Unveiling the absorption, translocation, and metabolism of penthiopyrad in pakchoi under hydroponic and soil-cultivated conditions.

The efficient use of pesticides has long been a topic of public concern, necessitating a thorough understanding of their movement in plants. This study investigates the translocation and distribution of penthiopyrad in pakchoi plants cultivated both in hydroponic and soil-cultivated conditions. Results indicate that penthiopyrad predominantly accumulates in the roots, with concentrations of 11.3-53.9 mg/kg following root application, and in the leaves, with concentrations of 2.0-17.1 mg/kg following foliar application. The bioconcentration factor exceeded 1, with values ranging from 1.2 to 23.9 for root application and 6.4 to 164.0 for foliar application, indicating a significant role in the absorption and accumulation processes. The translocation factor data, which were <1, suggest limited the translocations within pakchoi plants. The limitation may be attributed to the hydrophobic properties of penthiopyrad (log Kow = 3.86), as evidenced by its predominant distribution in the subcellular solid fractions of pakchoi tissues, accounting for 93.1% to 99.5% of the total proportion. Six metabolites (753-A-OH, M12, 754-T-DO, M11, PCA, and PAM) were identified in this study as being formed during this process. These findings provide valuable insights into the absorption, translocation, and metabolism of penthiopyrad in pakchoi.

Insights on the isolation, identification, and degradation characteristics of three bacterial strains against mandipropamid and their application potential for polluted soil remediation.

Bacteria-induced biodegradation techniques have become an effective approach for removing pesticide residues from polluted soils. However, their effect on chiral fungicides must be systematically evaluated and the efficiency and risk of each chiral enantiomer must be better understood. In this study, we isolated and enriched seven bacterial strains that are able to degrade mandipropamid from contaminated soil samples. Three bacterial strains with high degradation efficiency (63.6%-73.4%) were screened and identified as Pseudomonas sp. (M01), Mycolicibacterium parafortuitum (MW05), and Stenotrophomonas maltophilia (MW09) by morphological and 16S rRNA gene sequencing analyses. The degradation characteristics of three strains (M01, MW05, and MW09) was investigated and it was revealed that pH, temperature, and initial concentration of mandipropamid significantly impacted their degradation efficiency. The optimal conditions for degradation were a nutrient source of mandipropamid and an inoculation amount of 5%. We used a Box-Behnken model experiment and an analysis of variance to determine the most suitable conditions for degrading mandipropamid at various pH, temperature, and initial concentration levels. A response surface methodology analysis showed that the three strains had the highest mandipropamid degradation efficiency (> 96%) under various conditions (pH: 7.15-7.71, temperature: 28.61-30.76 °C, initial concentration: 5.524-5.934 mg/L). Mycelial, intracellular, and extracellular enzymes also had an impact on the degradation of mandipropamid enantiomers by the three strains. In soil remediation trials, the three bacterial strains could effectively enantioselectively degrade rac-mandipropamid residues in polluted sterilized and natural soil samples (R-enantiomer was degraded faster) and influence the activity of urease and ß-glucosidase in the soil. The results revealed several candidate bacterial strains for mandipropamid biodegradation and provide information on mandipropamid biological detoxification in soil environments.

Enantioselective evaluation of the chiral fungicide mandipropamid: Dissipation, distribution and potential dietary intake risk in tomato, cucumber, Chinese cabbage and cowpea.

