【作者】 韩文亮；

【导师】 傅家谟； 冯加良；

【作者基本信息】 上海大学 ， 环境工程， 2009， 博士

【摘要】 多溴二苯醚（PBDEs）与多氯联苯（PCBs）是两类含卤素（Br、Cl）的持久性有机污染物（POPs）,对人体有潜在的毒害作用。城市是PBDEs和PCBs的污染源区。上海市是我国最大的工业城市,各类以PBDEs为阻燃剂的电器等产品的生产和使用非常集中。由于没有化学键束缚,PBDEs在生产和使用中易于释放,其环境浓度不断增加。空气是人体对PBDEs暴露的首要媒介和重要储库,室内空气因人体暴露时间长（约90%）和污染物易于积累而尤其具有健康意义。选择典型城市对室内外空气中的PBDEs进行研究具有重要的理论和现实意义。目前国内仅有一篇使用主动采样技术研究广州室内外空气中PBDEs的报道。主动采样技术成本高,不便于多点同时采样,结果不便于比较,且因噪音大、耗电多而不便于推广使用。PUF-PAS被动采样技术以聚氨酯海绵盘为采样介质,通过物理扩散吸附采集空气样品,成本低廉,可多点同时采样,采样结果便于比较,无需电源、无噪音,得到了越来越多的应用。浙江省台州市是我国两大电子垃圾拆解区之一,年拆解电子垃圾超过200万吨,电子垃圾拆解（特别是无序焚烧）会向空气中释放大量的PBDEs和PCBs。近些年台州市政府对拆解业采取集中化、规范化管理措施,通过研究大气中的PBDEs和PCBs,可以为评估其管理成效,为我国电子垃圾拆解业的健康发展提供科学依据。同时,电子垃圾拆解区和邻近城区的对比研究可以使我们对PBDEs和PCBs从电子产品中的释放有更深入的认识。我们以上海市（电子产品生产和使用区）和浙江省台州市（电子垃圾拆解区）为研究地,首次使用被动采样技术研究了上海市主要城区室内外空气及室内降尘中PBDEs的浓度、组成、季节变化、可能的来源及人体呼吸暴露水平:采用主动采样技术系统研究了台州电子垃圾拆解区及市区对照点大气中PBDEs和PCBs的浓度、组成、季节变化、粒径分布、气-固分配,以及PBDEs和PCBs与OC/EC的关系。主要结论如下:1)上海市冬季室外空气中PBDEs的浓度(829.9±556.8 pg m^-3)约是夏季(468.0±334.8pg m^-3)的2倍。这主要是由气象条件（大气混合高度、风向）和污染源不同造成的。同系物组成上,BDE209占绝对优势（冬季:99±1%,夏季:95±3%）,由于BDE-209主要存在于颗粒相中,这与室外被动采样器由于风速较大,可以采到更多的颗粒物是一致的。工业排放是PBDEs的重要来源,其对大气中PBDEs浓度的影响大于含有PBDEs的产品在日常使用中的释放。中心城区由于使用PBDEs的产品多而密集,空气中PBDEs的浓度比郊区要高。室外空气中近地面的PBDEs浓度更多的受到局地环境的影响。2)上海市城区办公室室内空气中PBDEs的平均浓度(冬季:139.8±107.5 pg m^-3,夏季:401.1±551.5pg m^-3)高于家庭(冬季:97.5±70.7pg m^-3,夏季:300.0±246.6 pg m^-3),这与办公室内电器产品的密集使用是一致的。夏季办公室和家庭空气中PBDEs的浓度约是冬季的3倍。PBDEs同系物组成以BDE-209为主（家庭:冬季:73±20%,夏季:67±24%;办公室:冬季:55±24%,夏季:45±25%）,这表明上海市使用的PBDEs以十溴二苯醚为主,五溴二苯醚也有少量使用,且办公室高于家庭。八溴二苯醚则非常少。电器的使用是室内PBDEs的主要排放源,装修和家俱的作用较小。不同家庭和办公室中PBDEs的浓度差别较大（16～25倍）。除电器类型、新旧等的影响外,使用时间的长短和通风习惯也有重要的影响。除室内排放源以外,室外空气中PBDEs浓度水平对室内也有一定影响,这种影响在开窗通风较多的夏季更为明显。家电卖场的研究进一步证明电器是PBDEs的排放源,新生产的电器仍在使用PBDEs,且以十溴二苯醚为主。由此可以预见,在未来多年内,室内环境中PBDEs特别是BDE-209仍将维持较高浓度。3)上海市冬夏两季∑₁₆PBDEs的呼吸暴露水平分别为3.4±2.4和6.8±6.5 ng day^-1,与英国的伯明翰和加拿大的渥太华相近,但高于科威特的科威特城。4)上海家庭和办公室中∑₁₆PBDEs的沉降通量分别为10.9±8.2和14.2±11.9 ng m^-2 day^-1,在全世界城市中处于中等水平。办公室内的PBDEs沉降通量高于家庭。办公室环境中颗粒物沉降量较低,但颗粒物中PBDEs浓度明显高于家庭环境,也明显高于室外颗粒物。PBDEs室内沉降通量主要和降尘通量、电器数量及使用时间相关,而与室内装修程度、家俱数量的关系不明显。降尘中PBDEs同系物组成上以BDE209为主（88.2-99.2%）,表明上海家庭和办公室中的设备中使用的PBDEs工业品以十溴二苯醚为主。5)台州峰江电子垃圾拆解区附近大气中PBDEs的浓度(1662±769 pg m^-3,气相+颗粒相)远低于我国另一个主要的电子垃圾拆解区——广东贵屿,表明集中化、规范化的管理可以大大减少电子垃圾拆解业的污染排放。但与市区的对比（拆解区是市区的约7倍）表明电子垃圾拆解仍会显著提高大气中PBDEs的浓度。PBDEs同系物组成上以BDE-209为主（～70%）,表明台州电子垃圾中使用的PBDEs工业品以十溴二苯醚为主,五溴和八溴二苯醚也有少量使用,这与台州电子垃圾来自世界各地的现状是一致的。台州冬季PBDEs的气-固分配可能主要受控于颗粒物中有机质的吸收机制,而夏季则主要受控于颗粒物表面的吸附机制。∑₁₂PBDEs主要分布在细颗粒PM_2.5上,而BDE-209则更多的分布在粒径大于2.5μm的较粗颗粒物上,其远距离迁移能力也相应较弱。在PM_2.5以下的颗粒物中,∑₁₃PBDEs主要分布在粒径＜0.5μm的超细颗粒中（52%）,PBDEs各同系物的组成比例在PM_2.5各分段粒径中无明显差异。6)台州峰江电子垃圾拆解区附近大气中PCBs的浓度(12407±9592 pg m^-3,气相+颗粒相)远低于1999年该地区的研究结果,说明当地大气中的PCBs浓度近些年处于不断下降的过程中。也远低于广东贵屿,表明近些年台州市政府的集中规范管理取得了一定成效。但远高于路桥市区（54倍）,表明该地区的PCBs环境污染仍然不容忽视,受污染土壤是大气中PCBs的一个重要来源。PCBs同系物组成上以3～5Cl为主（～87%）,与全球历史上PCBs的生产和使用状况相同。气-固分配研究表明,台州峰江电子垃圾拆解区PCBs的气-固分配可能主要受控于颗粒物表面的吸附机制。粒径分布研究表明高氯代数的PCBs更多的分布于细颗粒(PM_2.5)中,因此其大气长距离传输能力也相应更强。在PM_2.5以下的颗粒物中,∑₃₈PCBs主要分布在粒径＜0.5μm的超细颗粒中（43.9%）,单位质量颗粒物中∑₃₈PCBs的质量随粒径的减小而减小。低氯代PCBs相对更多的分配在较粗的1.3～2.5μm颗粒中。更多还原

