GC-MS/MS法测定当归中禁限用农药残留量

目的：建立当归57种农药多残留的气相色谱-串联质谱（GC-MS/MS）检测方法，并应用于60批次样品初步筛查。方法：依据风险控制的基本原则，选择我国禁限用、高毒、高风险及当归种植中常用的农药品种为检测指标。对样品前处理方法、色谱分离、质谱检测条件进行了优化，经比较选择了QuEChERS方法处理样品，采用（50%苯基）-甲基聚硅氧烷为固定液的弹性石英毛细管柱（Agilent DB-17MS，0.25 mm×30 m，0.25μm）；载气为高纯氦气，柱流速1.3 mL·min^-1；进样口温度240℃；高压不分流进样；进样量1μL；升温程序为初始温度60℃，保持1 min，以30℃·min^-1升至120℃，以10℃·min^-1升至160℃，以2℃·min^-1升至230℃，以15℃·min^-1升至300℃，保持6 min，再以20℃·min^-1升至320℃，保持3 min。质谱条件为电子轰击源70 eV，离子源温度280℃，接口温度320℃；用动态多反应监测模式（dMRM）采集数据，并采用空白基质匹配-内标法计算以提高结果的准确性。结果：本方法在0.0020~13.243 ng·μL^-1之间线性关系良好，三水平加标回收率实验中全部指标回收率在60%~140%之间，符合痕量测定的要求。结论：该方法有针对性地检测了当归中高风险、高毒性的农药品种，涵盖了宜用GC-MS/MS检测的绝大多数禁限用农药，检测方法快速、准确，适用于当归农药多残留风险控制和日常检测。  

Objective: To establish a method for simultaneous determination of 57 kinds of pesticides in Chinese Angelica by using gas chromatography-tandem mass spectrometry and apply the method to screen 60 batches of samples. Methods: The forbidden, restricted, high-toxic, high-risk and customary pesticides were picked out as detecting indexes according to the principals of risk management. The factors affecting the extraction, purification and detection were optimized and the final condition was established as follows:the samples were extracted and purified by QuEChERS method. The separation of targeted compounds were performed by gas chromatographic method. Chromatographic conditions:Agilent DB-17MS capillary column (0.25 mm×30 m, 0.25 μm)was adopted;the inlet temperature was 240℃;splitless injection;the column temperature was progra mmed to start at 60℃ for 1 min, rising to 120℃ at a rate of 30℃·min^-1, rising to 160℃ at a rate of 10℃·min^-1, rising to 230℃ at a rate of 2℃·min^-1, rising to 300℃ at a rate of 15℃·min^-1, holding for 6 min, rising to 320℃ at a rate of 20℃·min^-1, holding for 6 min. Helium (1.3 mL·min^-1)was used as the carrying gas. The injection volume was 1 μL. The detector was triple quadrupole mass spectrometer. EI source was adopted, the ion energy was 70 eV, the source temperature was 280℃ and the transmission line temperature was 320℃. Quantitative analysis was carried out by GC-MS/MS with dMRM model. Blank matrix matching-internal standard method was applied to reduce matrix-induced enhancement and therefor ensure accuracy of the results. Results: The calibration curves were linear in the range of 0.002 0~13.243 ng·μL^-1 with 94.64% of target compounds' correction coefficients were greater than 0.950. The recoveries of all pesticides ranged from 60% to 140% at three spiked levels, which met the requirements of trace analysis. Conclusion: The detecting indexes in the method cover most of the forbidden and restricted pesticides which are suitable for gas chromatography-tandem mass spectrometry, which is meaningful for the safety supervision of the Chinese Angelica. With the advantage of rapidness and accuracy, this method can be used for routine determination of multi-pesticides in Chinese Angelica. 

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