本研究針對南台灣地區工業廢棄物焚化爐（IWI）、小型一般廢棄物焚化爐（MSWI）、醫療廢棄物焚化爐（MWI）、水泥窯（CK）以及火葬場（CR）共六座五種不同形式之固定污染源進行PCDD/Fs採樣檢測分析；此外也針對南台灣農廢露天燃燒盛行之地區，於農廢露天燃燒前及燃燒當時，進行大氣戴奧辛採樣分析以及土壤、灰燼採樣分析。由實驗數據顯示：小型一般廢棄物焚化爐（MSWI）與火葬場（CR）煙道廢氣中皆以PCDDs所佔比例較高。而工業廢棄物焚化爐（IWI）、醫療廢棄物焚化爐（MWI）以及水泥窯（CK）煙道廢氣中以PCDFs所佔比例較高。以Factor分析方法所得顯示，火葬場（CR）以及小型一般廢棄物焚化爐（MSWI）有相似之特徵指紋（Fingerprints），工業廢棄物焚化爐（IWIb）與醫療廢棄物焚化爐（MWI3）有相似之特徵指紋（Fingerprints）。以階層集群分析（Cluster Analysis）結果顯示，PCDD/Fs之特徵剖面分布於OCDD、1,2,3,4,6,7,8-HpCDF、2,3,4, 7,8-PeCDF與 1,2,3,4,6,7,8-HpCDD等四組中。PCDD/Fs之排放係數計算部分，此六座五種不同形式之固定污染源PCDD/Fs排放係數介於0.0433μg/ton-feedstock（水泥窯（CK））與18.7μg/ton-feedstock（小型一般廢棄物焚化爐（MSWI））之間。
在農業露天燃燒部份，針對兩處蓮霧園與一處稻草田露天燃燒前及燃燒時背景大氣採樣分析顯示：燃燒前農廢蓮霧園周界大氣總PCDD/Fs平均濃度為0.057 pg I-TEQ/Nm3，農廢蓮霧園燃燒時周界大氣總PCDD/Fs平均濃度為0.458 pg I-TEQ/Nm3，農廢蓮霧園燃燒時周界大氣總平均PCDD/Fs濃度為燃燒前背景值之8.1倍。燃燒前農廢稻草田周界大氣總PCDD/Fs平均濃度為0.089 pg I-TEQ/Nm3，農廢稻草田燃燒時周界大氣總PCDD/Fs平均濃度為0.409 pg I-TEQ/Nm3，農廢稻草田燃燒時周界大氣總平均PCDD/Fs濃度為燃燒前背景值之4.6倍。蓮霧園與稻草田燃燒後灰燼中PCDD/Fs之含量分別為1.393 ng I-TEQ/kg-ash與1.568 ng I-TEQ/kg-ash，蓮霧園與稻草田燃燒前土壤中PCDD/Fs之含量分別為2.258 ng I-TEQ/kg-ash與2.890 ng I-TEQ/kg-ash，如果露天燃燒持續好幾年，燃燒後灰燼落入土壤中經翻耕或累積會增加土壤中PCDD/Fs含量。

This work investigated the characteristics of polychlorinated dibenzo-p-dioxins anddibenzofurans (PCDD/F) in stack-flue gases from six stationary emission sources in five types ofincinerators: industrial waste incinerator (IWI), small-scale municipal solid waste incinerator(MSWI), medical waste incinerator (MWI), cement kilns (CK), and crematories (CR). These characteristics were further investigated using factor analysis and cluster analysis. Experimental results reveal that PCDDs dominate MSWI and CR, and PCDFs dominate IWIa, IWIb, CK and MWIs. The factor analysis results showed that CR and MSWI have similar fingerprints, as do IWIb and MWI3. The cluster analysis showed that if a vertical line is cut at a rescaled distance of four, then the PCDD/F congener profiles fall into four groups. The indicators of PCDD/Fs are OCDD, 1,2,3,4,6,7,8-HpCDF, 2,3,4,7,8-PeCDF, and 1,2,3,4,6,7,8-HpCDD. The emission factors of PCDD/Fs herein were from 0.0433

謝誌 I
摘要 II
總目錄 VI
表目錄 VIII
圖目錄 IX

第一章 緒論 1

第二章 文獻回顧 3
2.1 PCDD/Fs之性質 3
2.2 PCDD/Fs之濃度表示 4
2.3 PCDD/Fs之物理化學特性 6
2.4 PCDD/Fs之形成機制 8
2.4.1 de Novo合成反應 8
2.4.2 高溫合成(pyrosynthesis) 9
2.4.3 經由前驅物質之異相觸媒合成(precursor) 9
2.5 環境中PCDD/Fs之來源 10
2.6 國內外露天燃燒之排放PCDD/Fs研究 14

