【作者】 潘静；

【导师】 奚旦立；

【作者基本信息】 东华大学 ， 环境工程， 2008， 博士

【摘要】 持久性有机污染物具有突出的“三致”作用（致癌、致畸、致突变）和环境持久性、生物蓄积性,对人类健康危害极大,是世界各国重点控制的污染物。本文利用同位素稀释/高分辨率气相色谱-高分辨率质谱法对典型东部沿海发达城市青岛和上海崇明岛以及西部卧龙高山清洁地区沉积物、土壤、生物样品、河水以及冰雪中包括有机氯农药（OCPs）、多氯联苯（PCBs）、二噁英（PCDD/Fs）和多氯萘（PCNs）在内的持久性有机污染物（POPs）进行分析研究。旨在了解我国东、西部部分地区POPs的分布及来源情况,为我国履行POPs国际公约提供科学依据,为我国的有机氯污染物模型建立提供数据支持,可作为有机氯污染物污染控制策略及消除污染措施和相关法规条例制定的背景依据。论文研究了上述几类POPs在东部青岛和上海崇明岛沉积岩芯中的时空分布规律、沉积通量、毒性当量通量及污染状态随历史的变迁情况。探讨了POPs沿海拔高度在西部卧龙高海拔山区不同介质土壤、河水和冰、雪的梯度分布与运移规律,初步讨论可能的污染物质输送途径和区域污染来源。基于生物样品毒性当量（TEQ）及日常消费量的分析,对鱼、鸭及牦牛食用人群的潜在健康风险进行了初步评价。主要的研究结果如下:对崇明岛东滩及北部湿地柱状沉积物样品中OCPs（HCHs、DDTs）和7种指示性PCBs类进行了分析。东滩和北滩沉积物中OCPs含量范围分别为0.94～4.83 ngg^-1 dw（干重）和3.04～7.70 ng g^-1 dw。东滩沉积物中∑₇PCBs含量范围为0.14～0.40ng g^-1 dw。污染状况均属于轻度污染。HCHs、HCB和PCBs呈现明显的周期性变化。DDTs因p,p′-DDT受沉积物不同层段的氧化还原条件影响产生不同的降解产物,周期性则较差。采用时间序列分析方法,统计分析了近60年来东滩湿地沉积物中OCPs和PCBs变化的总体趋势与主要振荡周期。长期变化趋势表明:东滩沉积物中OCPs和PCBs在上世纪50年代初开始增长,高峰期出现在上世纪60至70年代。一些异构体在我国停止生产OCPs和PCBs后,没有明显的下降趋势。频谱分析结果表明OCPs和PCBs的分布表现出具有周期为大约8年的振荡特征,可能与气候变化周期相关。对青岛胶州湾表层和岩芯沉积物中的PCDD/Fs、共平面多氯联苯（co-PCBs）和PCNs进行了研究。表层沉积物中PCDD/Fs、co-PCBs和PCNs含量分别为4.1～232.4、46.1～1057.7和212～1209 pg g^-1 dw,最高点均出现在海泊河口处站位J06。胶州湾内、外两个沉积岩芯中PCDD/Fs、co-PCBs和PCNs污染较轻。湾内岩芯co-PCBs和PCNs含量随深度变化趋势与PCDD/Fs的趋势相似,而湾外岩芯受黄海周边国家和地区的影响有所不同。岩芯中PCDD/F的毒性当量（PCDD/F-TEQ）低于美国或日本等国家水体底泥中的背景水平(＜3 pg TEQ g^-1dw),co-PCB-TEQ(最大值0.14 pg TEQ g^-1 dw)低于国内一些水体底泥含量,PCN-TEQ＜0.05 pg TEQ g^-1 dw。PCDD/Fs沉积通量从50年代初年到80年代初基本上维持在一个稳定的水平,在80年代中期急剧增长,到90年代初期出现最大值,然后下降直到表层的近代。co-PCBs沉积通量变化趋势自50年代以来逐渐降低,反映了世界上PCBs的生产量及用量自从80年代逐渐减少的情况,表明青岛地区没有PCBs的重大污染源。PCNs沉积通量峰值分别出现在70年代中期（J94）和90年代末（J37）。异构体“指纹图”及主成分分析结果表明污染来源主要有城市污水排放、大气来源及海流环流搬运三种。五氯酚及其钠盐对青岛近海沉积物中PCDD/Fs的来源贡献并不占主要地位,但可能受到黄海周边地区和国家五氯酚使用的间接影响。湾外岩芯J94早期沉积物中PCB 118含量非常高,来源不同于90年代后期,推断日本的Kanechlor 300和Kanechlor400有可能是来源之一。PCNs在较早年代有来自城市固体废弃物焚烧的较大贡献,而在90年代初有较高的氯代PCN混合物如Halowaxes 1013和1014的输入。对东部沿海城市（青岛和上海崇明岛）的海鱼与淡水鱼以及家鸭样品中的PCDD/Fs、co-PCBs和PCNs的含量进行了分析测定,经过与世界卫生组织（WHO）规定的日容许摄取量（TDI）比较,对可能给饮食人群带来的健康风险进行了初步评价。崇明淡水鱼和青岛海鱼中总2,3,7,8-PCDD/Fs、co-PCBs和PCNs的平均含量分别为33.2和54.5 pg g^-1脂肪、3318和4041 pg g^-1脂肪、225和640 pg g^-1脂肪。崇明岛家鸭中2,3,7,8-PCDD/Fs、co-PCBs和PCNs含量分别为12.6、966和60.6 pg g^-1脂肪。崇明岛鱼、鸭中的PCDD/Fs和co-PCBs异构体分布指纹特征非常相似,表明这两类化合物具有相同的来源。青岛海鱼中PCNs同系物的组成（5-氯和3-氯为主）与崇明岛淡水鱼完全不同。与国内外其它地区鱼和家禽相比,PCDD/Fs、co-PCBs和PCNs含量较低。总毒性当量浓度（TEQ）为3.6～14.8 pg WTO-TEQ g^-1脂肪。根据当地人群饮食习惯,两地人群的二噁英类化合物每日摄入量远低于WHO规定的TDI值,对人群健康产生风险的可能性较小。卧龙高海拔地区夏冬季土壤、河水以及冰雪中OCPs和PCBs的研究表明:海拔高度2800m以上,土壤中HCHs和DDTs的总平均含量冬季(0.52和0.56ng g^-1 dw)高于夏季(0.29和0.32 ng g^-1 dw),PCB28、52含量浓度水平夏冬两季相近,且均与海拔高度呈负相关性。与国内外其它地区土壤相比,这些污染物污染水平较低。冬末新降雪、冰以及河水中的HCHs、DDTs两类污染物都低于国家标准《地表水环境质量标准》,含量与海拔梯度呈正相关性,表现出一定的“冷凝结”效应,说明卧龙地区在一个空间和气候尺度范围内相对比较小的区域中提供了观察污染物分馏作用的良好条件。远离人类活动的卧龙高海拔地区一些POPs具有比预想要高的浓度及大气沉降。OCPs和PCBs的大气远程输送和沉降对清洁的边远地区的影响不容忽视。不同海拔高度冬季土壤和牦牛样品中的PCDD/Fs、co-PCBs和PCNs的研究表明污染水平较低。土壤样品中总2,3,7,8-PCDD/Fs的含量范围为2.48～4.30 pg g^-1 dw,平均3.50 pg g^-1 dw,最高含量在海拔3927 m处。co-PCBs总含量平均9.14 pg g^-1 dw,最高值在海拔最高的4487 m的站点垭口。总2,3,7,8-PCDD/Fs和总co-PCBs含量随海拔高度的变化表现出正相关关系。不同海拔高度土壤中的PCDD/Fs和co-PCBs异构体的分布相似,表明具有相同的来源。总PCNs与海拔梯度呈负相关关系,最高含量出现在海拔3345 m处,平均21.4pg g^-1 dw,主要以以3-氯PCNs为主。与国内外其它地区土壤相比,这些污染物含量较低,可推断是由大气远距离传输造成的。卧龙牦牛肉和牦牛组织中PCDD/Fs总浓度分别为27.5和23.6 pg g^-1脂肪,总毒性当量浓度为4.04和4.06 pg TEQ g^-1脂肪。研究结果表明,牦牛中PCDD/Fs、co-PCBs和PCNs不会对卧龙地区食用人群导致健康的严重负面效应。更多还原