A chiral analytical method was developed and validated for the determination of mandipropamid enantiomers in tomato, cucumber, Chinese cabbage and cowpea. The linearity (R2 > 0.99), accuracy (recovery: 73.8-106%) and precision (relative standard deviation: < 11%) were adequate for the detection of mandipropamid enantiomers in four vegetables. Field trials were further conducted to investigate the dissipation and residue distribution of mandipropamid and the possible enantioselectivity in different vegetables. Due to the shorter half-lives, mandipropamid dissipated more rapidly in Chinese cabbage (1.8-2.0 d) and cowpea (1.6-2.4 d) than in tomato (5.0-8.4 d) and cucumber (2.4-5.5 d). The residues of mandipropamid were 45-179 µg/kg in tomato 14 d at low dose, 48-98 µg/kg in cucumber 7 d after spraying twice at low dose, and < 2.5-1942 µg/kg in Chinese cabbage and cowpea in all treatments, which were below the maximum residue limits of mandipropamid set by the European Union and Codex Alimentarius Commission. Enantioselectivity was observed during the mandipropamid dissipation process in four vegetables. The S-(+)-enantiomer dissipated more rapidly than the R-(-)-enantiomer in tomato and Chinese cabbage (enantiomeric fractions > 0.5). For cucumber and cowpea, the dissipation of the R-enantiomer was preferential (enantiomeric fractions < 0.5). According to the risk quotient data (<< 100%), the residues of mandipropamid in four vegetables were safe for Chinese consumers. This study could provide useful information for the dissipation fate and residue distribution of mandipropamid in vegetables at the enantiomer level and offer some guidance for the dietary intake risk evaluation of mandipropamid in vegetables.

Contamination, spatial distribution, and source contribution of persistent organic pollutants in the soil of Guiyang city, China: a case study.

The contamination of persistent organic pollutants (POPs), including dichlorodiphenyltrichloroethane (DDT), hexachlorocyclohexane (HCH), and polycyclic aromatic hydrocarbon (PAH), is the most studied environmental issue. In 2020, a total of sixty soil samples collected from ten locations in Guiyang were analyzed to assess the presence of four DDTs and HCHs and sixteen PAHs. The concentrations of total DDTs, total HCHs and Σ16PAHs in the soil were between 0.26 and 12.76, 0.23 and 51.80 µg/kg, and 10.02 and 1708.86 µg/kg, respectively. The mean and median concentrations of total DDTs, total HCHs and Σ16PAHs in the soil were 1.04 and 0.26 µg/kg, 4.32 and 0.23 µg/kg, 139.14 and 98.98 µg/kg, respectively. p,p'-DDT, p,p'-DDD and γ-HCH the dominant organochloride pollutants in the soil, while 4-ring PAHs were the dominant PAHs, occupying 41.1-53.6% of the total PAHs in the soil. The highest levels of PAHs in the soil were observed in areas of Guiyang with relatively larger population densities and more developed heave industries. Various diagnostic tools were used to identify the potential sources of the POPs in the soil. The data indicated that DDTs and HCHs were from past and recent common inputs and that mixtures of several combustion activities (biomass, coal and petroleum combustion, diesel, gasoline, and vehicular emissions) were the major sources of PAHs in the Guiyang soil. The results provide information for the assessment of the extent of POP pollution in the Guiyang soil and can help authorities establish environmental protection regulations and soil remediation techniques.

Stereoselective degradation behavior of the novel chiral antifungal agrochemical penthiopyrad in soil.

Penthiopyrad is a chiral carboxamide fungicide with a broad spectrum of fungicidal activity. However, there is no report on the analysis of the enantiomers of penthiopyrad and their environmental behavior. Soil is an important carrier for pesticides to affect the environment. Therefore, this study aimed to investigate the absolute configuration, stereoselective degradation, configuration stability and potential metabolites of this agrochemical in soil under different laboratory conditions. R-(-)-penthiopyrad and S-(+)-penthiopyrad were identified by the electronic circular dichroism method. Regarding the racemic analyte, the degradation half-lives of the stereoisomers ranged from 38.9 to 97.6 days, the S-(+)-stereoisomer degraded preferentially in four types of Chinese soil. However, enantiopure R-(-)-penthiopyrad degraded faster than its antipode, a finding that might be related to the microbial activity in soil. The organic matter (OM) content influenced the stereoselective degradation of rac-penthiopyrad. No configuration conversion was observed in both enantiopure analyte degradation processes. One possible metabolite, 753-A-OH, was detected in the treated soil samples, and the degradation pathway might be a hydroxylation reaction. This is the first report of the absolute configuration of penthiopyrad stereoisomers and the first comprehensive evaluation of the stereoselective degradation of penthiopyrad in Chinese soil. Stereoselective degradation of rac-penthiopyrad was observed in the four types of soil. And the stereoselectivity might be inhibited by OM. This study provides more accurate data to investigate the environmental behavior of penthiopyrad at the stereoisomer level.

