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 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 and residues of bispyribac-sodium in rice and environment

The dissipation and residues of bispyribac-sodium in rice cropping system were studied. Bispyribac-sodium residues were extracted by a simple analytical method based on QuEChERs and detected by LC-MS/MS. The limit of detection for bispyribac-sodium of this method was 0.375?×?10^?3 ng. The limit of quantification (LOQ) was 5.0 μg/kg for rice plant samples, 2.0 μg/kg for rice hull, 0.2 μg/kg for water, and 0.1 μg/kg for soil and husked rice samples. The average recoveries of bispyribac-sodium ranged from 74.7 to 108 %, with relative standard deviations less than 13 %. The half-lives of bispyribac-sodium in rice plant, water, and soil were in the range of 1.4–5.6 days. More than 90 % of bispyribac-sodium residue dissipated within 5 days. The final residues of bispyribac-sodium in rice were all below LOQ at harvest time.     

Dissipation and residue of metalaxyl and cymoxanil in pepper and soil

A simple and accurate method of determining metalaxyl and cymoxanil in pepper and soil was developed by ultra-performance liquid chromatography–photodiode array detection. The limits of detection were 0.015 mg/kg for metalaxyl and 0.003 mg/kg for cymoxanil. The limits of quantification were 0.05 mg/kg for metalaxyl in pepper and soil as well as 0.01 mg/kg for cymoxanil in pepper and soil. Recoveries of pepper and soil were investigated at three spiking levels and ranged within 77.52 to 102.05 % for metalaxyl and 87.15 to 103.21 % for cymoxanil, with relative standard deviations below 9.30 %. For field experiments, the half-lives of metalaxyl were 3.2 to 3.9 days in pepper and 4.4 to 9.5 days in soil at the three experimental locations in China. At harvest, pepper samples were found to contain metalaxyl and cymoxanil well below the maximum residue limit MRLs of the European Union (EU) following the recommended dosage and the interval of 21 days after last application.     

Environmental fate of chlorantraniliprole residues on cauliflower using QuEChERS technique

Chlorantraniliprole, an anthranilic diamide insecticide with novel mode of action is found effective against several lepidopteran as well as coleopteran, dipteran, and hemipteran pests. The present studies were carried out to study the dissipation pattern of chlorantraniliprole on cauliflower and to suggest suitable waiting period for the safety of consumers. Quick, easy, cheap, effective, rugged, and safe method was used for the extraction and cleanup of samples and the residues of chlorantraniliprole were estimated using high-performance liquid chromatograph (HPLC) and confirmed by liquid chromatograph–mass spectrometer and high-performance thin layer chromatograph. Following three applications of chlorantraniliprole (Coragen 18.5 SC) at recommended dose (9.25 g a.i.?ha^?1) and double the recommended dose (18.50 g a.i.?ha^?1), the average initial deposits of chlorantraniliprole were observed to be 0.18 and 0.29 mg kg^?1, respectively. These deposits were found to be less than the maximum residue limit of 2.0 mg kg^?1 prescribed by the Codex Alimentarius Commission. These residues dissipated below the limit of quantification of 0.10 mg kg^?1 after 3 and 5 days at recommended and double the recommended dosages, respectively. The half-life value (T _1/2) of chlorantraniliprole was worked out to be 1.36 days following its application at recommended dosages. Hence, the use of this pesticide at recommended dosages does not seem to pose any risk, and a waiting period of 1 day is suggested for safe consumption of cauliflower curds.     

