上海市地表水体中多环芳烃与多氯联苯的环境行为与风险研究

发布时间：2018-07-03 20:28

本文选题：多环芳烃 + 多氯联苯　；参考：《华东师范大学》2017年博士论文

【摘要】：多环芳烃(PAHs)和多氯联苯(PCBs)是两类典型的具有致癌、致畸和致突变的持久性有机污染物(POPs),可通过多种环境介质进行长距离迁移,且对人类健康和环境安全具有严重危害。地表水体是PAHs、PCBs等污染物的重要的环境受体,因此研究PAHs、PCBs在典型地表水体中的暴露水平、环境行为及其造成的环境风险具有重要的理论和现实意义。本研究在国家自然科学基金项目(No.41271472)、上海市科委社会发展重点项目(No.12231201900)的资助下,利用气相色谱法/质谱联用技术(GC/MS)测定了上海市河网、滴水湖及其环湖水系水、沉积物中PAHs、PCBs的暴露浓度,运用统计学和GIS等方法分析了 PAHs和PCBs的污染水平与时空分布规律,利用冗余分析(RDA)等方法探讨了 PAHs和PCBs的污染分布及分配行为与环境因子间的耦合关系,综合主成分分析(PCA)、绝对主成分/多元线性回归(APCS/MLR)及正定矩阵因子分解(PMF)等方法对比分析了其来源与来源贡献率。在此基础上,基于景观用水用途的暴露情境,分析了 PAHs、PCBs对上海市成人、儿童造成的致癌性健康风险和非致癌性健康风险,结合美国国家环境保护局(USEPA)推荐的定量结构-活性相关模型(QSAR)(ECOSAR)和北京大学开发的基于贝叶斯理论的风险评估模型(BMC-SSD)推导了符合研究区水系、水体特征的水生生物预测无效应浓度(PNEC),并利用商值法对其生态风险水平进行了表征。得出的主要结论如下:(1)研究区表层水、沉积物中16种PAHs整体处于轻微至中度污染水平,各相中PAHs均以3～5环成分为主,含量较高的单体有Phe、Ant和Flua。表层水中PCBs为轻中度污染,而沉积物中PCBs为轻微污染,各相中PCBs均以五氯联苯为主,主要的特征单体为PCB118、PCB105和PCB77。受河道水动力条件较弱、黑臭现象较严重等因素影响,中心城区以及城镇居民区河网水体中PAHs、PCBs污染相对严重。滴水湖环湖水系水体中的PAHs、PCBs含量普遍高于湖区。除秋季沉积物中的PCBs外,冬季表层水中的PAHs和PCBs均显著高于其他季节。(2)"盐析效应"、水质现状、总悬浮颗粒物(TSS)和溶解性有机质(DOC)是影响水中PAHs、PCBs分布的重要因素。沉积物中PAHs分布受沉积物的机械组成和碳黑(SC)影响显著,PCBs分布则受SC、TOC影响显著。水温、盐度及水中的TSS、DOC对PAHs、PCBs在颗粒物-水间的分配行为影响较大。PAHs、PCBs的沉积物-水分配行为均受沉积物机械组成影响显著,SOC及TOC含量对PAHs的沉积物-水分配行为影响显著,但对PCBs的影响不显著。现场数据较好地拟合了沉积物-水中PAHs的分配行为,但并不能很好地拟合沉积物-水中PCBs的分配行为。(3)正定矩阵分解法(PMF)较之主成分分析法(PCA)和绝对主成分/多元线性回归法(APCS/MLR)对PAHs源解析的结果更全面,源解析结果表明研究区地表水中PAHs主要来自于煤、薪柴和天然气等燃烧源以及焦化源排放,而沉积物中的PAHs受交通源的贡献最高,其次为燃烧源和焦化源。PCA法及PMF法均区分出了 PCBs的4类源,但贡献率计算结果存在一定差异。总体而言,研究区地表水体中PCBs主要来自国产PCB工业品的使用残留,但也受再生金属加工行业排放以及国外PCB产品的使用残留与远距离输送影响。(4)河网水体中PAHs、PCBs的成人的总致癌风险水平已超过了最大可接受致癌风险水平,儿童仅除崇明岛及农业区部分点位外,其他点位的总致癌风险也均超过了最大可接受风险水平。对于滴水湖及其环湖水系水体中PAHs、PCBs,仅有9.3%的点位成人总致癌风险及18.67%的点位儿童总致癌风险处于可接受水平。皮肤接触是景观用水暴露情境中PAHs、PCBs致癌风险的主要暴露途径,但不会造成明显的非致癌健康伤害。(5)利用ECOSAR及BMC-SSD模型推导的预测无效应浓度(PNEC)与其他研究具有较好的可比性。研究区存在较高生态风险水平的PAHs单体主要有水中的苯并[b]荧蒽(BbF)、苯并[k]荧蒽(BkF)、BghiP以及沉积物中菲(Phe)、荧蒽(Flua)和芘(Pyr),存在高生态风险水平的PAHs单体主要为Phe、蒽(Ant)、窟(Chry)、Flua和Pyr。水体中具有高生态风险水平的DL-PCBs单体主要为溶解态中的PCB105、颗粒态中的PCB118、PCB105和PCB77。
[Abstract]:Polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) are two types of typical carcinogenic, teratogenic and mutagenic persistent organic pollutants (POPs), which can carry long distance migration through a variety of environmental mediums, and have serious harm to human health and environmental safety. Surface water is an important environmental receptor for PAHs, PCBs and other pollutants. Therefore, the study of PAH The exposure levels of S, PCBs in typical surface waters, environmental behavior and environmental risks are of great theoretical and practical significance. Under the support of the National Natural Science Foundation (No.41271472) and the key social development project (No.12231201900) of the Shanghai Municipal Science and Technology Commission (No.12231201900), this study was determined by gas chromatography / mass spectrometry (GC/MS). The pollution level and spatio-temporal distribution of PAHs and PCBs were analyzed by statistics and GIS, and the pollution distribution of PAHs and PCBs and the coupling relationship between the distribution behavior and environmental factors were discussed by the methods of redundancy analysis (RDA) and so on. The pollution distribution of PAHs and PCBs were analyzed by the methods of statistics and GIS, and the pollution levels of PAHs and PCBs in the sediments and the exposure concentration of the sediments were analyzed. Principal component analysis (PCA), absolute principal component / multivariate linear regression (APCS/MLR) and positive definite matrix factorization (PMF) were used to compare their source and source contribution rates. Based on the exposure scenarios of landscape water use, the carcinogenic health risks and non carcinogenic health risks caused by PAHs and PCBs for children in Shanghai City were analyzed. Combined with the quantitative structure activity correlation model (QSAR) (ECOSAR) recommended by the national environmental protection agency of the United States (USEPA) and the Bayesian based risk assessment model (BMC-SSD) developed by the Peking University (BMC-SSD), this paper derives the ineffective stress concentration (PNEC) of aquatic organisms in accordance with the water system and water characteristics in the study area, and uses the quotient method for its ecological