Dissipation, adsorption-desorption, and potential transformation products of pinoxaden in soil.

This study established and validated a simple and sensitive analytical approach for determining pinoxaden residues in soil. The dissipation and adsorption-desorption of pinoxaden in four kinds of Chinese soil were comprehensively investigated for the first time, and the possible metabolic products and pathways were identified. The developed method was successfully applied in dissipation and adsorption-desorption trials. Several influential factors, including temperature, organic matter, and moisture content, affected the dissipation rate of pinoxaden in soil. During the dissipation process, 1 hydrolytic intermediate and 13 possible transformation products were identified, and predicted metabolic pathways were composed of electron rearrangement, oxidation, cyclization, carboxylation, and so on. Both the adsorption and desorption isotherms of pinoxaden in four kinds of Chinese soil followed the Freundlich equation, and the Freundlich Kf values were positively correlated with the soil cation exchange capacity. According to the calculated Gibbs free energies, the adsorption of pinoxaden was an endothermic reaction and mainly a physical process. These results could provide some useful data for the determination of pinoxaden in other matrices and the evaluation of the environmental fate of pinoxaden in soil and other ecosystems.

Determination, dissipation dynamics, terminal residues and dietary risk assessment of thiophanate-methyl and its metabolite carbendazim in cowpeas collected from different locations in China under field conditions.

BACKGROUND: Thiophanate-methyl and its metabolite carbendazim are broad-spectrum fungicides used on many crops. The residues of these chemicals could result in potential environmental and human health problems. Therefore, investigations of the dissipation and residue behaviors of thiophanate-methyl and its metabolite carbendazim on cowpeas and associated dietary risk assessments are essential for the safety of agricultural products. RESULTS: A simple analytical approach using liquid chromatography with tandem mass spectrometry was developed and validated for the determination of thiophanate-methyl and carbendazim concentrations in cowpeas. Good linearity (R2 > 0.998) was obtained, and the recoveries and relative standard deviations were 80.0-104.7% and 1.4-5.2%, respectively. The dissipation rates of thiophanate-methyl, carbendazim and total carbendazim were high (half-lives of 1.61-2.46 days) and varied in the field cowpea samples because of the different weather conditions and planting patterns. Based on the definition of thiophanate-methyl, the terminal residues of total carbendazim in cowpea samples were below the maximum residue limits set by Japan for other legumes. The acute and chronic risk quotients of three analytes were 0.0-27.6% in cowpea samples gathered from all terminal residue treatments, which were below 100%. CONCLUSION: An optimized approach for detecting thiophanate-methyl and carbendazim in cowpeas was applied for the investigation of field-trial samples. The potential acute and chronic dietary risks of thiophanate-methyl, carbendazim and total carbendazim to the health of Chinese consumers were low. These results could guide the safe and proper use of thiophanate-methyl in cowpeas and offer data for the dietary risk assessment of thiophanate-methyl in cowpeas. © 2021 Society of Chemical Industry.

Determination, residue and risk assessment of trifloxystrobin, trifloxystrobin acid and tebuconazole in Chinese rice consumption.

A simple and rapid analytical method for the detection of trifloxystrobin, trifloxystrobin acid and tebuconazole in soil, brown rice, paddy plants and rice hulls was established and validated by liquid chromatography with tandem mass spectrometry. Acceptable linearity (R2 > 0.99), accuracy (average recoveries of 74.3-108.5%) and precision (intra- and inter-day relative standard deviations of 0.9-8.8%) were obtained using the developed determination approach. In the field trial, the half-lives of trifloxystrobin and tebuconazole in paddy plants were 5.7-8.3 days in three locations throughout China, and the terminal residue concentrations of trifloxystrobin and tebuconazole were <100 and 500 µg/kg (maximum residue limits set by China), respectively, at harvest, which indicated that, based on the recommended application procedure, trifloxystrobin and tebuconazole are safe for use on rice. The risk assessment results demonstrated that, owing to risk quotient values of both fungicides being <100%, the potential risk of trifloxystrobin and tebuconazole on rice was acceptable for Chinese consumers. These data could provide supporting information for the proper use and safety evaluation of trifloxystrobin and tebuconazole in rice.

