Center for Food Safety and Applied Nutrition, US Food and Drug Administration, College Park, Maryland 20740-3835, USA.
J Agric Food Chem. 2010 May 26;58(10):5897-903. doi: 10.1021/jf903849n.
A high-throughput, QuEChERS (Quick, Easy, Cheap, Effective, Rugged, Safe) sample preparation and liquid chromatography-tandem mass spectrometry (LC-MS/MS) analytical method has been developed and validated for the determination of 191 pesticides in vegetation and fruit samples. Using identical LC analytical column and MS/MS instrumentation and operation parameters, this method was evaluated at the U.S. Food and Drug Administration (FDA), National Research Centre for Grapes (NRCG), India, and Ontario Ministry of the Environment (MOE) laboratories. Method validation results showed that all but 1 of these 191 pesticides can be analyzed by LC-MS/MS with instrument detection limits (IDL) in the parts per trillion (ppt) range. Matrix-dependent IDL studies showed that due to either the low ionization efficiency or matrix effect exerted, 14 of these 191 pesticides could not be analyzed by this method. Method recovery (%R) and method detection limits (MDLs) were determined by the three laboratories using four sample matrices in replicates (N = 4). With >79% of %R data from the fortification studies in the range from 80 to 120%, MDLs were determined in the low parts per billion range with >94% of MDLs in the range from 0.5 to 5 ppb. Applying this method to the analysis of incurred samples showed that two multiple reaction monitoring (MRM) transitions may not be enough to provide 100% true positive identification of target pesticides; however, quantitative results obtained from the three laboratories had an excellent match with only a few discrepancies in the low parts per billion levels. The %R data from the fortification studies were subjected to principal component analysis and showed the majority of %R fell into the cluster of 80% < %R < 120%. Due to the matrix effect exerted by ginseng and peach, outliers were observed at the lowest spiking levels of 10 and 25 ppb. The study also showed that QuEChERS samples should be analyzed as soon as prepared or stored in a freezer to avoid any adverse affect on the analytes evaluated.
建立并验证了一种用于植被和水果样品中 191 种农药残留检测的高通量 QuEChERS（Quick, Easy, Cheap, Effective, Rugged, Safe）样品前处理方法和液相色谱-串联质谱（LC-MS/MS）分析方法。本方法使用相同的 LC 分析柱和 MS/MS 仪器及操作参数，在美国食品药品监督管理局（FDA）、印度国家葡萄研究中心（NRCG）和安大略省环境部（MOE）实验室进行了评估。方法验证结果表明，在 191 种农药中，除 1 种外，其余 190 种均可通过 LC-MS/MS 进行分析，仪器检测限（IDL）达到 ppt 级。基质依赖性 IDL 研究表明，由于电离效率低或基质效应的影响，有 14 种农药无法用该方法进行分析。回收率（%R）和方法检测限（MDL）由三个实验室采用四种基质在重复（N=4）条件下进行测定。通过加标回收率研究，79%以上的%R数据在 80%至 120%范围内，MDL 则在低 ppb 级，其中 94%以上的 MDL 在 0.5 至 5 ppb 范围内。将该方法应用于实际样品分析表明，两个多重反应监测（MRM）转换可能不足以对目标农药进行 100%的准确鉴定；然而，三个实验室获得的定量结果非常吻合，仅在低 ppb 级水平存在少数差异。加标回收率研究的数据进行主成分分析后表明，大部分%R 落在 80%<%R<120%的聚类中。由于人参和桃对分析物的基质效应影响，在 10 和 25 ppb 的最低加标水平观察到了离群值。研究还表明，QuEChERS 样品应尽快进行分析或在冷冻状态下保存，以避免对评估的分析物造成任何不利影响。