第三章 研究方法 17
3.1固定污染源背景調查 17
3.2露天燃燒採樣規劃 19
3.3 採樣方法 27
3.3.1 煙道廢氣PCDD/Fs採樣 27
3.3.2 大氣PCDD/Fs採樣 27
3.3.3 土壤及灰燼採樣 29
3.4 檢測分析方法 29
3.4.1 煙道廢氣PCDD/Fs檢測分析 29
3.4.2 大氣PCDD/Fs檢測分析 31
3.4.3 土壤及灰燼PCDD/Fs檢測分析 32
3.5 特徵分析(Signature Analyses) 32
3.5.1 階層集群分析法(Cluster Analysis) 32
3.5.2 主成份分析法(Principal Component Analysis) 36

第四章 結果與討論 40
4.1 固定污染源煙道廢氣PCDD/Fs濃度 40
4.2 固定污染源煙道廢氣中 PCDD/Fs特徵剖面 44
4.3 因子分析(Factor Analysis) 46
4.4 階層集群分析(Cluster analysis) 50
4.5 固定污染源煙道廢氣PCDD/Fs指標 52
4.6 各形式固定污染源排放係數探討與比較 54
4.6.1 一般事業廢棄物焚化爐 54
4.6.2 醫療廢棄物焚化爐 54
4.6.3 水泥窯 55
4.6.3 火葬場 55
4.7 農廢蓮霧園與空氣品質監測站燃燒前與燃燒時背景大氣 PCDD/Fs濃度 59
4.8 農廢稻草田與空氣品質監測站燃燒前與燃燒時背景大氣 PCDD/Fs濃度 63
4.9 與國內外相關研究大氣PCDD/Fs濃度結果之比較 67
4.10農廢蓮霧園與農廢稻草田燃燒後土壤與灰燼中之PCDD/Fs含量 72
4.11 與國內外相關研究土壤之PCDD/Fs含量比較 76

第五章 結論與建議 83
5.1 結論 83
5.2 建議 87

參考文獻 88
作者簡歷 105
表目錄
表2-1 PCDD/Fs毒性當量因子 5
表2-2 2,3,7,8-TCDD物理化學特性 7
表2-3 美國境內不同來源之PCDD/Fs年排放量推估表 12
表2-4 台灣重要PCDD/Fs排放源之年排放量 13
表3-1 四座廢棄物焚化爐及水泥窯與火葬場具排放PCDD/Fs潛勢之特定固定污染源之基本資料 18
表3-2 露天燃燒前與燃燒時大氣戴奧辛採樣期程 23
表3-3 露天燃燒大氣採樣點之二度分帶座標 23
表3-4 露天燃燒大氣採樣點詳細基本資料 24
表4-1 六座固定污染源煙道廢氣中PCDD/Fs濃度 42
表4-2六座煙道廢氣中 PCDD/Fs特徵剖面主成分分析結果 48
表4-3 六座固定污染源煙道廢氣前三高之特徵剖面 53
表4-4 本研究不同污染源與其他文獻之PCDD/Fs排放係數 57
表4-5 兩處蓮霧園與空氣品質監測站燃燒前與燃燒時大氣PCDD/Fs濃度 61
表4-6 農廢稻草田與空氣品質監測站燃燒前與燃燒時大氣PCDD/Fs濃度 65
表4-7 本研究和國內不同地區之都市垃圾焚化爐周界大氣中PCDD/Fs濃度比較表 68
表4-8 國外相關文獻中大氣PCDD/Fs濃度 69
表4-9 兩處蓮霧園與一處農廢稻草田燃燒前之土壤與燃燒後之灰燼PCDD/Fs含量 74
表4-10 本研究和國內不同地區焚化廠周界土壤中PCDD/Fs含量比較表 77
表4-11 國外相關文獻中土壤PCDD/Fs含量 78
表4-12 國內外環境土壤中PCDD/Fs含量管制標準 82


圖目錄
圖2-1 PCDD/Fs之結構 4
圖3-1 蓮霧園燃燒之實景 21
圖3-2 稻田燃燒之實景 22
圖3-3 三處農廢露天燃燒採樣點位置圖與風向圖 25
圖3-4 三處農廢露天燃燒採樣點與空氣品質監測站相關位置圖 26
圖3-5 PS-1高量空氣採樣器 28
圖3-6 排放管道中戴奧辛及