【Abstract】 Due to their carcinogenicity,mutagenicity and teratogenicity,as well as persistence and bioaccumulation,the persistent organic pollutants（POPs） have gained utmost attention as contaminants of threat to human health.In this study,using isotope dilution mass spectrometry with high resolution gas chromatography and high resolution mass spectra（HRGC/HRMS） to study organochlorine pesticides（OCPs）,7 indicator polychlorinated biphenyls（PCBs）,polychlorinated dibenzo-p-dioxins and dibenzofurans（PCDD/Fs）,co-planar polychlorinated biphenyls（co-PCBs）,and polychlorinated naphthalenes（PCNs） in sediments,soils,fish,duck,yak,rivers,snow and ice collected from coastal waters of Qingdao,Chongming Wetland in Yangtze River Estuary of the East China Sea and Wolong high mountain area.The aiming was to fulfill the POPs international joint pledge for our country,provide the scientific basis and the effective data support for our country organic chlorine pollutant model establishment.It may be background basis for control strategy of the organic chlorine pollutant contamination,for the elimination pollution measure and for the correlation laws.The contamination levels,possible sources,deposition fluxes,toxic equivalent quantity fluxes,temporal and spatial distribution characteristics were studied in sediment cores collected from Qingdao and Chongming Island.The gradient distribution,transportation and possible regional sources of POPs in in soils,rivers, snow and ice with altitude from Woolong high mountain area were preliminarily discussed.Based on the toxic equivalent quantity（TEQ） and assumption,potential exposure risk to consumers with edible fish,duck and yak were also evaluated.The main conclusions were summarized as follows:Sediment cores taken from Dongtan Wetland in Yangtze River Estuary of the East China Sea and a tidal flat in the north Chongming Island were measured.The vertical distribution characteristics of OCPs concentration with the depth and possible influence by climate changes were preliminarily discussed.HCHs,DDTs,and HCB were found in all sediment layers.The total OCPs concentrations ranged from 0.94 to 4.83 ng g^-1 dw and from 3.04 to7.70 ng g^-1 dw,with the average of 2.68 ng g^-1 dw and 4.85 ng g^-1 dw for Dongtan Wetland and northern Chongming tidal flat,respectively, showing a low pollution level.The total concentrations of the 7 indicator PCB isomers （Σ₇PCBs） in each layers of the core were in the range of 0.14～0.40 ng g^-1 dw,with an average of 0.23 ng g^-1 dw.The vertical distributions of HCHs,HCB,and PCB isomers in the cores showed significant periodic variations while the vertical distributions of DDTs showing less periodicity were affected by the redox conditions down the core. Using time-series analysis,the long-term trends and frequency spectrum of OCPs and PCBs in the sediment core of Dongtan wetland during the