Residual behavior and risk assessment of flubendiamide on tomato at different agro-climatic conditions in India

Supervised field trials were conducted at four different agro-climatic zones in India to evaluate the dissipation pattern and risk assessment of flubendiamide on tomato. Flubendiamide 480 SC was sprayed on tomato at 48 and 96 g active ingredient (a.i.) ha^?1. Samples of tomato fruits were drawn at 0, 1, 3, 5, 7, 10, 15, and 20 days after treatment. Quantification of residues was done on a high-performance liquid chromatography (HPLC) device with a photo diode array detector. The limit of quantification (LOQ) of this method was found to be 0.01 mg kg^?1 while limit of detection (LOD) being 0.003 mg kg^?1. Residues of flubendiamide were found below the determination limit of 0.01 mg kg^?1 in 20 days at both the dosages in all the locations. The half-life of flubendiamide at an application rate of 48 g a.i.?ha^?1 varied from 0.33 to 3.28 days and at 48-g a.i. ranged from 1.21 to 3.00 days. On the basis of data generated under the All India Network Project on Pesticide Residues, a preharvest interval (PHI) of 1 day has been recommended, and the flubendiamide 480 SC has been registered for its use on tomato by the Central Insecticide Board and Registration Committee, Ministry of Agriculture, Government of India. The maximum residue limit (MRL) of flubendiamide on tomato has been fixed by the Ministry of Health and Family Welfare, Government of India under Food Safety Standard Authority of India, as 0.07 μg g^?1 after its risk assessment.     

Dissipation kinetics and effect of different decontamination techniques on the residues of emamectin benzoate and spinosad in cowpea pods

Dissipation and decontamination of the semisynthetic macrolide emamectin benzoate and the natural insecticide spinosad on cowpea pods were studied following field application at single and double doses of 11.0 and 22 and 73 and 146 g ai ha^?1, respectively. Residues of these naturalytes were estimated using LC-MS/MS. The initial deposit of 0.073 and 0.153 mg kg^?1 of emamectin benzoate dissipated below quantitation level on the fifth and seventh day at single and double dosage, respectively. For spinosad, the initial deposits of 0.94 and 1.90 mg kg^?1 reached below quantitation level on the 7th day and 15th day at single and double dosage, respectively. The half-life of emamectin benzoate and spinosad was 1.13–1.49 and 1.05–1.39 days with the calculated safe waiting period of 2.99–6.12 and 1.09–3.25 days, respectively, for single and double dosage. Processing of the harvestable pods with different decontamination techniques resulted in 33.82 to 100 % removal 2 h after the application of emamectin benzoate and 100 % removal 3 days after spraying, while the removal was 42.05 to 87.46 % 2 h after the application of spinosad and 38.05 to 68.08 % 3 days after application.     

Dissipation kinetics of tetraconazole in three types of soil and water under laboratory condition

Laboratory experiment was conducted to understand the persistence behavior of tetraconazole in three soils of West Bengal (alluvial, red lateritic, and coastal saline) and also in water maintained at three different pH (4.0, 7.0, and 9.2) conditions. Processed soil samples (100 g) were spiked at two treatment doses: 2.5 μg/g (T₁) and 5.0 μg/g (T₂). Double distilled buffered water (200 ml) was spiked at two treatment doses: 1.0 μg/ml (T₁) and 2.00 μg/ml (T₂). The tetraconazole dissipation followed first-order reaction kinetics and the residual half-life (T _1/2) values in soil were found to be in the range of 66.9–77.2 days for T₁ and 73.4–86.0 days for T₂. The persistence increased in the order red lateritic > new alluvial > coastal saline. Interestingly, the red lateritic soil exhibited the lowest pH (5.56) and organic carbon (0.52 %) content as compared to other two soils. However, the dissipation of tetraconazole in case of water was not pH dependant. The T _1/2 values in water were in the range of 94 to 125 days. The study indicated the persistent nature of tetraconazole in soil and water.     

Dissipation behavior and risk assessment of butralin in soybean and soil under field conditions

Dissipation behavior, final residue, and risk assessment of butralin in soybean, green soybean, plant, and soil were investigated. Butralin residues were extracted with acetonitrile and then soybean samples were detected with gas chromatography-mass spectrometer (GC-MS) and soil samples were determined with GC with nitrogen phosphorous detector (GC-NPD). The limit of quantification (LOQ) of the method was 0.01 mg/kg for soybean, green soybean, plant, and soil. Average recoveries ranged from 90.4 ~ 98.2% for green soybean, 86.2 ~ 86.6% for soybean, 86.0 ~ 98.8% for plant, and 85.0 ~ 106.8% for soil. The relative standard deviations (RSDs) were 2.0 ~ 7.2% for green soybean, 2.0 ~ 3.0% for soybean, 3.1 ~ 8.1% for plant, and 1.8 ~ 6.6% for soil. Half-lives of butralin in soil samples varied in the range of 11–22 days. At harvest time, final residues of butralin in soybean and green soybean were lower than LOQ. Risk assessment demonstrated that, at recommended dosage and frequency, butralin would not induce significant harm on humans. The study could be used as a quantitative basis for application of butralin on soybean.     

