Development and validation of modified QuEChERS method coupled with LC-MS/MS for simultaneous determination of cymiazole, fipronil, coumaphos, fluvalinate, amitraz, and its metabolite in various types of honey and royal jelly
Development and validation of modified QuEChERS method coupled with LC-MS/MS for simultaneous determination of cymiazole, fipronil, coumaphos, fluvalinate, amitraz, and its metabolite in various types of honey and royal jelly
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DOI：
10.1016/j.jchromb.2017.11.011
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发表时间：
2018-01-01
影响因子：
3
通讯作者：
Shin, Ho-Chul
中科院分区：
文献类型：
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作者：
Zheng, Weijia;Park, Jin-A.;Shin, Ho-Chul
在过去的几十年里，蜂蜜产品受到了各种污染物的污染，例如农药，这些污染物在农业中被广泛应用。本文建立了一种改进的快速、简便、廉价、有效、坚固、安全的提取方法（QuEChERS），用于同时测定四种蜂蜜（金合树、野生、栗子和麦芦卡）和蜂王浆中磺胺唑、氟虫腈、coumaphos、氟valinate、amitraz及其代谢物2,4-二甲基苯胺（2,4- dma）的残留量。样品用0.2 M二碱性磷酸钠（pH 9）缓冲，然后用乙腈作为提取溶剂。在液相色谱-电喷雾串联质谱（LC-ESI+/MS-MS）分析之前，使用伯仲胺（PSA）和C18吸附剂组合进行纯化。6个浓度水平下的线性关系呈现良好的相关系数(R-2) >= 0.99。从三种不同的添加水平计算得出，蜂蜜的回收率为62.06-108.79%，蜂王浆的回收率为67.58-106.34%，所有被测化合物的RSD < 12%。矩阵效应也被评估，大多数分析物呈现信号增强。各样品的定量限在0.001 ~ 0.005 mg/kg之间。这些都大大低于各监管机构设定的最大残留限量（MRL）。共对43份市场（国内和进口）样品进行了方法应用分析。在检测样品中，有3个样品仅检测到咪唑残留呈阳性（即检测并定量）。其余样品的残留检测，但未定量。我们的结论是，在这项工作中制定的方案是简单和通用的常规定量cymiazole， 2,4- dma，氟虫腈，coumaphos， amitraz和氟缬氨酸在各种类型的蜂蜜和蜂王浆。
Over the past few decades, honey products have been polluted by different contaminants, such as pesticides, which are widely applied in agriculture. In this work, a modified EN quick, easy, cheap, effective, rugged, and safe (QuEChERS) extraction method was developed for the simultaneous quantification of pesticide residues, including cymiazole, fipronil, coumaphos, fluvalinate, amitraz, and its metabolite 2,4-dimethylaniline (2,4-DMA), in four types of honey (acacia, wild, chestnut, and manuka) and royal jelly. Samples were buffered with 0.2 M dibasic sodium phosphate (pH 9), and subsequently, acetonitrile was employed as the extraction solvent. A combination of primary secondary amine (PSA) and C18 sorbents was used for purification prior to liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI+/MS-MS) analysis. The estimated linearity measured at six concentration levels presented good correlation coefficients (R-2) >= 0.99. The recovery, calculated from three different spiking levels, was 62.06-108.79% in honey and 67.58-106.34% in royal jelly, with an RSD < 12% for all the tested compounds. The matrix effect was also evaluated, and most of the analytes presented signal enhancement. The limits of quantification (LOQ) ranged between 0.001 and 0.005 mg/kg in various samples. These are considerably lower than the maximum residue limits (MRL) set by various regulatory authorities. A total of 43 market (domestic and imported) samples were assayed for method application. Among the tested samples, three samples were tested positive (i.e. detected and quantified) only for cymiazole residues. The residues in the rest of the samples were detected but not quantified. We concluded that the protocol developed in this work is simple and versatile for the routine quantification of cymiazole, 2,4-DMA, fipronil, coumaphos, amitraz, and fluvalinate in various types of honey and royal jelly.