last 60 years were discussed. The long-term trends of OCPs and PCBs in the wetlands showed that these chemicals began to rise in early 1950s with the maxima during 1960s to 1970s.Some isomers did not show significant declining trends after their productions being banned.The time-series generally show an 8-year periodicity,suggesting an influence of ENSO.PCDD/Fs,co-PCBs and PCNs were studied in seven surface sediments and two sediment cores near the costal sea of Qingdao.The total concentrations of PCDD/Fs, co-PCBs and PCNs ranged from 4.1～232.4,46.1～1057.7 and 212～1209 pg g^-1 dw, with the highest concentrations in station J06 near the Haibo River mouth.Sediments core J37 and J94 showed a low pollution level.The depth profiles of total concentrations PCDD/Fs,co-PCBs,and PCNs were similar in J37 sediment core inside Jiaozhou bay,while difference occurred in J94 sediment core outside Jiaozhou bay due to the effluence of regions and countries surrounding the Yellow Sea.PCDD/F-TEQ in sediments core were lower than that of background values(＜3 pg TEQ g^-1 dw) in America and Japan.Co-PCB-TEQ with the highest 0.14 pg TEQ g^-1 dw showed lower levels than some reports in China and PCN-TEQ was less than 0.05 pg TEQ g^-1 dw. The relative contribution toΣTEQ mainly comes from PCDD/Fs with average 92%. From 1950s to 1980s,the fluxes of 2,3,7,8-PCDD/Fs kept at stable levels,then significantly decreased in the middle of 1980s and exceeded all the levels in the beginning of 1990s.The fluxes of co-PCBs have been decreased steadily since 1950s reflecting the reduction of manufacture and use of PCBs in the world and showing no obvious contamination sources in Qingdao area.The fluxes peak of PCNs occurred in the middle of 1970s（J94） and the end of 1990s（J37）.The congener profiles of the pollutant and PCA showed that sewage sludges,atmospheric deposition and the frame of current circulations were the mostly major sources.The congener profiles of dioxins indicated that pentachlorophenol（PCP） and PCP-Na did not play an important role and the indirect effluence of regions and countries surrounding the Yellow Sea may be taken into account.The concentration of PCB 118 was very high in J94 sediment core outside the bay and had different sources with the end of 1990s,showing the products of Kanechlor 300 and Kanechlor 400 from Japan were one of the possible sources.The congener profiles of PCNs in sediments core indicated that the incineration of municipal solid waste contributed greatly in the early dated periods,while highly input of Halowaxe 1013 and 1014 occurred in the beginning of 1990s.Two food categories（fish and duck） were collected from farms and in Chongming Island,Shanghai and coastal waters of Qingdao,Shandong Peninisular in 2007. Concentrations of PCDD/Fs,co-PCBs and PCNs were measured and potential heath risk for consumption of the fish and duck were preliminarily discussed.The mean concentrations of total 2,3,7,8-PCDD/Fs,co-PCBs and PCNs in fish were 33.2 and 54.5 pg g^-1 lipid,3318 and 4041 pg g^-1 