Multi-residue method for the determination of pesticides and pesticide metabolites in honeybees by liquid and gas chromatography coupled with tandem mass spectrometry-Honeybee poisoning incidents
Multi-residue method for the determination of pesticides and pesticide metabolites in honeybees by liquid and gas chromatography coupled with tandem mass spectrometry-Honeybee poisoning incidents
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DOI：
10.1016/j.chroma.2016.01.045
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发表时间：
2016-02-26
影响因子：
4.1
通讯作者：
Posyniak, Andrzej
中科院分区：
文献类型：
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作者：
Kiljanek, Tomasz;Niewiadowska, Alicja;Posyniak, Andrzej
建立了蜜蜂样品中200种农药及其代谢物的测定方法。该方法中包含的近98%的化合物在欧盟范围内被批准使用，作为养蜂人用于控制蜂箱中狄斯瓦螨的植物保护产品或兽药产品的活性物质。许多重要的代谢物，如吡虫啉、噻虫啉、氟虫腈、甲硫威和双甲脒的代谢物，也有可能被检测到。样品制备基于缓冲QuEChERS方法。蜜蜂样品用含1%乙酸的乙腈提取，然后用新型Z-Sep+吸附剂和PSA进行分散固相萃取（dSPE）净化。大多数农药，包括类四环素及其代谢物，采用液相色谱串联质谱法（LC-MS/MS）分析，但一些农药，特别是拟除虫菊酯类杀虫剂，采用气相色谱串联质谱法（GC-MS/MS）分析。根据指南文件SANCO/12571/2013，在4个浓度水平（1、5、10和100 ng/g蜜蜂）下对该程序进行了验证，并在国际熟练度测试中进行了验证。以定量限（LOQ）加标的蜜蜂样品的分析显示平均回收率值（准确度）约为98%，97%的分析物显示回收率在70-120%的要求范围内，RSDr（精密度）低于20%。还确定了线性和基质效应。农药的定量限范围为1-100 ng/g。所开发的方法允许测定杀虫剂的浓度为10纳克/克或更低，除了阿维菌素和虫酰肼。LOQ值低于蜜蜂的半数致死剂量LD 50。该方法被用于调查70多起蜜蜂中毒事件。包括有关检测到的农药及其代谢物的数据。(C)© 2016 Elsevier B. V.版权所有。
A method for the determination of 200 pesticides and pesticide metabolites in honeybee samples has been developed and validated. Almost 98% of compounds included in this method are approved to use within European Union, as active substances of plant protection products or veterinary medicinal products used by beekeepers to control mites Varroa destructor in hives. Many significant metabolites, like metabolites of imidacloprid, thiacloprid, fipronil, methiocarb and amitraz, are also possible to detect. The sample preparation was based on the buffered QuEChERS method. Samples of bees were extracted with acetonitrile containing 1% acetic acid and then subjected to clean-up by dispersive solid phase extraction (dSPE) using a new Z-Sep+ sorbent and PSA. The majority of pesticides, including neonicotionoids and their metabolites, were analyzed by liquid chromatography tandem mass spectrometry (LC-MS/MS) but some of pesticides, especially pyrethroid insecticides, were analyzed by gas chromatography tandem mass spectrometry (GC-MS/MS). The procedure was validated according to the Guidance document SANCO/12571/2013 at four concentration levels: 1, 5, 10 and 100 ng/g bees and verified in the international proficiency test. The analysis of bee samples spiked at the limit of quantification (LOQ) showed about 98% mean recovery value (trueness) and 97% of analytes showed recovery in the required range of 70-120% and RSDr (precision) below 20%. Linearity and matrix effects were also established. The LOQs of pesticides were in the range of 1-100 ng/g. The developed method allows determination of insecticides at concentrations of 10 ng/g or less, except abamectin and tebufenozide. LOQ values are lower than the median lethal doses LD50 for bees. The method was used to investigate more than 70 honeybee poisoning incidents. Data about detected pesticides and their metabolites are included. (C) 2016 Elsevier B.V. All rights reserved.