本研究利用高流量空氣採樣器(PS1)，收集高雄近岸地區每月與日-夜間大
氣中顆粒相與氣相多環芳香烴(polycyclic aromatic hydrocarbons, PAHs)，分析
其濃度，並藉由多環芳香烴特徵比、群集分析(Hierarchical Cluster Analysis,
HCA)及主成份分析(Principal Component Analysis, PCA)等方法來探討可能的
污染來源。
各月總多環芳香烴濃度變化以五月(2.62 ngm-3)為最低，以12月(36.4 ngm-3)
最高，日夜分佈上，以夜間/日間比值介於0.35~2.52之間平均為1.65以夜間濃度
較高，氣態多環芳香烴為主要貢獻，所佔濃度百分比介於64.1~93.7 %之間。多
環芳香烴氣-顆粒態分佈上，2、3-Ring 大多以氣態為主，所佔比例分別為96.2
及96.5 %，4、5-Ring 大多以氣/顆粒態共存，4-Ring 傾向存在於氣態(73.0 %)，
而5-Ring 則較傾向與顆粒態結合(80.2 %)，6、7-Ring 高分子量多環芳香烴則以
顆粒態為主所佔比例分別為97.4及97.7 %。當有如中元節、沙塵暴等事件日，則
會增加大氣中多環芳香烴濃度，且每單位總懸浮微粒所含總多環芳香烴濃度也隨
著增加。
PAHs 與氣象條件相關性分析中，氣態與顆粒態多環芳香烴與溫度呈現顯著
負相關(r=-0.62、-0.57, p<0.01)，顯示季節變化對大氣中多環芳香烴濃度有明顯
的影響。
多環芳香烴特徵比、群集分析(HCA)及主成份分析(PCA)結果顯示，本研究
地點多環芳香烴主要來源為汽、柴油燃燒排放及工業排放。

A high-volume air sampler (PS-1) was used to measure the
concentrations of polycyclic aromatic hydrocarbons (PAHs) in the atmosphere
of Kaohsiung coast, PAHs diagnostic ratios,Hierarchical Cluster Analysis (HCA)
and Principal Component Analysis (PCA) were employed to determine the
potential sources of PAHs.
The results show that the lowest concentrations of PAHs occurred in May
(2.62 ngm-3), while the highest occurred in December (36.4 ngm-3). The
nighttime concentrations of PAHs are higher than daytime with average night /
day ratio of 1.65. The PAHs was more distributed in gas phase with
proportions between 64.1 to 93.7 %. The 2, 3-Ring PAHs were mostly present
in the gaseous phase (96.2 and 96.5 % respectively), 4-Ring also present
dominantly in the gaseous phase (73.0 %), 5-Ring present mostly in the
particle phase (80.2 %), 6, 7-Ring PAHs were mostly present in particulate
phase (97.4 and 97.7 % respectively). During the Ghost Festiva and Asian
dust storm events, atmospheric concentrations of PAHs and PAHs/TSP ratios
were both found increased.
It is found that gaseous and particulate PAHs correlate negatively with
ambient temperature(r=-0.62, -0.57).
Results from analyses of diagnostic ratios, HCA and PCA, the major
sources of pollution include gasoline, diesel exhaust and industrial emission.

摘要
Abstract
目錄 .……….…………………………………….………………… I
圖目錄 …………………………………………..…….…………… IV
表目錄 …....…………………………………..……………………. VI
附表目錄 …....…………………………………..……................... VIII
第一章 研究背景與動機………………………….……………..… 1
第二章 文獻回顧 ……………………………………….………… 3
2-1 PAHs 之物理及化學特性 …………………………….… 3
2-2 PAHs 的來源 ………………………………………….… 3
2-3 PAHs 之危害 ………………………...…………………. 4
2-4 PAHs 來源鑑定 ...……………………...…………….….. 5
2-5 高雄地區近十年氣象概述 ...…………………….…....... 6
2-6 高雄地區空氣品質變化趨勢 ...……………………….... 8
2-6-1 各空氣污染物濃度變化趨勢 ...………………… 8
2-6-2 高雄都會地區PAHs 污染現況...………………... 9
第三章 研究方法 ………………………….………………….…… 20
3-1 採樣地點及時間 …………………………………….…… 20
3-2 材料與儀器 …...…………………………………….…… 20
3-2-1 材料 ……...………………………………….…... 20
3-3-2 儀器設備 …...……………………………….…… 21
3-4 試藥及器具前處理 …...…………………………….…... 22
3-5 採樣方法 ………………...………………………….…... 23
3-6 樣品分析 …………………...……………………….…... 23
3-6-1 PAHs 分析 …...……..……………………….…… 23
3-6-2 品保與品管 ……………...……………………… 25
3-7 階層群集分析(Hierarchical Cluster Analysis, HCA) … 27
3-8 主成分分析法(Principal Component Anslysis, PCA) ... 28
第四章 結果與討論 ………………….……………………………. 42
4-1 大氣中多環芳香烴化合物(PAHs)濃度 …….……..…… 42
4-1-1 大氣中懸浮微粒濃度 …………………………… 42
4-1-2 大氣中總PAHs(TPAHs)濃度…………………… 43
4-1-3 PAHs 日夜濃度變化 …………………………..… 45
4-1-4 大氣中各環數PAHs 濃度分佈 ………………… 45
4-1-5 大氣中氣-顆粒態分布 …………………………... 46
4-1-6 PAHs 與氣象條件之相關性 …………………….. 47
4-2 PAHs 來源分析 …………………………………………. 48
