Wang Zhibin, Cao Yanzhong, Ge Na, Liu Xiaomao, Chang Qiaoying, Fan Chunlin, Pang Guo-Fang
College of Environmental and Chemical Engineering, Hebei Key Laboratory of Applied Chemistry, Yanshan University, Qinhuangdao, Hebei, 066004, China.
Technological Center of Qinhuangdao Entry-Exit Inspection and Quarantine Bureau, Qinhuangdao, Hebei, 066004, China.
Anal Bioanal Chem. 2016 Nov;408(27):7795-7810. doi: 10.1007/s00216-016-9883-3. Epub 2016 Aug 24.
This paper presents an application of ultra-high performance liquid chromatography-quadrupole time-of-flight mass spectrometry (UHPLC-QTOF-MS) for simultaneous screening and identification of 427 pesticides in fresh fruit and vegetable samples. Both full MS scan mode for quantification, and an artificial-intelligence-based product ion scan mode information-dependent acquisition (IDA) providing automatic MS to MS/MS switching of product ion spectra for identification, were conducted by one injection. A home-in collision-induced-dissociation all product ions accurate mass spectra library containing more than 1700 spectra was developed prior to actual application. Both qualitative and quantitative validations of the method were carried out. The result showed that 97.4 % of the pesticides had the screening detection limit (SDL) less than 50 μg kg and more than 86.7 % could be confirmed by accurate MS/MS spectra embodied in the home-made library. Meanwhile, calibration curves covering two orders of magnitude were performed, and they were linear over the concentration range studied for the selected matrices (from 5 to 500 μg kg for most of the pesticides). Recoveries between 80 and 110 % in four matrices (apple, orange, tomato, and spinach) at two spiked levels, 10 and 100 μg kg, was 88.7 or 86.8 %. Furthermore, the overall relative standard deviation (RSD, n = 12) for 94.3 % of the pesticides in 10 μg kg and 98.1 % of the pesticides in 100 μg kg spiked levels was less than 20 %. In order to validate the suitability for routine analysis, the method was applied to 448 fruit and vegetable samples purchased in different local markets. The results show 83.3 % of the analyzed samples have positive findings (higher than the limits of identification and quantification), and 412 commodity-pesticide combinations are identified in our scope. The approach proved to be a cost-effective, time-saving and powerful strategy for routine large-scope screening of pesticides.
本文介绍了超高效液相色谱-四极杆飞行时间质谱（UHPLC-QTOF-MS）在新鲜水果和蔬菜样品中同时筛查和鉴定427种农药的应用。通过一次进样，既进行了用于定量的全扫描模式，又进行了基于人工智能的产物离子扫描模式信息依赖采集（IDA），该模式可提供自动从母离子质谱切换到子离子质谱以进行鉴定。在实际应用之前，建立了一个包含1700多个质谱图的自碰撞诱导解离全产物离子精确质量谱库。对该方法进行了定性和定量验证。结果表明，97.4%的农药筛查检测限（SDL）低于50μg/kg，超过86.7%的农药可通过自制谱库中的精确子离子质谱得到确认。同时，绘制了覆盖两个数量级的校准曲线，在所研究的选定基质浓度范围内（大多数农药为5至500μg/kg）呈线性。在10μg/kg和100μg/kg两个加标水平下，四种基质（苹果、橙子、番茄和菠菜）中的回收率在80%至110%之间，分别为88.7%或86.8%。此外，在10μg/kg加标水平下，94.3%的农药和在100μg/kg加标水平下98.1%的农药的总体相对标准偏差（RSD，n = 12）小于20%。为了验证该方法对常规分析的适用性，将其应用于从不同当地市场购买的448个水果和蔬菜样品。结果显示，83.3%的分析样品有阳性结果（高于鉴定和定量限），在我们的检测范围内鉴定出412种商品-农药组合。该方法被证明是一种用于农药常规大范围筛查的经济高效、节省时间且强大的策略。