【Abstract】 Polybrominated diphenyl ethers（PBDEs） and Polychlorinated biphenyls（PCBs） are two classes of halogenated persistent organic pollutants（POPs）,which have potential toxicity to human being. Cities are pollution sources of PBDEs and PCBs.As the largest industial city in China,the production and usage of polybrominated diphenyl ethers as flame retardants in products such as electrical and electronic products are intensive in Shanghai. Since not chemically bound to materials,PBDEs can be easily released and their environmental concentrations are rising.Air is primary transport medium and an important sink of PBDEs.Indoor air is particularly important to human health because of the long exposure time（90%） and elevated concentration of contaminants.So,reseaches on PBDEs in the indoor and outdoor air in typical cities are important scientifically and practically.By far,only one reseach on PBDEs in the indoor and outdoor air in Guangzhou was reported using high volume air sampler,which is expensive,unable to collect samples at multi-sites simultaneously and thus the results are not adequate for comparison,and not suitable for popularization for its noise and power consumption.Using polyurethane foam disk to collect air samples through diffusive adsorption,PUF-PAS has been more and more widely used because of cost-effective,simultaneous monitoring at multi-sites and consequently with comparable results,no need for electricity and noise free operation.Taizhou of Zhejiang province is one of the two major e-waste dismantling areas in China.More than two million tons of e-wastes were dismantled there every year.Centralized and standardized management on the e-waste dismantling activities is adopted by the local government of Taizhou in recent years.Through research on the atmospheric PBDEs and PCBs,effectiveness of the management measures can be assessed,which can provide scientific basis for the healthy development of e-waste dismantling industry in China.Better understanding of the release process of PBDEs and PCBs from products can be achieved through comparative study of the e-waste dismantling area and urban site.Shanghai（electrical and electronic products producing and using area） and Taizhou of Zhejiang province（e-waste dismantling area） were thus selected as the reseaching sites for PBDEs and PCBs in indoor and outdoor air.Passive air samplers were used to investigate the concentrations,seasonal variations,congener profiles,possible sources and human inhalation exposure to PBDEs in indoor and outdoor air and indoor dry deposition of Shanghai for the first time.High volume air sampler were used to collect atmospheric samples at the e-waste dismantling site and an urban comparing site in Taizhou to systemantically investigate the concentrations,seasonal variations,congener profiles, gas-particle partitioning,size distribution and correlations of OC/EC with PBDEs and PCBs for the first time.The major findings are listed below: 1) The average outdoor air concentrations of PBDEs of Shanghai in winter(829.9±556.8 pg m^-3) was 2 times higher than that of summer(468.0±334.8 pg m^-3),which was mainly caused by the variations of meteorological