英文參考文獻
Adab, E., Caixach, J., Rivera, J. “ PCDD/Fs from emission sources and ambient air in Northeast Spain,” Chemosphere, Vol. 35(3), pp.453-463. 1997.
Abad, E.; J Caixach, O.; Rivera, J.; Gustems, L.; Massagu, G.; Puig, O. “Surveillance Programme on Ddioxin Levels in Ambient Air Sites in Catalonia (Spain)” Chemosphere, Vol.49, pp. 697–702, 2002.
Alcock, R. E.; Gemmill, R.; Jones, K. C. “Improvements to the UK PCDD/F and PCB Atmospheric Emission Inventory following An Emissions Measurement Programme” Chemosphere, Vol. 38, pp. 759-770, 1999.
Bakoglu, M., Karademir A., Durmusoglu E., “Evaluation of PCDD/F levels in ambient air and soils and estimation of deposition rates in Kocaeli, Turkey” Chemosphere, Vol 59, pp. 1373-1385, 2005.
Ballschmiter, K., Zoller, W., Scholtz, C. and Nottrodt, A., “Destruction of PCDD and PCDF in Bleached Pulp by Chlorine Dioxide Treatment”, Chemosphere,Vol.12, pp.585-597,1983
Ballschmiter, K.; Zoller, W.; Buchert, H.; Class, T. F. Z., “ Analytical Chemistry”, Vol. 322, pp. 587, 1985.
Blifford, I. H.; Meeker, G. O. “ A Factor Analysis Model of Large Scale Pollution”, Atmospheric Environment, Vol. 1, pp. 147-157, 1967.
Braga, A. M. C. B., Krauss, T., Santos, C. R. R., “PCDD/F-contamination in a hexachlorocyclohexane waste site in Rio de Janeiro,Brazil”, Chemosphere, Vol46, pp.1329-1333, 2002.
Buekens, A.; Cornelis, E.; Huang, H.; Dewettinck, T. “ Fingerprints of Dioxin from Thermal Industrial Processes” Chemosphere, Vol. 40, pp. 1021-1024, 2000.
Caserini, S.; Monguzzi, A. M. “PCDD/Fs Emissions Inventory in the Lombardy Region: Results and Uncertainties” Chemosphere, Vol.48, pp. 779-786, 2002.
Chen, S. J.; Lee, W. S.; Guo-Ping, C. C.; Wang, L. C.; Lee, W. J., Kao, J.-H. ; Hu, M.T. “Characterizing polychlorinated dibenzo-p-dioxins and dibenzofurans in the surrounding environment and workplace of a secondary aluminum smelter”, Atmospheric Environment, Vol. 38(22) pp.3729-3732, 2004.
Cleverly, D.; Schaum, J.; Winter, D.; Schweer, G.; O'Rourke, K. “The Inventory of Sources of Dioxin in the United States”, Organohalogen Compounds, Vol. 36, pp. 1-6, 1998.
De Jones, A. P. J. M.; Liem, A. K. D.; Hoogerbrugge, R. “Study of Polychlorinated Dibenzodioxins and Furans from Municipal Waste Incinerator Emissions in Netherlands:Analytical Methods and Levels in the Environment and Human Food Chain” Journal of Chromatography, Vol.643, pp.91-106, 1993.
Dickson, L. C.; Lenoir, D.; Hutzinger, O. “ Surface-catalyzed formation of chlorinateddibenzodioxins and dibenzofurans during incineration”, Chemosphere, Vol.19 pp. 277-282, 1989.
Dickson, L. C.; Lenoir, D.; Hutzinger, O. “Quantitative comparison of de Nova and formation of polychlorinated dibenzo-p-dioxins under simulated municipal solid waste incinerator post-combustion conditions, ” Environmental Science and Technology, Vol. 26 pp. 1822-1828, 1992.
Domingo, J. L., Schuhmacher, M., Agramunt, M. C., Llobet, J. M., Rivera, J., Muller, L. “ PCDD/F levels in the neighbourhood of a municipal solid waste incinerator after introduction of technical improvements in the facility,” Environment International, Vol. 28, pp. 19-27, (2002).
Duarte-Davidson, R.; Clayton, P.; Coleman, P.; Davis, B., Halsall, C.;Harding-Jones, P.; Pettit, K.; Woodfield, M. and Jones, K. “Polychlorinated Dibenzo-p-Dioxins and Furans in Urban Air and Deposition in the United Kingdom” Environmental Science and Polluant Research, Vol. 4, pp.262-270, 1994.