Dissipation kinetics and assessment of processing factor for chlorpyrifos and lambda-cyhalothrin in cardamom

The dissipation kinetics and method for estimation of residues of chlorpyrifos and lambda-cyhalothrin in cardamom were studied and developed. The limit of detection and limit of quantitation arrived for the compounds were 0.01 and 0.025 μg?g^?1, respectively. Gas chromatographic response of chlorpyrifos and lambda-cyhalothrin residues was linear in the range of 0.01–0.50 μg?g^?1 and the mean recovery obtained was 97.3 % for chlorpyrifos and 98.9 % for lambda-cyhalothrin with satisfactory relative standard deviation values. The mean initial residues of chlorpyrifos applied at a concentration of 0.05 % in cardamom was 2.5 μg?g^?1 and the residue was 8.1 μg?g^?1 after processing, with a processing factor of 3.24, while lambda-cyhalothrin when applied at 0.0025 % resulted in initial residues of 1.63 μg?g^?1 that magnified to 4.86 μg?g^?1 on curing, with a processing factor of 2.98. The half-life of chlorpyrifos was in the range of 5.1–5.24 days while that of lambda-cyhalothrin was in the range of 4.40–4.55 days. The processing factor arrived at in the above experiment lead to the conclusion that the residues of chlorpyrifos got magnified to 3.24–3.68 times and that of lambda-cyhalothrin got magnified to 2.98–3.46 times of initial residues, consequent to loss of weight due to dehydration during curing.     

Dissipation kinetics and residues of triazolopyrimidine herbicides flumetsulam and florasulam in corn ecosystem

The dynamic and residues of florasulam and flumetsulam in corn field ecosystem were investigated using quick, easy, cheap, effective, rugged, and safe (QuEChERS) procedure with high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The limits of quantification (LOQs) of the proposed method ranged from 0.005 to 0.01 mg/kg. Mean recoveries and relative standard deviations (RSDs) of the two compounds in all samples at three spiking levels ranged 94–110 % and 2.0–9.2 %, respectively. Florasulam and flumetsulam degradation followed first-order kinetics with half-lives 1.7–2.9 and 3.3–8.7 days in soil and 1.3–1.8 and 0.9–1.7 days in plant, respectively. The residues in all the samples were found to be less than the LOQs at preharvest intervals of 53 and 78 days. The results suggest that the combined use of florasulam and flumetsulam on corn is considered to be safe under the recommended conditions and can be utilized for establishing the maximum residue limit (MRL) of florasulam in corn in China.     

Dissipation and residue of azoxystrobin in banana under field condition

A method was developed for determining azoxystrobin in banana and cultivation soil using gas chromatography. The dissipation and residue of azoxystrobin in banana fields at GAP conditions were investigated. The average recoveries ranged from 80.3 to 96.0 % with relative standard deviations of 2.9 to 7.2 % at three different spiking levels for each matrix. The results indicated that the half-life of azoxystrobin in bananas and soil ranged from 7.5 to 13.5 days in Guangdong and from 8.7 to 12.7 days in Fujian. The dissipation rates of azoxystrobin in banana and soil were almost the same. Terminal residues in banana and banana flesh (0.01 mg/kg) were all below the maximum residue limit (2 mg/kg by Codex Alimentarius Commission and China). The results demonstrated that the safety of using azoxystrobin at the recommended agriculture dosage to protect bananas from diseases.     

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

In this study, changes in heavy metal accumulation in U. rigida J. Agardh taxon and seawater have been investigated with respect to different stations and seasons. For this purpose, the severity of heavy metal pollution in the Dardanelles has been presented through the determination of Cu, Pb, Zn, and Cd concentrations in U. rigida macroalgae and seawater taken seasonally from the stations located on six different regions on the strait. While the metal concentrations in alga specimens were found to be high in spring and winter in all stations; the metal concentrations in the seawater, particularly the Pb concentration, were found to be high in all seasons.     