conditions（atmospheric mixing heights,wind direction） and pollution sources.Congener profiles showed that BDE-209 was the dominant component（winter:99±1%, summer:95±3%）,which was consist with the higher wind speed and consequently more particles can be trapped by the passive air samplers in outdoor air since BDE-209 was mainly in the particulate phase.Industrial zones are the key sources of PBDEs,which was more important than the emissions of PBDEs from products in daily usage.PBDEs concentrations in central urban areas were higher than that of suburban areas because of the intensive usage of PBDEs containing products.PBDEs concentrations in the near ground places were more affected by the local environment.2) The indoor air concentrations of PBDEs in offices of Shanghai(winter:139.8±107.5 pg m^-3, summer:401.1±551.5 pg m^-3) were higher than that of homes(winter:97.5±70.7 pg m^-3,summer: 300.0±246.6 pg m^-3),consisting with the intensive usage of electric and electronic equipments in offices.The indoor air concentrations of PBDEs in homes and offices in summer were about 3 times that of winter.Congener profiles showed that BDE-209 was the major component（home:winter:73±20%,summer:67±24%;office:winter:55±24%,summer:45±25%）,indicating that Deca-BDE was the major commercial PBDEs used in Shanghai.Penta-BDE was also used and their proportions in offices were higher than that of homes.Octa-BDE was very rare there.The usage of electric and electronic equipments was the main source of PBDEs in indoor environment,and interior decoration and furniture were of minor importance.PBDEs concentration variations were large in different homes and offices（16-25 times）.Besides types and ages of electric and electronic equipments,the usage time and ventilation habits are also important.In addition to indoor sources,PBDEs levels in outdoor air also had some impact on the indoor air,and this was especially true in summer days when the ventilation was much more frequent.Researches on the indoor air of stores selling household electrical appliances showed that electric and electronic equipments was the sources of PBDEs,and PBDEs was still being used in the new products,indicating that the indoor air concentration of PBDEs（especially BDE-209） will retain high level for many years.3) The inhalation exposure of∑₁₆PBDEs were 3.4±2.4 and 6.8±6.5 ng day^-1 in winter and summer respectively for adults in Shanghai,which was comparable to that of Birmingham of UK and Ottawa of Canada,but higher than that of Kuwait.4) The particulate deposition flux of PBDEs in homes and offices were 10.9±8.2 and 14.2±11.9 ng m^-2 day^-1 respectively in Shanghai,and offices were higher than that of homes,ranked in the middle level comparing with other cities around the world.The particulate deposition flux in the offices was relatively low than that of homes,but this was contrary for the concentration of PBDEs in the particle,which was also significantly higher the outdoor particles.The indoor deposition flux of PBDEs mainly correlated with the flux of particle depositon,the quantity and using