Dwernychuk L.W., Cau H.D., Hatfield C.T., Boivin T.O., Hung T.M., Dung P.T., Thai N.D., “ Dioxin reservoirs in southern Viet Nam-a legacy of Agent Orange. ” Chemosphere Vol.47, pp. 117-137.2002.
Dyke, P.; Coleman, P.; James, R. “ Dioxins in Ambient Air, Bonfire Night 1994,” Chemosphere, Vol.34, pp.1191-1201, 1997.
Eduljee, G. H.; Dyke, P. “An Updated Inventory of Potential PCDD and PCDF Emission Sources in the UK” The Science of the Total Environment, Vol. 177, pp. 303-321, 1996.
Eitzer, B. D.; Hites, R. A. “Polychlorinated Dibenzo-p-dioxins and
Dibenzofurans in the Ambient Atmosphere of Bloomington, Indiana ?? Environmental Science and Technology, Vol. 23, pp.1389-1395, 1989.
Eljarrat, E.; Caixach, J.; Rivera, J.; ”Levels of Polychlorinated Dibenzo-p-dioxins and Dibenzofurans in Soil Samples from Spain” Chemosphere, Vol. 44, pp. 1383-1387, 2001.
Fiedler, H., Hutzinger, O. and Timms, C. W., “Dioxins-Sources of Environmental Load and Human Exposure,”Toxicological and Environmental Chemistry, Vol.29, pp. 157-234, 1990
Fiedler, H., “ Sources of PCDD/PCDF and impact on environment ” Chemosphere, Vol.32, pp.335-348, 1996.
Gaus C., Papke O., Dennison N., Hzynes D., Shaw G.R., Connell D.W., Muller J.F., “Evidence for the presence of a widespread PCDD source in coastal sediments and soils form Queensland, ” Australia.Chemosphere Vol.43, pp.544-548. 2001
Gulletta, B.; Touati, A. “ PCDD/F Emissions from Burning Wheat and Rice Field Residue” Atmos. Environ, Vol.37, pp.4893-4899,2003.
Hagenmaier, H.; Kraft, M.; Brunner, H.; Haag, R. “Catalytic Effects of Fly Ash from Waste Incineration Facilities on the Decomposition of Polychlorinated Dibenzo-p-dioxins and Polychlorinated Dibenzofurans” Environmental Science and Technology, Vol. 21, pp. 1080-1084, 1987.
Hagenmaler, H.; Undig, C.; She, J. “Correlation of Environmental Occurance of Polychlorinated Dibenzo-p-Dioxins and Dibenzofurans with Possible Sources” Organohalogen Compounds, pp.271-274, 1993.
Hiester, E.,Bruckmann, p., Bohm, R., Eynck, P., Gerlach, A., Muder, W., Ristoe, H., “Pronounced decrease of PCDD/PCDF burden in ambient air, ” Chemophere, Vol 34, pp.1231-1243, 1997.
Hilscherova, K.; Blankenship, A.L.; Nie, M.; Coady, K.K.; Upham, B.L.; Trosko, J.E.; Giesy, J.P. “Oxidative stress in liver and brain of the hatchling chicken (Gallus domesticus) following in ovo injection with TCDD” Comparative Biochemistry and Physiology, Part C Vol: 136, pp. 29-45, 2003.
Japan Ministry of the Environment, The Environmental Monitoring Report on the Persistent Organic Pollutants (POPs) in Japan. 2002.
Jimenez, B.; Eljarrant, E.; Hernanded, L. M.; Rivera, J.; Gonzalez, L. M. “ Polychlorinated Dibenzo-p-dioxins, Dibenzofurans in Soil near Clinical Waste Incinerators in Mardrin, Spain. Chemometric comparison with Other Pollution Sources and Soils,” Chemosphere, Vol. 32, pp.1327-1348, 1996.
Johnson, R. A.; Wichern, D. W. “ Applied Multivariate Statistical Analysis.” 5th ed., Prentice-Hall , Inc., New Jersey, USA. 2002.
Jolliffe, I. T. “ Principal Component Analysis”, Springer-Verlag, 1986.
Kaupp, H., McLachlan, M. S. “ Atmospheric particle size distributions of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polycyclic aromatic hydrocarbons (PAHs) and their implications for wet and dry deposition”, Atmospheric Environment, Vol. 31, pp.86-95, 1998.
Kim, E. J.; Oh, J. E.; Chang, Y. S. “Does Forest Fire Increase the PCDD/Fs Level in Soil?” Organohalogen Compd. Vol.50, pp.386-389, 2001.
