北京城区典型地表水中有机卤素污染物的测定及其种态分布的研究

发布时间：2018-06-21 11:28

本文选题：地表水 + 有机氯农药　；参考：《成都理工大学》2014年硕士论文

【摘要】：在快速发展的城市化进程形势下，集政治、经济和文化中心为一体的北京市对环境中各项指标的要求也越来越严格。其中地表水污染已成为一个事关公共安全和人类健康的重要社会问题。作为主要指标之一的有机卤素污染物，由于它具有持久性有机污染物（POPs）的特征即难挥发、难降解和长距离迁移，导致其在水环境中对人类和生态系统危害较大。水污染的严重程度直接导致了我国城市缺水现象的发生。目前北京市水质比较好的只有京密、永定河引水渠和长河，其余有水河流均是劣五类水，19个湖泊中，劣五类水体占的比例为三分之一。根据我国多年监测研究的结果，，在所有有机污染物张，有机卤素污染物所占的比例约为45%。因此，有机卤素污染物是环境化学和环境毒理学研究工作者的重点研究对象。本文针对国内外地表水研究指标范围窄（主要集中于常规检测、重金属、无机盐、多环芳烃及部分含氯有机污染物）、研究种态数量少、研究区域不全面（如北京地区主要是官厅水库和永定河）及检测手段不理想等问题，分别以北京地区的玉渊潭和通惠河作为研究对象，以GC-MS及GC-MS/MS为测试手段，通过对地表水中四类共115种有机卤素污染物（21种有机氯农药（OCPs）、84种多氯联苯（PCBs）、8种多溴联苯醚（PBDEs）和2种多氯萘（PCNs））分析和研究，完成了色谱仪器检测方法和解谱方法的建立，探讨了所研究的有机卤素污染物的含量水平、组成特征、空间分布及来源解析，并且跟国内外的有机卤素污染物含量进行了对比，总结了北京城区地表水中有机卤素污染物的污染程度。另外，通过穿透试验即树脂用量的比较来优化样品前处理过程，完成了地表水中有机卤素污染物的提取和净化方法。所完成的主要工作及结论如下：（1）完成了对北京城区地表水中有机卤素污染物采样方法的探索，并根据采样方法设置了采样点数以及确定了每个采样点的具体地理位置；进行穿透试验即树脂用量的比较优化了样品前处理过程。采用XAD-2树脂吸附有机卤素污染物、索氏提取技术和硅胶柱分离净化方法，建立了以GC-MS同时检测地表水中21种OCPs和84种PCBs的仪器检测方法和以GC-MS/MS同时检测地表水中8种PBDEs和2种PCNs的仪器测定方法。通过采取一系列质量保证和质量控制（QA/QC）措施，使分析结果的准确度得到有效保证。研究发现，试剂空白的谱图与标准物质完全不吻合，说明试剂中不含有待测有机污染物；所有被测有机污染物线性方程的相关系数均在0.99以上；空白加标回收率和样品加标回收率符合美国EPA关于痕量有机物分析的回收率在100%+40%范围内的要求。（2）与国内外其他地区相比较，北京城区地表水中有机氯农药的浓度较高（5.47+0.27ng/L），污染程度属于中等偏上污染水平。研究发现，玉渊潭中总有机氯农药的浓度比通惠河高，且含量最高的地点为玉渊潭出水口处，含量最低的在入水口处；HCHs是所监测的21种有机氯农药中最主要的一种，HCHs中又以β-HCH为主要污染物；该地区的HCHs主要来自于长时间降解后的农药残留；未检出的其他有机氯农药与历史上很少使用这类杀虫剂有关。（3）北京城区地表水中多氯联苯的浓度较高（50.19+0.10ng/L），污染程度属于中等偏上污染水平。其中，通惠河中多氯联苯的含量较玉渊潭高。北京城区地表水多氯联苯污染主要以低氯为主，尤其是三氯联苯中PCB-18污染最严重，这与我国历史上多氯联苯的生产和使用状况是一致的。其中，采自商业繁华地带的建国门水样的PCBs浓度最高，而人流量相对较少的玉渊潭出口处含量最低。（4）北京城区地表水中多溴联苯醚的浓度较低（13.62+0.26ng/L），污染程度属于中等偏下水平。其中，玉渊潭中多溴联苯醚的含量较通惠河高。BDE-209是北京城区地表水中的主要污染物，可能的主要原因是：①十溴代联苯醚（BDE-209）具有低挥发性、高的logKow值及在环境中比较稳定的特性；②BDE-209含量高与我国历史上长期大量生产和使用含有该类物质的阻燃剂有关。（5）北京城区地表水中多氯萘的浓度较低（6.15+0.42ng/L），污染程度属于中等偏下水平。其中，玉渊潭中多氯萘的含量较通惠河高。PCNs中1,2,3,4,6,7-CNs（CN-66）的浓度较1,3,5,7-CNs（CN-42）高。通惠河通州段（周围有大量工厂和居民）的多氯萘浓度最高，玉渊潭中采样点8（周围有多家饭店和大量居民）的浓度最高。可能的主要原因包括：①在燃煤等燃料的燃烧过程中，多氯萘作为副产物生成，通过大气沉降进入到水环境中；②较多地使用了含有多氯萘的工业制品，如电容器介质及防腐剂等。
[Abstract]:In the rapid development of urbanization process, the Beijing City, which integrates political, economic and cultural centers, is becoming more and more stringent. Surface water pollution has become an important social problem related to public safety and human health. The characteristics of persistent organic pollutants (POPs) are difficult to volatilize, difficult to degrade and long distance migration, resulting in great harm to human and ecological system in water environment. The severity of water pollution directly leads to the occurrence of water shortage in China's cities. The only good water quality in Beijing is the Jing mi, the Yongding river diversion canal and the long river, and the rest of the water pollution. Water rivers are inferior to five types of water, and the proportion of inferior five types of water in 19 lakes is 1/3. According to the results of years monitoring and research in China, the proportion of organic halogen pollutants is about 45%. in all organic pollutants, and the organic halogen pollutants are the key research of environmental and environmental toxicology researchers. Elephant.
In this paper, the target range of domestic surface water research is narrow (mainly concentrated on conventional detection, heavy metals, inorganic salts, polycyclic aromatic hydrocarbons and some chlorinated organic pollutants), and the research area is less and the research area is not comprehensive (for example, Beijing area is mainly Guanting reservoir and Yongding River) and the detection means are not ideal, respectively, in Beijing area, respectively. As the research object, the Yuan Tan and Tonghui River were used to analyze and study four kinds of organic halogen pollutants (21 kinds of organochlorine pesticides (OCPs), 84 polychlorinated biphenyls (PCBs), 8 polybrominated diphenyl ethers (PBDEs) and 2 polychlorinated naphthalene (PCNs) in surface water, and the method of chromatographic instrument detection and spectral method was completed. The content level, composition characteristics, spatial distribution and source analysis of the organic halogen pollutants are discussed and compared with the content of organic halogen pollutants at home and abroad, and the pollution degree of organic halogen pollutants in the surface water of Beijing city is summarized. The sample pretreatment process has completed the extraction and purification methods of organic halogen pollutants in surface water. The main work and conclusions are as follows:
