通过式净化结合超高效液相色谱-串联质谱快速检测牛羊奶中有机磷农药残留

Determination of organophosphorus pesticide residues in milk of cows and sheep by ultra-high-performance liquid chromatography- tandem mass spectrometry combined with passing type purification method

目的建立通过式固相萃取净化前处理技术快速测定牛羊奶中敌敌畏、敌百虫、倍硫磷、倍硫磷砜、倍硫磷亚砜、氧倍硫磷、倍硫磷氧砜、倍硫磷氧亚砜、辛硫磷、巴胺磷、马拉硫磷、二嗪农、蝇毒磷13种常见有机磷农药及其代谢产物残留的液相色谱-串联质谱的检测方法。方法牛羊奶采用乙腈沉淀蛋白,4℃离心除脂后经通过式固相萃取柱净化,超高效液相色谱-串联质谱于电喷雾正离子模式和多反应监测扫描模式下进行测定,基质匹配标准曲线外标法定量。结果13种目标化合物阴性加标水平在5、10和20μg/L下,回收率为81.5%~107.5%,精密度为1.24%~6.23%。13种目标化合物的检出限为0.015~0.15μg/L,定量限为0.05~0.50μg/L。对20件牛羊奶样品进行目标化合物的检测,未检测到有机磷农药残留。结论该方法线性相关性良好、检出限低,精密度和准确度均符合要求,可拓展多种类的农药检测,适用牛羊奶及相关制品的日常监测。

OBJECTIVE A method for the rapid determination of dichlorvos, trichlorfon, fenthion, fenthion-sulfone, fenthion-sulfoxide, fenthion-oxon, fenthion-oxon-sulfone, fenthion-oxon-sulfoxide, phoxim, propetamphos, malathion, diazinon and coumaphos 13 common organophosphorus pesticides and their metabolites poison residues in milk of cows and sheep by ultra-high-performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS) with passing type solid phase extraction(SPE) purification was developed.METHODS After centrifugation at 4 ℃,the milk was purified by passing type SPE with acetonitrile precipitating protein and determined by UPLC-MS/MS in electrospray positive ion mode(ESI+) and multi-reaction monitoring scanning(MRM),external standard method for quantitative analysis with matrix matching standard curve.RESULTS The recoveries of 13 target compounds were between 81.5% and 107.5% and relative standard deviation was between 1.24% and 6.23% at three spiked levels of 5,10,20 μg/L. The detection limits of 13 target compounds were between 0.015 and 0.15 μg/L, and the quantitative limits were between 0.05 and 0.50 μg/L. No organophosphorus pesticide residues were detected in 20 samples of cows and sheep milk. CONCLUSION The method has the advantages of good linear independence, low detection limit, high precision and accuracy, and can be used for daily monitoring of milk and related products.