衍生化结合分散固相萃取–UPLC–MS/MS法测定果品中EBDCs类农药残留

建立了果品中乙撑双二硫代氨基甲酸酯(盐)类(简称EBDCs)残留的液质串联确证快速检测方法。果品样品中的EBDCs经碘甲烷甲基衍生化后用分散固相萃取(QuEChERS)提取和净化,利用超高效液相色谱—串联质谱(UPLC–MS/MS)在多反应离子监测模式下进行检测,采用基质匹配标准曲线校正,外标法定量。以碎片离子对m/z 241.1/117.1、m/z 241.1/193.0进行定性分析、m/z 241.1/134.0进行定量分析。结果表明,代森锌、代森锰、代森锰锌、代森钠和代森联的甲基化衍生产物亚乙基–1,2–双二硫代氨基甲酸甲酯在不同水果中具有不同的基质效应;在0.005~1.000 mg·kg~(-1)(以二硫化碳计)之间具有良好的线性关系,相关系数为0.9948~0.9996。在苹果、桃、葡萄、柑橘和香蕉果实样品中添加不同水平乙撑双二硫代氨基甲酸酯(盐)时,回收率为82.6%~98.8%,相对标准偏差为0.7%~8.8%。本方法的检出限(以CS2计)为0.6~1.0μg·kg~(-1),定量限(以CS2计)为10μg·kg~(-1)。本方法简便、快速、准确,可用于果品中乙撑双二硫代氨基甲酸酯(盐)的残留确证检测。

Determination of EBDCs Residues in Fruit by Ultra Performance Liquid Chromatography-Mass Spectrometry with Derivatization and QuEChERS Treatment

In this study,a rapid method has been developed for the determination of germicide EBDCs residues in fruits.The EBDCs of fruits sample,which was methylated by methyl iodide (CH3I),was extracted by the Quick,Easy,Cheap,Effective,Rugged and Safe method (QuEChERS) and detected by ultra performance liquid chromatography-mass spectrometry under multiple reaction monitoring mode,then quantified by matrix-match standard solution.The qualitative results were obtained based on the characteristic m/z 241.1/117.1 ion and m/z 241.1/193.0 ion.The quantitation results were on the intension of the characteristic m/z 241.1/134.0 ion.The results show that the derivative of Maneb,Zineb,Mancozeb,Disodium and Metiram have different matrix effect in different fruits and good linearity in the ranges of 0.005-1.000 mg · kg-1 (in CS2),and the correlation are between 0.9948 and 0.9996.The recoveries for apple,peach,grape,citrus and banana samples at the different fortified levels ranged from 82.6％ to 98.8％ with relative standard deviations (RSD) of 0.7％-8.8％.Limits of detection of EBDCs were 0.6-1.0 μg· kg-1 (in CS2),while limits of quantification were 10 μg· kg-1 (in CS2).The method is simple,rapid,and accurate,and can meet the requirements of the domestic and international legislation.