加速溶剂萃取(ASE)-气相色谱/串联质谱(GC-MS/MS)法测定食用菌中25种农药残留

Determination of 25 pesticide residues in edible fungi by accelerated solvent extraction (ASE) and gas chromatography tandem mass spectrometry (GC-MS/MS)

采用加速溶剂萃取(ASE)-气相色谱/串联质谱(GC-MS/MS)技术建立了5种食用菌香菇、蘑菇、黑木耳、银耳和金针菇中25种常用农药多残留同时检测方法,样品于加速溶剂萃取仪上进行提取,以乙酸乙酯作为提取剂,然后用活性炭和PSA混合SPE小柱进行净化,待测物在气相色谱/串联质谱仪(GC-MS/MS)上测定.分析物在10～500μg/L浓度范围内,线性相关系数均大于0.99,线性良好.分析目标物添加水平为0.005～0.16mg/kg时,回收率范围为70%～108%,RSD范围为4.0%～14.7%,符合残留分析的要求.25种农药的最低检出限为0.1～0.8μg/kg,最低定量限为1.0～3.2μg/kg.应用加速溶剂萃取提高回收率和实验稳定性,同时避免有机溶剂和人体长期接触;GC-MS/MS母离子和子离子一一对应的多反应监测模式有效去除基体杂质干扰和假阳性现象.该方法具有简便快捷、灵敏度高、定性准确等特点,对保障食用菌安全,促进食用菌出口具有重要的意义.利用文中建立的分析方法,在1419份样品中检出的农药残留包括甲胺磷、毒死蜱、甲氰菊酯及联苯菊酯,检出浓度在0.016～0.63mg/kg.

An effective method for the trace analysis of 25 agrochemical multi-residues in edible fungi was developed using accelerated solvent extraction （ASE） and gas chromatography tandem mass spectrometry （GC-MS/MS）, including methamidophos, BHC, malathion, chlorpyriphos, dicofol, fipronil, endosulfan, DDT, buprofezin, bifenthrin, fenpropathrin, tetradifon, cyhalothrin, cypermethrin, fenvalerate, deltamethrin, and so on. Samples were extracted by ASE with ethyl ester and then purified using activated carbon and solid-phase extraction （SPE） columns. The extracts were analyzed by GC-MS/MS. The multiple reaction monitoring （MRM） scheme used involved transitions of the precursor ions to selected two product ions. With the concentration range of application was 0.005~ 0.16mg/kg, the recoveries ranged from 70%~108% and the relative standard deviations were 4.0%~14.7% （n=6）.The detection limits （LODs） and the limits of quantification （LOQs） of the studied compounds ranged from 0.1~0.8 μg/kg and 1.0~3.2 μg/kg in mushromm, agaricus, auricularia, tremelaa ,and flammulina, respectively.The method developed in this work was applied to the trace determination of 25 pesticides mentioned above in 1419 real samples from Fujian provincial markets, of which methamidophos, chlorpyriphos, fenpropathrin, and bifenthrin were found with the concentration range of 0.016~0.63 mg/kg.