Determination, residue analysis, risk assessment and processing factors of tebufenozide in okra fruits under field conditions.

BACKGROUND: Ensuring the yield, quality, and profitability of okra by preventing and controlling pests with the application of insecticides has increased in the last decade. Some insecticide residues might remain in edible parts of okra (fruits) and lead to several potential human health problems. Therefore, research on the residue behaviour, risk assessment and removal approach of insecticides on okra fruits is important for food safety, together with the proper application and residual elimination of insecticides in okra. RESULTS: A simple liquid chromatography with tandem mass spectrometry (LC-MS/MS) method was established and validated for determining the tebufenozide residues in okra fruits. The recoveries of tebufenozide in okra fruits were >72% with relative standard deviations of 0.6 to 6.1%. The dissipation rates of tebufenozide were different in okra fruits cultivated under open land and glasshouse field conditions because of the discriminating humidity and temperature conditions. The dietary intake of the tebufenozide residues from okra fruit consumption for Chinese consumers was fairly low, with approximately no potential health risk. The processing factor values of washing, blanching, washing + blanching and soaking were all less than one, which indicated that these processes could effectively reduce the residual hydrazide in the okra fruit. CONCLUSION: The developed method for analysing tebufenozide in okra fruits was applicable for field studies on this insecticide. The potential health risk of tebufenozide in okra fruits could be negligible to the health of different age groups of Chinese consumers. The soaking process effectively removed tebufenozide residues from okra fruits. The obtained data will help Chinese governments establish a maximum residue limit of tebufenozide in okra and provide data for the risk assessment and removal of tebufenozide in other crops. © 2019 Society of Chemical Industry.

A liquid chromatography with tandem mass spectrometry method to simultaneously determinate chlorpyrifos, imidacloprid and imidacloprid metabolites in wheat.

A liquid chromatography with tandem mass spectrometry method was developed and validated to simultaneously determine chlorpyrifos, imidacloprid, and imidacloprid metabolites in soil, wheat grain, and wheat straw matrices. Satisfactory linearity (R2 ≥ 0.9965) of the method was obtained for all analytes. The ranges of limits of detection and limits of quantification for seven analytes in three matrices were 0.17-66.7 and 0.5-200 µg/kg, respectively. Average recoveries were 72.85-81.25% for chlorpyrifos, 78.54-84.70% for imidacloprid, 73.83-81.03% for imidacloprid olefin, 71.47-80.61% for 5-hydroxy imidacloprid, 71.79-81.32% for imidacloprid urea, 70.42-82.20% for imidacloprid nitroguanidine, and 70.91-82.46% for imidacloprid 6-chloronicotinic acid in soil, wheat grain, and wheat straw. The intra- and interday relative standard deviations were less than 8%. The established method was successfully applied for the residual analysis of chlorpyrifos, imidacloprid, and imidacloprid metabolites in actual soil, wheat grain, and wheat straw samples. The results indicated that the established method could be used to detect trace amounts of chlorpyrifos, imidacloprid, and imidacloprid metabolites in wheat and that the method might be able to provide some data on the detection of these seven compounds in other crops.

A liquid chromatography-tandem mass spectrometry method to simultaneously determinate dichlorvos and phoxim in tobacco.

A simple pretreatment method with liquid chromatography-tandem mass spectrometry (LC-MS/MS) was developed and validated to simultaneously determine dichlorvos and phoxim in tobacco and soil matrices. Satisfactory linearity (R2 ≥ 0.9991) of the method was obtained for both analytes. The limits of detection and limits of quantification for dichlorvos and phoxim in three matrices were 0.0015-0.006 and 0.005-0.02 mg/kg, respectively. Average recoveries were 78.24-92.21% for dichlorvos and 76.62-100.51% for phoxim in soil, green tobacco leaves and cured tobacco leaves. The intra- and inter-day relative standard deviations were <6%. The established method was successfully applied for the residual analysis of dichlorvos and phoxim in real soil and tobacco samples. The results indicated that the established method could be used to detect trace amounts of dichlorvos and phoxim in tobacco. The data could also help the Chinese government establish maximum residue limits of dichlorvos and phoxim on tobacco and establish proper and safe use of dichlorvos and phoxim on tobacco plants in China.

