Preliminary Study on the Microscopic Morphology and Chemical Composition, and Its Source of PM2.5 in Guangzhou
-
摘要: PM2.5是近年来影响我国城市大气环境的首要污染物,其成因机制复杂。本文采用扫描电镜和ICP-MS研究了广州市大气颗粒物PM2.5的显微形貌及其化学组成特征,并应用富集因子法进行源解析。结果表明,PM2.5的颗粒形态以无定形态为主;主要物质表现为含Fe、Mg、Al、K、Na的硅酸盐组合,具有道路扬尘、建筑施工排放等一次粒子特征;单个无定形颗粒物能谱表现出硫酸盐+硝酸盐的组合特征,为汽车尾气所排放的前体污染气体NOx和SO2进入大气环境中,在特定的物理化学条件下通过成核作用发生相态改变所形成的二次粒子。PM2.5中高度富集Cd、Se、Zn、Cu、Pb、As等重金属,异常富集的Br主要为当地普遍使用的阻燃剂十溴联苯醚和拆解电子垃圾所致,稀土元素的浓度在0.022~0.582 ng/m3之间,具有重稀土元素富集的特征。这些特征反映出广州市PM2.5颗粒物的组成既有一次粒子,也有二次粒子,物质来源具有多重性。Abstract: PM2.5 is the primary pollutant which has influenced the urban atmospheric environment in recent years, and its genetic mechanism is complicated. The microscopic morphology and trace element concentration of PM2.5 in the Guangzhou urban area were determined by Scanning Electron Microscope and Inductively Coupled Plasma-Mass Spectrometry, respectively. The enrichment factor method was adopted to constrain the source of PM2.5. The results show that PM2.5 mainly occurs as amorphousness fine particles. A silicate combination containing Fe, Mg, Al, K and Na is the main chemical composition of PM2.5, characterized by the first fine particles from road dust and buildings. An energy spectrum diagram of single amorphous particle shows the combination characteristics of sulfate and nitrate. These particles may have been secondary fine particles formed from pollution gases of SO2 and NOx from automobile exhaust in the atmospheric environment, through the nucleation induced phase behavior change under specific physical and chemical conditions. Heavy metals were highly enriched in PM2.5, including Cd, Se, Zn, Cu, Pb, and As. Local widespread use of deca bromine biphenyl ether as a flame retardant and a large number of E-waste dismantling are the main factors for abnormal enrichment of Br in the fine particles. The concentration of rare earth elements ranges from 0.022 to 0.582 ng/m3, with the relative enrichment of heavy rare earth elements in PM2.5. These features indicate that the composition of PM2.5 in the Guangzhou urban area are not only made up of primary particles, but also made up of secondary particles, characterized by multiple sources.
-
-
表 1 广州市PM2.5 4件样品中44个微量元素浓度(ng/m3)
Table 1. The trace elements concentrations of four samples PM2.5 in Guangzhou
元素 含量最小值 含量最大值 含量平均值 富集因子(EF) 元素 含量最小值 含量最大值 含量平均值 富集因子(EF) Ti 13.2 16.4 15.2 1 Ba 4.57 4.97 4.72 - V 1.97 4.81 3.1 7.24 W 0.499 0.591 0.541 - Cr 2.93 5.02 4.43 15.5 Hg 0.011 0.034 0.025 126 Mn 10.3 16.2 12.5 11.8 Tl 0.238 0.357 0.285 - Co 0.153 0.351 0.233 5.52 Pb 74.9 93.7 83.3 424 Ni 1.70 3.47 2.38 31.5 Bi 4.38 6.40 4.99 - Cu 23.9 59.2 33.5 533 Y 1.97 3.52 2.85 - Zn 196 241 211 660 Zr 1.65 4.17 2.64 - Ga 1.00 1.21 1.10 - La 0.280 0.342 0.314 - Ge 0.133 0.418 0.235 - Ce 0.519 0.740 0.582 - As 17.6 35.6 25.4 470 Pr 0.042 0.077 0.051 - Se 2.47 3.64 2.97 914 Nd 0.155 0.546 0.278 - Br 120 347 202 - Sm 0.034 0.323 0.130 - Rb 2.25 2.74 2.43 - Eu 0.007 0.104 0.041 - Sr 0.763 0.971 0.859 - Gd 0.059 0.747 0.297 - Mo 1.23 2.30 1.63 - Tb 0.012 0.167 0.065 - Cd 2.69 3.95 3.20 9250 Dy 0.067 1.180 0.466 - In 0.097 0.129 0.110 - Ho 0.014 0.225 0.089 - Sn 1.30 2.78 2.07 - Er 0.038 0.664 0.271 - Sb 18.5 24.5 20.5 - Tm 0.003 0.085 0.034 - Te 0.226 0.681 0.381 - Yb 0.033 0.508 0.198 - Cs 0.364 0.508 0.413 - Lu 0.004 0.057 0.022 - 注：富集因子计算中，土壤背景值单位除Ti为%,其余为mg/kg；土壤背景值中Ti取自文献[21]，其余元素取自文献[22]。富集因子栏中“-”表示无对应元素土壤背景值。 
下载: 导出CSV
-
[1] 杨洪斌,邹旭东,汪宏宇,等.大气环境中PM2.5的研究进展与展望[J].气象与环境学报,2012,28(3):77-82.
