【作者】 刘劲松；

【导师】 刘维屏；

【作者基本信息】 浙江大学 ， 环境科学， 2008， 博士

【摘要】 本文在建立环境中持久性有机污染物分析方法的基础上，分别对浙江省典型地区环境空气、土壤、河流沉积物及污染源废气中持久性有机污染物的污染现状、分布规律及来源解析进行了研究。主要创新点及研究成果如下：1)本文系统研究了城市大型生活垃圾焚烧炉排放废气对周边地区的环境影响。生活垃圾焚烧炉排放废气、环境空气及土壤之间二恶英异构体分布规律几乎相同，相关性非常强。17种二恶英类化合物对毒性当量贡献最大的均是2，3，4，7，8-PentaCDF，分别占总毒性当量的52．9±1．4％、50．5±2．8％及77．2％。环境空气和土壤中的二恶英主要来源于污染源废气的排放。2)对具有中国特色的农村小型生活垃圾闷烧炉焚烧特点、二恶英排放特征、排放量及其对周边地区的环境影响进行了研究。根据闷烧炉内含氧量、一氧化碳、焚烧温度及风量的变化及实际观察情况，将闷烧炉的焚烧过程分为垃圾脱水阶段、自燃阶段、燃后阶段和余烬阶段四个过程。不同阶段二恶英排放浓度分别为235、27．6、44．9、69．2 ng I-TEQ／m³。17种毒性较强的二恶英单体对废气及灰渣样品毒性当量贡献最大的均为2，3，4，7，8-PentaCDF，平均贡献率达到53．8％±14．0％。污染源周边环境土壤中二恶英国际毒性当量均值为4．64 I-TEQ pgI-TEQ／g，高于土壤背景值0．537 pg I-TEQ／g。污染源附近的松针和松枝样品中二恶英毒性当量分别为0．847和0．173 pg I-TEQ／g。通过对不同样品二恶英分布规律进行分析，发现废气、灰渣和植物样品中的二恶英的分布相关性较好，与土壤样品相关性较差。但数据分析显示，排放源排放的二恶英对周边地区土壤有一定贡献。3)通过对浙江省典型地区的背景点土壤、拆解园区重点污染源周边的土壤及河流沉积物中二恶英及二恶英类多氯联苯的组成分布进行了系统研究，发现该地区背景土壤中二恶英和二恶英类多氯联苯的总WHO毒性当量浓度范围在0．017-5．04 Pg／g（干基）之间，土壤中二恶英类污染物污染情况总体较好。在拆解源主导风向下风向的土壤及水系沉积物中二恶英和二恶英类多氯联苯的总WHO毒性当量浓度范围在6．52-16．7 Pg／g及2．25-34．6 Pg／g之间，检测结果远远高于背景土壤。随着和污染源距离的加大，土壤及沉积物二恶英类污染物毒性当量逐渐降低。通过对污染区域土壤和沉积物样品中二恶英和二恶英类多氯联苯的分布规律进行研究，发现沉积物和土壤中的二恶英和多氯联苯有相同的来源，沉积物中的污染物基本上来自于陆地土壤的流失。4)通过对不同季节杭州市大气环境PM_2．5中多环芳烃的时间、空间和粒径分布特征分析，并结合以多环芳烃和特征无机元素为标记物的化学质量平衡模型，定性定量地分析了杭州市大气中PM_2．5和多环芳烃的污染现状、污染物组成分布规律、以及污染源的贡献率。研究发现：1)杭州市环境大气中PM_2．5污染较为严重，不同功能区PM_2．5污染状况不尽相同，但都呈现春夏季节污染相对较低、秋冬季节则相对较高的现象；2)大气环境PM_2．5中PAHs总量不高，苯并[a]芘的监测浓度春、夏、秋三季基本上低于国家标准，但冬天测定结果基本超标。3)大气颗粒物污染来源中，燃煤烟尘的贡献率最大，占39．2％，其次为土壤尘、钢铁尘、机动车尘、地面扬尘、及燃油尘的影响，分别为19．1％、17．2％、11．1％、、10．7％和2．7％，说明杭州市大气气溶胶PM_2．5中依旧以燃煤污染为主，但钢铁企业和机动车辆的污染不可小视，而且从部分地区的分析结果来看，二者还可能是主要污染源。4)大气气溶胶中多环芳烃的主要来源为机动车尘的影响，占总量的43％，其次分别为土壤尘和燃煤尘的影响，分别占21％，而钢铁尘对PAHs的影响则较小，只有9％的贡献率，扬尘源的贡献率为6％。更多还原