Dissipation and the effects of thidiazuron on antioxidant enzyme activity and malondialdehyde content in strawberry.

BACKGROUND: Increasing numbers of fruit swelling agents have been used to improve the fruit rate and production yield of strawberries in recent years. The abuse of fruit swelling agents could lead to an increase in the deformation rate and abnormal coloration of strawberry and a decrease in quality at harvest. Therefore, understanding the harmful effects of fruit swelling agents on strawberry will provide guidance for their reasonable use. RESULTS: The residual determination method for measuring thidiazuron (TDZ) in strawberry was developed and validated by liquid chromatography and tandem mass spectrometry (LC-MS/MS). The recoveries of TDZ in strawberry were 97.9-108.5% with relative standard deviations of 0.9% to 5.3%. The dissipation rates of TDZ were different in strawberries cultivated under field and indoor conditions due to the differences in temperature and humidity. The ascorbic acid content increased when TDZ was applied at 2 mg kg-1 . The SOD (superoxide dismutase), POD (peroxidase) and CAT (catalase) activities of strawberry tended to decrease and subsequently increase following the application of TDZ, and the opposite changes occurred on the malondialdehyde (MDA) content of TDZ-treated strawberry. CONCLUSIONS: The analytical method for measuring TDZ in strawberry that was developed was suitable for dissipation studies on this compound. Antioxidant enzyme activities and the MDA content of strawberry were altered, and some reverse effects, such as membrane damage, were inhibited when TDZ was applied. The data obtained in this study might provide suggestions to reduce the adverse effects of TDZ on strawberry and may help to guide the safe and proper use of TDZ in strawberry. © 2019 Society of Chemical Industry.

Simultaneous determination of residues of thiamethoxam and its metabolite clothianidin in tobacco leaf and soil using liquid chromatography-tandem mass spectrometry.

A simple analytical method was developed to simultaneously determine thiamethoxam and its metabolite, clothianidin, in fresh tobacco leaf, soil and cured tobacco leaf using liquid chromatography with tandem mass spectrometry. Thiamethoxam and clothianidin in tobacco and soil samples were extracted with acetonitrile containing 0.1% formic acid and purified using an NH2 -SPE column. The optimized method provided good linearity with coefficients of determination R2 ≥ 0.9981. The limits of detection and quantification were between 0.006-0.12 and 0.02-0.4 mg/kg, respectively. Intra- and inter-day recovery assays were used to validate the established method. The average recoveries of thiamethoxam and clothianidin in fresh tobacco leaf, soil and cured tobacco leaf were 75.04-100.47%, 75.86-86.40% and 89.83-99.39%, respectively. The intra- and inter-day relative standard deviations were all <9%. The developed method was successfully applied for the analysis of thiamethoxam and clothianidin residues in actual tobacco and soil samples. The results indicated that the established method met the requirements for the analysis of trace amounts of thiamethoxam and clothianidin in fresh tobacco leaf, soil and cured tobacco leaf.

Enantioseparation and determination of dufulin enantiomers in cucumber and soil by chiral liquid chromatography-tandem mass spectrometry.

A simple and rapid method for enantioselective determination of dufulin in cucumber and soil was developed by liquid chromatography with tandem mass spectrometry. The enantiomers were separated on a Superchiral S-OD chiral cellulose tris(3,5-dimethylphenylcarbamate) column at 20°C, with a mixture of acetonitrile and water (0.1% formic acid; 52:48, v/v) as mobile phase at a flow rate of 0.65 mL/min. The pretreatment conditions were optimized using an orthogonal test, and the optimized method showed good linearity and sensitivity. The limits of detection and limits of quantification of two dufulin enantiomers were 0.006 and 0.02 mg/kg, respectively. The average recoveries of S-enantiomer and R-enantiomer in cucumber and soil were 80.61-99.83% and 80.97-102.96%, respectively, with relative standard deviations of 1.30-9.72%. The method was successfully applied to determine dufulin in real cucumber and soil samples. The results demonstrate that the method could facilitate further research on the differences between individual dufulin enantiomers with respect to metabolites and environmental fate and finally help reveal the complex interactions that exist between dufulin, humans and the environment.

