Chemical Composition and Source Apportionment of PM2.5 in Key Cities of Fujian Province

大气PM2.5是造成城市大气能见度下降和居民呼吸道慢性病增加的主要因素之一，在化学组成的基础上建立适合本地区的大气PM2.5源解析模型，是制定科学有效减排措施的关键。本研究在福建省厦门（洪文站）、泉州（环保局）、莆田（秀屿区政府）和福州（紫阳观测站）设置采样站点，于2011年10月、2011年11月、2012年1月、2012年4月和2012年7月进行采样，并对样品中的水溶性离子、碳成分和无机元素进行分析，并结合本地区源排放PM2.5的组成特征，采用因子分析（FA）和受体模型（CMB、PMF）等手段对大气PM2.5的污染来源进行了解析，主要获得如下结论： 1.厦门、泉州、莆田和福州四个站点PM...PM2.5 can influence atmospheric visibility and residents respiratory diseases to a great extent, and its source apportionment based on the chemical compositions is very important for local government to take scientific measures to reduce its atmospheric level. Four sampling sites including Xiamen Hongwen Primary School (XM), Environmental Proctection Burean of Quanzhou (QZ), Xiuyu District Governm...学位：理学硕士院系专业：海洋与环境学院_环境科学学号：2262010115141

Compositions of Organic Acids in PM_(10) Emission Sources in Xiamen Urban Atmosphere

对厦门城区大气颗粒物PM10中有机酸的可能来源,如烹调油烟、生物质燃烧颗粒、汽车尾气和土壤/路面扬尘等4种不同排放源,采用再悬浮混合箱得到PM10样品.采用bf3/正丁醇衍生-gC/MS分析方法,测定了包括二元羧酸、脂肪酸和芳香酸共15种有机酸.结果表明,烹调油烟中有机酸的含量远高于其它颗粒物,最高可达53%,其中亚油酸和油酸的含量最高,为24%±14%;而汽车尾气颗粒物中乙二酸的含量最高,其次为邻苯二甲酸PH;汽油燃烧颗粒物中己二酸与壬二酸的比值显著高于其它样品,可用于环境大气中二元羧酸的人为和生物来源的定性判断.除发电机排放样品外,其它样品中丙二酸与丁二酸的比值(0.07~0.44)远低于环境样品中该比值范围(0.61~3.93),表明丙二酸与丁二酸的比值可用于环境大气中二元羧酸的一次/二次来源的定性判断.The possible organic acid emission sources in PM10 in Xiamen urban atmosphere such as cooking,biomass burning,vehicle exhaust and soil/dust were obtained using a re-suspension test chamber.A total of 15 organic acids including dicarboxylic acids,fatty acids and aromatic acids were determined using GC/MS after derivatization with BF3/n-butanol.The results showed that the highest total concentration of 15 organic acids(53%) was found in cooking emission and the average concentration of the sum of linoleic acid and oleic acid was 24%±14%.However,oxalic acid was the most abundant species followed by phthalic acid in gasoline vehicle exhaust.The ratios of adipic to azelaic acid in gasoline combustion emissions were significantly higher than those in other emission sources,which can be used to qualitatively differentiate anthropogenic and biological source of dicarboxylic acids in atmospheric samples.The ratios of malonic to succinic acid in source emissions(except gasoline generator emissions) were lower(0.07-0.44) than ambient PM10samples(0.61-3.93),which can be used to qualitatively differentiate the primary source and the secondary source of dicarboxylic acids in urban PM10.国家自然科学基金项目(40971257;41171365); 环境保护公益性行业科研专项(201009004); 福建省自然科学基金计划项目(2009J05106