Dissipation studies of fentrazamide (YRC-2388) in soil under anaerobic condition

Dissipation of fentrazamide in soil and water under flooded (anaerobic) conditions was studied. Fentrazamide was applied to soil at 100 g ha(-1). Soil was extracted with 0.1 N HCl?:?acetone (1?:?1 v/v) followed by partition and cleanup with silica SPE. Separation was achieved in an ODS-II column with a mobile phase of acetonitrile?:?water (70?:?30 v/v) and detection at 214 nm. Recovery of fentrazamide varied from 75.2-90.4% and 89.9-97.8% in soil and water, respectively. Fentrazamide dissipated rapidly and fentrazamide residues were not detected after 100 and 35 days of application in soil and water, respectively. Half life in soil and water was 9.06 and 3.66 days, respectively. Dissipation followed monophasic first order kinetics pattern. No fentrazamide was detected in soil, rice grain and rice straw at harvest of crop. Calibration curves for quantification were linear and relative standard deviation (RSD) was 1.78%. LOD for instrument was 0.002 μg mL(-1) and LOQ for methods were 0.005 μg g(-1) for soil and water.     

Assessment of biological and biochemical indicators in soil under transgenic Bt and non-Bt cotton crop in a sub-tropical environment

There is concern that transgenic Bt-crops carry genes that could have undesirable effects on natural and agro-ecosystem functions. We investigated the effect of Bt-cotton (expressing the Cry 1Ac protein) on several microbial and biochemical indicators in a sandy loam soil. Bt-cotton (MRC-6301Bt) and its non-transgenic near-isoline (MRC-6301) were grown in a net-house on a sandy clay loam soil. Soil and root samples were collected 60, 90, and 120 days after sowing. Soil from a control (no-crop) treatment was also included. Samples were analysed for microbial biomass C, N and P (MBC, MBN, MBP), total organic carbon (TOC), and several soil enzyme activities. The microbial quotient (MQ) was calculated as the ratio of MBC-to-TOC. The average of the three sampling events revealed a significant increase in MBC, MBN, MBP and MQ in the soil under Bt-cotton over the non-Bt isoline. The TOC was similar in Bt and non-Bt systems. Potential N mineralization, nitrification, nitrate reductase, and acid and alkaline phosphatase activities were all higher in the soil under Bt-cotton. Root dry weights were not different (P > 0.05), but root volume of Bt-cotton was higher on 90 and 120 days than that of non-Bt cotton. The time of sampling strongly affected the above parameters, with most being highest on 90 days after sowing. We concluded from the data that there were some positive or no negative effects of Bt-cotton on the studied indicators, and therefore cultivation of Bt-cotton appears to be no risk to soil ecosystem functions.     

Dissipation pattern and risk quotients assessment of amisulbrom in Korean melon cultivated in plastic house conditions

Amisulbrom formulated as suspension concentrate was applied at the rate recommended for Korean melon to determine the dissipation pattern (at two different sites), the pre-harvest residue limit (PHRL), and risk assessments. Samples collected over 10 days were extracted using liquid-liquid extraction (LLE) and cleaned up with solid-phase extraction (SPE) Florisil cartridge. Residual concentrations were determined using liquid chromatography-ultraviolet detector (LC-UVD) and confirmed by liquid chromatography-tandem mass spectrometry (LC-MS/MS). The standard showed good instrument response linearity with a correlation coefficient (R ²) = 0.9999, and the recovery ranged from 87.5 to 93.7%. The dissipation half-life calculated from two different sites were found to be 7.0 and 8.8 days for sites 1 and 2, respectively. A PHRL graph constructed from the data indicated that if the residue levels were less than 0.55–0.59 mg/kg 3 days before harvest or less than 0.61–0.74 mg/kg 7 days before harvest, then they would be lower than the maximum residue limits (MRLs) at harvest. Risk assessments showed that the risk quotient (RQ) was 4.39–3.47% at 0 day, declined to 1.53–1.63% at 10 days. Therefore, the current data indicate that the amisulbrom can be applied safely to Korean melon; hence, it is unlikely to induce adverse health effects in consumers.     

