非禁用和新型卤系阻燃剂的环境与生物地球化学行为与过程研究

This project was initiated to study the unresolved scientific problems related to the the environmentally geochemical and biogeochemical behaviors and processes of halogenated flame retardardants (HFRs) by field investigation and laboratory adiministrated experiments. The target compouds in this project will focus on non-regulated and novelly alterative HFRs. Compound-specific isotope analysis (CSIA) will be introduced in this project to trace the HFR sources on a local and regional scale, and to identify and quanatify the (bio)degradation processes of HFRs in abiotic and biotic environment. The HFRs in environmental samples from contaminated regions representative of different sources will be characterized. The degradation behaviors of HFRs in various environment conditions and the different environmental behaviors of different stereo and chiral isomers will be investigated. The mechanism on biotransformation of HFRs in different organism will be studied. We aim to acquire several indicators and/or parameters (such as compound-specific isotope fingerprinting, characteristic markers and its ratio, and stereo and chiral isomer ratios) which can be used to trace the sourcs of HRFs and to identify the geochemical and biogeochemical behaviors and processes of HFRs in environment. In addition, the bioaccumulation and trophic transfer of HFRs in terrestrial food wed will be investigated and the bioaccumulation factors and biomagnification factors of HFRs in terrestrial ecosystem will be obtained in this study. Finally, we will use these acquired indicators and/or parameters to allocate the HFR sources and to assess the geochemical and biogeochemical behaviors and processes of HFRs in complexly contaminated environment. This project contributes to understanding the contamination trends of novelly alterative HFRs in Chinese environment and provides scientific knowledge on assessing the potential environmental and ecological risk of these currently non-regulated and novel HFRs. The results from this project will also contribute to the decision-making process when we implement the Stockholm Convention.

本项目将针对当前卤系阻燃(HFRs)环境与生物地球化学行为和过程的一些未解决问题,在已有基础上,以仍在使用的和新型替代品HFRs为目标物,通过野外调查和室内模拟,引入分子稳定同位素示踪技术，剖析受不同来源典型污染地区HFRs的源特征,探讨不同环境因子影响下HFRs的降解行为、立体和手性异构体的行为差异、HFRs在不同生物体内的转化机制;力求获得能用于示踪HFRs来源及其环境和生物地球化学行为和过程的指标参数(如分子稳定同位素指纹、特征标志物及参数、立体和手性异构体参数).研究HFRs在陆地食物网中生物富集与迁移,获取HFRs在陆地生态系统中的生物累积与放大参数;利用所获得的指标参数来示踪受多种HFRs复合污染区域中HFRs的来源和生物地球化学行为过程.结果对了解我国环境中新型HFRs的污染态势、评估HFRs的环境与生态风险有重要意义,也为国家建立控制对策和应对"履约"策略提供科学依据.

项目围绕卤系阻燃(HFRs)的环境与生物地球化学行为和过程开展研究，在新型HFRs的分析方法、典型污染地区环境中HFRs的源特征、新型HFRs的立体和手性异构体环境行为、HFRs的生物体代谢与转化、食物链累积与放大等方面取得了研究进展。主要成果有①开发了一种用于复杂基质样品中多溴联苯醚（PBDEs）单体稳定碳同位素（CSIA）高精度分析方法，并成功地利用CSIA对PBDEs在水生食物链传递过程中的脱溴代谢进行了定量示踪。②揭示了我国典型电子垃圾拆卸地、电子信息产业地和阻燃剂生产基地环境中HFRs的污染特征；评估了《RoHS指令》实施后了珠三角环境中HFRs污染演变趋势，发现近年来DBDPE等替代HFRs在我国环境中的污染逐年递增。③以东江流域为研究区域，通过分析表层沉积物、沉积柱、水体和鱼类样品中的HFRs，阐明了六溴环十二烷（HBCDs）手性和立体异构体、敌克隆（DP）立体异构体在水体环境的时空分布、相分配、生物富集等生物地球化学行为；利用污染物的组成分布结合CSIA探讨了PBDEs在沉积物中的降解行为。④明晰了HFRs大气-植物交换的机制，揭示出由交换机制的变化所导致的log KPA（植物/大气分配系数）与化合物的log KOA（辛醇-气分配系数）之间的多段性线性关系。⑤利用体内和体外暴露实验，研究了PBDEs、HBCD和DP在水生生物（不同鱼类）中的代谢与转化。指出鱼体对PBDEs的脱卤潜力和脱卤途径差异是造成鱼类对PBDEs富集物种差异性的原因；确定了PBDE在鲤科鱼类中脱溴代谢中的结构-活性关系。⑥研究了HFRs在陆地猛禽中的生物放大规律，发现HFRs在陆地生物中的生物放大规律与水生生物中的明显不同， 并具有强烈的食物链依赖性。评估了HFRs在模式鸟类（鸡）中的代际传递能力。研究结果对了解我国环境中新型HFRs的污染态势、评估HFRs的环境与生态风险有重要意义,也为国家建立控制对策和应对“履约”策略提供科学依据。