Fillatre Yoann, Rondeau David, Daguin Antoine, Communal Pierre-Yves
Groupement Interrégional de Recherche sur les Produits Agropharmaceutiques (GIRPA), Angers Technopole, 9 Avenue du Bois de l'Abbé, 49071 Beaucouze, France; Institut des Sciences et Technologies Moléculaires d'Angers (MOLTECH), CNRS UMR 6200, Université d'Angers, 2 Boulevard Lavoisier, 49045 Angers Cedex 01, France.
Institut d'Electronique et de Télécommunication de Rennes, CNRS UMR 6164, Université de Rennes 1, Campus de Beaulieu, 263 Avenue du General Leclerc, 35042 Rennes Cedex, France; Université de Bretagne Occidentale, Département de Chimie, 6 Avenue le Gorgeu, 29238 Brest Cedex 03, France.
Talanta. 2016;149:178-186. doi: 10.1016/j.talanta.2015.11.052. Epub 2015 Nov 22.
This paper describes the determination of 256 multiclass pesticides in cypress and lemon essential oils (EOs) by the way of liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI/MS/MS) analysis using the scheduled selected reaction monitoring mode (sSRM) available on a hybrid quadrupole linear ion trap (QLIT) mass spectrometer. The performance of a sample preparation of lemon and cypress EOs based on dilution or evaporation under nitrogen assisted by a controlled heating were assessed. The best limits of quantification (LOQs) were achieved with the evaporation under nitrogen method giving LOQs≤10µgL(-1) for 91% of the pesticides. In addition the very satisfactory results obtained for recovery, repeatability and linearity showed that for EOs of relatively low evaporation temperature, a sample preparation based on evaporation under nitrogen is well adapted and preferable to dilution. By compiling these results with those previously published by some of us on lavandin EO, we proposed a workflow dedicated to multiresidue determination of pesticides in various EOs by LC-ESI/sSRM. Among the steps involved in this workflow, the protocol related to mass spectrometry proposes an alternative confirmation method to the classical SRM ratio criteria based on a sSRM survey scan followed by an information-dependent acquisition using the sensitive enhanced product ion (EPI) scan to generate MS/MS spectra then compared to a reference. The submitted workflow was applied to the case of lemon EOs samples highlighting for the first time the simultaneous detection of 20 multiclass pesticides in one EO. Some pesticides showed very high concentration levels with amounts greatly exceeding the mgL(-1).
本文描述了采用液相色谱 - 电喷雾电离串联质谱法（LC - ESI/MS/MS），利用混合四极杆线性离子阱（QLIT）质谱仪上的定时选择反应监测模式（sSRM），测定柏树和柠檬精油（EOs）中的256种多类农药。评估了基于在可控加热辅助下氮气稀释或蒸发的柠檬和柏树EOs样品制备方法的性能。氮气蒸发法获得了最佳定量限（LOQs），91%的农药的LOQs≤10µgL⁻¹。此外，回收率、重复性和线性方面获得的非常令人满意的结果表明，对于蒸发温度相对较低的EOs，基于氮气蒸发的样品制备方法非常适用且优于稀释法。通过将这些结果与我们之前发表的有关醒目薰衣草EOs的结果相结合，我们提出了一种通过LC - ESI/sSRM对各种EOs中的农药进行多残留测定的工作流程。在该工作流程涉及的步骤中，与质谱相关的方案提出了一种替代经典SRM比率标准的确认方法，该方法基于sSRM全扫描，随后使用灵敏的增强产物离子（EPI）扫描进行信息依赖型采集以生成MS/MS谱图，然后与参考谱图进行比较。所提交的工作流程应用于柠檬EOs样品的案例，首次突出显示了在一种EO中同时检测20种多类农药。一些农药显示出非常高的浓度水平，含量大大超过mgL⁻¹。
