QuEChERS-高效液相色谱-串联四极杆/静电场轨道阱高分辨质谱法同时测定水产品中62种农药残留

Simultaneous determination of 62 kinds of pesticides in aquatic products by QuEChERS-high-performance liquid chromatography coupled with quadrupole/orbitrap high resolution mass spectrometry

中文关键词:  高效液相色谱串联四极杆/静电场轨道阱高分辨质谱  QuEChERS  农药  水产品

英文关键词:high-performance liquid chromatography coupled with quadrupole/orbitrap high-resolution mass spectrometry  QuEChERS  pesticides  aquatic products

中文摘要:

      建立QuEChERS结合超高效液相色谱串联四极杆/静电场轨道阱高分辨质谱法(high performance liquid chromatography coupled with quadrupole/orbitrap high-resolution mass spectrometry, HPLC/Q-Orbitrap HRMS)快速测定水产品中甲胺磷、毒死蜱、三唑酮、西马津和溴氰菊酯等62种农药残留量的方法。To establish a method for rapid determination of 62 kinds of pesticide residues such as methamidophos, chlorpyrifos, triazolone, simazine and deltamethrin in aquatic products by QuEChERS high performance liquid chromatography coupled with quadrupole/orbitrap method high-resolution mass spectrometry, HPLC/Q-Orbitrap HRMS).方法 样品采用1%甲酸乙腈/水溶液提取, 300 mg N-丙基乙二胺(primary secondary amine, PSA)和C18分散吸附剂进行净化, 上清液氮吹浓缩后结合HPLC/Q-Orbitrap HRMS进行定性定量测定。结果 62种农药在1~200 μg/L质量浓度范围内呈良好的线性关系, 相关系数r2均大于0.99(甲基毒死蜱除外), 方法定量限(limit of quantification, LOQ)为2~10 μg/kg之间。在大菱鲆、南美白对虾、扇贝3种基质中, 分别进行1倍LOQ、2倍LOQ和10倍LOQ 3个水平的加标试验, 62种农药化合物3种添加水平回收率分别为61.4%~112.4%、63.7%~119.6%、66.2%~113.5%, 相对标准偏差分别为2.1%~11.5%、2.6%~13.4%以及2.7%~15.2%。基质效应评价实验中, 大菱鲆相对于南美白对虾和扇贝有更强的基质效应, 其中51.2%化合物表现出弱基质效应, 46.8%化合物为基质抑制效应。利用该方法对当地市场中30批样品进行农药残留的检测, 结果发现共有5批大菱鲆样品和2批南美白对虾中检测出农药残留化合物。主要是除草剂和杀虫杀菌剂等, 例如西马津、扑草净、毒死蜱、溴氰菊酯和毒草胺等。通过定量分析, 各化合物浓度均低于国内外相关标准限量。结论 该研究可以快速、准确地检测鱼肉产品中的农药残留化合物, 为食品安全监测提供了有力的技术支持。

英文摘要:

      ABSTRACT: Objective To establish an analytical method for simultaneous and rapid determination of 62 pesticides residues in aquatic products including methamidophos, chlorpyrifos, triazolone, simazine, deltamethrin, QuEChERS-high performance liquid chromatography coupled with quadrupole/orbitrap high-resolution mass spectrometry, was developed as a method of detecting. Methods The samples were extracted by 1% acidified acetonitrile/water, cleaned-up by 300 mg primary secondary amine (PSA) and C18. The supernatant was concentrated using nitrogen and qualitatively and quantitatively determined by HPLC/Q-Orbitrap HRMS. Results The 62 kinds of pesticides showed a good linear relationship in the concentration range from 1 to 200.0 μg/L. Except for chlorpyrifos-methyl, the correlation coefficient r2 was greater than 0.99. The limit of quantification (LOQ) ranges from 2 to 10 μg/kg. In the turbot, shrimp and scallop, spiking experiments were performed at three levels: 1 times LOQ, 2 times LOQ, and 10 times LOQ. The recovery rates of three samples ranged from 61.4%–112.4%、63.7%–119.6%、66.2%–113.5%, respectively, while the relative standard deviation values ranging from 2.1%–11.5%、2.6%~13.4% and 2.7%–15.2%, respectively. In the matrix effect evaluation experiment, 51.2% of the compounds in turbot showed weak matrix effects, while 46.8% exhibited matrix suppression effects. Compared to shrimp and scallop, turbot exhibited a stronger matrix effect. The method was used to determine 30 samples from local market. The results showed that there are 5 turbots and 2 scallops that have pesticide residue compounds detected, mainly herbicides, insecticides, fungicides, etc., such as simazine, prometryn, chlorpyrifos, deltamethrin and propachlor. Through quantitative analysis, the concentration of each compound is lower than the relevant standard limits both domestically and internationally. Conclusions This study provides an effective method for rapid and accurate detection of pesticide residues in fish products, offering strong technical support for food safety monitoring.