四溴双酚A衍生物及其副产物的分析方法与环境行为研究

Tetrabromobisphenol A (TBBPA) is one of endocrine disruptors, which can interfere the endocrine pathways by impact different nuclear receptors, causing reproductive and developmental disorders. Structural analysis showed that some TBBPA derivatives and their byproducts may have more toxic effects. With the increasing use of these derivatives, their pollution and risks become an important environmental problem that cannot be neglected. However, few studies were reported on these chemicals. There is no analytical method available now and the environmental evidence is still little. Therefore, this project will be focused on four common derivatives of TBBPA and five corresponding byproducts. Sensitive and accurate methods for analysis of these chemicals in different environmental and biological samples will be established. The distribution, transportation, transformation and bioaccumulation of these chemicals in typical regions will be studied in detail. Their source and sink, exposure pathways and potential risks will also be discussed. The results of this project will provide a scientific basis for further in-depth understanding of the environmental and health risks of brominated flame retardants and developing strategies for their control.

四溴双酚A（TBBPA）是一类内分泌干扰物，可以通过影响不同的核受体干扰内分泌通路，造成生殖发育障碍。结构分析表明，TBBPA的衍生物及其生产过程中产生的副产物，可能具有更强的毒性效应。随着这些衍生物使用比例的不断增加，其造成的健康危害将成为不可忽视的重要环境问题。然而这方面的研究工作尚没有系统开展，缺乏分析方法，实验证据甚少。本项目拟针对TBBPA的4种衍生物及5种相应的副产物，建立灵敏、准确的分析方法，系统研究这些化合物在典型区域环境中的分布、迁移、转化及生物富集过程，明确其在环境中的来源、传输及归趋，探讨不同化合物的暴露途径与潜在风险，为进一步深入了解溴代阻燃剂的环境与健康风险及制定有关防控对策提供科学依据。

开发了基于电喷雾萃取电离质谱技术(EESI–MS)、高分辨静电场轨道阱组合质谱（Orbitrap Fusion HRMS）、HPLC-ESI-MS/MS和在线银离子柱后衍生的新型分析方法，用于环境中四溴双酚A/S衍生物和副产物的分析，提高了衍生物检测的灵敏度和选择性，为此类污染物的环境行为和环境归趋研究提供了必需的技术手段。应用建立的质谱新方法，在我国土壤、底泥、河水和海洋生物中鉴定出20余种TBBPA/S相关溴代污染物，并通过合成标准化学品进一步揭示了这些副产物的结构。对渤海生物样品的分析发现，TBBPA/S副产物主要呈现食物链稀释的趋势，对低等生物的危害更大。细胞毒性评价实验表明，TBBPA/S衍生物和副产物具有更高的神经毒性作用。相关研究结果为TBBPA类衍生物的环境行为和综合评价TBBPA类溴代阻燃剂的环境风险提供重要科学支持，共发表SCI论文11篇，包括2篇Environ Sci Technol、1篇Anal Chem和1篇TrAC-Trends Anal Chem，获2017年中国分析测试协会科学技术特等奖。