【作者】 王旭；

【导师】 任南琪；

【作者基本信息】 哈尔滨工业大学 ， 环境工程， 2009， 博士

【摘要】 持久性有机污染物（Persistent Organic Pollutants,简称POPs）具有高毒性、持久性和生物累积性,其对人类健康和环境的影响已经引起全球的广泛关注。而城市作为人群聚居地区,大气和土壤环境中POPs水平的高低直接会影响城市居民的健康。大气是人体暴露于POPs污染的主要媒介,土壤是POPs类有机物在地表环境中的主要蓄积库,所以研究城市大气土壤环境中的POPs对于研究城市生态环境有非常重要的意义,而有机氯农药（Organochlorine Pesticides, OCPs）和溴代阻燃剂（Brominated flame Retardants,BFRs）是典型POPs污染物。本研究选择哈尔滨市为研究区域,以被禁止使用多年的OCPs和当前正在广泛使用的BFRs为研究对象,探讨其在城市大气土壤环境中残留水平,污染特征及迁移归趋。研究了城市及其周围地区土壤中有机氯农药的残留现状,研究结果表明土壤中六六六（HCH）浓度范围136 -51,760 pg g^-1 dw,均值为7,120 pg g^-1 dw,滴滴涕（DDT）浓度范围72 - 28,222 pg g^-1 dw,均值为5,425 pg g^-1 dw,六氯苯（HCB）浓度范围64-3,942 pg g^-1 dw,均值为1,039 pg g^-1 dw。采用分子标志示踪的方法分析有机氯农药的来源,结果表明工业品HCH和林丹在当地已经很长时间没有新源输入,该地区土壤HCH的残留来自历史上较低量的工业品HCH的使用,同时兼有通过长距离迁移而来,在高纬度寒冷地区土壤冷凝下来。DDT和硫丹在当地有少量使用或者来自长距离的迁移,氯丹在土壤的残留源自长距离迁移。主成分分析对OCPs的来源进行分析得出了一致结论。土壤中BFRs的含量中六溴环十二烷（HBCD）贡献最大,其次是十溴联苯醚（BDE-209）,二者之和占全部目标化合物的90%以上,表明六溴环十二烷和十溴联苯醚工业品的在当地用量最大。城市范围包括市郊多溴联苯醚（PBDE）和非PBDEs浓度明显高于农业用地和环境背景,进一步反映了城市是BFRs的使用源,轻重组分发生城市分馏现象,并推断出城市是PBDE、HBCD的使用源。研究大气中OCPs的空间分布特征,结果表明含量最高的三种OCPs依次为HCB、α-HCH和p,p’-DDT。大气中HCH总量在农村最高,硫丹的总量在郊区最高,硫丹在郊区很可能是蔬菜用地有少量使用,HCB在城市含量最高,而且从城市到背景点的趋势是依次降低,说明HCB在城市工业生产过程中使用或排放,DDT和氯丹在城市、郊区和农村测得的总量无明显变化,DDT和氯丹在当地并没有大量的使用,大气中的含量还可能来自长距离的输运。大气中总量最高的BFRs依次为BDE 209和HBCD,研究还发现人口密度影响大气中BFRs的含量,大学校园检测到的浓度高于其他采样点。轻重组份PBDE同系物受季节温度的影响差异较大。考察大气中BFRs浓度与温度的关系,结果表明气相PBDEs（不含209）的同系物浓度与温度成正相关性,BDE 209在颗粒相中与温度呈正相关,可以推测PBDE（非BDE 209）从气相凝结到颗粒相受温度控制,而BDE 209从颗粒相挥发到气相受温度控制。低溴取代的PBDE在气相浓度与颗粒相分配的比值与温度的相关性高,但高溴类化合物的这种趋势并不明显。大气中OCPs浓度相对均一,而土壤中OCPs浓度变化较大,应用逸度理论研究土-气交换过程的分配行为,计算出土气交换的HCH和HCB逸度商更趋近于0.5,即更趋近于达到土气交换平衡,pp’-DDE和pp’-DDT也不排除接近平衡的可能性,其他有机氯农药如氯丹和硫丹土气交换的逸度商远远小于0.15,可以确定土气交换以大气沉降为主。PBDEs在大气中逸度远高于土壤逸度,逸度商在10^-2到10^-5数量级远低于0.5的交换平衡时的值,说明大气向土壤的干沉降是PBDEs的主要交换过程。应用多介质逸度模型模拟哈尔滨地区p,p’-DDT在多介质环境中的分布归趋,得出结论p,p’-DDT向土壤分配的趋势最高,其次是向底泥,水和大气分配。在各介质中土壤最终成为p,p’-DDT的蓄积库,占总量99.4%,其次是底泥占总量0.589%,p,p’-DDT最终将在土壤微生物分解或水解光解等过程降解为产物。更多还原

