环境中四溴双酚A及其典型衍生物/副产物 的生物分析方法、污染特征与环境行为研究

Tetrabromobisphenol A (TBBPA) is one of endocrinedisruptors with reproductive toxicity, some TBBPA derivatives and their byproducts may have more toxic effects, which was considered as potentially persistent organic pollutants, and the pollution and risks caused by these containments gradually become serious environmental problems and health hazards. However, currently only a few instrumental analytical methods were established for determination of TBBPA, and several derivatives or byproducts, and they suffered from expensive instruments, great costs for samples analysis, time consuming to pre-concentrate and separate targets from matrices, complicated procedures in sample pretreatment, all of which caused the lack of systematic research for these organic pollutants. Therefore, this project will be focused on TBBPA, three typical derivatives of TBBPA and four corresponding byproducts. Four monoclonal antibodies against TBBPA and three typical derivatives of TBBPA will be produced, and four specific antibodies recognizing corresponding byproducts also be generated, based on which, multiply targeted, high-throughput, quick, sensitive time-resolved fluoroimmunoassay could be developed for analysis of these chemicals from a large number of different environmental, biological and human samples, as a consequence of this, the distribution, pattern, transformation and bioaccumulation of these chemicals in contaminated regions will be studied in detail, and their source, transmission and exposure pathways 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 these containments.

四溴双酚A(TBBPA)是一种具有生殖毒性的内分泌干扰物，其衍生物和生产过程中产生的副产物可能具有更强毒性，是潜在的持久性污染物，可能会带来严重的健康危害和环境污染问题。然而，目前仅有极少的针对个别衍生物/副产物的仪器分析方法，而且存在仪器昂贵、测试成本高、分析时间长、前处理复杂等不足，限制了对此类污染物的系统研究。本项目拟针对TBBPA及其3种典型衍生物和对应的4种副产物，分别制备4种可识别TBBPA及其衍生物的单克隆抗体、4种可识别TBBPA副产物的抗体。在此基础上，建立多标记、高通量、高灵敏、快速的时间分辨荧光免疫分析方法，并对典型区域的环境样品、生物样品、人体样本进行分析，系统研究这类化合物的污染水平及特征，揭示其在不同植物和动物体内的累积差异，明确其来源、传输及生物富集规律，了解其在污染区域人群中的暴露途径与浓度水平，为进一步评估这些化合物对普通人群的环境暴露风险提供科学依据。

由于TBBPA及部分衍生物/副产物的测定方法均基于仪器分析方法，其缺点明显：所用仪器极其昂贵，而且存在测试成本高、分析时间长、检测所需样品量大及前处理步骤繁琐等不足，无法在较大范围内系统、全面、快速分析环境中TBBPA及部分衍生物/副产物的含量。因此，现有环境中此类污染物调查数据大多零散、缺乏系统性，难以得出规律性的结论，导致了此类污染物对环境影响研究的滞后。同时，另有部分TBBPA衍生物/副产物还没有分析方法，其污染水平及特征、环境风险尚不明确。为解决以上问题，本项目对此类化合物进行了分子改造，设计了多种半抗原，并以此制备了相应的单/多克隆抗体，在此基础上，构建了灵敏度高、分析过程简单、快速的生物分析体系。.利用所构建的分析方法，对环境中此类污染物的污染现在进行了调查研究，首次在江苏苏州某水体中发现了TBBPA DHEE的存在；对浙江台州的电子垃圾拆解地进行系统分析的结果表明，JJP（椒江湾）和RIB（台州金属资源再生产业基地）两个区域TBBPA衍生物污染严重（水样和土壤样本检出率超过90%），而集中焚烧等方式对此类污染没有明显的改善作用；同时，FJ（峰江街道）的测定结果说明，对于电子垃圾废弃地的持续治理，大大降低了此类污染物的含量。研究还发现，生物样本中TBBPA衍生物含量显著高于水样和土壤样本，呈现明显的富集效应；此外，采用环境影响度评估、生态风险评估、健康风险评估三种方式对浙江省台州市、山东省寿光市、湖南省浏阳河流域三地环境介质中的DHEE、MHEE进行了环境生态安全与健康安全风险评估，结果表明：通过饮用水成人暴露于TBBPA-DHEE、TBBPA-MHEE引起的非致癌风险是可以忽略的，但是通过饮用水儿童暴露于TBBPA-DHEE、TBBPA-MHEE引起的非致癌风险是很高的，在X3中点健康风险值为4.9863，风险超出了可接受范围，需要引起有关部门的重视。