Del Mar Gómez-Ramos María, Rajski Łukasz, Heinzen Horacio, Fernández-Alba Amadeo R
European Union Reference Laboratory for Pesticide Residues in Fruit & Vegetables, Agrifood Campus of International Excellence (ceiA3) Department of Hydrogeology and Analytical Chemistry, University of Almeria, Ctra. Sacramento S/N°, La Cañada de San Urbano, 04120, Almería, Spain.
Anal Bioanal Chem. 2015 Aug;407(21):6317-26. doi: 10.1007/s00216-015-8709-z. Epub 2015 May 6.
This paper describes the application of LC/Q-Orbitrap MS for the analysis of pesticide residues in fruit and vegetable commodities. LC/Q-Orbitrap MS working in full scan simultaneously with a single MS/MS scan was used to analyse 139 pesticide residues in QuEChERS extracts of tomato, pepper, orange and green tea. Full scan data were obtained at a resolution of 70,000 whereas MS/MS data were obtained at a resolution of 17,500. Quantitation and detection was carried out using full scan data while MS/MS data were used only for identification. MS/MS scans did not have a negative influence on quantitation under the applied conditions. Some peak area reproducibility problems were the consequence of the low sensitivity for some compounds (aldicarb, chlorpyriphos methyl, fenitrothion and fipronil) under the applied conditions. The relation between the operational parameters (viz. automatic gain control (AGC) target, maximum injection time (IT), underfill ratio, isolation window and apex trigger) and the number of automatically identified compounds was investigated. Mass error and minimal intensity of selected fragment ions were also studied. Various working modes were compared, such as full scan with single MS/MS scan and full scan with multiple MS/MS scans. In both cases, the number of automatically reported pesticides was the same. However full scan with single MS/MS scan ensured more points per peak in full scan mode and better peak area reproducibility. The evaluation of the identification and quantitation capabilities of the instrument was performed through the analysis of 100 real samples. The samples were also analysed by LC-QqQ MS/MS and the results of both analytical systems were compared. The comparison revealed that the two instruments were consistent with each other. They found the same pesticides and neither false positive nor false negatives were reported. Nevertheless the Q-Orbitrap MS allowed one to work in high resolution mass spectrometry, increasing the selectivity and, in full scan mode, permitting the retrospective analysis of the data feature that cannot be achieved with QqQ.
本文描述了液相色谱/四极杆-轨道阱质谱（LC/Q-Orbitrap MS）在果蔬商品中农药残留分析的应用。采用LC/Q-Orbitrap MS在全扫描同时进行单次二级质谱（MS/MS）扫描，分析番茄、辣椒、橙子和绿茶的QuEChERS提取物中的139种农药残留。全扫描数据在分辨率70000下获得，而MS/MS数据在分辨率17500下获得。定量和检测使用全扫描数据，而MS/MS数据仅用于鉴定。在所应用的条件下，MS/MS扫描对定量没有负面影响。一些峰面积重现性问题是由于在所应用条件下某些化合物（涕灭威、甲基毒死蜱、杀螟硫磷和氟虫腈）灵敏度低导致的。研究了操作参数（即自动增益控制（AGC）目标、最大进样时间（IT）、填充不足率、隔离窗口和顶点触发）与自动识别化合物数量之间的关系。还研究了质量误差和选定碎片离子的最小强度。比较了各种工作模式，如全扫描与单次MS/MS扫描以及全扫描与多次MS/MS扫描。在这两种情况下，自动报告的农药数量相同。然而，全扫描与单次MS/MS扫描在全扫描模式下每个峰确保有更多的点，并且峰面积重现性更好。通过分析100个实际样品对仪器的鉴定和定量能力进行了评估。这些样品也用液相色谱-三重四极杆质谱（LC-QqQ MS/MS）进行了分析，并比较了两个分析系统的结果。比较结果表明，这两种仪器相互一致。它们检测到相同的农药，且未报告假阳性或假阴性结果。尽管如此，Q-Orbitrap MS允许在高分辨率质谱下工作，提高了选择性，并且在全扫描模式下允许对三重四极杆质谱无法实现的数据特征进行追溯分析。