Residues and dissipation of trifloxystrobin and its metabolite in tomatoes and soil

A simple residue analytical method using the quick, easy, cheap, effective, rugged, and safe (QuEChERS) procedure for the determination of trifloxystrobin and its metabolite trifloxystrobin acid (CGA321113) in tomato and soil was developed using high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The limits of detection were 0.0005 mg/kg for trifloxystrobin and 0.001 mg/kg for trifloxystrobin acid, respectively. The average recoveries in tomato and soil ranged from 73–99 % for trifloxystrobin and 75–109 % for trifloxystrobin acid, with relative standard deviations below 15 %. The method was then used to study the dissipation and residues in tomato and soil. The dissipation half-lives of trifloxystrobin in tomato were 2.9 days (Beijing) and 5.4 days (Shandong), while in soil were 1.9 days (Beijing) and 3.0 days (Shandong), respectively. The final results showed that the major residue compound was trifloxystrobin in tomato whereas it was its metabolite, trifloxystrobin acid, in soil. The final residues of total trifloxystrobin (including trifloxystrobin acid) were below the EU maximum residue limit of 0.5 mg kg^?1 in tomato 3 days after the treatment.     

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 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 and residue of triforine in strawberry and soil

Two independent field trials were performed in Guangdong and Hubei, China in 2011 to investigate the dissipation and residue levels of triforine in strawberry and soil. A fast and simple method using gas chromatography with electron capture detector was developed and validated to determine triforine levels in strawberry and soil. The average recovery of triforine in strawberry ranged from 87.46 to 104.32 % with a relative standard deviation (RSD) of 0.72 to 4.54 %; that in soil ranged from 83.82 to 103.01 % with an RSD of 3.89 to 4.36 %. The limit of quantification of the proposed method was 0.01 mg/kg for both strawberry and soil. The results suggest that the triforine dissipation curves followed the first-order kinetic. The half-lives of triforine in strawberry from Guangdong and Hubei were 3.58 and 4.42 days, respectively; those in soil were 3.53 and 4.10 days, respectively. The terminal residues of triforine in strawberry ranged from 0.032 to 0.264 mg/kg at preharvest intervals of 0.5, 1, and 3 days. These values are lower than the maximum residue limit of 1 mg/kg in strawberry set by the Codex Alimentarius Commission.     

Comparative assessment of pesticide residues in grain, soil, and water from IPM and non-IPM trials of basmati rice

The integrated pest management (IPM) modules of pesticide schedule on Basmati rice were validated at field experiments conducted in Northern India for consecutive 3 years (2005–2008). The pesticide residues were found below the detectable limit (<0.01–0.001 mg/kg) in soil and irrigation water samples of Kaithal region. In Dehra Dun region of Uttrakhand, the residues of carbendazim in rice grains and soil were detected below <0.01 mg/kg level. In second year experiments (2006–2007), only four non-IPM soil samples indicated the presence of chlorpyrifos and endosulfan in the range of ND <0.001 to 0.07 mg/kg, out of 45 samples analyzed. Carbendazim applied as seed treatment at Dehradun and Kaithal field trials was found below detectable limit in both IPM and non-IPM rice grains (<0.01 mg/kg) and irrigation water (0.01 μl/ml). Chlorpyrifos was detected in five water samples from Kaithal and one from Pant Nagar in the range of 0.003–0.006 μl/L, α- and β-isomer of endosulfan in the range of 0.005–0.03, and 0.005–0.02 μl/ml, respectively, in one sample from Pant Nagar and two from Kaithal, out of a total of 22 samples. In the region of Uttrakhand and Uttar Pradesh during 2007–2008, four non-IPM samples of soil indicated trace levels of endosulfan, out of 16 samples analyzed. The residues were detected below detection limit for carbendazim (<0.01 mg/kg) in soil samples of Dehradun IPM fields and for endosulfan and carbendazim (0.001–0.01 μl/L) in water samples each from IPM and non-IPM fields of Uttar Pradesh. The results of 3-year trials of IPM module indicated basmati rice as safe and economical with pesticide residue-free rice grains.     