4-3 階層群集分析(HCA)結果 ………………………….…… 49
4-4 主成分分析(PCA) 結果 …………………………..…… 50
第五章 結論與建議 ……………………………………………... 76
5-1 結論 .......................................................................... 76
5-2 建議 ........................................................................... 77
參考文獻 ........................................................................... 78
附錄..................................................................................... 85

Bamford, H.A. and Baker, J.E., 2003. Nitro-polycyclic aromatic hydrocarbon concentrations and sources in urban and suburban atmospheres of the Mid-Atlantic region. Atmospheric Environment, 37(15): 2077-2091.
Bi, X., Sheng, G., Peng, P., Chen, Y., Zhang, Z.Fu, J., 2003. Distribution of particulate- and vapor-phase n-alkanes and polycyclic aromatic hydrocarbons in urban atmosphere of Guangzhou, China. Atmospheric Environment, 37(2): 289-298.
Caricchia, A.M., Chiavarini, S.Pezza, M., 1999. Polycyclic aromatic hydrocarbons in the urban atmospheric particulate matter in the city of Naples (Italy). Atmospheric Environment, 33(23): 3731-3738.
Cavalieri, E.L. and Rogan, E.G., 1995. Central Role Of Radical Cations In Metabolic-activation Of Polycyclic Aromatic-hydrocarbons. Xenobiotica, 25(7): 677-688.
Cincinelli, A., Bubba, M.D., Martellini, T., Gambaro, A.Lepri, L., 2007. Gas-particle concentration and distribution of n-alkanes and polycyclic aromatic hydrocarbons in the atmosphere of Prato (Italy). Chemosphere, 68(3): 472-478.
Dipple, A., 1976. Polycyclic aromatic carcinogens In: Searle CE (ed) Chemical carcinogens (ACS Monograph Series 3). American Chemical Society(Washington, D.C): 245-314.
Duan, J., Bi, X., Tan, J., Sheng, G.Fu, J., 2005. The differences of the size distribution of polycyclic aromatic hydrocarbons (PAHs) between urban and rural sites of Guangzhou, China. Atmospheric Research, 78(3-4): 190-203.
Esen, F., Siddik Cindoruk, S.Tasdemir, Y., 2008. Bulk deposition of polycyclic aromatic hydrocarbons (PAHs) in an industrial site of Turkey. Environmental Pollution, 152(2): 461-467.
Fang, G.-C., Chang, C.-N., Wu, Y.-S., Fu, P.P.-C., Yang, I.L.Chen, M.-H., 2004a. Characterization, identification of ambient air and road dust polycyclic aromatic hydrocarbons in central Taiwan, Taichung. Science of The Total Environment, 327(1-3): 135-146.
Fang, G.-C., Chang, K.-F., Lu, Chungsying., B., Hsunling., 2004b. Estimation of PAHs dry deposition and BaP toxic equivalency factors (TEFs) study at Urban, Industry Park and rural sampling sites in central Taiwan, Taichung. Chemosphere, 55(6): 787-796.
Fang, G.-C., Wu, Y.-S., Chen, J.-C., Chang, C.-N.Ho, T.-T., 2006. Characteristic of polycyclic aromatic hydrocarbon concentrations and source identification for fine and coarse particulates at Taichung Harbor near Taiwan Strait during 2004-2005. Science of The Total Environment, 366(2-3): 729-738.
Fang, G.-C., Wu, Y.-S., Chen, J.-C., Fu, P.P.-C., Chang, C.-N., Ho, T.-T.Chen, M.-H., 2005. Characteristic study of polycyclic aromatic hydrocarbons for fine and coarse particulates at Pastureland near Industrial Park sampling site of central Taiwan. Chemosphere, 60(3): 427-433.
Grimmer, G., 1983. Environmental Carcinogens: Polycyclic Aromatic Hydrocarbons Chemistry. Occurrence, Biochemistry, Carcinogenicity(CRC Press, Boca Raton, FL ).
