Uptake and translocation of fungicide picarbutrazox in greenhouse cabbage: the significance of translocation factors and home processing.

This study evaluated the uptake and translocation of the fungicide picarbutrazox (PBZ) and its isomer in greenhouse cabbage. Two distinct treatments, including foliar spray and soil application of PBZ, were used in this study. In the foliar application, the fungicide was sprayed thrice at intervals of 7 days from 30, 21, and 14 days before harvest following the OECD guidelines of fungicides in crops, whereas in soil treatment, PBZ was applied for one time at concentrations of 2 and 10 mg/kg, and cabbage was cultivated for 68 days. Additionally, the role of root and translocation factors during residual fungicide distribution was demonstrated. The quality control of the analytical study exhibited excellent linearity (R2 ≥ 0.99), the limit of quantification (LOQ 0.005 mg/kg), accuracy (recovery within the range of 70-120%), and precision (relative coefficient within 0.3-13.8%) for studied PBZ and its metabolites. In the foliar application, initially higher amount of residual PBZ was evident in the outermost leaf of the cabbage, whereas in soil treatment, the highest residual PBZ was observed in the soil and roots. Therefore, the application method of picarbutrazox is a critical factor for defining the initial entry route of pesticides and the subsequent translocations through the investigated crops.

Optimization of a Multi-Residue Analytical Method during Determination of Pesticides in Meat Products by GC-MS/MS.

In this study, a multi-residue analysis was developed for 32 compounds, including pesticides and metabolites, in five meat products using gas chromatography-tandem mass spectrometry (GC-MS/MS). The validation of the developed analytical method was also evaluated in accordance with Codex Alimentarius guidelines. Aminopropyl (NH2), C18, and florisil solid phase extraction (SPE) cartridges were used to evaluate and optimize the cleanup procedure of the tested samples prior to GC-MS/MS analysis. Based on the analytical performance, the C18 SPE cartridge was deemed to be the most suitable among the examined SPE cartridges. The optimized method demonstrated that 29 out of 32 tested compounds acquired good linearity (R2 ≥ 0.99), and 25 tested compounds displayed the method limit of quantification (MLOQ) ≤ 0.01 mg/kg. Out of the 32 tested compounds, only 21 compounds met the acceptable analytical criteria for the lard and tallow samples, compared to 27 compounds in the beef, pork, and chicken samples that falls within the acceptable standards for recovery (70-120%) and analytical precision (relative standard deviation RSD ≤ 20%). The average matrix effect was widely varied (20.1-64.8%) in the studied meat samples that were affected by either ion enhancement or suppression. In particular, in the lard sample, 13 compounds showed poor recovery and analytical precision due to ion suppression. Thus, the matrix effect (ME) was considered a critical factor during multi-residue pesticide analysis in different meat products. In conclusion, this developed analytical method can be used as a routine monitoring system for residual pesticide analysis in livestock products with acceptable analytical standards. Further meticulous analytical studies should be optimized and validated for multi-residue pesticide analysis in diversified meat products.

Dissipation characteristics of spirotetramat and its metabolites in two phenotypically different Korean vegetables under greenhouse conditions.

This study involved analysis and method validation of spirotetramat applied to two phenotypically different Korean vegetables (e.g. Korean cabbage and shallots) to determine the safe pre-harvest residue limit (PHRL) and comparative dissipation patterns. Two steps of the investigation involved greenhouse monitoring during crop cultivation followed by LC-MS/MS analysis. Commercial spirotetramat was sprayed twice with seven-day intervals according to the spray schedule (0, 3, 7, 10, 14, and 21 days before harvest) at the dose recommended by the Ministry of Food and Drug Safety (MFDS), Korea. During the validation of the analytical method, good linearity, specificity, and acceptable recoveries (82%-114% for Korean cabbage and 82%-111% for shallot) were established for spirotetramat and its four metabolites. The calculated biological half-life derived from the first-order reaction (t1/2) of spirotetramat was 4.8 days for Korean cabbage and 4.0 days for shallot, respectively. The safe PHRL for Korean cabbage was suggested at 7 days, due to permissible spirotetramat concentration in terms of an acceptable MRL. The findings of the study will be used as the analytical reference point for developing spirotetramat safety guidelines for use in the vegetables investigated.

Residue Monitoring and Risk Assessment of Cyazofamid and Its Metabolite in Korean Cabbage Under Greenhouse Conditions.

The residual characteristics and risk assessment with respect to cyazofamid and its metabolite 4-chloro-5-p-tolylimidazole-2-carbonitrile were monitored in case of Korean cabbage at different preharvest intervals during a greenhouse trial. The 0.02 kg a.i/ha of cyazofamid was sprayed twice on seven-day intervals (i.e., on day 0, 7, 14, and 21 before harvest). The liquid chromatography-tandem mass spectrometry analysis was used to monitor the residual amount of fungicide. The matrix-matched calibration curves with respect to the cyazofamid in Korean cabbage exhibited good linearity (R2 ≥ 0.999) and acceptable recoveries of 84.1%-114.9%. The biological half-life of cyazofamid in Korean cabbage was 3.18 days. During the treatment, the preharvest residue of cyazofamid in Korean cabbage 14 days before harvest (0.80 mg/kg) was lower than that specified by the MFDS-MRL (Ministry of Food and Drug Safety-Maximum Residue Limit, 2.0 mg/kg) and should be recommended as the safe preharvest-interval application limit. The hazard quotient showed low toxicity (70.58%) during the risk assessment study of cyazofamid.

Comparative catalytic degradation of a metabolite 3,5-dichloroaniline derived from dicarboximide fungicide by laccase and MnO2 mediators.

A ternary catalysis system was investigated to evaluate the comparative degradation of toxic fungicide metabolite 3,5-dichloroaniline (3,5-DCA) by laccase and MnO2 with mediators. In this study, copper based fungal enzyme laccase (Trametes versicolor origin) and metal catalyst MnO2 with various combinations of phenolic mediators (catechol, syringaldehyde, syringic acid, caffeic acid and gallic acid) were monitored to optimize and screen the better one for 3,5-DCA degradation assay. Catechol showed better potentiality in reduction of 3,5-DCA among the studied mediators. Catechol (2mM) showed the highest reduction rate (99-100%) followed by syringaldehyde (40.51%) with 2U/mL of laccase at 25 °C within 24 h reaction time. Similarly, complete degradation of 3,5-DCA was obtained by catechol (2mM) with 2 mg/mL of MnO2 in MnO2-mediator assay. The notable finding of current study indicated the triggering of catechol for better 3,5-DCA degradation at higher pH condition but inertness in laccase-mediator assay due to laccase destabilization. The reaction pathways of optimized mediator-based catalysis for laccase and MnO2 were proposed. Finally, the optimized laccase-catechol based degradation was considered as a pioneer green catalysis approach to reduce the toxic metabolite 3,5-DCA concentrations in aqueous medium as compared to MnO2-catechol catalysis.

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 (CPHRL) 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 CPHRL 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 CPHRL calculation provides more accurate information for farmers to produce agricultural products safe from pesticide residues.