RESUMEN
To prevent pesticides from exceeding maximum residue limits (MRLs) in crops during export and shipment, it is necessary to manage residue levels during the pre-harvest stages. Therefore, the Republic of Korea establishes pre-harvest residue limits (PHRLs) per crop and pesticide. This study was conducted to set PHRLs for penthiopyrad and tebufenpyrad in angelica leaves, where the exceedance rates of MRLs are expected to be high. The LOQ of the analytical method used was 0.01 mg/kg and it demonstrated good linearity, with a correlation coefficient of 0.999 or higher within the quantitation range of 0.005 to 0.5 mg/kg. The recovery and storage stability accuracy values were in the range of 94.5-111.1%, within the acceptable range (70-120%, RSD ≤ 20%). The matrix effect for both pesticides was in the medium-to-strong range, and it did not significantly impact the quantitative results as a matrix-matched calibration method was employed. Using the validated method, residue concentrations of penthiopyrad 20 (%) EC and tebufenpyrad 10 (%) EC were analyzed. Both pesticides exhibited a decreasing residue trend over time. In Fields 1-3 and their integrated results, the biological half-life was within 2.6-4.0 days for penthiopyrad and 3.0-4.2 days for tebufenpyrad. The minimum value of the regression coefficient in the dissipation curve regression equation was selected as the dissipation constant. The selected dissipation constants for penthiopyrad in Fields 1-3 and their integration were 0.1221, 0.2081, 0.2162, and 0.1960. For tebufenpyrad, the dissipation constants were 0.1451, 0.0960, 0.1725, and 0.1600, respectively. The dissipation constant was used to calculate PHRL per field. Following the principles of the PHRL proposal process, residue levels (%) on PHI dates relative to MRLs were calculated, and fields for proposing PHRLs were selected. For penthiopyrad, since the residue level (%) was less than 20%, the PHRL for Field 3 with the largest dissipation constant was proposed. For tebufenpyrad, as the residue level (%) exceeded 80%, the PHRL proposal could not established. It is deemed necessary to reassess the MRL and 'guidelines for safe use' for tebufenpyrad in angelica leaves.
RESUMEN
The matrix effect refers to the change in the analytical signal caused by the matrix in which the sample is contained, as well as the impurities that are co-eluted with the target analyte. In crop sample analysis using LC-MS/MS, the matrix effect can affect the quantification results. Chinese chives are likely to exhibit a strong matrix effect when co-extracted with bifenthrin and butachlor due to the presence of phytochemicals and chlorophyll. A novel analytical method was developed to reduce the matrix effects of bifenthrin and butachlor to a negligible level in Chinese chives. The established method had a limit of quantitation of 0.005 mg/kg and correlation coefficients greater than 0.999 within the range of 0.005-0.5 mg/kg. Matrix effects were found to be negligible, with values ranging from -18.8% to 7.2% in four different sources of chives and two leafy vegetables. Compared to conventional analytical methods for the LOQ and matrix effect, the established method demonstrated improved performances. The analytical method was further applied in a residual study in chive fields. The active ingredient of butachlor 5 granule (GR) was not detected after soil admixture application, while that of bifenthrin 1 emulsifiable concentrate (EC) showed a range from 1.002 to 0.087 mg/kg after foliar spraying. The dissipation rate constant (k) of bifenthrin was determined to be 0.115, thus its half-life was calculated to be 6.0 days. From the results, PHI and safety use standards of both pesticides were suggested. The developed analytical method can be applied to accurately determine bifenthrin and butachlor residues in Chinese chives and provides a foundation for further research on the fate and behavior of these pesticides in the environment.