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采用动态顶空和气相色谱-质谱联用技术(dHS-GC-MS)同时测定暴露工人尿液中的芳香族和氯化化合物。

Simultaneous determination of aromatic and chlorinated compounds in urine of exposed workers by dynamic headspace and gas chromatography coupled to mass spectrometry (dHS-GC-MS).

机构信息

INRS, Department Toxicology and Biomonitoring, Laboratory of Biomonitoring, 1 rue du Morvan CS 60027, 54519 Vandœuvre Cedex, France.

INRS, Department Toxicology and Biomonitoring, Laboratory of Biomonitoring, 1 rue du Morvan CS 60027, 54519 Vandœuvre Cedex, France.

出版信息

J Chromatogr B Analyt Technol Biomed Life Sci. 2019 Sep 1;1125:121724. doi: 10.1016/j.jchromb.2019.121724. Epub 2019 Jul 18.

Abstract

Mixed exposure to chemical products is a topical issue for occupational health and often includes exposure to volatile organic compounds (VOCs). As very few methods are available for evaluating these mixed exposures, the aim of this work was to develop a simple biomonitoring method to assess simultaneous occupational exposures to chlorinated and aromatic VOCs by analyzing the unmetabolized fraction of the VOCs in the urine of workers. Volatile organic compounds were analyzed using dynamic headspace gas chromatography coupled to mass spectrometry (dHS-GC-MS), and 11 unmetabolized urinary VOCs were measured into headspace phase, without any time-consuming pretreatment. Simultaneously, a standardized collection protocol was designed to avoid VOC losses or the contamination of urinary samples. The calibration samples were real urines, spiked with known amounts of the VOC mixtures studied. Test investigations were performed on potentially exposed workers in three factories in order to assess the effectiveness of both the collection protocol and analytical method. A satisfactory level of sensitivity was achieved, with limits of quantification (LOQ) between 10 and 15 ng/L obtained for all VOCs (except for styrene at 50 ng/L). Calibration curves were linear in the 0-20 μg/L range tested, with R correlation coefficients of 0.991 to 0.998. At the lowest concentration tested (0.08 μg/L), within-day precision varied from 2.1 to 5.5% and between-day precision ranged from 2.7 to 8.5%. Sample stability at -20 °C required that urinary samples be analyzed within 3 months. Even though the urinary concentrations of VOCs used in the plants were mostly quite low, significant differences between post-shift and pre-shift were observed. In conclusion, a fast, sensitive, specific and easy-to-use method has been developed for extracting VOCs from human urine using dHS-GC-MS. The method described has proven to be reliable for assessing current occupational exposure to chlorinated and aromatic VOCs in France.

摘要

混合暴露于化学制品是职业健康的一个热门话题,通常包括暴露于挥发性有机化合物(VOC)。由于评估这些混合暴露的方法很少,因此本工作的目的是开发一种简单的生物监测方法,通过分析工人尿液中未代谢的 VOC 部分来评估同时职业暴露于氯化和芳香族 VOC。使用动态顶空气相色谱法与质谱联用(dHS-GC-MS)分析挥发性有机化合物,并在顶空相中测量 11 种未代谢的尿液 VOC,无需耗时的预处理。同时,设计了标准化的收集方案以避免 VOC 损失或尿液样品的污染。校准样品是真实尿液,用研究的 VOC 混合物的已知量进行了加标。在三个工厂中对潜在暴露的工人进行了测试研究,以评估收集方案和分析方法的有效性。所有 VOC 的检测限(LOQ)均在 10-15ng/L 之间,达到了令人满意的灵敏度水平(除了苯乙烯为 50ng/L)。在测试的 0-20μg/L 范围内,校准曲线呈线性,R 相关系数为 0.991 至 0.998。在测试的最低浓度(0.08μg/L)下,日内精密度在 2.1-5.5%之间,日间精密度在 2.7-8.5%之间。在-20°C 下的样品稳定性要求尿液样品在 3 个月内进行分析。尽管工厂中使用的 VOC 尿液浓度大多较低,但仍观察到轮班后和轮班前之间存在显著差异。总之,使用 dHS-GC-MS 从人尿中提取 VOC 开发了一种快速、灵敏、特异且易于使用的方法。该方法已被证明在法国可靠地用于评估当前职业暴露于氯化和芳香族 VOC。

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