QuEChERS-GC/UHPLC-MS/MS法测定党参和白及中12种农药残留

Determination of 12 pesticide residues in Codonopsis pilosula and Bletilla striatabyQuEChERS-GC/UHPLC-MS/MS

[目的]通过优化QuEChERS法并结合气相色谱(GC)和超高效液相色谱-串联质谱(UHPLC-MS/MS),建立苯醚甲环唑等12种农药在党参和白及中的残留分析方法。[方法]溴氰菊酯、高效氯氟氰菊酯和联苯菊酯3种菊酯类农药采用GC检测,样品经过乙酸乙酯提取;苯醚甲环唑、咪鲜胺、毒死蜱、甲基硫菌灵、戊唑醇、三唑酮、吡虫啉、啶虫脒和多菌灵9种农药采用UHPLC-MS/MS检测,样品经1.0%乙酸-乙腈提取。所有提取液经C18和GCB净化,采用基质外标法定量。[结果]白及和党参中12种农药在0.005~1.0 mg/L质量浓度范围内线性关系良好(R^(2)>0.99),在3个添加水平0.01、0.1、1.0 mg/kg下平均回收率为72%~116%,RSD为0.41%~11.89%,方法定量限LOQ为0.01 mg/kg。市场抽样检测发现党参检出高效氯氟氰菊酯、多菌灵和戊唑醇3种农药,白及中检出联苯菊酯、高效氯氟氰菊酯、溴氰菊酯、多菌灵、吡虫啉、三唑酮和戊唑醇7种农药。[结论]该方法具有操作简单快速、可靠、灵敏、实用等优点,且前处理过程安全、环保,适用于白及和党参中12种农药的残留快速检测分析,有助于推动中药材农药残留标准体系完善。

[Aims]Residue analysis methods of 12 pesticides such as difenoconazole in Codonopsis pilosula and Bletila striata were devolped with modified QuEChERS method combined with GC or UHPLC-MS/MS.[Methods]3 Pyrethroid pesticides including deltamethrin,lambda-cyhalothrin and bifenthrin were extracted by ethyl acetate and detected by GC.9 Pesticides including difenoconazole,prochloraz,chlorpyrifos,thiophanate-methyl,tebuconazole,triadimefon,imidacloprid,acetamiprid and carbendazim were extracted by acetonitrile containing 1.0%acetic acid and detected by UHPLC-MS/MS.All the extracts were purified by Cis and GCB,and quantified by matrix external standard method.[Results]Good linear relationships(R^(2)>0.99)were performed in the concentration range of 0.005-1.0 mg/L for the 12 pesticides.The average recoveries were 72%-116%at 3 spiked levels of 0.01,0.1 and 1.0 mg/kg,with RSDs of 0.41%-11.89%.L0Q was 0.01 mg/kg.The samples collected from the market were determined by the established methods.Lambda-cyhalothrin,carbendazim and tebuconazole were detected in C.pilosula,and 7 pesticides including bifenthrin,lambda-cyhalothrin,deltamethrin,carbendazim,imidacloprid,triadimefon and tebuconazole were detected in B.striata.[Conclusions]The established methods are simple,fast,reliable,sensitive,and practical with safe and environmentally friendly pre-treatment process.It is suitable for the fast determination of the 12 pesticides in B.striata and C.pilosula,and helpful to the improvement of pesticide residue standard system in Chinese herbal medicines.