Dissipation kinetics,safety evaluation,and assessment of pre-harvest interval (PHI) and processing factor for kresoxim methyl residues in grape

A field dissipation study was conducted to evaluate the pre-harvest interval (PHI) and processing factor (PF) for kresoxim methyl (Ergon 44.3 SC) residues in grapes and during raisin making process at recommended dose (RD) and double the recommended dose (DRD). Kresoxim methyl residues dissipated following 1st-order kinetics with a half-life of 10 and 18 days at RD and DRD, respectively. The PHIs with respect to the European Union maximum residue limit (EU-MRL) of 1 mg kg^?1 for grapes were 13 and 30 days at RD and DRD, respectively. The degradation data during grape to raisin making process were best fitted to nonlinear 1st?+?1st-order kinetics with a half-life ranging between 4 and 8 days for both shade drying and with raisin dryer at different doses. The PFs were 1.19 and 1.24 with shade drying and 1.09 and 1.10 with raisin dryer, respectively, which indicates concentration of the residues during raisin making process. The dietary exposure of kresoxim methyl on each sampling day was less than the respective maximum permissible intake both at RD and DRD. The residues of kresoxim methyl in market samples of grapes and raisins were well below the EU-MRL and were also devoid of any risk of acute toxicity related to dietary exposure.     

Mobility of spiromesifen in packed soil columns under laboratory conditions

On percolating water equivalent to 1,156 mm of rainfall, spiromesifen formulation did not leach out of 25-cm long columns, and 62.7 % of this was recovered in 5–10-cm soil depth. In columns treated with the analytical grade, 52.40 % of the recovered spiromesifen was confined to 0–5-cm soil depth, with 0.04 % in leachate fraction, suggesting high adsorption in soil. Results revealed that percolating 400 mL of water, residues of enol metabolite of spiromesifen was detected up to 20–25-cm soil layer, with 23.50 % residues of spiromesifen in this layer and 1.73 % in the leachate fraction indicating that metabolite is more mobile as compared to the parent compound. Results suggested a significant reduction in leaching losses of enol metabolite in amended soil columns with 5 % nano clay, farmyard manure (FYM), and vermicompost. No enol spiromesifen was recovered in the leachate in columns amended with nano clay, vermicompost, and FYM; however, 85.30, 70.5, and 65.40 %, respectively, was recovered from 0–5 cm-soil depth of column after percolating water equivalent to 1,156 mm of rainfall. Spiromesifen formulation is less mobile in sandy loam soil than analytical grade spiromesifen. The metabolite, enol spiromesifen, is relatively more mobile than the parent compound and may leach into groundwater. The study suggested that amendments were very effective in reducing the downward mobility of enol metabolite in soil column. Further, it resulted in greater retention of enol metabolite in the amendment application zone.     

Simulation of pyrite oxidation in fresh mine tailings under near-neutral conditions

Sulphidic residual products from ore processing may produce acid rock drainage, when exposed to oxygen and water. Predictions of the magnitude of ARD and sulphide oxidation rates are of great importance in mine planning because they can be used to minimize or eliminate ARD and the associated economic and environmental costs. To address the lack of field data of sulphide oxidation rate in fresh sulphide-rich tailings under near-neutral conditions, determination and simulation of the rate was performed in pilot-scale at Kristineberg, northern Sweden. The quality of the drainage water was monitored, along with oxygen and carbon dioxide concentrations. The chemical composition of the solid tailings was also determined. The field data were compared to predictions from simulations of pyrite oxidation using a 1-D numerical model. The simulations' estimates of the amount of Fe and S released over a seven year period (52 kg and 178 kg, respectively) were in reasonably good agreement with those obtained by analysing the tailings (34 kg and 155 kg, respectively). The discrepancy is probably due to the formation of secondary precipitates such as iron hydroxides and gypsum; which are not accounted for in the model. The observed mass transport of Fe and S (0.05 and 1.0 kg per year, respectively) was much lower than expected on the basis of the simulations and the core data. Neutralization reactions involving carbonates in the tailings result in a near-neutral pH at all depths except at the oxidation front (pH < 5), indicating that the dissolution of carbonates was too slow for the acid to be neutralized, which instead neutralized deeper down in the tailings. This was also indicated by the reduced abundance of solid Ca at greater depths and the high levels of carbon dioxide both of which are consistent with the dissolution of carbonates. It could be concluded that the near-neutral pH in the tailings has no decreasing effect on the rate of sulphide oxidation, but does reduce the concentrations of dissolved elements in the drainage water due to the formation of secondary minerals. This means that sulphide oxidation rates may be underestimated if determined from drainage alone.     

