山楂中农药使用情况调研及基于LC-ESI-MS/MS的农药残留分析

Survey on pesticide use in Crataegi Fructus and analysis of pesticide residues based on LC-ESI-MS/MS

为研究药用山楂的农药残留情况,该实验以基地山楂农药调研为基础,结合课题组前期搭建的LC-ESI-MS/MS农药筛查平台的盲筛结果,建立适合药用山楂实际情况的农药残留(主要包含杀虫剂和杀菌剂)分析方法,并对来自于山东、河北、河南、山西、辽宁(主要栽培产区)的药用山楂进行农药残留分析。采用改良的Qu ECh ERS方法进行样品前处理,样品用乙腈-水(9∶1)提取,经PSA,C18,GCB,硅胶净化后,采用LC-MS/MS进行分离和检测,离子源为ESI源,扫描模式为正离子,11种农药在5~300μg獉kg^-1线性关系良好(R2>0. 996 9),定量限(S/N=10)为0. 2~10μg獉kg^-1,在低、中、高3个添加水平,所有农药的加标回收率为70. 02%~112. 0%,RSD≤17%。检测结果中多菌灵、毒死蜱、苯醚甲环唑检出率最高,高达79%,82%,56%,部分山楂中检出中药材中禁用农药克百威,提示其安全风险。该研究为山楂的风险评估和政府监管提供方法参考和基础数据。

In order to study the pesticide residues of the medicinal Crataegi Fructus,this study aims to establish an analysis method for pesticide residues( mainly containing insecticides and fungicides) suitable for the actual situation of medicinal Crataegi Fructus based on the survey of the pesticides of the Crataegi Fructus base,combined with the blind screening results of the LC-ESI-MS/MS pesticide screening platform established by the research team in the early stage. Then,the pesticide residues in medicinal Crataegi Fructus from Shandong,Hebei,Henan,Shanxi,and Liaoning( main cultivation areas) were analyzed. The samples were pretreated by the modified Qu ECh ERS method,i.e.,extracted with acetonitrile-water( 9 ∶1),purified by PSA,C18,GCB,silica gel. The detection of pesticides was performed by LC-MS/MS. The ion source was ESI with positive scanning mode,and the linearity of 11 kinds of pesticides in the range of 5-300 μg·kg^-1 was acceptable( R2>0. 996 9). All the recoveries of pesticides were within 70. 02%-112. 0% in the low,medium and high levels,with RSD≤17%. The results showed that the detection rate of carbendazim,chlorpyrifos and difenoconazole is 79%,82%,56%,respectively. Besides,the prohibition pesticide carbofuran were detected in some of the batches,indicating the security risk. This study provides methodological references and basic data for risk assessment of Crataegi Fructus and government regulation.