分析保护剂补偿基质效应-气相色谱-质谱法快速测定水果中40种农药残留

Rapid determination of 40 pesticide residues in fruits using gas chromatography-mass spectrometry coupled with analyte protectants to compensate for matrix effects

建立了水果中40种农药化合物的气相色谱-质谱(GC-MS)多残留检测方法,评价了添加分析保护剂对农药残留分析的补偿基质效应和对定量结果可靠性的影响。采用可以溶于丙酮有机溶剂的聚乙二醇Polyethylene Glycol400(PEG 400)和橄榄油作为保护剂组合进行定量分析。水果样品采用乙腈提取,微型固相萃取小柱净化,大体积进样,GC-MS选择离子监测(SIM)模式检测。40种农药化合物在1～200μg/L范围内线性关系良好,线性相关系数在0.99以上,检出限(以信噪比为3计)为0.1～3.0μg/L。除乐果外,其他化合物的添加回收率为75%～119%,相对标准偏差均小于16.6%。通过对添加分析保护剂的校准曲线与基质匹配校准曲线的定量准确性的比较,发现加入分析保护剂方法可以代替基质匹配校正方法,同时采用大体积进样和微型固相萃取净化相结合的方法,大大减少了样品前处理量。将所建立的分析保护剂方法用于苹果、桃子、橙子、香蕉和葡萄等水果样品的分析,基质补偿效应良好,有效地克服了水溶性分析保护剂对气相色谱分析有影响的缺点。

A gas chromatography-mass spectrometry （GC-MS） method was developed for the determination of 40 pesticides in fruits. The effects of adding analyte protectants were evaluated for compensating matrix effects and the impacts on the quantitative results. A new combi- nation of analyte protectants - Polyethylene Glycol 400 （ PEG 400） and olive oil combination, which can be dissolved in acetone, was used for the quantitative analysis. The pesticides were extracted from fruit samples with acetonitrile and the extracts were cleaned up using micro-sol- id phase extraction. A GC-MS method in selective ion monitoring （SIM） mode coupled with large volume injection was finally developed. Using the newly developed analyte protectantcombination of PEG 400 and olive oil, a good linearity was obtained in the range of 1 - 200 μg/L with coefficients better than 0.99, and the detection limits were between 0. 1 - 3.0 μg/L. The mean recoveries of the pesticides were 75% - 119% with the relative standard deviation val- ues less than 16.6% except for dimethoate. The performance of the analyte protectants was compared with matrix-matched standards calibration curves in terms of quantitative accuracy. The results showed that the method of adding analyte protectants can replace the matrix- matched standard calibration, and can also reduce the sample pretreatment. When the devel-oped method was used for the analysis of apple, peache, orange, banana, grape and other fruit samples, a good matrix compensation effect was achieved, and thus effectively reduced the bad effects of the water-soluble agents to the gas chromatographic column.