Fate of multi-residue insecticides and their metabolites in the process of vinification: Analytical method validation, dissipation kinetics, processing factor, and risk assessment.

In viticulture, the use of synthetic chemical formulations introduces insecticide residues into harvested grapes and further into processed grape products, posing a safety concern to consumers. This study investigated the fate of ten insecticide residues and their metabolites from vine to wine. A rapid validated multi-residue approach using QuEChERS extraction and LC-MS/MS configuration was employed for targeted analysis in grape, pomace, and wine. The targeted insecticides showed satisfactory mean recoveries (76.03-111.95%) and precision (RSD = 0.75-7.90%) across the three matrices, with a matrix effect ranging from -16.88 to 35.18%, particularly higher in pomace. Preliminary grape washing effectively removed 15.52-61.31% of insecticide residues based on water solubility and systemic nature. Residue dissipation during fermentation ranged from 73.19% to 87.15% with a half-life spanning from 1 to 5.5 days. The mitigation rate was observed at 12.85-26.81% for wine and 17.76-51.55% for pomace, with the highest transfer rate for buprofezin (51.55%) to pomace and fipronil (25.72%) to wine. Calculated processing factors (PF) for final wine ranged from 0.16 to 0.44, correlating strongly with the octanol-water partition ratio of targeted insecticides. The reported PF, calculated hazard quotient (HQ) (0.003-5.800%), and chronic hazard index (cHI) (2.041-10.387%) indicate reduced residue concentrations in wine and no potential chronic risk to consumers, ensuring a lower dietary risk to wine consumers.

Method development and validation in the curry leaf matrix employing advanced mass spectrometry: quantitative screening of 490 multiclass pesticides by buffered ethyl acetate technique.

Curry leaf is an evergreen herb with culinary, pharmaceutical, and nutraceutical applications. As pesticide residue in curry leaf has garnered significant regulatory attention in recent years, here we report a reliable method, which was validated for the determination of 265 and 225 pesticides using LC-MS/MS and GC-MS/MS, respectively. At first, the sample was comminuted after adding water (1:2). The sample preparation workflow included extraction of 10 g homogenized sample with 10 mL ethyl acetate (+1% acetic acid), cleanup by dispersive solid phase extraction (d-SPE, 50 mg PSA + 50 mg C18 + 10 mg GCB + 150 mg Na2SO4) and the final analysis by tandem mass spectrometry. The cleanup step adeptly removed co-extractives. The method effectively reduced matrix effects and offered an LOQ of 0.01 mg kg-1 for most compounds. The method's accuracy and precision results fulfilled the requirements of SANTE/11312/2021 guidelines at 0.01 mg kg-1 and higher levels of fortification. The accuracy and precision results were comparable for all pesticides. The successful screening of market samples indicates its high extraction efficiency and precision for incurred residue analysis. Due to its robustness and conformity with regulatory criteria, food testing laboratories worldwide can use the method to monitor pesticide levels in curry leaves.

Dissipation kinetics, safety evaluation, and decontamination of residues of the combo-formulation iprovalicarb 8.4% + copper oxychloride 40.6% WG in/on grapes (Vitis vinifera L.).

A field experiment was conducted to study the dissipation behavior and decontamination of iprovalicarb and copper oxychloride in grapes. After thorough validation, the analysis was carried out by employing LC-MS/MS for iprovalicarb and AAS for copper oxychloride. The dissipation pattern of residues followed a linear first-order kinetics model for both the test fungicides. The half-life values for iprovalicarb were 9.5-13.5 days, and for copper oxychloride was 24.5 days. Based on the study, a pre-harvest interval (PHI) of 17 days is proposed for the formulation. In decontamination studies, combination treatment of 0.1% sodium bicarbonate + ultrasonication and 2% lemon water + ultrasonication has shown the highest reduction of iprovalicarb (90.02% reduction) and copper oxychloride (80.14% reduction) residues, respectively. The safety evaluation data suggest that the daily exposure at all the sampling points was less than the maximum permissible intake (MPI) calculated indicating, safety to consumers. This study will be useful for promoting effective residue management and the safe use of these chemicals for controlling fungal diseases in grapes.