Kaczynski Piotr, Hrynko Izabela, Lozowicka Bozena
Plant Protection Institute - National Research Institute, Laboratory of Pesticide Residues, Chelmonskiego 22, 15-195 Bialystok, Poland.
Plant Protection Institute - National Research Institute, Laboratory of Pesticide Residues, Chelmonskiego 22, 15-195 Bialystok, Poland.
Ecotoxicol Environ Saf. 2017 May;139:124-131. doi: 10.1016/j.ecoenv.2017.01.033.
Highly toxic insecticides (HTIs) belonging to different chemical groups are dangerous to pollinating organisms, even in sublethal doses. An important objective of this study was to develop a method to determine over fifty HTIs at very low concentrations in the bee matrix. The novelty of this research involved obtaining extract completely free from beewaxes, lipids and proteins using EMR-lipid (enhanced matrix removal-lipid), chitin and Z-Sep+ (zirconium oxide and C18 dual-bonded to silica) as clean-up sorbents. Different parameters, such as weight of bees, extraction solvent, and freezing time were evaluated. Determinations were made using liquid chromatography-tandem mass spectrometry (LC-MS/MS). EMR-lipid allows for removing most of the fatty co-extracts and increases the overall performance of the method by reducing the matrix effects (ME) without significant analyte loss. The established modified QuEChERS method based on 1% acetic acid in acetonitrile extraction followed by EMR-lipid clean-up was validated at three different spiking levels (0.001, 0.01 and 0.1mgkg). Precision, calculated as relative standard deviation (RSD), was below 20%. The proposed method was used to determine sublethal doses of these insecticides in real samples of dead honeybees.
属于不同化学类别的高毒性杀虫剂（HTIs）即使在亚致死剂量下也对传粉生物有害。本研究的一个重要目标是开发一种方法，用于测定蜜蜂基质中极低浓度的五十多种高毒性杀虫剂。这项研究的新颖之处在于，使用EMR-脂质（增强型基质去除-脂质）、几丁质和Z-Sep+（氧化锆和C18双键合到硅胶）作为净化吸附剂，获得完全不含蜂蜡、脂质和蛋白质的提取物。评估了不同参数，如蜜蜂重量、提取溶剂和冷冻时间。使用液相色谱-串联质谱法（LC-MS/MS）进行测定。EMR-脂质能够去除大部分脂肪共提取物，并通过减少基质效应（ME）提高方法的整体性能，而不会导致显著的分析物损失。基于乙腈中1%乙酸萃取然后用EMR-脂质净化建立的改良QuEChERS方法在三个不同加标水平（0.001、0.01和0.1mg/kg）下进行了验证。以相对标准偏差（RSD）计算的精密度低于20%。所提出的方法用于测定死蜜蜂实际样品中这些杀虫剂的亚致死剂量。
