Residue risk assessment and enantioselective analysis of Fenpropimorph in tea and agricultural products by UHPLC-MS/MS
文献类型: 外文期刊
作者: Xinzhong Zhang;Min Wang;Yating Ning;Yue Hu;Yan Zhao;Mei Yang;Hezhi Sun;Xinru Wang;Li Zhou;Fengjian Luo
作者机构:
关键词: Enantioselective residue;Fenpropimorph;Risk assessment;Tea;UHPLC-MS/MS
期刊名称: Microchemical Journal
ISSN: 0026-265X
年卷期: 2025 年 219 卷
页码:
收录情况: SCIE(2025版)
摘要: Fenpropimorph was specifically developed for controlling powdery mildew and other various plant diseases. However, despite its widespread use in agricultural production, there have been few reports on the enantiomeric residues of fenpropimorph. In this research, a modified QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) extraction and purification method combined with ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) analysis was first established and validated for quantifying the residues of fenpropimorph enantiomers in various tea varieties and other agricultural products. Enantiomeric separation of fenpropimorph was successfully achieved using a Lux 3 μ Cellulose-3 chiral column. The mobile phases consisted of water containing 5 mmol/L ammonium acetate and acetonitrile containing 0.1 % formic acid, and a gradient elution program was employed. Under these conditions, (−)-fenpropimorph was eluted prior to (+)-fenpropimorph. This is the first report on the separation of fenpropimorph enantiomers via reversed-phase liquid chromatography (RPLC), which clarifies both the configurations and elution sequences of fenpropimorph enantiomers. For method validation, recoveries of fenpropimorph enantiomers at four spiked levels in different samples ranged from 74.3 % to 112.0 %, with relative standard deviations (RSDs) below 17.8 %. The limits of quantification (LOQs) were determined to be 0.0005 mg/kg in romaine lettuce, 0.001 mg/kg in wheat flour, peas, and fresh tea leaves, and 0.0025 mg/kg in dried pepper and various tea samples. This newly developed method was subsequently applied to track the residue dynamics of fenpropimorph enantiomers throughout the green tea production chain, from tea cultivation to the final cup of tea. The results showed that the half-lives (t1/2) of (−)-fenpropimorph and (+)-fenpropimorph in growing tea plants were 3.45 days and 3.48 days, respectively, with enantiomeric fraction (EF) values ranging from 0.496 to 0.504. Five days after the application of fenpropimorph at a rate of 300 g active ingredient (a.i.) per hectare, the terminal residues of (−)-fenpropimorph and (+)-fenpropimorph were determined to be 1.92 mg/kg and 1.89 mg/kg in fresh tea leaves, and 7.43 mg/kg and 7.92 mg/kg in processed green tea, respectively. Based on these findings and combined with a dietary intake risk assessment, it is recommended that the pre-harvest interval (PHI) for fenpropimorph in tea gardens be set at 5 days, additionally, the maximum residue limit (MRL) for both (−)-fenpropimorph and (+)-fenpropimorph in green tea can be set at 10 mg/kg.
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