Chemistry Division, Federal Office for Civil Protection, Spiez Laboratory, 3700 Spiez, Switzerland.
Department of Chemistry, University of Fribourg, 1700 Fribourg, Switzerland.
Anal Chem. 2022 Dec 6;94(48):16579-16586. doi: 10.1021/acs.analchem.2c01867. Epub 2022 Nov 22.
Chlorine, as a dual-use chemical, is an essential industrial chemical which has been used as a chemical weapon in the past due to its toxicity and availability. The retrospective verification of chlorine intoxication is often especially challenging, and unambiguous markers are still missing. In this study, the effects of different chlorinating and oxidizing agents on human hair were investigated. Samples were exposed to a variety of chlorinating chemicals for a short time and then completely hydrolyzed by a HBr solution to break down their keratin proteins into individual amino acids. After derivatization and targeted liquid chromatography-mass spectrometry analysis, 3-chlorotyrosine and 3,5-dichlorotyrosine were unambiguously identified from human hair exposed to chlorine, hypochlorite, and sulfuryl chloride. Our results show long-term stability of these markers in the biological matrix, as the chlorotyrosines can still be found 10 months post-exposure at the same levels. Finally, an untargeted analysis was able to discriminate between some of the different intoxicants.
氯作为一种两用化学品，是一种必不可少的工业化学品，由于其毒性和易得性，过去曾被用作化学武器。氯中毒的回溯验证通常特别具有挑战性，而且仍然缺乏明确的标记物。在这项研究中，研究了不同的氯化和氧化试剂对人类头发的影响。将样本短时间暴露于各种氯化化学品中，然后用 HBr 溶液完全水解，将其角蛋白分解成单个氨基酸。经过衍生化和靶向液相色谱-质谱分析，在暴露于氯气、次氯酸盐和亚硫酰氯的人类头发中，明确鉴定出 3-氯酪氨酸和 3,5-二氯酪氨酸。我们的结果表明，这些标记物在生物基质中的长期稳定性，因为在暴露后 10 个月仍能以相同水平检测到这些氯代酪氨酸。最后，非靶向分析能够区分一些不同的中毒剂。