Investigation on diazinon and oxydemeton-methyl residues in cucumbers grown in Kerman greenhouses

Pesticides are considered as the most polluting substances. The residue of pesticides in agricultural crops, especially in greenhouse harvests, has been reported critical. Cucumber, considered as a vegetable, is an agricultural product which is commonly found in the Iranian food basket. The current study aims to assess the level of diazinon and oxydemeton-methyl existing in cucumbers sampled from Kerman greenhouses. The pesticide residue was extracted by acetone and dichloromethane. The extracts were cleaned up according to the solid-phase extraction method. The pesticide residues were then determined by capillary gas chromatography with nitrogen-phosphorus detection. The recoveries were 83 and 85 %, the limit of detection was 0.028 and 0.034 mg/kg, and the limits of qualification were 0.093 and 0.113 mg/kg for diazinon and oxydemeton-methyl in cucumber samples, respectively. The median of diazinon residue was detected 0.582 mg/kg, which was 11.64 times the national maximum residue limit (MRL) (0.05 mg/kg), and the median for oxydemeton-methyl was 1.910 mg/kg, being 1.91 times the MRL (1 mg/kg).     

Dissipation and residue of 2,4-<Emphasis Type="SmallCaps">d</Emphasis> in citrus under field condition

The dissipation, residues, and risks of 2,4-dicholrophenoxyacetic acid (2,4-d) in citrus under field condition were investigated based on a simple ultra-performance LC (UPLC)-MS/MS method. The results indicated that the residue level of 2,4-d in citrus did not degrade gradually with sampling time under field condition. At pre-harvest intervals (PHI) of 20–40 days, 2,4-d residues were 0.021–0.269 mg/kg in citrus flesh, 0.028–0.337 mg/kg in whole citrus, and 0.028–0.376 mg/kg in citrus peel, all bellow the China maximum residue limit in citrus (1 mg/kg). Risks of 2,4-d were assessed by calculation of risk quotient, and the results revealed no significant health risks after consumption of citrus.     

Dissipation and residues determination of propamocarb in ginseng and soil by high-performance liquid chromatography coupled with tandem mass spectrometry

Two-year field trials were performed at two experimental sites to investigate dissipation and terminal residues of propamocarb in ginseng root, stem, leaf, and soil by high-performance liquid chromatography coupled with tandem mass spectrometry (HPLC-MS/MS). Mean recoveries ranged from 80.5 to 95.6 % with relative standard deviations (RSDs) of 5.5–9.1 % at fortified levels of 0.01, 0.02, 0.05 and 0.20 mg kg^?1. The half-lives of propamocarb were 5.00–11.36 days in root, 5.07–11.46 days in stem, 6.83–11.31 days in leaf and 6.44–8.43 days in soil. The terminal residues of propamocarb were below the maximum residue limits (MRLs) of EU (0.20 mg kg^?1) and South Korea (0.50 mg kg^?1 in fresh ginseng and 1.0 mg kg^?1 in dried ginseng) over 28 days after last spraying at recommended dosage. The results provide a quantitative basis for establishing the MRL and give a suggestion of safe and reasonable use of propamocarb in ginseng.     

Dissipation dynamic and residue distribution of flusilazole in mandarin

In this paper, dissipation dynamic and terminal residue of flusilazole in mandarin and soil, as well as residue distribution of flusilazole in mandarin, were studied at three sites in China. Mandarin peel, mandarin pulp, whole mandarin, and soil samples were extracted by acetonitrile, cleaned up with dispersive solid-phase extraction, then analyzed by gas chromatography–mass spectrometry. The dissipation half-lives of flusilazole in mandarin and soil at all three experiment sites were 6.3–8.4 days and 5.5–13.4 days, respectively, with the exception of the soil dissipation at the Hunan site, which showed an increase–decrease process. Flusilazole residue levels in whole mandarin were all below 0.1 mg/kg on 14 days after the last application. Terminal residue study showed that flusilazole was mostly distributed in mandarin peel, which indicates minimal risk for eating mandarin pulp. These results could provide guidance for the proper and safe use of flusilazole on citrus fruits, and further our understanding of pesticide distribution in citrus fruits.     

Persistence and dissipation of flubendiamide and its risk assessment on gherkin (Cucumis anguria L.)