Yang H B,Zou X D,Wang H Y,et al.Study Progress on PM2.5 in Atmospheric Environment[J].Journal of Meteorology and Environment,2012,28(3):77-82.
[2] Mitkus R J,Powell J L,Zeisler R,et al.Comparative Physicochemical and Biological Characterization of NIST Interim Reference Material PM2.5 and SRM1648 in Human A549 and Mouse RAW264.7 Cells[J].Toxicology in Vitro,2013,27:2289-2298.
[3] Zhou S Z,Yuan Q,Li W J,et al.Trace Metals in Atmospheric Fine Particles in One Industrial Urban City:Spatial Variations,Sources,and Health Implications[J].Journal of Environmental Sciences,2014,26:205-213.
[4] 郭新彪,魏红英.大气PM2.5对健康影响的研究进展[J].科学通报,2013,58(13):1171-1177.
Guo X B,Wei H Y.Progress on The Health Effects of Ambient PM2.5 Pollution[J].Chinese Science Bulletin,2013,58(13):1171-1177.
[5] Andrade M,Miranda R M,Fornaro A,et al.Vehicle Emissions and PM2.5 Mass Concentrations in Six Brazilian Cities[J].Air Quality,Atmosphere and Health,2012,5:79-88.
[6] Voutsa D,Samara C,Manoli E,et al.Ionic Composition of PM2.5 at Urban Sites of Northern Greece:Secondary Inorganic Aerosol Formation[J].Environmental Science and Pollution Research,2014,21:4995-5006.
[7] Cao J J,Zhen X S,Chow J C,et al.Winter and Summer PM2.5 Chemical Compositionsin Fourteen Chinese Cities[J].Journal of the Air & Waste Management Association,2012,62(10):1214-1226.
[8] Wang X H,Bi X H,Sheng G Y,et al.Chemical Composition and Sources of PM10 and PM2.5 Aerosols in Guangzhou,China[J].Environmental Monitoring and Assessment ,2006,119:425-439.
[9] 张延君,郑玫,蔡靖,等.PM2.5源解析方法的比较与评述[J].科学通报,2015,60(2):109-121.
Zhang Y J,Zheng M,Cai J,et al.Comparison and Overview of PM2.5 Source Apportionment Methods[J].Chinese Science Bulletin,2015,60(2):109-121.
[10] 冯茜丹,党志,黄伟林.广州市秋季PM2.5中重金属的污染水平与化学形态分析[J].环境科学,2008,29(3):569-575.
Feng X D,Dang Z,Huang W L.Pollution Level and Chemical Speciation of Heavy Metals in PM2.5 during Autumn in Guangzhou City[J].Environmental Science,2008,29(3):569-575.
[11] Al-Momani I F.Trace Elements in Atmospheric Precipitation at Northern Jordan Measured by ICP-MS:Acidity and Possible Sources[J].Atmospheric Environment,2003,37(32):4507-4515.
[12] Mouli P C,Mohan S V,Balaram V,et al.A Study on Trace Elemental Composition of Atmospheric Aerosols at a Semi-arid Urban Site Using ICP-MS Technique[J].Atmospheric Environment,2006,40(1):136-146.
[13] 帅琴,杨薇,胡圣虹,等.微波消解-电感耦合等离子体质谱测定大气颗粒物中痕量稀土元素[J].分析科学学报,2005,21(4):375-377.
Shuai Q,Yang W,Hu S H,et al.Determination of Trace Rare Earth Elements in Air Particulate Matter by ICP-MS with Microwave Digestion[J].Journal of Analytical Science,2005,21(4):375-377.
[14] 李泽熙,邵龙义,樊景森,等.北京市不同天气条件下单颗粒形貌及元素组成特征[J].中国环境科学,2013,33(9):1546-1552.
Li Z X,Shao L Y,Fan J S,et al.Morphologies and Elemental Compositions of Individual Particles under Different Weather Conditions in Beijing[J].China Environmental Science,2013,33(9):1546-1552.
[15] 冯茜丹,明彩兵,刘晖,等.2011年秋季广州城区大气PM2.5微观形貌和粒度分布[J].中国环境科学,2015,35(4):1013-1018.
Feng X D,Ming C B,Liu H,et al.Microscopic Morphology and Size Distribution of PM2.5 in Guangzhou Urban Area in Fall,2011[J].China Environmental Science,2015,35(4):1013-1018.
[16] 董树屏,刘涛,孙大勇,等.用扫描电镜技术识别广州市大气颗粒物主要种类[J].岩矿测试,2001,29(3):202-207.
Dong S P,Liu T,Sun D Y,et al.Identification of Major Particle Classes in Guangzhou Aerosol by Scanning Electron Microscopy[J].Rock and Mineral Analysis,2001,29(3):202-207.