Guo, H., Lee, S.C., Ho, K.F., Wang, X.M.Zou, S.C., 2003a. Particle-associated polycyclic aromatic hydrocarbons in urban air of Hong Kong. Atmospheric Environment, 37(38): 5307-5317.
Guo, Z.G., Sheng, L.F., Feng, J.L.Fang, M., 2003b. Seasonal variation of solvent extractable organic compounds in the aerosols in Qingdao, China. Atmospheric Environment, 37(13): 1825-1834.
Harrison, R.M., Smith, D.J.T.Luhana, L., 1996. Source Apportionment of Atmospheric Polycyclic Aromatic Hydrocarbons Collected from an Urban Location in Birmingham, U.K. Environmental Science and Technology, 30(3): 825-832.
Ho, K.F., Lee, S.C.Chiu, G.M.Y., 2002. Characterization of selected volatile organic compounds, polycyclic aromatic hydrocarbons and carbonyl compounds at a roadside monitoring station. Atmospheric Environment, 36(1): 57-65.
Hong, H., Yin, H., Wang, X.Ye, C., 2007. Seasonal variation of PM10-bound PAHs in the atmosphere of Xiamen, China. Atmospheric Research, 85(3-4): 429-441.
Katz, M. and Chan, C., 1980. Comparative distribution of eight polycyclic aromatic hydrocarbons in airborne particulates collected by conventional high-volume sampling and by size fractionation. Environmental Science and Technology, 14(7): 838-843.
Keller, C.D. and Bidleman, T.F., 1984. Collection of airborne polycyclic aromatic hydrocarbons and other organics with a glass fiber filter-polyurethane foam system. Atmospheric Environment (1967), 18(4): 837-845.
Khalili, N.R., Scheff, P.A.Holsen, T.M., 1995. PAH source fingerprints for coke ovens, diesel and, gasoline engines, highway tunnels, and wood combustion emissions. Atmospheric Environment, 29(4): 533-542.
Kulkarni, P. and Venkataraman, C., 2000. Atmospheric polycyclic aromatic hydrocarbons in Mumbai, India. Atmospheric Environment, 34(17): 2785-2790.
Kume, K., Ohura, T., Noda, T., Amagai, T.Fusaya, M., 2007. Seasonal and spatial trends of suspended-particle associated polycyclic aromatic hydrocarbons in urban Shizuoka, Japan. Journal of Hazardous Materials, 144(1-2): 513-521.
Lee, W.-J., Wang, Y.-F., Lin, T.-C., Chen, Y.-Y., Lin, W.-C., Ku, C.-C.Cheng, J.-T., 1995. PAH characteristics in the ambient air of traffic-source. Science of The Total Environment, 159(2-3): 185-200.
Li, C.-S. and Ro, Y.-S., 2000. Indoor characteristics of polycyclic aromatic hydrocarbons in the urban atmosphere of Taipei. Atmospheric Environment, 34(4): 611-620.
Liu, Y.N., Tao, S., Dou, H., Zhang, T.W., Zhang, X.L.Dawson, R., 2007. Exposure of traffic police to Polycyclic aromatic hydrocarbons in Beijing, China. Chemosphere, 66(10): 1922-1928.
Mandalakis, M., Tsapakis, M., Tsoga, A.Stephanou, E.G., 2002. Gas-particle concentrations and distribution of aliphatic hydrocarbons, PAHs, PCBs and PCDD/Fs in the atmosphere of Athens (Greece). Atmospheric Environment, 36(25): 4023-4035.
Mantis, J., Chaloulakou, A.Samara, C., 2005. PM10-bound polycyclic aromatic hydrocarbons (PAHs) in the Greater Area of Athens, Greece. Chemosphere, 59(5): 593-604.
Miller, J.S. and Olejnik, D., 2001. Photolysis of polycyclic aromatic hydrocarbons in water. Water Research, 35(1): 233-243.
Naumova, Y.Y., Offenberg, J.H., Eisenreich, S.J., Meng, Q., Polidori, A., Turpin, B.J., Weisel, C.P., Morandi, M.T., Colome, S.D., Stock, T.H., Winer, A.M., Alimokhtari, S., Kwon, J., Maberti, S., Shendell, D., Jones, J.Farrar, C., 2003. Gas/particle distribution of polycyclic aromatic hydrocarbons in coupled outdoor/indoor atmospheres. Atmospheric Environment, 37(5): 703-719.
Odabasi, M., Vardar, N., Sofuoglu, A., Tasdemir, Y.Holsen, T.M., 1999. Polycyclic aromatic hydrocarbons (PAHs) in Chicago air. The Science of The Total Environment, 227(1): 57-67.