A supervised open field trial was conducted to evaluate the dissipation pattern and risk assessment of flubendiamide in gherkin fruits following foliar application of Fame 480 SC at 60 and 120 g a.i.?ha^?1. Samples of gherkin fruits were drawn at different time intervals and quantified by HPLC-DAD. The maximum initial deposits of flubendiamide on gherkin were found to be 0.79 and 1.52 mg kg^?1, respectively, at recommended and double the recommended doses. The dissipation pattern of flubendiamide followed a first-order kinetics with half-lives of 1.87 to 2.16 days at 60 and 120 g a.i.?ha^?1, respectively. The limit of quantification of flubendiamide and desiodo flubendiamide was observed to be 0.01 mg kg^?1 for gherkin fruit and soil substrates. Theoretical maximum residue contribution (TMRC) for flubendiamide was calculated and found to be well below the maximum permissible intake (MPI) on gherkin fruits. Thus, the application of flubendiamide at the recommended dose on gherkin fruits presents no human health risks and safe to consumers.     

Improved dissipation kinetic model to estimate permissible pre-harvest residue levels of pesticides in apples

Prediction of residual concentrations of applied pesticides during the pre-harvest period may be required to ensure the safety of agricultural products. In this study, time-dependent dissipation trends of carbaryl (CB), kresoxim-methyl (KM), flubendiamide (FB), flufenoxuron (FN), bitertanol (BT), and chlorantraniliprole (CN) applied to apples at recommended and threefold greater doses were modeled to estimate pre-harvest residue limit concentrations (C_PHRL) indicating permissible pesticide concentrations during the pre-harvest period. Double-exponential (DE) model results best fit the dissipation trends of all tested pesticides (correlation coefficients of 0.91–0.99) compared to zero-, first-, and second-order models. Among the pesticides examined, CB half-lives in apples of 2.9 and 6.6 days were the shortest, while those of FN (21.1–32.7 days) were the longest. The C_PHRL values for each pesticide in apples were estimated with DE model parameter values and could be used to determine harvest dates for safe apples with pesticide concentrations below their maximum residue limits. Application of the DE model for C_PHRL calculation provides more accurate information for farmers to produce agricultural products safe from pesticide residues.     

Persistence of insecticides in ready-mix formulations and their efficacy against Lipaphis erysimi (Kalt) in cauliflower

Persistence of cypermethrin, deltamethrin, profenofos, and triazophos in cauliflower curd was studied, following application of two premix formulations viz: Roket 44EC (profenofos 40 % + cypermethrin 4 %) and Anaconda Plus 36EC (triazophos 35 % + deltamethrin 1 %) at recommended (1.0 L ha^?1) and double doses (2.0 L ha^?1). In the case of Roket 44EC, residues of cypermethrin dissipated with the half-life values of 1.5–2.1 days, whereas residues of profenofos dissipated with the half-life of 2.9–3.3 days on cauliflower curd. In the case of Anaconda, residues of triazophos and deltamethrin dissipated from curd with the half-life values of 2.6–3.0 and 2.2–2.6 days, respectively. Both the combination mix significantly reduced the aphid population up to 14 days after spray and increased the yield by 155–160 % over control. Anaconda (2.0 L ha^?1) treated plots yielded the highest number of marketable curds. Based on risk assessment analysis, safe waiting period of 3 and 5 days has been suggested for Roket 44EC and Anaconda Plus 36EC, respectively, in cauliflower at recommended dose of application.     