Simultaneous determination of boscalid and fludioxonil in grape and soil under field conditions by gas chromatography/tandem triple quadrupole mass spectrometry.

A gas chromatography-tandem mass spectrometry method was developed and validated to simultaneously determine boscalid and fludioxonil in grape and soil samples. These samples were extracted with 10 mL of acetonitrile and purified using a mixed primary secondary amine/octadecylsilane sorbent. The method showed good linearity (R2 > 0.99) in the calibration range 0.005-2 µg/mL for both pesticides. The limits of detection and quantification for the two analytes in grape and soil were 0.006 and 0.02 mg/kg, respectively. Fungicide recoveries in grape and soil were 81.18-92.11% for boscalid and 82.73-97.67% for fludioxonil with relative standard deviations of 1.31-10.31%. The established method was successfully applied to the residual analysis of boscalid and fludioxonil in real grape and soil samples. The terminal residue concentrations of boscalid and fludioxonil in grape samples collected from Anhui and Guizhou were <5 mg/kg (the maximum residue limit set by China) 7 days after the last application and 1 mg/kg (the maximum residue limit set by USA) 14 days after the last application. These results could provide guidance for the proper and safe use of boscalid and fludioxonil in grape and help the Chinese government to establish an MRL for fludioxonil in grape.

Simultaneous determination of residues of metalaxyl, cyazofamid and a cyazofamid metabolite in tobacco leaves and soil by liquid chromatography with tandem mass spectrometry.

A simple method was developed and validated for the simultaneous determination of metalaxyl, cyazofamid and the cyazofamid metabolite 4-chloro-5-p-tolylimidazole-2-carbonitrile (CCIM) by liquid chromatography with tandem mass spectrometry. The three target compounds were extracted from tobacco and soil with acetonitrile containing 0.1% acetic acid, and the extracts were purified using octadecylsilane. The proposed method showed satisfactory linearity (R2 ≥ 0.9985) for the target compounds. The limits of detection for metalaxyl, cyazofamid and CCIM were 0.006, 0.06 and 0.06 mg/kg in soil and green tobacco leaves and 0.03, 0.3 and 0.3 mg/kg in cured tobacco leaves, respectively. The limits of quantification for metalaxyl, cyazofamid and CCIM were 0.02, 0.2 and 0.2 mg/kg in soil and green tobacco leaves and 0.1, 1 and 1 mg/kg in cured tobacco leaves, respectively. The average recoveries from soil and tobacco were 72.91-98.40% for metalaxyl, 76.73-105.80% for cyazofamid and 74.48-106.45% for CCIM. The relative standard deviation range was 1.23-6.99%. The developed method was successfully applied to analysis of residues of metalaxyl, cyazofamid and CCIM in real soil and tobacco samples. The results indicated that the established method could meet the requirement for the analysis of trace amounts of all three analytes in soil and tobacco.

Simultaneous determination and method validation of clethodim and its metabolites clethodim sulfoxide and clethodim sulfone in tobacco by LC-MS/MS.

A simple method was developed and validated for the simultaneous determination of clethodim, clethodim sulfoxide, and clethodim sulfone in soil and tobacco by liquid chromatography with tandem mass spectrometry. The three target compounds were extracted from tobacco and soil with acetonitrile, and the extracts were purified using octadecyl silane. The proposed method showed satisfactory linearity (R2 ≥ 0.9973) for the target compounds. The limits of detection and quantitation of the three analytes in all matrices were 0.024-0.06 and 0.08-0.2 mg/kg, respectively. The recovery was tested in blank soil and tobacco leaf samples and calculated to be 74.8-104.4% with relative standard deviations of 1.9-12.1%. The developed method was successfully applied to the analysis of residues of clethodim, clethodim sulfoxide and clethodim sulfone in real soil and tobacco samples. The results indicated that the developed method can meet the requirements for the analysis of trace amounts of all three analytes in soil and tobacco.

