典型有机磷酸酯阻燃剂在太湖中的存在水平、分布特征及其环境行为研究

Environmental and ecological effects of organophosphorus ester flame retardants (OPEs) which are defined as a "re-emerging" pollutants in the international environmental scicence field, have already become one of the hot research projects in the whole world. This project focuses on the development of an analytical method for OPEs in varied environmental media based on the preparation and characterization of a novel nanopore ionic liquid soild phase microextraction (SPME) coating combined with gas chromatography tandem mass spectrometry (GC/MS), and on the establishment of quality control and quality assurance (QA/QC) system. Then Tai lake is selected as the interest area, and nine typical OPEs are as the target pollutants. The occurrence patten, level, distribution characteristics and environmental behaviors of OPEs will be investigated systematically. Valuation of pollution status and the interpretation of the spatial and seasonal variations of OPEs in Tai lake will be obtaind through the sampling and analysis of surface water, sedimnets and aquatic lives in whole Tai lake using the established pretreatment and instrumental analysis method. According to the pollutant status, the heavy pollution sampling sites, estuary and the wasterwaer treatment plants (WWTPs) in the upstream will be choosed as the priority study objects. The surface water, suspended substance, surface sediments, core sediments, interstitial water and typical aquatic lives samples in the heavy pollution sites, the surface water and sediment on the estuary and the Influent, effluent and sludge samples of the WWTPs will be collected and analyzed. To comprehensively analyze the distribution, migrationand conversion of OPEs in multi-environment interface, the adsorption/desorption behavior of OPEs in water/sediment interface will be investigated in laboratory. Additional, the typical aquatic life Zebrafish exposure experiment will be simulated in laboratory to evaluate the biaaccumulation and biomagnification effects. The achievements of this project will provide a theoretical basis and technical support for the further study of the environmental processes and toxicological effects of OPEs and also will be of great significance for prevention and controlling OPEs pollutian and its harmful to human health.

有机磷酸酯（OPEs）阻燃剂是目前国际环境科学领域又一新兴的污染物，其环境生态效应已成为研究的热门和前沿课题。本项目通过制备新型纳米孔离子液体固相微萃取涂层，结合气相色谱串联质谱，建立多环境介质中OPEs的分析方法，完善质量控制与质量保证体系。并以太湖为研究区域，以9种典型OPEs为研究对象，对太湖中OPEs的赋存形态、存在水平、分布特征和环境行为进行研究。通过采样分析，评价OPEs在太湖中的污染现状，阐明其时空分布特征；通过对重污染点位、入湖河口以及来水上游污水处理厂进行采样分析，结合在实验室内模拟OPEs在水/沉积物界面的吸附解吸以及典型水生生物斑马鱼的暴露试验，全面剖析OPEs在多环境界面间的分配、迁移、转化及生物累积与生物放大作用，揭示OPEs的迁移转化特点，为深入研究OPEs的环境过程与毒性效应研究提供理论基础和技术支持，对预防及控制其污染和危害人体健康具有重要意义。

近年来，有机磷酸酯类阻燃剂一直是国内外环境科研工作者的研究热点。本课题从不同环境介质中OPEs的分析方法入手研究了9种典型OPEs在太湖水环境中的赋存形态、存在水平、分布特征以及生物可利用性。建立了基于新型纳米孔离子液体固相微萃取涂层的水样、底泥以及鱼体中OPEs的前处理及仪器分析方法。制备的[AMIM][BF4]溶胶-凝胶涂层热稳定性好、化学稳定性强、使用寿命长并有较好的重现性（RSD<9.4%）。建立的不同介质中OPEs的分析方法灵敏度高，检测限低，线性范围宽，可满足实际环境样品痕量分析的要求。以底泥为例，方法在0.8-100ng/g的加标沉积物中呈线性关系，检测限低至0.008ng/g，RSD<9.8%。在此基础上，研究了太湖及出入湖河流水体中目标物的污染现状，研究表明，太湖水体中OPFRs的总浓度值为375-3079ng/L，TCPP、TCEP、TPPO和TEP是太湖水体最主要的OPFRs，其浓度分别为81-1967ng/L、53-1478ng/L、74-872ng/L和20-1125ng/L。北部湖区和西部湖区OPFRs浓度最高，南部湖区OPFRs浓度最低;太湖底泥中OPFRs总浓度水平为42-680μg/kg。TnBP为最主要的OPFRs，其浓度范围为2.9-347μg/kg。太湖底泥中OPFRs没有明显的空间分布特征。Σ9OPEs在太湖入湖河流和出湖河流表层水中的浓度范围分别是223.6-2934.2ng/L，340.1-1529.2ng/L；在沉积物中，Σ9OPEs分别处于55.5-4511.0μg/kg（入湖）和47.3-106.9μg/kg（出湖）。9种化合物中，TCPP和TCEP是浓度较高的污染物。OPEs在太湖及其周边河流样品中都呈现出北高南低的趋势；污染程度较高的区域在望虞河附近以及常州武进区内的河流。采用PCA-MLR的多元统计结果表明，水样主要有5种来源；底泥有三种来源。利用自制涂层作为微损耗SPME萃取纤维，结合Tenax提取技术评估了沉积物中氯代有机磷酸酯的生物可利用性，微损耗SPME和6 h Tenax提取量与颤蚓体内累积的量有很好的相关关系（p<0.05）。nd-SPME比Tenax提取更能准确地评估沉积物中氯代有机磷酸酯的生物可利用性。本研究为深入探讨OPEs的环境过程与毒性效应提供了技术与数据支撑，对控制其污染具有重要意义。