Kim, B.H., Lee, S.J., Mun, S.J., Chang, Y.S. “A case study of dioxin monitoring in and around an industrial waste incinerator in Korea.” Chemosphere Vol.58, pp.1589-1599, 2005.
Launhardt, T.; Thoma, H., “Investigation on Organic Pollutants from a Domestic Heating System Using Various Solid Biofuels” Chemosphere, Vol. 40, pp. 1149-1157,2000.
Lee, W. S.; Chang Chien, G. P.; Chen, S. J.; Wang, L. C.; Lee, W.-J. ; Wang, Y.-H. “Removal of Polychlorinated Dibenzo-p-dioxins and Dibenzofurans in Flue Gases by Venturi Scrubber and Bag Filter ” Aerosol and Air Quality, Vol.4(1): pp. 27-37, 2004.
Lee, W. S.; Guo-Ping, C. C.; Wang, L. C. “Emissions of Polychlorinated Dibenzo-p-Dioxins and Dibenzofurans from Stack Gases of Electric Arc Furnaces and Secondary Aluminum Smelters ” Journal of the Air & Waste Management Association, Vol.55: pp.219-226,2005.
Lin, L. F.; Lee, W. J.; Li, H. W.; Wang, M. S.; Chang-Chien, G. P. Characterization of Polychlorinated Dibenzo-p-dioxins and Dibenzofurans in the Stack Flue Gases of Coal-fired Power Plants; Chemosphere 2007, Accepted.
Lohmann, R.; Nelson, E.; Eisenreich, S.; Jones, K. C. “Evidence for Dynamic Air-Water Exchange of PCDD/Fs: A Study in the Rarttan Bay/HudsonRiver Estuary” The Science of the Total Environment, Vol. 34, pp.3086-3093, 2000.
Lohmann, R.; Brunciakb, P. A.; Dachsb, J.; Gigliottib, C. L.; Nelsonb, E.;Ryb, D. V.; Glennb, T.; Eisenreichb, S. J.; Jonesa, J. L.; Jones, K. C.“Processes Controlling diurnal Variations of PCDD/Fs in the NewJersey Coastal Atmosphere?? Atmospheric Environment, Vol. 37,pp.959-969, 2003.
Lorber, M.; Pinsky, P.; Gehring, C. and Sovocool, W.,“Relationships between Dioxins in Soil, Air, Ash and Emissions from a Municipal Solid Waste Incinerator Emitting Large Amounts of Dioxin”, Chemosphere, Vol. 37, pp. 2173-2197, 1998.
Luijk, R.; Akkerman, D. M.; Slot, P.; Olie, K.; Kapteijn, F. “Mechanism of Formation of Polychlorinated Dibenzo-p-dioxins and Dibenzofurans in the Catalyzed Combustion of Carbon”, Environmental Science and Technology, Vol. 28, pp.312-321,1994.
Mandalakis, M.; Tsapakis, M.; Tsoga, A.; Stephanou, E.G. “Gas-Particle concentrations and distribution of Aliphatic Hydrocarbons ” Atmospheric Environment, Vol. 36, pp.4023-4035, 2002.
Milligan, M. S.; Altwicker, E. “The Relationship between de Novo Synthesis of Polychlorinated Dibenzo-p-dioxins and Dibenzofurans and Low-Temperature Carbon Gasification in Fly Ash ” Environmental Science and Technology, Vol. 27, pp.1595-1601, 1993.
Ogura, I.; Masunaga, S; Nakanishi, J. “Atmospheric Deposition of Polychlorinated Dibenzo-p-dioxins, Polychlorinated Dibenzofurans, and Dioxin-Like Polychlorinated Biphenyls in the Kanto Region, Japan?? Chemosphere, Vol. 44, pp. 1473-1487, 2001.
Oh, J. E.; Lee, K. T.; Lee, J. W.; Chang, Y. S. “The Evaluation of PCDD/Fs from Various Korean Incinerators”, Chemosphere, Vol. 38, pp. 2097-2108, 1999.
Oh, J.-E.; Choi, J.-S.; Chang, Y.-S.; “Gas/particle partitioning of polychlorinated dibenzo-p-dioxins and dibenzofurans in atmosphere; evaluation of predicting models” AtmosphericEnvironment, Vol. 35, pp. 4125-4134, 2001.
Park, Jin-Soo; Kim, Jong-Guk “Regional measurements of PCDD/PCDF concentrations in Korean atmosphere and comparison with gas–particle partitioning models” Chemosphere Vol: 49, pp. 755-764, 2002.
Prange J.A., Gaus C., Papke O., Muller J.F., “ Investigations into the PCDD contamination of topsoil, river sediments and kaolinite clay in Queensland, Australia. ” Chemosphere Vol: 46, pp. 1335-1342.2002.
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