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采用固相萃取结合液相色谱-电喷雾飞行时间质谱法测定果汁中的采后杀菌剂。

Determination of postharvest fungicides in fruit juices by solid-phase extraction followed by liquid chromatography electrospray time-of-flight mass spectrometry.

作者信息

Gilbert-López Bienvenida, García-Reyes Juan F, Mezcua Milagros, Molina-Díaz Antonio, Fernández-Alba Amadeo R

机构信息

Department of Physical and Analytical Chemistry, University of Jaén, Spain.

出版信息

J Agric Food Chem. 2007 Dec 26;55(26):10548-56. doi: 10.1021/jf072272s. Epub 2007 Dec 4.

Abstract

A multiresidue method using liquid chromatography-time-of-flight mass spectrometry (LC-TOFMS) has been developed for the quantitative analysis of five widely used postharvest fungicides (carbendazim, thiabendazole, imazalil, prochloraz, and iprodione) and two of their transformation products (imazalil and prochloraz metabolites) in fruit juices. LC-TOFMS in positive electrospray ionization mode was used to quantify and confirm trace levels of these fungicides in fruit juices. The proposed method consists of a sample treatment step based on solid-phase extraction using hydrophilic-lipophilic-balanced polymer-based reverse-phase SPE cartridges (Oasis HLB) and methanol as an eluting solvent. Fruit-juice extracts spiked at different fortification levels (10 and 20 microg L(-1)) yielded average recoveries in the range of 71-109% with RSD (%) below 15%. Subsequent identification, confirmation, and quantitation were carried out by LC-TOFMS analysis. The confirmation of the target species was based on accurate mass measurements of protonated molecules ([M+H]+) and fragment ions, obtaining routine accuracy errors lower than 2 ppm in most cases. The obtained limits of detection (LODs) of the proposed method were in the range of 0.08-0.45 microg L(-1). Finally, the proposed method was successfully applied to the analysis of 23 fruit juice samples collected from different European countries and the United States, showing the potential applicability of the method in routine analysis. Over 50% of the samples tested contained pesticide residues, but relatively low concentration levels were found.

摘要

已开发出一种使用液相色谱 - 飞行时间质谱法(LC - TOFMS)的多残留方法,用于定量分析果汁中五种广泛使用的采后杀菌剂(多菌灵、噻菌灵、抑霉唑、咪鲜胺和异菌脲)及其两种转化产物(抑霉唑和咪鲜胺代谢物)。采用正电喷雾电离模式的LC - TOFMS对果汁中这些杀菌剂的痕量水平进行定量和确证。所提出的方法包括一个基于固相萃取的样品处理步骤,使用亲水亲脂平衡聚合物基反相固相萃取柱(Oasis HLB),并用甲醇作为洗脱溶剂。在不同加标水平(10和20 μg L⁻¹)下加标的果汁提取物的平均回收率在71 - 109%范围内,相对标准偏差(RSD,%)低于15%。随后通过LC - TOFMS分析进行鉴定、确证和定量。目标物质的确证基于质子化分子([M + H]⁺)和碎片离子的精确质量测量,在大多数情况下常规准确度误差低于2 ppm。所提出方法的检测限(LOD)在0.08 - 0.45 μg L⁻¹范围内。最后,所提出的方法成功应用于分析从不同欧洲国家和美国收集的23个果汁样品,表明该方法在常规分析中的潜在适用性。超过50%的测试样品含有农药残留,但发现的浓度水平相对较低。

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