農產品中極性農藥及其代謝物之多重殘留分析方法開發   全文下載

Development of the Multi-Residue Analytical Method for Polar Pesticides and their Metabolites in Foods

本研究參考歐盟QuPPe方法（Quick Polar Pesticides Method），建立以液相層析串聯質譜儀（Liquid Chromatography/Tandem Mass Spectrometer, LC-MS/MS）分析蔬果類、穀類及乾豆類、茶類與植物油類中8項極性農藥及其代謝物，包括嘉磷塞、嘉磷塞代謝物1（Aminomethylphosphonic acid, AMPA）、嘉磷塞代謝物2（N-acetyl-glyphosate）、固殺草（Glufosinate-ammonium）、固殺草代謝物1（3-（Methylphosphinico）propionic acid, MPPA）、固殺草代謝物2（N-Acetyl-glufosinate）、益收生長素（Ethephon）及福賽得（Fosetyl-Al）之多重殘留檢驗方法。其前處理流程先依基質調整水分含量，添加內部標準品後以含1%甲酸之甲醇溶液（植物油基質改以含1%甲酸之70%甲醇溶液）萃取，置於-20℃冷凍90分鐘，依基質複雜程度搭配乙腈或C18吸附劑淨化後以LC-MS/MS分析。本研究選用Anionic Polar Pesticide（APP）層析管柱，以1.2%甲酸之水溶液及含0.5%甲酸之乙腈溶液為移動相進行層析。確效試驗以含6項內標校正之標準曲線進行蘋果、白米、茶葉及菜籽油等4種代表性農產品基質中8項極性農藥及其代謝物之添加回收試驗，變異係數除茶葉中AMPA於添加濃度0.05 ppm時為23.7%外，其餘極性農藥品項之平均回收率範圍介於55.4-133.4%，變異係數皆小於17.6%，皆符合歐盟SANTE/11312/2021規範，定量極限（0.01-0.1 ppm）於各基質中皆符合我國農藥殘留容許量標準要求，亦可接軌多數國際標準。本研究使用APP層析管柱可穩定分析8項極性農藥及其代謝物，適用基質涵蓋蔬果類、穀類、茶類及植物油，可供例行監測使用，保障民眾健康安全。

This study developed a multi-residue analytical method for 8 polar pesticides and their metabolites in vegetables, fruits, grains, legumes, tea, and vegetable oils using a liquid chromatograph tandem mass spectrometer (LC-MS/MS) with reference to the European Union’s QuPPe (Quick Polar Pesticides) method. The target analytes included glyphosate, glyphosate metabolites [aminomethylphosphonic acid (AMPA) and N-acetyl-glyphosate], glufosinate-ammonium, glufosinate metabolites [3-(methylphosphinico)propionic acid (MPPA) and N-acetyl-glufosinate], ethephon, and fosetyl-Al. The sample preparation process involved adjusting water content based on the matrix, adding internal standards, extracting with methanol containing 1% formic acid (with 70% methanol for vegetable oil), freezing at -20℃for 90 minutes, subsequently purifying using acetonitrile or C18 adsorbents depending on matrix complexity, prior to LC-MS/MS analysis. The method employed an Anionic Polar Pesticide (APP) column with 1.2% formic acid and acetonitrile containing 0.5% formic acid as the mobile phase. Method validation was conducted through spiking 8 polar pesticides and their metabolites in four representative agricultural product matrices (apple, rice, tea, and canola oil), and constructing standard curves with 6 isotope-labeled internal standards. The method demonstrated average recoveries of 55.4- 133.4% with coefficients of variation below 17.6%, except for AMPA in tea at 0.05 ppm (23.7%). These results meet the European Union SANTE/11312/2021 guidelines. The limits of quantification (LOQs) were satisfied with Taiwan’s“Standards for Pesticide Residual Limits in Foods”requirements for polar pesticide residues (0.01-0.1 ppm) and aligned with international standards. This developed method used the APP column demonstrated reliable analysis of the 8 polar pesticides and their metabolites without the need for additional column equilibration. It is applicable for diverse food matrices across fruits, vegetables, grains, legumes, tea, and vegetable oil, contributing for routine inspection to ensure the public health and safety.