and submerged moisture regimes. The initial deposits of 0.09, 1.11 and 10.1 mg kg(-1) dissipated with time and 78.4-100% loss was recorded at 90 days. The half-life values varied from 7.8 to 41.8 days. The rate of dissipation decreased as the rate of application increased under field capacity and submerged conditions. However, under air-dry conditions, the effect was less pronounced, and half-life values showed a reverse trend. Persistence of beta-cyfluthrin under different moisture regimes followed the trend: air-dry > field capacity > submerged. The trend could be attributed to the effect of moisture on number and type of microbes. Leaching was studied in a packed soil column under saturated flow conditions. beta-Cyfluthrin was found to be highly immobile in alluvial soil. No residues were detected in any leachate fraction under the experimental conditions. In column soil, residues were detected at 0-10 cm depth and the major amount (>99%) was recovered from 0-5 cm depth. Although beta-cyfluthrin showed moderate persistence in alluvial soil, the possibility of its leaching to ground water is negligible as a result of its immobility.

Effect of concentration, moisture and soil type on the dissipation of flufenacet from soil.

Effect of concentration, moisture and soil type on dissipation of flufenacet from soil has been studied under laboratory condition. The treated soil samples (1 and 10 microg/g levels) were incubated at 25+/-1 degrees C. The effect of moisture was studied by maintaining the treated soil samples (10 microg/g level) at field capacity and submerged condition. In general, flufenacet persisted for 60-90 days at lower and beyond 90 days at high rate. The dissipation of flufenacet from soil followed first order kinetics with half-life (DT50) values ranging from 10 to 31 days. The dissipation of flufenacet was faster at low rate than high rate of application. The slow dissipation at high rate could be attributed to inhibition of microbial activity at high rate. There was little overall difference in rate of dissipation in Ranchi and Nagpur soil maintained at field capacity and submerged condition moisture regimes. In Delhi soil net dissipation was faster under field capacity moisture than submerged condition. Soil types greatly influenced the dissipation of flufenacet. Dissipation was fastest in Delhi soil (DT50 10.1-22.3 days) followed by Ranchi soil (DT50 10.5-24.1 days) and least in Nagpur soil (DT50 29.2-31.0 days). The difference in dissipation could be attributed to the magnitude of adsorption and desorption of flufenacet in these soils.