Shashi Bala Singh

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

Metabolism of 14C-azoxystrobin in water at different pH

Metabolism of 14C-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 CO2 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 to158 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.

Optimization of enzymatic saccharification of alkali pretreated Parthenium sp. using response surface methodology.

Parthenium sp. is a noxious weed which threatens the environment and biodiversity due to its rapid invasion. This lignocellulosic weed was investigated for its potential in biofuel production by subjecting it to mild alkali pretreatment followed by enzymatic saccharification which resulted in significant amount of fermentable sugar yield (76.6%). Optimization of enzymatic hydrolysis variables such as temperature, pH, enzyme, and substrate loading was carried out using central composite design (CCD) in response to surface methodology (RSM) to achieve the maximum saccharification yield. Data obtained from RSM was validated using ANOVA. After the optimization process, a model was proposed with predicted value of 80.08% saccharification yield under optimum conditions which was confirmed by the experimental value of 85.80%. This illustrated a good agreement between predicted and experimental response (saccharification yield). The saccharification yield was enhanced by enzyme loading and reduced by temperature and substrate loading. This study reveals that under optimized condition, sugar yield was significantly increased which was higher than earlier reports and promises the use of Parthenium sp. biomass as a feedstock for bioethanol production.

Gas chromatographic analysis of polychlorinated dibenzo-p-dioxins and dibenzofurans

Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans are toxic compounds formed during natural processes and human activities. The extraction and clean-up for these compounds from various environmental and biological sources has been described. The gas chromatographic analysis of polychlorinated dibenzo dioxins/furans with different columns and detectors has been reviewed. The advantages of using a mass detector in the analysis are discussed.

Analysis of metsulfuron-methyl residues in wheat field soil: a comparison of HPLC and bioassay techniques

BACKGROUND Metsulfuron-methyl is a low-application-rate sulfonylurea herbicide that is widely used to control broad-leaved weeds in wheat. Owing to its persistent nature, its residues may be present at phytotoxic levels for the next crop in rotation. Therefore, a comparative evaluation of HPLC and bioassay techniques was made for the analysis of this herbicide in wheat field soil. RESULTS Metsulfuron-methyl was applied to wheat crop at different rates (4, 8 and 12 AI ha(-1)) at 28 days after sowing as a post-emergence application, and the soil was analysed for metsulfuron-methyl residues by HPLC and lentil seed bioassay techniques. The bioassay was found to be the more sensitive technique. At the recommended rate of application, 4 g AI ha(-1), the bioassay technique could detect the residue up to 30 days in surface soil, while, with HPLC, residues were not detectable on the 15th day. The half-lives of metsulfuron-methyl by HPLC and bioassay were calculated as 6.3-7.8 and 17.5 days respectively. Under field conditions, residues of metsulfuron-methyl were also detected in subsurface soil by the bioassay technique at trace levels, but were not detected by the solvent extraction/HPLC method. CONCLUSION Lentil seed bioassay is a more sensitive technique than HPLC. Traces of residues detected in subsurface soil indicated the mobility of metsulfuron-methyl into lower layers.

Determination of Pesticide Residues in Integrated Pest Management and Nonintegrated Pest Management Samples of Apple (Malus pumila Mill.)

Studies were undertaken to analyze the residues of commonly used pesticides viz. chlorpyrifos, endosulfan, dicofol, cypermethrin, fenvalerate, propargite, malathion, phorate, carbendazim, carbosulfan, thiamethoxam, and mancozeb in apple of integrated pest management (IPM) and non-IPM samples collected from the IPM and non-IPM fields of Shimla. We also present a method for the determination of these pesticides in apple samples. Residues of chlorpyrifos, endosulfan, dicofol, cypermethrin, fenvalerate, and propargite were analyzed by gas chromatography, while residues of carbendazim, carbosulfan, and thiamethoxam were analyzed by high-performance liquid chromatography. Residues of mancozeb were determined by a colorimetric method. Recoveries of all of the pesticides ranged from 61.30 to 95.46% at 0.1, 0.2, and 1.0 microg g(-1) levels of fortification with relative standard deviations ranging between 0.8 and 8.7. Apples from IPM and non-IPM orchards were analyzed for these pesticides using a developed method. Except for carbendazim and chlorpyrifos, the residues of all of the pesticides analyzed were below detectable limits. Although residues of carbendazim and chlorpyrifos were below the prescribed limits of maximum residue levels in both IPM and non-IPM orchards, residues were lower in apples from IPM orchards.

