RECETOX Centre, Faculty of Science, Masaryk University, Kamenice 753/5, Brno 625 00, Czech Republic.
RECETOX Centre, Faculty of Science, Masaryk University, Kamenice 753/5, Brno 625 00, Czech Republic.
J Chromatogr B Analyt Technol Biomed Life Sci. 2021 Mar 1;1166:122542. doi: 10.1016/j.jchromb.2021.122542. Epub 2021 Jan 11.
This study presents a novel sample preparation method for the determination of both specific and non-specific pesticide metabolites in human urine samples. The method combines a deconjugation step with QuEChERS-based method and solid-phase extraction. In total, 15 pesticide metabolites (diethyl phosphate; diethyl thiophosphate; dimethyl phosphate; diethyl thiophosphate; 2,4-dichlorophenoxyacetic acid; 3-phenoxybenzoic acid; 4-fluoro-3-phenoxybenzoic acid; coumaphos; diethyl dithiophosphate; malathion dicarboxylic acid; p-nitrophenol; cis/trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane carboxylic acid; 3,5,6-trichloro-2-pyridinol; N,N-diethyl-3-methylbenzamid and 2-isopropyl-4-methyl-6-hydroxypyrimidine) were separated using liquid chromatography coupled to a mass spectrometer and isotope dilution method for quantitation. The method was validated using recovery tests with recoveries generally ranging from 80 to 120%. Additionally, 20 urine samples collected from South African children were analysed using the presented method. The median levels of pesticide metabolites found in the urine samples ranged from not detected (N,N-diethyl-3-methylbenzamid) to 22.36 µg/g creatinine (dimethyl phosphate). The novel method developed in this study is sensitive, selective, robust and reproducible while also conserving the amount of sample, chemicals, material and time required. Due to the low limits of detection obtained for individual pesticide metabolites, the method is capable of quantifying trace levels of pesticide metabolites in urine, which thus makes it an ideal tool for biomonitoring studies.
本研究提出了一种新颖的样品前处理方法，用于测定人尿液样本中特定和非特定农药代谢物。该方法结合了去共轭步骤、QuEChERS 方法和固相萃取。总共分离了 15 种农药代谢物（磷酸二乙酯；二乙基硫代磷酸酯；磷酸二甲酯；二乙基硫代磷酸酯；2,4-二氯苯氧基乙酸；3-苯氧基苯甲酸；4-氟-3-苯氧基苯甲酸；保棉磷；二乙基二硫代磷酸酯；马拉硫磷二酸；对硝基苯酚；顺/反-3-(2,2-二氯乙烯基)-2,2-二甲基环丙烷羧酸；3,5,6-三氯-2-吡啶醇；N,N-二乙基-3-甲基苯甲酰胺和 2-异丙基-4-甲基-6-羟基嘧啶），采用液相色谱-质谱联用和同位素稀释法进行定量分析。该方法通过回收率测试进行验证，回收率通常在 80%至 120%之间。此外，还使用所提出的方法分析了来自南非儿童的 20 个尿液样本。在尿液样本中发现的农药代谢物的中位数水平范围从未检出（N,N-二乙基-3-甲基苯甲酰胺）到 22.36µg/g 肌酐（磷酸二甲酯）。本研究中开发的新方法具有灵敏度高、选择性好、稳健性和重现性，同时还能节省样品、化学物质、材料和时间的消耗。由于对各个农药代谢物获得了较低的检测限，该方法能够定量分析尿液中痕量水平的农药代谢物，因此成为生物监测研究的理想工具。