wind. The main conclusions are as follows: (1) the surface water of the study area, 16 kinds of PAHs in the sediments are in the mild to moderate pollution level, and the PAHs in each phase is dominated by 3~5 ring components, the monomer with higher content is Phe, the PCBs in the surface water of Ant and Flua. is light medium pollution, and the PCBs in the sediments is slightly polluted and PCBs in each phase. The main characteristics are five chlorinated biphenyls, the main characteristic monomers are PCB118, PCB105 and PCB77. are influenced by the weak river hydrodynamic conditions and the serious black odor. The pollution of PAHs in the river net water of the central urban area and the urban residential area is relatively serious. The PAHs in the water system of the drip lake lake water system is generally higher than that in the lake area. Except for the autumn deposition, the content of PCBs is generally higher than that in the lake area. The PAHs and PCBs in surface water in winter are significantly higher than those of other seasons. (2) "salting out effect", water quality, total suspended particles (TSS) and dissolved organic matter (DOC) are important factors affecting the distribution of PAHs and PCBs in water. The PAHs distribution in the sediments is influenced significantly by the mechanical composition of the sediments and the carbon black (SC), while PCBs distribution is SC, TO. The effect of C on water temperature, salinity and TSS in water, DOC to PAHs, PCBs in the distribution of particles and water has great influence on.PAHs, and the sediment water distribution behavior of PCBs is greatly influenced by the mechanical composition of sediment, SOC and TOC content has a significant influence on the sediment water distribution behavior of PAHs, but the effect on PCBs is not significant. Field data is well proposed. The distribution behavior of PAHs in sediment water can not be well fitted to the distribution behavior of PCBs in the sediment water. (3) the positive definite matrix decomposition (PMF) is more comprehensive than the principal component analysis (PCA) and the absolute principal component / linear regression (APCS/MLR) for the analysis of PAHs source. The source analysis results show that the PAHs master in the surface water of the study area is dominant. It is derived from coal, firewood, natural gas and other combustion sources, as well as the source of coking source, and the PAHs in the sediment is the highest contribution to the traffic source. Secondly, the 4 sources of PCBs are separated from the combustion source, the focal.PCA method and the PMF method, but the calculation results of the contribution rate are different. In general, the PCBs in the surface water of the study area is mainly from the domestic PC. The use of B industrial products remains, but it is also affected by regenerated metal processing industry emissions and the use of residual and remote delivery of foreign PCB products. (4) the total cancer risk level for adults of PAHs, PCBs in river network waters has exceeded the maximum acceptable level of carcinogenic risk. Children are only in addition to some points in Chongming Island and agricultural areas, and the total number of other points. The risk of carcinogenesis also exceeded the maximum acceptable risk level. For PAHs, PCBs, only 9.3% of the total oncogenic risk and 18.67% of the total oncogenic risk of children in the water drops lake and its lake water system, skin contact is the main way of exposure of PAHs, PCBs cancer risk in the landscape water exposure situation, but not (5) the predicted ineffective concentration (PNEC) derived from the ECOSAR and BMC-SSD models has better comparability with other studies. The high ecological risk levels of PAHs monomers in the study area are mainly benzene and [b] fluoranthene (BbF), benzo [k] fluoranthene (BkF), BghiP, and phenanthrene (Phe), fluoranthene (F). Lua) and pyrene (Pyr), the PAHs monomers with high ecological risk level are mainly Phe, anthracene (Ant), grottoes (Chry), and DL-PCBs monomers with high ecological risk in Flua and Pyr. water bodies are mainly PCB105 in the dissolved state, PCB118, PCB105 and minerals in the granular state.
【学位授予单位】：华东师范大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：X52

【参考文献】