Persistence and risk assessment of spiromesifen on tomato in India: a multilocational study

Supervised field trials were conducted at four different agro-climatic locations of India to evaluate the dissipation pattern and risk assessment of spiromesifen on tomato. Spiromesifen 240 SC was sprayed on tomato at 150 and 300 g a.i.?ha^?1. Samples of tomato fruits were drawn at 0, 1, 3, 5, 7, 10 and 15 days after treatment and soil at 15 days after treatment. Quantification of residues was done on gas chromatograph–mass spectrophotometer in selective ion monitoring mode in the mass range of 271–274 (m/z). The limit of quantification of the method was found to be 0.05 mg kg^?1, while the limit of determination was 0.015 mg kg^?1. Residues were found below the LOQ of 0.05 mg kg^?1 in 10 days at both the doses of application at all the locations. Spiromesifen dissipated with a half-life of 0.93–1.38 days at the recommended rate of application and 1.04–1.34 days at the double the rate of application. Residues of spiromesifen in soil were detectable level (<0.05 mg kg^?1) after 15 days of treatment. A preharvest interval (PHI) of 1 day has been recommended on tomato on the basis of data generated under All India Network Project on Pesticide Residues. Spiromesifen 240 SC has been registered for its use on tomato by Central Insecticide Board and Registration Committee, Ministry of Agriculture, Government of India. The maximum residue limit (MRL) of spiromesifen on tomato has been fixed by Food Safety Standard Authority of India, Ministry of Health and Family Welfare, Government of India as 0.3 μg/g after its risk assessment.     

Determination and study on dissipation and residue determination of cyhalofop-butyl and its metabolite using HPLC-MS/MS in a rice ecosystem

Cyhalofop-butyl is an aryloxyphenoxypropionate postemergence herbicide with good control of barnyard grass in rice paddies. In this study, method for the determination of cyhalofop-butyl and its metabolite was developed with high-performance liquid chromatography tandem mass spectrometry. Dissipation and residue levels of cyhalofop-butyl and its metabolite in rice ecosystems were also investigated. Recoveries and relative standard deviations of cyhalofop-butyl and cyhalofop acid in six matrices at three spiking levels ranged from 76.1 to 107.5 % and 1.1 to 8.2 %, respectively. The limit of quantitation (LOQ) of cyhalofop-butyl and cyhalofop acid was 0.01 mg/kg in paddy water, paddy soil, rice plant, rice straw, rice hulls, and husked rice. For field experiments, the results showed that cyhalofop-butyl degraded to cyhalofop acid quickly, and the half-lives of cyhalofop acid in paddy water, paddy soil, and rice plant were 1.01–1.53, 0.88–0.97, and 2.09–2.42 days, respectively. Ultimate residues of cyhalofop-butyl and its metabolite in the rice samples were not detectable or below 0.01 mg/kg at harvest.     

Occurrence of phthalic acid esters in Gomti River Sediment, India

Cadmium and lead are important environmental pollutants with high toxicity to animals and human. Soils, though have considerable metal immobilizing capability, can contaminate food chain via plants grown upon them when their built-up occurs to a large extent. Present experiment was carried out with the objective of quantifying the limits of Pb and Cd loading in soil for the purpose of preventing food chain contamination beyond background concentration levels. Two separate sets of pot experiment were carried out for these two heavy metals with graded levels of application doses of Pb at 0.4–150 mg/kg and Cd at 0.02–20 mg/kg to an acidic light textured alluvial soil. Spinach crop was grown for 50 days on these treated soils after a stabilization period of 2 months. Upper limit of background concentration levels (C _ul) of these metals were calculated through statistical approach from the heavy metals concentration values in leaves of spinach crop grown in farmers’ fields. Lead and Cd concentration limits in soil were calculated by dividing C _ul with uptake response slope obtained from the pot experiment. Cumulative loading limits (concentration limits in soil minus contents in uncontaminated soil) for the experimental soil were estimated to be 170 kg Pb/ha and 0.8 kg Cd/ha. Based on certain assumptions on application rate and computed cumulative loading limit values, maximum permissible Pb and Cd concentration values in municipal solid waste (MSW) compost were proposed as 170 mg Pb/kg and 0.8 mg Cd/kg, respectively. In view of these limiting values, about 56% and 47% of the MSW compost samples from different cities are found to contain Pb and Cd in the safe range.