中国珠江与长江河口地区传统及新兴卤系阻燃剂环境分布特征与生态风险评估

Coastal environment of China has been undergoing strong modifications due to rapid economic growth and industrialization. These may increase the demand for flame retardants used in the manufacture of products for both domestic use and export, so it is not surprising that huge amounts of halogenated flame retardants (HFRs) are found in this region. Among the HFRs, polybrominateddiphenyl ethers (PBDEs) has become one of the most concerned environmental contaminants because of their persistence, bioaccumulative tendencies and potential adverse effects on organisms, as well as their large scale of use. Consequently, this has resulted in strict bans of Penta- and Octa-BDE formulations. The phase-out of PBDEs is expected to reduce the world market demand for these compounds, but other HFRs may consequently take their place in product manufacturing. Previous monitoring studies on sediment and biological samples revealed the widespread occurrence of conventional HFR including PBDEs and hexabromocyclododecanes in the Chinese coastal region. Recently, a number of emerging HFRs are detected in the environment and the presence of several of these new chemicals in biota indicates that they are bioavailable and can be absorbed and bioaccumulated. However, the information regarding the environmental occurrence, distribution and fate of these chemicals is still scanty. An increasing number of studies indicated that several novel HFRs such as Dechlorane Plus are of particular concern in China and elsewhere. Our recent studies has shown the relatively high levels of TBPH and TBB, in blubber samples of Indo-Pacific humpbackdolphins and finless porpoises and indicated the presence of a potential source of these new brominated flame retardants in Pearl River Delta region. This has led to the suspicion that similar types of new HFRs may be extensively used in the estuarine areas, and raises our attention on the status of these new chemicals in other Chinese estuaries. Pearl River Delta in south China and Yangtzu River Delta in central China are the two important estuarine systems. With the rapid industrialization and urbanization, this may, as a result, increase the stresses on the environment and ecosystem of these places and assessment of novel HFRs in these places is strongly needed. To assess a variety of emerging HFRs in different environmental matrices, an ultra-performance liquid chromatography coupled with atmospheric pressure chemical ionization tandem mass spectrometry was developed for simultaneous quantification of PBDEs, HBCDs, and other new HFRs. Information regarding the environmental occurrence of novel HFRs is still limited. This study, therefore, proposes to provide information on concentration, distribution and accumulation of novel HFRs in different environment matrices including sediment and biological samples. These results would also help prioritize which HFRs merit study, and will assist in modeling their environmental fate and transport.

卤系阻燃剂(HFRs)是常用的有机阻燃剂，研究表明在中国沿海地区环境中除了国际上禁用的传统五溴和八溴联苯醚之外，新兴HFRs在环境和生物样品中都有检出。然而，我国对于HFRs在环境中分布与归趋的研究还相对缺乏。在我们早期研究发现香港海洋哺乳动物样品中检测到高含量HFRs，说明珠三角地区是HFRs的污染源,由此推测这类化合物在河口地区有着广泛分布，因此在我国最重要的河口体系- - 珠江和长江三角洲开展系统的新兴HFRs研究显得尤为紧迫。本项目拟开发基于高效液相色谱大气压化学电离多级质谱联用技术，以同时精确定量检测各种传统和新兴HFRs；并将新分析技术应用于测定目标区域沉积物及生物样品检测，从而获得环境HFRs时空分布特征和生物累积水平；确定各类HFRs构成比例及其生态风险；并为后续的HFRs环境转化、行为模式等研究提供技术支持和理论依据。

珠三角和长三角地区快速经济增长和工业化造成沿海环境发生巨大改变。产品制造业对持久稳定化合物需求持续增加，因此，两个地区均发现大量卤化阻燃剂 (HFRs)，如PBDEs，其同系物Penta和Octa-BDE已被列入持久性有机污染物清单。由于PBDEs生产和使用受限，其替代物需求增加，随之而来的环境问题受到极大关注。本研究项目组开发了可同时定量不同环境样品中PBDEs及其替代物（如DBDPEs、DPs、TBPH、TBB、BTBP和HBCDs）新方法并应用于长三角海洋与河流沉积物分析。在众多HFRs中，PBDEs、DBDPE和TBECH检出率最高，PBDEs与DBDPE显著相关性揭示它们可能具有相同排放源。DBDPE生产和使用快速增长及其与PBDEs浓度比较说明DBDPE很可能成为未来环境中HFRS的主要化合物。珠三角地区重要海洋顶级捕食者中华白海豚和江豚鲸脂HFRs调查发现，DPs、DBDPE、BTBPE、TBPH和TBB检出显示华南地区是新兴HFRs潜在污染源，HFRs浓度显著时间演变证实了该地区化合物使用由PBDEs转向其替代物，原因可能与PBDEs商品混合物生产和使用受限及其替代物使用增加有关，这些污染物频繁检出和高浓度表明该地区是PBDEs替代阻燃剂源。其他两组重要PBDEs潜在替代物CPs（SCCP和MCCP）与OPFRs（TDCPP）在本研究中亦被检出。2004~2014年鲸脂SCCPs和MCCPs呈现正时间变化趋势，表示过去十年∑SCCP和∑MCCP浓度明显上升，揭示CPs生产和使用对海洋哺乳类体内CPs富集具有重要影响，化合物组成时间转变反映污染源通过大气传送、海洋陆架海流运输和营养转移等复杂环境沉淀造成鲸豚类相异的富集水平和同系物模式。与此同时本研究针对TDCPP对水生生物风险开展暴露实验。长时期低浓度暴露可显著增加斑马鱼雌性血浆雌二醇和睾酮水平，同时降低产卵能力，影响斑马鱼生殖。另一个实验证实了亲代暴露会造成后代甲状腺激素内分泌和神经发育不良，甲状腺激素水平降低和TDCPP对大脑直接作用会妨碍大脑和神经系统发育介导子一代发育神经毒性。这些结果充分证实了TDCPP具有生物毒性作用，其对生态系统和人类健康存在潜在负面影响。总之，本研究提供了有关水生环境HFRs及其PBDEs替代物现状信息和负面影响。这些结果可帮助人们更好地认识新兴污染物对海洋生态系统的潜

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