Analytical and Bioanalytical Chemistry ( IF 3.8 ) Pub Date : 2021-09-08 , DOI: 10.1007/s00216-021-03638-4 Marie Marques 1 , Anne Maitre 1 , Luc Choisnard 2 , Christine Demeilliers 1 , Renaud Persoons 1
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A new gas chromatography–tandem mass spectrometry method for the determination of mono- and dihydroxylated polycyclic aromatic hydrocarbon metabolites (OH-PAHs and diol-PAHs) in urine was developed and validated. Various sample preparation procedures were compared, namely liquid–liquid extraction (LLE), dispersive solid-phase extraction (dSPE), and SPE, alone or combined. A novel two-stage derivatization approach using 2 silylation reagents was developed, and an experimental procedure design was used to optimize the programmed temperature vaporization–solvent vent injection (PTV-SV) GC parameters. The method focused on 11 target compounds resulting from four- to five-ring suspected carcinogenic PAHs. SPE was identified as an acceptable and more convenient extraction method for all tested metabolites, with extraction rates ranging from 63 to 86% and relative standard deviations lower than 20%. The two-stage derivatization approach successfully allowed first the derivatization of OH-PAHs by MTBSTFA (N-tert-butyldimethylsilyl-N-methyltrifluoroacetamide) and then diol-PAHs by BSTFA (N,O-bis(trimethylsilyl)trifluoroacetamide) in a single run. The limits of quantification were in the range of 0.01–0.02 μg l−1 for OH-PAHs and 0.02–0.2 μg l−1 for diol-PAHs. The intra- and interday precisions were lower than 10%. The method was applied to determine PAH metabolites in urine collected at the beginning and at the end of the working week from 6 workers involved in aluminum production. The mean diol-PAH levels at the end of the week were 10 to 20 times higher (0.86–2.34 μg g−1 creatinine) than those of OH-PAHs (0.03–0.30 μg g−1). These results confirmed the usefulness of this new analytical technique for detecting and characterizing metabolic patterns of PAHs in urine and assessing carcinogenic occupational exposures.
Graphical abstract
中文翻译：
在 SPE 和两阶段衍生化后通过 GC-MS-MS 同时分析 PAH 尿液单羟基化和二羟基化代谢物
开发并验证了一种用于测定尿液中单羟基和二羟基化多环芳烃代谢物（OH-PAH 和二醇-PAH）的新型气相色谱-串联质谱法。比较了各种样品制备程序，即单独或组合的液液萃取 (LLE)、分散固相萃取 (dSPE) 和 SPE。开发了一种使用 2 种甲硅烷基化试剂的新型两阶段衍生化方法，并使用实验程序设计来优化程序温度汽化-溶剂排放 (PTV-SV) GC 参数。该方法侧重于由四到五环疑似致癌 PAHs 产生的 11 种目标化合物。SPE 被确定为所有测试代谢物的可接受且更方便的提取方法，提取率在 63% 到 86% 之间，相对标准偏差低于 20%。两阶段衍生方法首先成功地允许通过 MTBSTFA 衍生 OH-PAHs（N-叔丁基二甲基甲硅烷基-N-甲基三氟乙酰胺），然后是 BSTFA 的二醇-PAH（N，O-双（三甲基甲硅烷基）三氟乙酰胺）在一次运行中。OH-PAHs的定量限在 0.01-0.02 μg l -1范围内，二醇-PAHs 的定量限在 0.02-0.2 μg l -1范围内。日内和日间精度均低于 10%。该方法用于测定 6 名参与铝生产的工人在工作周开始和结束时收集的尿液中的 PAH 代谢物。周末的平均二醇-PAH 水平（0.86-2.34 μg g -1肌酐）比 OH-PAH（0.03-0.30 μg g -1 ）高 10 到 20 倍）。这些结果证实了这种新的分析技术在检测和表征尿液中 PAHs 的代谢模式和评估致癌职业暴露方面的有用性。
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