Chlorinated dioxins are labeled and recognized by both the World Health Organization and the United Nations Environmental Programme (UNEP) as “persistent organic pollutants”. Their potential for high toxicity is one of the primary factors behind intense public and regulatory scrutiny and the need to measure the compounds at very low limits, specifically the isomer 2,3,7,8‐tetrachlorodibenzo‐p‐dioxin (2,3,7,8‐TCDD). This article highlights the early mass spectrometry methods to investigate, detect, confirm, and quantify chlorinated dioxins and the initial applications involving human biomonitoring, as attempts were made to attribute health effects to TCDD exposure. This effort represented a complex and difficult scientific response to the pressing need to investigate expected exposures and alleged subsequent medical effects, which in the case of the Viet Nam veterans was being attempted a decade or more after their exposure. It is noteworthy that this method and its development touched on delicate issues involving human subjects, war veterans, environmental contamination, and was difficult not only scientifically, but for ethical and political reasons as well. Stable‐isotope dilution with analysis by gas chromatography/high‐resolution mass spectrometry (GC/HRMS) became the method of choice because of its ability to monitor characteristic ions and isotope ratios to quantify and qualify/confirm the analyte in the presence of coextracting and coeluting interferences at these low levels with the highest possible confidence. This method was rigorously tested and validated before it was used to discover and monitor levels in the environment and in various populations at then unprecedented low levels. These early studies demonstrated the feasibility of monitoring dioxins in humans even decades after exposure, and led to the detection of 2,3,7,8‐TCDD in the general population as well as specific overexposed populations. These studies also provided strong evidence regarding the origins of the 2,3,7,8‐isomer in the environment. © 2020 John Wiley & Sons Ltd. Mass Spec Rev

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开发用于对包括越南退伍军人在内的环境和生物样品中的氯化二恶英进行超痕量分析的高分辨率质谱方法

氯化二恶英被世界卫生组织和联合国环境规划署 (UNEP) 标记并认可为“持久性有机污染物”。其高毒性潜力是后面激烈的公开和监管审查，并测量在非常低的限制化合物的需要的主要因素之一，特别是异构体2,3,7,8-四氯代p-二恶英（2,3,7,8-TCDD）。本文重点介绍了用于调查、检测、确认和量化氯化二恶英的早期质谱方法以及涉及人体生物监测的初始应用，因为已尝试将健康影响归因于 TCDD 暴露。这项工作代表了对调查预期暴露和所谓的后续医学影响的迫切需要的复杂和困难的科学反应，就越南退伍军人而言，在暴露十年或更长时间后才尝试进行调查。值得注意的是，这种方法及其发展涉及涉及人类受试者、退伍军人、环境污染的微妙问题，不仅在科学上困难重重，而且出于伦理和政治原因也困难重重。用气相色谱/高分辨质谱 (GC/HRMS) 进行分析的稳定同位素稀释成为首选方法，因为它能够监测特征离子和同位素比率，以便在存在共提取和鉴定的情况下量化和定性/确认分析物。以尽可能高的置信度对这些低水平的共流出干扰物进行分析。这种方法在用于发现和监测环境和各种人群中当时前所未有的低水平的水平之前，经过了严格的测试和验证。这些早期研究表明，即使在接触二恶英几十年后，监测人类二恶英的可行性，并导致在一般人群和特定过度暴露人群中检测到 2,3,7,8-TCDD。这些研究还提供了关于 2、3、7、8-异构体在环境中。© 2020 John Wiley & Sons Ltd. 质谱修订版