Carbonate induced dissolution of uranium containing precipitates under cement leachate conditions

The effects of carbonate on uranium (VI) solubility under aerobic and cementitious conditions have been investigated. The information is of relevance to low level nuclear waste disposal. Aqueous NaOH, KOH, Ca(OH)2 and a cement leachate solution were added to uranyl nitrate solution. Afterwards, increasing amounts of ammonium carbonate were added to re-dissolve the precipitates. The precipitates were characterised by means of X-ray powder diffraction (XRPD) measurements and modelling studies. The model calculations were performed using the MINTEQA2 speciation code, with an expanded database incorporating uranium stability constants taken from the HATCHES database. The measured and predicted amounts of CO3(2-) needed to dissolve the precipitates were compared. The knowledge gained from the 'pure' systems was used to rationalise the precipitation and re-dissolution behaviour observed in the leachate system. The lack of uranium solubility at low carbonate levels brought into question literature formation constants for UO2(OH)3- and UO2(OH)4(2-). An approximate log K value of 26.8 for K2U2O7 formation was estimated from the KOH results at pH 12. Generally, uranium solubilities are expected to be insignificant at low level nuclear waste sites because anaerobic conditions should persist. However, this study has demonstrated that solubility in leachate could rise at high pH and high carbonate levels, if aerobic conditions were to develop. Soluble U(VI) species would be formed. The novel part of the study has been to reproduce the effects and to correlate enhanced solubilities with model predictions. Consequently, the study has re-emphasised the need for appropriate environmental monitoring of such sites.     

The dissipation of ethofenprox in cabbage and soil under open conditions

The dissipation of ethofenprox in cabbage and soil under open conditions was investigated at two primary cabbage-growing regions, Beijing and Kunming in China. Samples were extracted with acetonitrile and determined by ultra-performance liquid chromatography with a single quadrupole detector. Dissipation of ethofenprox from cabbage and soil can be best explained by a first-order decay process. The half-lives of ethofenprox were 1.9 and 2.3 days in cabbage and 20.0 and 13.0 days in soil at Beijing and Kunming, respectively. The concentration of ethofenprox residue was reduced by 90% taking 7 and 60 days in cabbage and soil. Dissipation rates in cabbage and soil at two geographically separated experimental fields differed, suggesting that this was affected by complicated factors, such as local climate and soil characteristics. These data could provide guidance for the proper and safe use of this pesticide on cabbage in China.     

Persistence of fipronil and its metabolites in soil under field conditions

Fipronil belongs to phenylpyrazole class of chemical compounds. Degradation of fipronil in sandy loam soil was investigated under field conditions by applying fipronil (Regent 5 % SC) at 50 (T ₁) and 100 g a.i. ha^?1 (T ₂) in field. Samples were drawn periodically in triplicate on 0 (1 h after treatment), 1, 3, 7, 10, 15, 30, 60, and 90 days after treatment and analyzed on GC-ECD system equipped with capillary column. The residues of fipronil in both the doses dissipated in the range of 93.33–100 % in 90 days. Limit of detection (LOD) and limit of determination (LODe/LOQ) were 0.0003 and 0.001 mg kg^?1, respectively. Dissipation followed a biphasic first-order kinetics with half-life values of 10.81 and 9.97 days for fipronil alone and 8.14 and 13.05 days for fipronil along with metabolites in soil at (T ₁) and (T ₂) treatments, respectively.     

Monitoring of growth and physiological activities of biofilm during succession on polystyrene from activated sludge under aerobic and anaerobic conditions

The present research work monitored the successive biofilm development and its catabolic role in the degradation of polystyrene (PS). PS material was artificially colonized with biofilm by incubating it with activated sludge under aerobic and anaerobic conditions. Biofilm formation was monitored by gravimetric weight analysis, spectrophotometric absorbance technique, heterotrophic plate count, and scanning electron microscopy under aerobic and anaerobic conditions. The wet weight (1.59 and 1.17 g) and dry weight (0.41 and 0.08 g) of a biofilm showed a significant constant increase under aerobic and anaerobic conditions, respectively, from first till 9 weeks of incubation. Plate count of the selected bacteria (Escherichia coli, Salmonella typhimurium, Shigella dysenteriae, Pseudomonas aeruginosa) considerably declined (90–99 %) in the biofilm after seventh and fifth weeks of incubation under aerobic and anaerobic conditions, respectively, indicating a positive shift from pathogenic to beneficial microbial community. While most probable number index of fecal coliforms and E. coli in the sludge showed more reduction (98 and 99 %) under aerobic as compare to anaerobic conditions (86 and 91 %) after 9 weeks of biofilm formation on PS cubes. Correspondingly, the decreasing levels of chemical oxygen demand and biochemical oxygen demand (up to 73 %) showed signs of sludge digestion. Scanning electron microscope coupled with energy dispersive X-ray spectroscope revealed nature of PS media containing high carbon content. However, biofilm development proved to be involved in the biochemical transformation of the PS medium as indicated by Fourier transform infrared spectroscopy.