lipid,225 and 640 pg g^-1 lipid,and in duck meat were 12.6,966 640 and 60.6 pg g^-1 lipid.The total 2,3,7,8-TCDD equivalents were ranged from 0.39 to 13 pg WHO-TEQ g^-1 lipid for the fish and duck meat.The congener profiles of 2,3,7,8-PCDD/Fs and co-PCBs in fish and duck from Chongming Island were similar,suggesting common sources,while the homologue profiles of PCNs for fish from Qingdao and Chongming Island were quite different..Based on the food consumption patterns of the local populations,the average daily intake values of dioxin-like compounds by consumption of the fish and duck were estimated to be less than the tolerable daily intake（TDI） 1～4 pg WHO-TEQ kg^-1 body weight,suggesting low health risk for the local people.Concentrations of OCPs and PCBs in soils,rivers,snow and ice with altitude from Wolong high mountain area were analyzed with HRGC-HRMS.The total average concentrations of HCHs and DDTs showed higher levels in winter(0.52 and 0.56 ng g^-1 dw,respectively) soils than that in summer(0.29 and 0.32 ng g^-1 dw,respectively) at stations above 2800 m,which suggesting the inverse correlations with altitudes. Similar concentrations levels of PCBs occurred in both summer and winter soil samples and also showed the inverse relationship with altitudes.Concentrations of HCHs and DDTs in rivers,snow and ice were under the required limitation of national standard and positive correlations with altitudes have been identified,showing the cold condensation roles.The effluence of long-range transportation and deposition of OCPs and PCBs should not be ignored.The total PCDD/Fs concentrations in the surface soils ranged between 2.48～4.30 pg g^-1 dw,averaging 3.50 pg g^-1 dw with the highest concentration at 3927 m altitude.The total co-PCB concentrations averaged 9.14 pg g dw with the highest concentration at 4487 m.The total 2,3,7,8-PCDD/Fs and total co-PCB concentrations showed positive co-relationships with altitude.The congener profiles of both 2,3,7,8-PCDD/Fs and total co-PCB at different altitudes showed similar patterns,suggesting common sources.The total PCNs,averaging 21.4 pg g^-1 dw,showed a negative co-relationship with altitude,with the highest concentration at 3345 m altitude.The total PCNs was dominated by tri-Cl-CNs.Compared with soils in other areas in China and abroad,the contaminations of these compounds are less.The atmospheric transportation is likely the sources for them.TEQ in the soils were in the range of 0.29～0.43 pg g^-1 dw.The total concentrations of PCDD/Fs in the yak meat and tissue were 27.5 and 23.6 pg g^-1 lipid,respectively,while the total TEQ in the yak meat and tissue were 4.04 and 4.06 pg TEQ g^-1 lipid,respectively,which is unlikely to cause adverse health effect to the yak meat consuming people.The cold-trapping effect of these compounds found in Wolong high altitude area soils suggested that the area with both limited space scale and climate scale could provide necessary conditions for observation of fractionation of semi-volatile organic pollutants.更多还原