Simultaneous determination and method validation of difenoconazole, propiconazole and pyraclostrobin in pepper and soil by LC-MS/MS in field trial samples from three provinces, China.

A liquid chromatography-electrospray ionization tandem mass spectrometry method was developed for simple and accurate detection of the fungicides difenoconazole, propiconazole and pyraclostrobin in peppers and soil. Three fungicides residues were extracted from samples by acetonitrile and cleaned up by dispersive solid-phase extraction before instrumental analysis. The accuracy and precision of the method were evaluated by conducting an intra- and inter-day recovery experiment. The limits of quantification and detection of difenoconazole, propiconazole and pyraclostrobin in pepper and soil were 0.005 and 0.0015 mg/kg, respectively. The recoveries were investigated by spiking pepper and soil at three levels, and were found to be in the ranges 79.62-103.15% for difenoconazole, 85.94-103.35% for propiconazole and 80.14-97.69% for pyraclostrobin, with relative standard deviations <6.5%. Field experiments were conducted in three locations in China. The half-lives of difenoconazole, propiconazole and pyraclostrobin were 5.3-11.5 days in peppers and 6.1-32.5 days in soil. At harvest, pepper samples were found to contain difenoconazole, propiconazole and pyraclostrobin well below the maximum residue limits of European Union at the interval of 21 days after last application following the recommended dosage.

Simultaneous determination and risk assessment of metalaxyl and azoxystrobin in potato by liquid chromatography with tandem mass spectrometry.

A liquid chromatography with tandem mass spectrometry method was developed and validated to simultaneously determine metalaxyl and azoxystrobin in soil, potato, and potato foliage samples. The samples were extracted by 20 mL of acetonitrile and purified with dispersive solid-phase extraction using octadecyl silane as sorbent. The method showed good linearity (determination coefficients ≥ 0.9926) for metalaxyl (2.5-500 ng/mL) and azoxystrobin (5-1000 ng/mL). The limits of detection and quantification for both fungicides were 1.5-20 µg/kg. The average recoveries in soil, potato, and potato foliage were 83.07-92.87% for metalaxyl and 82.71-98.53% for azoxystrobin. The intra- and inter-day relative standard deviations were all less than 9%. The method was successfully applied on the residual analysis of metalaxyl and azoxystrobin in field trial samples. The results showed that the concentrations of metalaxyl and azoxystrobin in potato samples collected from Guizhou and Hunan were below 50 and 100 µg/kg (maximum residue limit set by China), respectively, at 5 days after the last application. When following the recommended application manual, metalaxyl and azoxystrobin do not present health concerns to the population because the risk quotients are far below 100%. All the above data could help and promote the safe and proper use of metalaxyl and azoxystrobin in potato.

Stereoselective determination of dufulin in watermelon under field conditions using chiral ultra high performance liquid chromatography with high-resolution mass spectrometry.

An effective and sensitive chiral analytical method was established to investigate the stereoselective dissipation of rac-dufulin in watermelon using ultra high performance liquid chromatography with a superchiral S-OD chiral column (4.6 × 150 mm i.d., 5 µm) coupled with high-resolution mass spectrometry. To optimize the pretreatment method for detecting rac-dufulin in the three matrixes, different extraction solvents, extractant volumes, extraction times, and absorbents were investigated to improve extraction efficiency. Moreover, analysis of variance was used to perform method validation for determination of the two dufulin enantiomers in the three matrixes. Using the optimized method, good linearity was obtained (determination coefficient > 0.999). The limits of detection and quantification of the two dufulin enantiomers in soil, watermelon, and pulp were 0.15 and 0.5 µg/kg, respectively. The average recoveries of the two enantiomers in the three matrixes at four spiked levels ranged from 75.0 to 107.8%, with intra- and inter-day relative standard deviations of 0.4-10.4%. In field trials, the R enantiomer was preferentially dissipated in watermelon. These method validation results confirmed that the developed method was convenient and reliable for the stereoselective determination of enantiomers of rac-dufulin in watermelon.