【Abstract】 A rapid,inexpensive and accurate analysis method for polychlorinateddibenzo-p-dioxins （PCDDs）and dibenzofurans （PCDFs）,dioxin-like polychlorinatedbiphenyls （dioxin-like PCBs）,polycyclic aromatic hydrocarbons （PAHs）inenvironmental matrix was evaluated in this research with gas chromatography / lowresolution mass spectrometry （HRGC/LRMS）at first.With this method,thedistribution,pollution and source analysis of the Persistent Organic Pollutants （POPs）in fule gas of pollution source,ambient air,soil and sediment in typical area ofZhejiang Province in China was researched.The main conclusions and innovationwere below:1)The influence of the PCDD/Fs emission from a large-scale municipal solidwaste incinerator （MSWI）was evaluated by the research of the relativity among theemission gas,the ambient air and soil.It found that the most abundant congener ofPCDD/Fs in different mateixes was 2,3,4,7,8-PentaCDF,with 52.9±1.4%,50.5±2.8%,and 77.2% respectivally.Through the comparativity of the profile of different matrix,the correlation of the PCDD/Fs was very good,which means that the PCDD/Fs inambient air and soil was come from the emission of the MSWI.2)According to the variance of the content of oxygen,carbon oxygen,temperature,gas flow rate and the observation of the furnace of the rural solid wasteincinerator （RSWI）,the burning of the solid waste could be divided into four steps（baking step,buring step,post-burning step and ember step）,with a level of PCDD/Fsemission of 235,27.6,44.9 and 69.2 ng I-TEQ/m³ correspondingly.The mostabundant congener of PCDD/Fs was 2,3,4,7,8-PentaCDF,with 53.8%±14.0% inemission gas and the residua.The levels of the PCDD/Fs in soil samples around theemission source was 4.64 pg I-TEQ/g which was almost ten times of backgroundsample （0.537 pg I-TEQ/g）,and the concentrations of the pine needle and the pinestem closed the RSWI were 0.847,0.173 pg I-TEQ/g respectively.Research thecorrelation of the PCDD/Fs profile in different matrix,the correlativity of the fule gas,residual of the incineration,and the plant samples was good which means that thesource of the PCDD/Fs in plant was come from the emission of the RSWI.Although the correlation of the PCDD/Fs in soil samples and other samples was not very good,the influence of the PCDD/Fs in RSWI to soil samples was still exist.3)The distribution and concentrations of PCDD/Fs and dioxin-like PCBs in atypical area of China was evaluated by analysis of soil and sediment samples whichcollected from a typical disassembling electronic solid waste area of Zhejiang Provine.The range of WHO-TEQ values for the PCDD/Fs and dioxin-like PCBs in 17 soilsamples representing the background investigation in the study area was 0.017-5.04pg/g dw,which means that the levels of dioxin pollution over the major part of thisdistrict were low.However,the WHO-TEQ values for PCDD/Fs and dioxin-likePCBs in soil samples to the leeward of a known pollution source was much higherthan that of the background investigation （6.52-16.7 pg/g dw）,and the levels ofsediment samples downstream of this area was in the range 2.25-34.6 pg/g dw.Theconcentration levels in soil and sediment decreased with increasing distance from thepolluted area.The correlation of PCDD/Fs and dioxin-like PCBs in soil and sedimentindicated that the major source of PCDD/Fs and dioxin-like PCBs in the sedimentcame from soil loss.4)The distribution,level,source resolution of Polycyclic AromaticHydrocarbons （PAHs）in PM_2.5with chemical mass balance （CMB）were researchedin ambient air in Hangzhou city.Research found:1)the pollution of PM_2.5in ambientair was relative serious in Hangzhou.2)the levels of PAHs in PM_2.5in Spring,Summer and Autumn season were relative gentle,and the results in winter wasrelative serious.3)according to the source resolution with CMB with several labeledcompounds,including PAHs,sulfur,chloroine and other selected materials,thecontribution to PM_2.5in ambient air was 39.2%,19.1%,17.2%,11.1%,10.0%,and2.7% to coal burning dust,soil,steel dust,vehicle dust,dust and oil burningrespectively;4)the contribution to PAHs in ambient air was 43%,21%,21% 9%,and6% in vehicle,soil,coal burning,steel,and dust respectively.更多还原