Road Dust Loading and Chemical Composition at Major Cities in Fujian Province

采集并分析了福建省重点城市厦门、漳州、泉州和莆田城区具有代表性的57个地面扬尘和16个土壤样品的26种无机元素、8种水溶性离子和碳成分等组成.不同城市粒径≤100μM的路面尘负荷平均值在6.99 g.M-2与10.11 g.M-2之间,而粒径≤2.5μM的路面尘(PM2.5)负荷平均值在4.0 Mg.M-2和12.5 Mg.M-2之间.不同城市土壤尘和路面尘PM2.5中浓度最高的元素都是SI、CA、Al、fE和k,路面尘中CA元素明显富集,而主要人为来源的重金属元素如Cu、Pb、zn、Cr在路面尘PM2.5中的浓度显著高于土壤尘.漳州城区路面尘PM2.5中二次离子nH4+、nO3-和SO24-的含量明显高于其它地区,厦门、漳州和泉州城区路面尘PM2.5中Mg2+和CA2+之间都存在显著的正相关关系.四城市路面尘中有机碳(OC)的含量均高于济南、石家庄以及北京地面扬尘OC的含量,元素碳(EC)的含量均低于北京地区路面扬尘EC的含量.泉州和莆田两地OC和EC的相关性较好,说明路面尘中OC和EC有相同或相似的来源.质量平衡结果显示泉州和莆田路面尘PM2.5中含量最高的是土壤尘,其次为有机物.按化学组成特征对路面尘PM2.5进行聚类解析,得到受大气沉降影响、受土壤尘影响、受大气沉降和土壤尘共同作用以及受土壤尘和建筑尘共同作用4类样品.A total of 57 road dust and 16 urban soil samples were collected from four cities,Xiamen,Zhangzhou,Quanzhou and Putian in Fujian Province,China.Twenty-six elements,eight water soluble ions,organic carbon and elemental carbon in the fraction of particulate diameter less than 2.5 μm(PM2.5) derived through a suspension chamber were analyzed.The average loading of road dust with diameter less than 100 μm in the four cities ranged from 6.99 g·m-2 to 10.11 g·m-2,while the loading of PM2.5 ranged from 4.0 mg·m-2 to 12.5 mg·m-2.Both the soil and road dust samples were characterized with much higher concentrations of Si,Ca,Al,Fe and K.But for the anthropogenic elements such as Cu,Pb,Zn,Cr and Ti,much lower levels were found in the soil PM2.5 than those in the road dust PM2.5.Significantly higher levels of NH+4,NO-3 and SO2-4 were found in the road dust PM2.5 from Zhangzhou in comparison with those from other cities in this study.The calcium ion(Ca2+) content was significantly positively correlated with the Mg2+ content in the road dust PM2.5 from Xiamen,Zhangzhou and Quanzhou.The levels of organic carbon(OC) in the road dust PM2.5 in these four cities were higher than those reported in Ji'nan,Shijiazhuang and Beijing while the levels of elemental carbon(EC) were all lower than those in the urban road dust from Beijing,Significant positive correlation between EC and OC was found in samples from Quanzhou and Putian,suggesting the same and/or similar sources.The result of mass balance indicated that higher percentage compositions were soil and OM in both Quanzhou and Putian.Based on the cluster analysis,the 57 road dust samples were divided into four types: influenced by atmospheric deposition,influenced by soil dust,influenced by atmospheric deposition and soil dust,and influenced by soil and construction dust.国家自然科学基金项目(40971257;41171365); 环境保护公益性行业科研专项(201009004); 福建省自然科学基金计划项目(2009J05106

Uncertainty Analysis of Gas/Particle Partitioning of Atmospheric Polycyclic Aromatic Hydrocarbons

