Zheng Weijia, Park Jin-A, Abd El-Aty A M, Kim Seong-Kwan, Cho Sang-Hyun, Choi Jeong-Min, Yi Hee, Cho Soo-Min, Ramadan Amer, Jeong Ji Hoon, Shim Jae-Han, Shin Ho-Chul
Department of Veterinary Pharmacology and Toxicology, College of Veterinary Medicine, Konkuk University, Seoul 143-701, Republic of Korea.
Department of Veterinary Pharmacology and Toxicology, College of Veterinary Medicine, Konkuk University, Seoul 143-701, Republic of Korea; Department of Pharmacology, Faculty of Veterinary Medicine, Cairo University, 12211, Giza, Egypt.
J Chromatogr B Analyt Technol Biomed Life Sci. 2018 Jan 1;1072:60-69. doi: 10.1016/j.jchromb.2017.11.011. Epub 2017 Nov 8.
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 0.2M 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)≥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 0.005mg/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.
在过去几十年里，蜂蜜产品受到了不同污染物的污染，比如农业中广泛使用的农药。在这项研究中，开发了一种改进的EN-快速、简单、廉价、高效、耐用且安全（QuEChERS）提取方法，用于同时定量分析四种蜂蜜（刺槐蜜、野花蜜、板栗蜜和麦卢卡蜂蜜）和蜂王浆中的农药残留，包括嘧菌唑、氟虫腈、蝇毒磷、氟胺氰菊酯、双甲脒及其代谢物2,4-二甲基苯胺（2,4-DMA）。样品用0.2M磷酸氢二钠（pH 9）缓冲，随后用乙腈作为提取溶剂。在液相色谱-电喷雾电离串联质谱（LC-ESI/MS-MS）分析之前，使用伯仲胺（PSA）和C18吸附剂的组合进行净化。在六个浓度水平下测得的估计线性呈现出良好的相关系数（R）≥0.99。从三个不同加标水平计算得出的回收率，在蜂蜜中为62.06 - 108.79%，在蜂王浆中为67.58 - 106.34%，所有测试化合物的相对标准偏差（RSD）<12%。还评估了基质效应，大多数分析物呈现信号增强。各种样品中的定量限（LOQ）在0.001至0.005mg/kg之间。这些远低于各监管机构设定的最大残留限量（MRL）。共对43个市售（国产和进口）样品进行了方法应用检测。在测试的样品中，有三个样品仅检测出嘧菌唑残留呈阳性（即被检测到并定量）。其余样品中的残留被检测到但未定量。我们得出结论，本研究中开发的方案对于常规定量分析各种蜂蜜和蜂王浆中的嘧菌唑、2,4-DMA、氟虫腈、蝇毒磷、双甲脒和氟胺氰菊酯而言简单且通用。