time of electrical and electronic products.No obvious correlations were found between the indoor deposition flux of PBDEs with the interior decoration and the amount of furniture.Congener profiles showed that BDE-209 was the major congener（88.2-99.2%）,indicating that Deca-BDE was the major commercial PBDEs product being used in Shanghai.5) The atmospheric concentration of PBDEs near the e-waste dismantling area in Taizhou(1662 pg m^-3,gas+particle phase) was much lower than that of Guiyu,another major e-waste dismantling area in Guangdong province of China,indicating that strict regulating measures and centralized management of the e-waste recycling activities can greatly reduce the pollutants emission.But it was about 7 times of the values from the reference urban site,indicating that the e-waste dismantling activities can significantly elevate the atmospheric concentration of PBDEs.BDE-209 was the major component of the airborne PBDEs in Taizhou,accounting for about 70%of the total PBDEs, indicating that Deca-BDE was the major commercial PBDEs contained in the E-wastes dismantled at FJ,and Penta-BDE and Octa-BDE products were also used,consisting with the fact that e-wastes in Taizhou were imported from all over the world.Gas-particle partitioning analysis suggested that the dominant mechanism was probably adsorption onto particle surface in summer and absorption by the organic matter in winter.Size distribution showed that∑₁₂PBDEs was mainly in the finer particle (PM_2.5),while BDE-209 was mainly in coarse particles,which could not be transported too far from the sources.In PM_2.5,∑₁₃PBDEs were manirdy in the ultrafine particles（＜0.5μm,52%）.Percentiles of PBDEs congeners in different sized particles of PM_2.5 were similar to each other.6) The atmospheric concentration of PCBs near the e-waste dismantling area in Taizhou(12407±9592 pg m^-3,TSP plus gas phase) was substantially lower than the decade ago result（～3%）,indicating the declining trend of atmospheric PCBs level there.The atmospheric PCBs level in Taizhou was also much lower than Guiyu,another e-waste dismantling area in China,indicating the centralized and standardized management adopted by the local government of Taizhou in recent years has made some progress.Though declining,the atmospheric PCBs level near the e-waste dismantling area was 54 times of the urban comparing site,indicating the PCBs pollution was still significant there,and the historically polluted soil was an important source.Tr-PeCBs were dominant homologues（～87%）, consisting with their dominant global production.Gas-particle partitioning of PCBs showed that the dominant mechanism might be adsorption onto particle surface.Size distribution of PCBs showed that higher chlorinated CBs tended to partition more in the fine particles(PM_2.5),facilitating its long range air transportation.In PM_2.5,PCBs were maninly in the ultrafine particles（＜0.5μm,43.9%）.The concentration of PCBs in per unit mass decreased with the size.Lower chlorinated congeners were found more in the 1.3-2.5μm cut than other size cuts.更多还原