title: Wide-scope screening of pesticides in fruits and vegetables using information-dependent acquisition employing UHPLC-QTOF-MS and automated MS/MS library searching.
abstract: 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-1and 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-1for 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-1, 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-1and 98.1 % of the pesticides in 100 μg kg-1spiked 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.
authors: College of Environmental and Chemical Engineering, Hebei Key Laboratory of Applied Chemistry, Yanshan University, Qinhuangdao, Hebei, 066004, China.
authors: Zhibin
authors: Z
authors: Wang
authors: Technological Center of Qinhuangdao Entry-Exit Inspection and Quarantine Bureau, Qinhuangdao, Hebei, 066004, China.
authors: Yanzhong
authors: Y
authors: Cao
authors: Technological Center of Qinhuangdao Entry-Exit Inspection and Quarantine Bureau, Qinhuangdao, Hebei, 066004, China.
authors: Na
authors: N
authors: Ge
authors: Technological Center of Qinhuangdao Entry-Exit Inspection and Quarantine Bureau, Qinhuangdao, Hebei, 066004, China.
authors: Xiaomao
authors: X
authors: Liu
authors: College of Environmental and Chemical Engineering, Hebei Key Laboratory of Applied Chemistry, Yanshan University, Qinhuangdao, Hebei, 066004, China.|Chinese Academy of Inspection and Quarantine, Chaoyang District, Beijing, 100123, China.
authors: Qiaoying
authors: Q
authors: Chang
authors: Chinese Academy of Inspection and Quarantine, Chaoyang District, Beijing, 100123, China.
authors: Chunlin
authors: C
authors: Fan
authors: College of Environmental and Chemical Engineering, Hebei Key Laboratory of Applied Chemistry, Yanshan University, Qinhuangdao, Hebei, 066004, China. ciqpang@163.com.|Chinese Academy of Inspection and Quarantine, Chaoyang District, Beijing, 100123, China. ciqpang@163.com.
authors: Guo-Fang
authors: GF
authors: Pang
mesh_terms: D002138:Calibration; D002851:Chromatography, High Pressure Liquid / Q000295:instrumentation / Q000379:methods*; D032084:Citrus sinensis / Q000737:chemistry; D005638:Fruit / Q000737:chemistry*; D057230:Limit of Detection; D018551:Solanum lycopersicum / Q000737:chemistry; D027845:Malus / Q000737:chemistry; D010575:Pesticides / Q000302:isolation & purification*; D015203:Reproducibility of Results; D054852:Small Molecule Libraries / Q000302:isolation & purification*; D019032:Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization; D018724:Spinacia oleracea / Q000737:chemistry; D053719:Tandem Mass Spectrometry; D014675:Vegetables / Q000737:chemistry*
chemical_list: D010575:Pesticides; D054852:Small Molecule Libraries
keywords: Fruit and vegetable; Information-dependent acquisition; MS/MS library; Pesticides; UHPLC-QTOF-MS