Quantitative determination of gibberellins by high performance liquid chromatography from various gibberellins producing Fusarium strains

High performance liquid chromatographic (HPLC) method was developed for analysis of seven gibberellins, i.e., GA3, GA4, GA7, GA3 methyl ester, GA7 methyl ester 3,13 diacetate, GA7 methyl ester, and fusaric acid, using an isocratic system. Method was used for estimation of gibberellins from different Fusarium strains. Gibberellins were extracted from 28 strains of Fusarium, out of which six strains of Fusarium were isolated from soil of different parts of India and 22 strains were procured from the Indian Type Culture Collection, Indian Agricultural Research Institute, New Delhi. Extracts were analyzed for qualitative and quantitative estimation of gibberellins by thin layer chromatography and HPLC, respectively. On the basis of quantitative analysis of produced gibberellins by HPLC, they were categorized as low, moderate, and high gibberellin producing strain. For the first time, Fusarium solani was also reported as high GA3 producing strain.

Effect of moisture and compost on fate of azoxystrobin in soils

The effect of compost-amendment and moisture status on the persistence of azoxystrobin [methyl (E)-2-{2-(6-(2-cyanophenoxy) pyrimidin-4-yloxy) phenyl}-3-methoxyacrylate], a strobilurin fungicide, in two rice-growing soils was studied. Azoxystrobin is more sorbed in the silt loam (K f – 4.66) soil than the sandy loam (K f – 2.98) soil. Compost-amendment at 5 % levels further enhanced the azoxystrobin sorption and the respective K f values in silt loam and sandy loam soils were 8.48 and 7.6. Azoxystrobin was more persistent in the sandy loam soil than the silt loam soil. The half–life values of azoxystrobin in nonflooded and flooded silt loam soil were 54.7 and 46.3 days, respectively. The corresponding half–life values in the sandy loam soils were 64 and 62.7 days, respectively. Compost application enhanced persistence of azoxystrobin in the silt loam soil under both moisture regimes and half-life values in non–flooded and flooded soils were 115.7 and 52.8 days, respectively. However, compost enhanced azoxystrobin degradation in the sandy loam soil and half-life values were 59 (nonflooded) and 54.7 days (flooded). The study indicates that compost amendment enhanced azoxystrobin sorption in the soils. Azoxystrobin is more persistent in non-flooded soils than the flooded soils. Compost applications to soils had mixed effect on the azoxystrobin degradation.

Kinetics and mechanism of the hydrolysis of thiamethoxam

The degradation of thiamethoxam [(EZ)-3-(2-chloro-1,3-thiazol-5-yl-methyl)-5-methyl-1,3,5-oxadiazinan-4-ylidene (nitro) amine] insecticide in buffers at different pH and temperature levels was investigated in laboratory studies. Acidic hydrolysis under conventional heating conditions and alkaline hydrolysis under both conventional heating and microwave conditions were carried out. Different hydrolysis products were found to form under alkaline and acidic conditions. Hydrolysis of thiamethoxam in acidic, neutral and alkaline buffers followed first-order reaction rate kinetics at pH 4, 7 and 9.2, respectively. Thiamethoxam readily hydrolyzed in alkaline buffer but was comparatively stable in neutral buffer solution. The main products formed under different conditions were characterized on the basis of infrared (IR), 1H-NMR and Mass spectroscopy. The possible mechanisms for the formation of these hydrolysis products have also been proposed.

Persistence of herbicide fenoxaprop ethyl and its acid metabolite in soil and wheat crop under Indian tropical conditions

The persistence of fenoxaprop ethyl {Ethyl (RS)-2-[4-(6-chloro-1,3-benzoxazol-2-yloxy) phenoxy] propionate} herbicide and its active metabolite fenoxaprop acid was investigated in soil and wheat crop. Fenoxaprop acid was prepared by alkaline hydrolysis of fenoxaprop ethyl. A HPLC method was developed in which fenoxaprop ethyl herbicide and its acid metabolite showed sharp single peak at 6.44 and 2.61 min respectively. The sensitivity of the method for ester and acid was 2 and 1 ng respectively with limit of detection of 0.1 and 0.05 μg mL−1. The recovery of fenoxaprop ethyl and fenoxaprop acid from soil, wheat straw and grain ranged between 73.8–80.2%. In a field experiment fenoxaprop ethyl (Puma super® 10 EC) when applied to wheat crop at the rate of 120 g and 240 g a.i. ha-1 as post emergence spray, fenoxaprop ethyl converted to fenoxaprop acid. Residues of fenoxaprop ethyl and acid dissipated in soil with a half-life of 0.5 and 7.3 days, respectively. At harvest no detectable residues of fenoxaprop ethyl or acid were observed in soil, wheat grain and straw samples.