(1) the sampling method of organic halogen pollutants in the surface water of Beijing city was completed, and the sampling points were set up according to the sampling method and the specific geographical location of each sampling point was determined. Through the penetration test, the resin dosage was used to optimize the sample pretreatment process. The XAD-2 resin was used to adsorb the organic halogen pollutants. The method of extracting 21 kinds of OCPs and 84 kinds of PCBs in surface water with GC-MS and measuring 8 kinds of PBDEs and 2 PCNs in surface water by GC-MS/MS are established. A series of quality assurance and quality control (QA/QC) measures are adopted to make the accuracy of the analysis result. The study found that the spectrum of the reagent blank was completely inconsistent with the standard substance, indicating that the reagent did not contain the organic pollutants to be tested; the correlation coefficients of all the linear equations of the organic pollutants were above 0.99; the blank addition recovery rate and the recovery rate of the sample added were in accordance with the EPA of the United States on the analysis of trace organic matter. The requirement of the yield in the range of 100%+40%.
(2) compared with other areas, the concentration of organochlorine pesticides in the surface water of Beijing city is higher (5.47+0.27ng/L), and the degree of pollution belongs to the level of moderate pollution. It is found that the concentration of total organochlorine pesticides in Yuyuan pool is higher than that of Huihe River, and the highest content is in the outlet of Yuyuan pool, and the lowest content is at the inlet of the water inlet. HCHs is the most important one of the 21 kinds of organochlorine pesticides monitored. In HCHs, beta -HCH is the main pollutant; the HCHs in this area is mainly from pesticide residues after a long time degradation; other organochlorine pesticides are not detected in history with little use of these insecticides.
(3) the concentration of polychlorinated biphenyls in the surface water of Beijing city is high (50.19+0.10ng/L), and the pollution level belongs to the level of moderate pollution. Among them, the content of PCBs in Tonghui river is higher than that of Yuyuan Tan. The pollution of polychlorinated biphenyls in the surface water of Beijing city is mainly low chlorine, especially in the three chlorinated biphenyl, which is the most serious in the history of China. The production and use of polychlorinated biphenyls are consistent. Among them, Jianguomen water samples collected from commercial areas have the highest concentration of PCBs and the lowest in the Yuyuan Lake outlet.
(4) the concentration of polybrominated diphenyl ethers in the surface water of Beijing city is low (13.62+0.26ng/L), and the degree of pollution belongs to the lower level. Among them, the content of polybrominated diphenyl ethers in yuyunan is the main pollutant in the surface water of Beijing City, and the main cause is: (1) ten brominated diphenyl ether (BDE-209) has low volatility, The high logKow value and the stable characteristics in the environment; (2) the high content of BDE-209 is related to the long term production and use of the flame retardant containing this kind of substance in our country.
(5) the concentration of polychlorinated naphthalene in the surface water of Beijing city is low (6.15+0.42ng/L), and the pollution degree belongs to the lower level. Among them, the concentration of polychlorin in Yuyuan lake is higher than that of 1,3,5,7-CNs (CN-42) in the high.PCNs of Huhe River higher than that of 1,3,5,7-CNs (CN-42). The concentration of polychlorinated naphthalene in the Tongzhou section of tonghuhe River (around a large number of factories and residents) is the highest. The concentration of 8 (a number of restaurants and a large number of residents around) is the highest in the pool. The main reasons are: (1) polychlorinated naphthalene is produced as a byproduct during combustion of coal and other fuels, and enters into the water environment through atmospheric deposition; and more industrial products containing polychlorinated naphthalene, such as capacitor media and preservatives, are used. Wait.
【学位授予单位】：成都理工大学
【学位级别】：硕士
【学位授予年份】：2014
【分类号】：X832

【参考文献】