PSA-LC-MS/MS法测定菊花药材中12种农药残留

Determination of 12 kinds of pesticide residues in Chrysanthemi Flos by PSA-LC-MS

目的：建立用N-丙基乙二胺（PSA）净化，液相色谱-三重四极杆串联质谱联用法（LC—MS／MS）测定菊花药材中12种有机磷等多类农药残留的方法，并对产于6个省的4个规格的28批菊花样品进行农药残留测定．对菊花使用的安全性进行评价。方法：菊花样品加乙腈、活性炭和氧化铝提取，过PSA柱净化，采用LC—MS／MS方法在多反应监测（MRM）模式下测定，以磷酸三苯酯为内标进行定量分析。结果：12种农药成分在相应的测定范围内线性关系良好，相关系数在0．9961。0．9999内，12种农药在0．018、0．06、0．18mg·kg^-13个添加水平下，加标回收率范围为68．9％～120．4％，RSD（n=3、6、3）范围为1．4％-7．7％，各农药的检出限和定量限分别在0．05～4．1μg·kg^-1和0．2—18．4μg·kg^-1之间；28批菊花样品共检出了多菌灵、吡虫啉、毒死蜱等8种农药残留。但均符合标准规定。结论：该方法经方法学验证可应用于菊花药材中甲胺磷、多菌灵、敌百虫、吡虫啉、敌敌畏、甲霜灵、三唑酮、二嗪磷、甲拌磷、辛硫磷、毒死蜱、氟啶脲12种农药残留的同时检测。

Objective ： To develop a method based on PSA - LC - MS/MS for the determination of 12 kinds of pes- ticide residues in crude drug Chrysanthemi Flos, and to quantify 28 lots of Chrysanthemi Flos of four specifications produced in 6 provinces for the evaluation of safety usage of Chrysanthemi Flos. Methods： Chrysanthemi Flos sam- ples were extracted with acetonitrile, active carbon and aluminum oxide, and purified using a small column of N - propylethylenediamine（PSA）. The prepared samples were analyzed by LC -MS/MS in a multiple reaction monito- ring（MRM） mode,and the pesticides were quantified by triphenylphosphat internal standard method. Results： All the 12 pesticides showed good linearity in their reasonable ranges（r =0. 9961 -0. 9999）. The average recoveries of all the pesticides at three spiked levels of 0. 018,0. 06 and 0. 18 mg ·kg^-1 were in the range of 70. 3% - 96. 2%, 72. 4% - 120. 4% and 68.9% - 118. 5% ;the RSDs（n =3,6,3） were 2. 4% -7. 7%,3.5% -5. 9% ,and 1.4% - 6. 6% ,respectively;and the LOD and LOQ were all in the range of 0. 05 -4. 1 μg·kg^-1and 0. 2 - 18. 4μg·kg^-1 , respectively. Totally 8 kinds of pesticide residues, namely methamidophos, carbendazim, imidacloprid, dichlorvos, metalaxy,triadimefon, phoxim, and chlorpyrifos, were detected in 28 lots of Chrysanthemi Flos samples, and con- formed to safety standards. Conclusion： The methodology validation shows that the method is suitable for simultane- ous multi-residues analysis of 12 kinds of pesticides in Chrysanthemi Flos, such as methamidophos, carbendazim, tri- chlorfon, imidaeloprid, dichlorvos, metalaxyl, triadimefon, diazinon, phorate, phoxim, chlorpyrifos, and chlorfluazuron.