【Abstract】 Persistent organic pollutants （POPs） have been of great concern due to their persistence in the environment, their bioaccumulation potential in the tissues of animals and humans.Organochlorine pesticides and brominated flame retardants is typical with carcinogenic, teratogenic, mutagenic of POPs substances. It is important to study the residues level, mode of occurrence and environmental behavior for the guidance to control pollution and reduce emissions. Urban are densely populated areas, POPs level in air and soil directly affect the health of urban residents, the atmosphere is the major media for human exposure to POPs pollution and the soil are the sinks of POPs in the surface environment. So it has great significance to study OCPs and BFRs on of urban atmospheric and soil environment for the study of the ecological environment in urban. Harbin is the study area to investigate the OCPs and BFRs residue levels in atmosphere and soil environment to study the pollution characteristics, migration and fate.Study of the city and its surrounding areas of organochlorine pesticides in the soils of the residual levels, results show that the concentration of the soilΣHCH ranged from 136 pg g^-1 dw to 51760 pg g^-1 dw, with mean of 7120 pg g^-1 dw,ΣDDT concentration ranged from 72 to 28222 pg g^-1 dw, with mean of 5425 pg g^-1 dw, HCB concentration ranged from 64 to 3942 pg g^-1 dw, with mean of 1039 pg g^-1 dw. Molecular markers was used to analyze the source of organochlorine pesticides, results show that the industrial HCH and lindane haven’t new source for a long time at the local, the HCH residues in soil from the history with very lower amount of usage, or come from long-distance migration. Chlordane residues in the soil from the long-distance migration, endosulfan is from localtion with very low usage or long-distance migration. Principal component analysis of OCPs draw the same conclusion.HBCD is the predominate compound in soils, followed by BDE-209, both compounds contributed more than 90%, this also indicated that HBCD and PBDE 209 are the most large of consumption. Concentration of PBDE and non-PBDEs BFRs were significantly higher than those of agricultural land and background, reflects the city is the source BFRs, urban fractionation phenomenon was observed occurred, and also indicated urban was the sources of PBDE, HBCD and BTBPE. The largest amount of OCPs in atmospheric is HCB, followed byα-HCH and p, p’-DDT. The highest concentration of HCH in atmosphere is in the rural areas, indicating that HCH was used in agricultural land, The highest concentration of endosulfan in the suburban are probably from a small amount of vegetable land use, HCB was the highest in the city, followed by suburban, rual and background indicated industrial production process is the emissions source. There was no significant change amount DDT and chlordane in urban, suburban and rural areas, so DDT and chlordane may not be use in location and also come from long-distance transport.The highest amount of BFRs in atmospheric was BDE 209 followed by HBCD, university campuses was detected the concentration higher than that of other sampling points so it was found that the population density are important influencing factor for BFRs concentration. PBDE Homologues was influented by seasonal temperature. PBDEs （excluding 209） in gas were positively correlated with temperature, and BDE 209 in particle phase was positively correlated with temperature, it can be assumed PBDE （non-BDE 209） from the gas condensation to the particle phase controlled by temperature, and BDE 209 from the particle to the gas controlled by temperature. The ratios of gas to particle were temperature-related for low-bromine compounds, but for high bromine compounds, this trend is not obvious.OCPs concentration in the atmosphere is relatively uniform, while large changes in soil concentrations. Fugacity fraction was applied to study the soil– air distribution in the process exchanged, Fugacity fraction of HCH and HCB in soil/air exchanged are more close to 0.5, that is, more close to reaching a balanced, pp’-DDE and pp’-DDT may probably closed to balance, and other organochlorine pesticides such as chlordane and endosulfan for fugacity fraction was far less than 0.15, atmospheric deposition was mainly action. Fugacity fraction of PBDEs in the atmosphere is much higher than that in the soil, fugacity fraction ranged from 10^-2 to 10^-5 far below 0.5 for balance, which mean that dry deposition of atmosphere to soil is the main exchange process.Multi-media fugacity model was used to simulated the distribution and fate of p,p’-DDT in Harbin. The results show that p, p’-DDT is trended to distribute in the soil, followed by the sediment, water and atmospheric. p,p’-DDT will accumulate eventually in soil, accounting for 99.4% of total, followed by sediment total 0.589%, p,p’-DDT will finally transform to the degradation products undergo microbial decomposition, hydrolysis or photolysis process.更多还原