于2010年8月10~14日用双层石英膜和双层聚氨酯泡沫(Puf)的方法采集并分析了厦门大学海洋楼顶大气中气态和颗粒态多环芳烃(PAHS),并采用标准误差传递方法对气/粒分配系数(kP)的不确定度进行了分析.测量结果显示,低分子量PAHS如萘、苊、二氢苊和芴在Puf吸附体系中的穿透能力最强,穿透率接近50%;如考虑第一层石英滤膜对气态萘、苊和二氢苊的吸附影响,则校正后的kP值比校正前相应的kP值低1个数量级以上.采用标准误差传递方法得到PAHS气/粒分配系数kP的不确定度,介于28.14%~50.37%之间,且表现为易挥发和难挥发性PAHS的kP值皆具有较高的不确定度,而半挥发性PAHS的kP值的不确定度则较小.kP值的不确定度来源分析显示,气态PAHS浓度的不确定度的影响最大(方差贡献均值=77.9%),其次为颗粒态PAHS浓度的不确定度(方差贡献均值=22.0%),大气颗粒物浓度的不确定度影响最小(方差贡献均值=0.1%).因此,选择合适的采样系统以获取更加准确的气态PAHS的浓度,是提高PAHS气/粒分配系数准确度的关键.During the period from August 10,2010 through August 14,2010,particle and gas phase PAHs were collected and analyzed using double filters plus PUFs(Poly Urethane Foam) sampling system,and the uncertainties of gas/particle partitioning coefficients of PAHs were investigated using the propagation of errors formulas.The results showed that low-molecular weight PAHs such as naphthalene,acenaphthylene,acenaphthene and fluorene possessed the strong breakthrough capacity with the breakthrough rates close to 50% in double PUF cartridges.The corrected Kp values based on the sorption of PAHs to the primary filter were more than an order of magnitude higher than those without sorption correction for naphthalene,acenaphthylene and acenaphthene.The uncertainties for all the 19 PAHs ranged from 28.14% to 50.37% based on the standard error propagation formulas,with higher values for volatile and involatile PAHs and lower values for semi-volatile PAHs.The results also showed that the uncertainties of Kp were mainly contributed from the measurements of particle(average variance contribution was 77.9%) and gas(average variance contribution was 22.0%) phase PAHs while the contributions of total suspended particle were ignorable.Thus,getting more accurate data for gaseous PAHs using an appropriate sampling system is the key to increase the accuracy of gas/particle partitioning coefficients of PAHs.国家自然科学基金项目(40971257);环保公益性行业科研专项项目(201009004);国家海洋局近海海域生态环境重点实验室开放基金项目(200911

Compositions of Organic Acids in PM10 Emission Sources in Xiamen Urban Atmosphere

对厦门城区大气颗粒物PM10中有机酸的可能来源,如烹调油烟、生物质燃烧颗粒、汽车尾气和土壤/路面扬尘等4种不同排放源,采用再悬浮混合箱得到PM10样品.采用BF3/正丁醇衍生-GC/MS分析方法,测定了包括二元羧酸、脂肪酸和芳香酸共15种有机酸.结果表明,烹调油烟中有机酸的含量远高于其它颗粒物,最高可达53%,其中亚油酸和油酸的含量最高,为24%±14%;而汽车尾气颗粒物中乙二酸的含量最高,其次为邻苯二甲酸Ph;汽油燃烧颗粒物中己二酸与壬二酸的比值显著高于其它样品,可用于环境大气中二元羧酸的人为和生物来源的定性判断.除发电机排放样品外,其它样品中丙二酸与丁二酸的比值(0.07～0.44)远低于环境样品中该比值范围(0.61～3.93),表明丙二酸与丁二酸的比值可用于环境大气中二元羧酸的一次/二次来源的定性判断。Abstract：The possible organic acid emission sources in PM10 in Xiamen urban atmosphere such as cooking，biomass burning，vehicle exhaust and soil /dust were obtained using a re-suspension test chamber． A total of 15 organic acids including dicarboxylic acids，fatty acids and aromatic acids were determined using GC/MS after derivatization with BF3 /n-butanol． The results showed that the highest total concentration of 15 organic acids ( 53%) was found in cooking emission and the average concentration of the sum of linoleic acid and oleic acid was 24% ± 14%． However，oxalic acid was the most abundant species followed by phthalic acid in gasoline vehicle exhaust． The ratios of adipic to azelaic acid in gasoline combustion emissions were significantly higher than those in other emission sources，which can be used to qualitatively differentiate anthropogenic and biological source of dicarboxylic acids in atmospheric samples． The ratios of malonic to succinic acid in source emissions ( except gasoline generator emissions) were lower ( 0. 07-0. 44) than ambient PM10 samples ( 0. 61-3. 93) ，which can be used to qualitatively differentiate the primary source and the secondary source of dicarboxylic acids in urban PM10 .国家自然科学基金项目(40971257,41171365);环境保护公益性行业科研专项(201009004);福建省自然科学基金计划项目(2009J05106