Li Jie, Ju Xiang, Wang Yan-Li, Tian Qi-Yan, Liang Xiu-Qing, Li Hai-Xia, Liu Yan-Ming
Shandong Institute for Food and Drug Control, Key Laboratory of Supervising Technology for Meat and Meat Products for State Market Regulation, Shandong Research Center of Engineering and Technology for Quality Control of Food for Special Medical Purposes, Shandong Research Center of Engineering and Technology for Safety Inspection of Food and Drug, Jinan 250101, China.
Se Pu. 2023 Jul;41(7):610-621. doi: 10.3724/SP.J.1123.2022.10010.
Improvements in living standards have led to an increase in the consumption of animal-derived foods. Pesticides may be used illegally during animal breeding as well as meat production and processing for pest control and preservation. Pesticides applied to crops may also be enriched in animal tissues through the food chain, thereby increasing the risk of pesticide residue accumulation in muscles and visceral tissues and endangering human health. China has stipulated maximum residue limits for pesticide residues in livestock and poultry meat and their viscera. Many other major developed countries and organizations, including the European Union, Codex Alimentarius Commission, and Japan, have also set maximum residue limits for these residues (0.005-10, 0.004-10, and 0.001-10 mg/kg, respectively). Research on pretreatment technologies for pesticide residue detection in plant-derived foods is widely available, but insufficient attention has been paid to animal-derived foods. Thus, high-throughput detection technologies for pesticide residues in animal-derived foods are limited. The impurities that can interfere with the detection process for plant-derived foods mainly include organic acids, polar pigments, and other small molecular compounds; by contrast, the matrix of animal-derived foods is much more complex. Macromolecular proteins, fats, small molecular amino acids, organic acids, and phospholipids can interfere with the detection of pesticide residues in animal-derived foods. Thus, selecting the appropriate pretreatment and purification technology is of great importance. In this study, the QuEChERS technique was combined with online gel permeation chromatography-gas chromatography-tandem mass spectrometry (GPC-GC-MS/MS) to determine 196 pesticide residues in animal-derived foods. The samples were extracted with acetonitrile, purified using the QuEChERS technique coupled with online GPC, detected by GC-MS/MS, determined in multiple reaction monitoring mode (MRM), and quantified using the external standard method. The effects of the extraction solvent and purification agent type on the extraction efficiency and matrix removal of the method were optimized. The purification effect of online GPC on the sample solution was investigated. The optimal distillate receiving time was obtained by studying the recoveries of the target substances and matrix effects over different distillate receiving periods to achieve the effective introduction of target substances and efficient matrix removal. Further, the advantages of the QuEChERS technique combined with online GPC were evaluated. The matrix effects of 196 pesticides were assessed; ten pesticide residues showed moderate matrix effects, while four pesticide residues showed strong matrix effects. A matrix-matched standard solution was used for quantification. The 196 pesticides showed good linearity in the range of 0.005-0.2 mg/L, with correlation coefficients greater than 0.996. The limits of detection and quantification were 0.002 and 0.005 mg/kg, respectively. The recoveries of 196 pesticides at spiked levels of 0.01, 0.05, and 0.20 mg/kg were 65.3%-126.2%, with relative standard deviations (RSDs) of 0.7%-5.7%. The proposed method is rapid, accurate, and sensitive; thus, it is suitable for the high-throughput screening and detection of multiple pesticide residues in animal-derived foods.
生活水平的提高导致了动物源性食品消费量的增加。在动物养殖以及肉类生产和加工过程中,可能会非法使用农药进行害虫防治和保鲜。施用于农作物的农药也可能通过食物链在动物组织中富集,从而增加农药残留在肌肉和内脏组织中积累的风险,危害人类健康。中国已规定了畜禽肉及其内脏中农药残留的最大限量。包括欧盟、食品法典委员会和日本在内的许多其他主要发达国家和组织也对这些残留设定了最大限量(分别为0.005 - 10、0.004 - 10和0.001 - 10毫克/千克)。关于植物源性食品中农药残留检测的预处理技术研究广泛,但对动物源性食品的关注不足。因此,动物源性食品中农药残留的高通量检测技术有限。能够干扰植物源性食品检测过程的杂质主要包括有机酸、极性色素和其他小分子化合物;相比之下,动物源性食品的基质要复杂得多。大分子蛋白质、脂肪、小分子氨基酸、有机酸和磷脂会干扰动物源性食品中农药残留的检测。因此,选择合适的预处理和净化技术至关重要。在本研究中,将QuEChERS技术与在线凝胶渗透色谱 - 气相色谱 - 串联质谱(GPC - GC - MS/MS)相结合,用于测定动物源性食品中的196种农药残留。样品用乙腈提取,采用QuEChERS技术结合在线GPC进行净化,通过GC - MS/MS检测,在多反应监测模式(MRM)下测定,并采用外标法进行定量。优化了提取溶剂和净化剂类型对该方法提取效率和基质去除效果的影响。研究了在线GPC对样品溶液的净化效果。通过研究不同馏分接收时间段内目标物质的回收率和基质效应,获得了最佳馏分接收时间,以实现目标物质的有效引入和基质的高效去除。此外,评估了QuEChERS技术与在线GPC相结合的优势。评估了196种农药的基质效应;10种农药残留表现出中等基质效应,4种农药残留表现出强基质效应。采用基质匹配标准溶液进行定量。196种农药在0.005 - 0.2毫克/升范围内线性良好,相关系数大于0.996。检测限和定量限分别为0.002和0.005毫克/千克。在0.01、0.05和0.20毫克/千克加标水平下,196种农药的回收率为65.3% - 126.2%,相对标准偏差(RSD)为0.7% - 5.7%。所提出的方法快速、准确、灵敏;因此,适用于动物源性食品中多种农药残留的高通量筛查和检测。