Plant Protection Institute-National Research Institute, Laboratory of Pesticide Residues, Chełmońskiego 22, Postal Code: 15-195 Bialystok, Poland.
Ecotoxicol Environ Saf. 2013 Nov;97:210-22. doi: 10.1016/j.ecoenv.2013.07.010. Epub 2013 Jul 31.
A simple multiresidue method based on matrix solid phase dispersion (MSPD) combined with clean-up has been developed for the simultaneous screening of 153 pesticides in honeybees suspected of suffering from pesticide poisoning during field spraying. Extraction and clean-up were carried out in a glass column containing anhydrous sulphate, 2.0g of octadecyl (C18) and a 2.0-g sample of bees (23 insects on average) macerated with 4.0g of Florisil. An additional layer of anhydrous sodium sulphate was added, and acetonitrile was used as the elution solvent. This combination of clean-up steps ensured an efficient purification. A gas chromatograph with dual selective detectors for electron capture and nitrogen-phosphorous was used. The results presented in this paper demonstrate that matrix solid-phase dispersion (MSPD) with the one-step clean-up procedure is the most effective extraction technique. MSPD method recoveries ranged from 70 to 118%, with precision values expressed as a relative standard of <20%, except for 10 pesticides that had recoveries of 50-70% and two with 120-130%. Low limits of detection (0.003-0.04μg/g) and quantification (0.005-0.05μg/g) were readily achieved with this method for all tested pesticides. A "top down" empirical model was used to estimate the expanded uncertainty at 28% on average (coverage factor k=2, confidence level 95%). The MSPD method was successfully used on real bee samples to analyse four acaricides, 55 fungicides, 16 herbicides and 78 insecticides from various regions of Poland. A total of 33 honeybee samples from suspected pesticide poisoning incidents were analysed, in which 17 different pesticides were determined (14 insecticides and three fungicides). The pesticides most often found in honeybees were cypermethrin (in 51% of the samples, 0.008-0.563µg/bee), chlorpyrifos (27%, 0.001-51.5µg/bee) and biphentin (21%, 0.002-0.012µg/bee).
基于基质固相分散（MSPD）的简单多残留方法结合了净化，已被开发用于同时筛选怀疑在田间喷雾期间遭受农药中毒的蜜蜂中的 153 种农药。提取和净化在含有无水硫酸盐、2.0g 十八烷基（C18）和 2.0g 蜜蜂样品（平均 23 只昆虫）的玻璃柱中进行，样品用 4.0g Florisil 捣碎。加入一层无水硫酸钠，乙腈作为洗脱溶剂。这种净化步骤的组合确保了有效的净化。使用具有电子捕获和氮磷双重选择性检测器的气相色谱仪。本文介绍的结果表明，带有一步净化程序的基质固相分散（MSPD）是最有效的提取技术。MSPD 方法的回收率在 70%至 118%之间，除了 10 种回收率为 50-70%和 2 种回收率为 120-130%的农药外，精度值以<20%的相对标准表示。该方法很容易实现所有测试农药的低检测限（0.003-0.04μg/g）和定量限（0.005-0.05μg/g）。使用这种方法，对所有测试的农药平均采用“自上而下”的经验模型来估计扩展不确定度，置信水平为 95%（覆盖因子 k=2）。MSPD 方法成功地用于分析来自波兰不同地区的四种杀螨剂、55 种杀菌剂、16 种除草剂和 78 种杀虫剂的实际蜜蜂样本。分析了 33 个疑似农药中毒事件的蜜蜂样本，其中确定了 17 种不同的农药（14 种杀虫剂和 3 种杀菌剂）。在蜜蜂中最常发现的农药是氯菊酯（51%的样本中，0.008-0.563μg/只）、毒死蜱（27%，0.001-51.5μg/只）和双苯丁锡（21%，0.002-0.012μg/只）。