Omar, N.Y.M.J., A, bas, M.R.B., Ketuly, K.A.Tahir, N.M., 2002. Concentrations of PAHs in atmospheric particles (PM-10) and roadside soil particles collected in Kuala Lumpur, Malaysia. Atmospheric Environment, 36(2): 247-254.
Park, S.S., Kim, Y.J.Kang, C.H., 2002. Atmospheric polycyclic aromatic hydrocarbons in Seoul, Korea. Atmospheric Environment, 36(17): 2917-2924.
Ravindra, K., Sokhi, R.Van Grieken, R., 2008. Atmospheric polycyclic aromatic hydrocarbons: Source attribution, emission factors and regulation. Atmospheric Environment, 42(13): 2895-2921.
Schauer, J.J., Kleeman, M.J., Cass, G.R.Simoneit, B.R.T., 1999. Measurement of Emissions from Air Pollution Sources. 2. C1 through C30 Organic Compounds from Medium Duty Diesel Trucks. Environmental Science and Technology, 33(10): 1578-1587.
&#352;i&#353;ovi&#263;, A., &#352;krbec, A., Vadji&#263;, V., Kalini&#263;, N.Hr&#353;ak, J., 2002. PAH Levels and Profiles in the Suspended Particulate Matter in Zagreb through Four Seasons. Environmental Monitoring and Assessment, 74(3): 217-224.
St-Amand, A.D., Mayer, P.M.Blais, J.M., 2008. Seasonal trends in vegetation and atmospheric concentrations of PAHs and PBDEs near a sanitary landfill. Atmospheric Environment, 42(13): 2948-2958.
Tamamura, S., Sato, T., Ota, Y., Wang, X., Tang, N.Hayakawa, K., 2007. Long-range transport of polycyclic aromatic hydrocarbons (PAHs) from the eastern Asian continent to Kanazawa, Japan with Asian dust. Atmospheric Environment, 41(12): 2580-2593.
Tasdemir, Y. and Esen, F., 2007. Dry deposition fluxes and deposition velocities of PAHs at an urban site in Turkey. Atmospheric Environment, 41(6): 1288-1301.
Tham, Y.W.F. and Sakugawa, H., Polycyclic aromatic hydrocarbons (PAHs) associated with atmospheric particles in Higashi Hiroshima, Japan: Influence of meteorological conditions and seasonal variations. Atmospheric Research, In Press, Accepted Manuscript: 260.
Tham, Y.W.F., Takeda, K.Sakugawa, H., 2008. Polycyclic aromatic hydrocarbons (PAHs) associated with atmospheric particles in Higashi Hiroshima, Japan: Influence of meteorological conditions and seasonal variations. Atmospheric Research, 88(3-4): 224-233.
Vecchi, R., Marcazzan, G.Valli, G., 2007. A study on nighttime-daytime PM10 concentration and elemental composition in relation to atmospheric dispersion in the urban area of Milan (Italy). Atmospheric Environment, 41(10): 2136-2144.
Wang, H.K., Chen, K.S., Lu, J.J., Peng, Y.P., Wang, W.C., Tsai, M.Y.Lai, C.H., 2007. Dry Deposition of Airborne Particles and Characteristics of Polycyclic Aromatic Hydrocarbons in Urban Kaohsiung, Taiwan. Aerosol and Air Quality Research, 7: 106-120.
Yamasaki, H., Kuwata, K.Miyamoto, H., 1982. Effects of ambient temperature on aspects of airborne polycyclic aromatic hydrocarbons. Environmental Science and Technology, 16(4): 189-194.
Yang, H.-H. and Chen, C.-M., 2004. Emission inventory and sources of polycyclic aromatic hydrocarbons in the atmosphere at a suburban area in Taiwan. Chemosphere, 56(10): 879-887.
Yang, H.-H., Jung, R.-C., Wang, Y.-F.Hsieh, L.-T., 2005. Polycyclic aromatic hydrocarbon emissions from joss paper furnaces. Atmospheric Environment, 39(18): 3305-3312.
Yang, H.-H., Lai, S.-O., Hsieh, L.-T., Hsueh, H.-J.Chi, T.-W., 2002. Profiles of PAH emission from steel and iron industries. Chemosphere, 48(10): 1061-1074.
Yang, H.-H., Lee, W.-J., Chen, S.-J.Lai, S.-O., 1998. PAH emission from various industrial stacks. Journal of Hazardous Materials, 60(2): 159-174.
呂局校, 2006. 高雄市大氣中多環芳香烴化合物濃度特徵之調查分析, 國立中山大學環境工程研究所碩士論文.
廖琇怡, 2004. 高雄市臭氧特性與氣象因子之相關性探討, 國立中山大學環境工程研究所碩士論文.