[17] 朱倩茹,刘永红,徐伟嘉,等.广州PM2.5污染特征及影响因素分析[J].中国环境监测,2013,29(2):15-21.
Zhu Q R,Liu Y H,Xu W J,et al.Analysis on the Pollution Characteristics and Influence Factors of PM2.5 in Guangzhou[J].Environmental Monitoring in China,2013,29(2):15-21.
[18] 崔明明,王雪松,苏杭,等.广州地区大气可吸入颗粒物的化学特征及来源解析[J].北京大学学报(自然科学版),2008,44(3):459-466.
Cui M M,Wang X S,Su H,et al.Chemical Characters and Sources Identification of PM10 in Guangzhou Area[J].Acta Scientiarum Naturalium Universitatis Pekinensis,2008,44(3):459-466.
[19] Behera S N,Sharma M.Reconstructing Primary and Secondary Components of PM2.5 Composition for an Urban Atmosphere[J].Aerosol Science and Technology,2010,44:983-992.
[20] 张小曳,孙俊英,王亚强,等.我国雾-霾成因及其治理的思考[J].科学通报,2013,58(13):1178-1187.
Zhang X Y,Sun J Y,Wang Y Q,et al.Factors Contributing to Haze and Fog in China[J].Chinese Science Bulletin,2013,58(13):1178-1187.
[21] 中国环境监测总站编著.中国土壤元素背景值[M].北京：中国环境科学出版社,1990:330-492.
China National Environmental Monitoring Centre.Elements Background Values of Soils in Chian[M].Beijing:China Environmental Science Press,1990:330-492.
[22] 张山岭,杨国义,罗薇,等.广东省土壤无机元素背景值的变化趋势研究[J].土壤,2012,44(6):1009-1014.
Zhang S L,Yang G Y,Luo W,et al.Changes of Background Values of Inorganic Elements in Soils of Guangdong Province[J].Soils,2012,44(6):1009-1014.
[23] Song X H,Polissar A V,Hopke P K.Sources of Fine Particle Composition in the Northeastern US[J].Atomspheric Environment,2001,35: 5227-5286.
[24] Lim M C H,Ayoko G A,Morawska L.Characterization of Elemental and Polycyclic Aromatic Hydrocarbon Compositions of Urban Air in Brisbane[J].Atomspheric Environment,2005,39:463-476.
[25] Hu X,Zhang Y,Ding Z H,et al.Bioaccessibility and Health Risk of Arsenic and Heavy Metals (Cd,Co,Cr,Cu,Ni,Pb,Zn and Mn) in TSP and PM2.5 in Nanjing,China[J].Atmospheric Environment,2012,57:146-152.
[26] Chen J M,Tan M G,Li Y L,et al. A lead Isotope Record of Shanghai Atmospheric Lead Emissions in TotalSuspended Particles during the Period of Phasing out of Leaded Gasoline[J].Atmospheric Environment,2005,39:1245-1253.
[27] Chow J C,Watson J G,Kuhns H,et al.Source Profiles for Industrial,Mobile,and Area Sources in the Big Bend Regional Aerosol Visibility and Observational Study[J].Chemosphere,2004,54(2):185-208.
[28] 陈来国,麦碧娴,许振成,等.多溴联苯醚在不同粒径大气颗粒物上的分布及总有机碳的影响[J].环境化学,2010,29(3):363-368.
Chen L G,Mai B X,Xu Z C,et al.Particle Size Distribution of Polybrom Inated Diphenyl Ethers and the Influence of Total Organic Carbon[J].Environmental Chemistry,2010,29(3):363-368.
[29] 陈来国,麦碧娴,许振成,等.广州市夏季大气中多氯联苯和多溴联苯醚的含量及组成对比[J].环境科学学报,2008,28(1):150-159.
Chen L G,Mai B X,Xu Z C,et al.Comparison of PCBs and PBDEs Concentrations and Compositions in the Guangzhou Atmosphere in Summer[J].Acta Scientiae Circumstantiae,2008,28(1):150-159.
[30] 陈多宏,李丽萍,毕新慧,等.典型电子垃圾拆解区大气中多溴联苯醚的污染[J].环境科学,2008,29(8)2105-2110.
Chen D H,Li L P,Bi X H,et al.PBDEs Pollution in the Atmosphere of a Typical E-waste Dismantling Region[J].Environment Science,2008,29(8):2105-2110
[31] 杨雪,刘大锰,孙俊玲.北京市大气PM2.5中多溴联苯醚污染水平与来源分析[J].现代地质,2010,24(2):355-361.
Yang X,Liu D M,Sun J L.Pollution Level and Source Analysis of Polybrom Inated Diphenyl Ethers (PBDEs) from Atmospheric Matter PM2.5 in Beijing[J].Geoscience,2010,24(2):355-361.
-
图(3)
表(1)
计量
- 文章访问数: 1593
- PDF下载数: 22
- 施引文献: 0