QuEChERS-UPLC-MS/MS测定果蔬中4种残留抗凝血杀鼠剂

Determination of Four Anticoagulant Rodenticides Residues in Vegetables and Fruits using QuEChERS-UPLC-MS /MS

采用QuEChERS前处理方法，结合超高效液相色谱-串联质谱技术建立了测定蔬菜、水果中灭鼠灵、杀鼠迷、溴鼠灵、氟鼠酮等4种抗凝血杀鼠剂残留量的方法．于WatersDisQue提取管中，粉碎匀浆的样品由含体积分数1％乙酸的乙腈提取并净化后，UPLCBEHC18液相色谱柱分离，流动相用甲醇和含5mmol／L乙酸铵和体积分数0．1％甲酸的水溶液梯度洗脱，ESI-[M—H]-电离，多反应监测模式，外标法定量．对比在DisQue净化管中分别补加PSA（N-丙基二乙胺键合硅胶）和GCB（石墨化碳黑）填料净化对回收率的影响，结果显示5mg的GCB可以取得满意的效果．方法中灭鼠灵和杀鼠迷在0．5～100／μg／L线性相关，方法检出限为0．25μg/kg，溴鼠灵和氟鼠酮在2～250μgg／L线性相关，LOD为1．0μgg／kg．在低、中、高三个添加水平的加标回收率为86％～128％，相对标准偏差2．4％～16％．

Using the QuEChERS pretretment, a method was established to detect warfarin, coumatetra lyl, brodifacoum, and flocoumafen in vegetables and fruits with ultra high performance liquid chromatography-tandem mass spectrometry （UPLC-MS/MS）. Grounded and homogenized samples were extracted using acetonnitrile containing 1% （V/V） glacial acetic acid in Waters DisQae tubes and cleaned up. Components in the supernatant were separated by an UPLC BEI-I C,a column and eluted by methanol and 5 mmol/L ammonium acetate and 0.1% （V/V） formic acid solution with gradient elution. Analysis was accomplished by ESI-[ M-H ] - with a multiple reaction monitor （MRM） mode and external standard quantification. In order to eliminate matrix effect, DisQue purification tubes with additional PSA and GCB, were tested and discussed. The results showed that 5 mg GCB had good effects. Moreover, warfa- rin and coumatetralyl were in a linear corelation with the range of 0.5 - 100 μg/L and the detection of limits （LOD） was 0.25μg/kg. Brodifacoum and flocoumafen were in a linear correahion with the range of 2 -250 μg/L and the LOD was 1.0 μg/kg. Spiked recoveries at low, medium, and high concentration levels were in the range of 86% - 128% with RSD of 2.4% - 16%.