本研究針對污染源及大氣中戴奧辛/呋喃(PCDD/Fs)之特徵進行探討，參考世界各主要工業國家其最大之PCDD/Fs排放源，並考量國內社會與經濟之活動，選擇台灣地區本土13座大型都市垃圾焚化爐、5座醫療廢棄物焚化爐、4座燒結爐、4座電弧爐、4座二次鋁精煉廠與2座火葬場進行PCDD/Fs排放之研究，以建立國內重要PCDD/Fs排放源之排放係數並推估臺灣地區PCDD/Fs之年排放量。此外亦以主要成分分析法探討廢棄物中氯含量與PCDD/Fs生成機制之關係。最後評估都市垃圾焚化爐所排放PCDD/Fs對大氣環境之影響。所得結論歸納如下：1.都市垃圾焚化爐、醫療廢棄物焚化爐、使用SCR之燒結爐、無SCR之燒結爐、電弧爐、二次鋁精煉廠及火葬場煙道廢氣PCDD/Fs之排放係數分別為0.0961、20.0、0.970、3.13、1.82、21.5 μg I-TEQ/ton-(waste or feedstock)及9.86 μg I-TEQ/body。2.台灣都市垃圾焚化爐、醫療廢棄物焚化爐、燒結爐、電弧爐、二次鋁精煉廠及火葬場等重要PCDD/Fs排放源之年排放量分別為0.750、0.369、44.7、19.9、9.52與0.838 g I-TEQ/year。在台灣地區這六種重要排放源排放PCDD/Fs至大氣之年排放量合計為76.1 g I-TEQ/year。若考慮其佔總固定污染源排放量之60～80％，則每年台灣地區固定污染源排放PCDD/Fs至大氣之量預估約為95.1～127 g I-TEQ/year。本研究結果亦顯示，台灣都市垃圾焚化爐之PCDD/Fs年排放量與金屬冶煉業之值比較起來顯的非常小，此現象與其他先進國家不同。其原因為台灣地區對都市垃圾焚化爐實施嚴格之PCDD/Fs排放標準(0.1 ng I-TEQ/Nm3)。3. 以質量與毒性之觀點來看，選擇性觸媒轉換器(SCR)對總PCDD/Fs之去除率分別為75.4％與69％。大部分的PCDD/Fs已被SCR分解而不僅是將PCDD/Fs去氯化作用。4. 都市垃圾焚化爐與醫療廢棄物焚化爐之指標PCDD/Fs分別為OCDD、1,2,3,4,6,7,8-HpCDD、OCDF與1,2,3,4,7,8,9-HpCDF、1,2,3,7,8-PeCDF、OCDF；金屬冶煉之指標PCDD/Fs則為2,3,7,8-TeCDF、1,2,3,7,8-PeCDF、2,3,4,7,8- PeCDF。5. 當廢棄物中氯含量低於0.8% - 1.1%閥值時，PCDDs具有生成之優勢，然而，當廢棄物中氯含量高於0.8% - 1.1%閥值時，PCDFs具有生成之優勢，原因可能與當PCDD/Fs由PAHs生成時，PCDFs之生成速率高於PCDDs有關。6. 國家空氣品質背景監測站大氣中PCDD/Fs濃度為0.00634 pg I-TEQ/Nm3。7. 火葬場對周遭大氣之影響較焚化廠來的顯著，其原因為缺乏空氣污染防治設備及煙囪高度太低，使煙道廢氣擴散不佳所致。8. 台灣南部地區七座空氣品質監測站大氣PCDD/Fs平均濃度為0.0931 pg I-TEQ/Nm3，與KC與KS焚化廠最大著地濃度處大氣PCDD/Fs平均濃度相近，但約為大氣PCDD/Fs背景濃度之15倍。此結果顯示台灣南部地區具有PCDD/Fs之污染排放源。9. 由主要成份分析、階層集群分析與指標PCDD/Fs可知，台灣南部地區大氣之主要疑似PCDD/Fs污染源為金屬冶煉，而交通污染源對大氣中PCDD/Fs之影響亦不可忽視。

This study investigates the characteristics of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from emission sources and in the atmosphere. By consulting the PCDD/F inventories of other countries, 13 municipal solid waste incinerators (MSWIs), five medical waste incinerators (MWIs), four sinter plants, four electric arc furnaces (EAFs), four secondary aluminum smelters (secondary ALSs) and two crematories were chosen to investigate after considering the social and industrial activities in Taiwan. The emission factors of PCDD/Fs from the stack flue gases of these emission sources were determined and the overall PCDD/F emission quantities to the atmosphere in Taiwan is estimated. In addition, this study attempts to clarify the effects of chlorine content in the waste on the formation mechanisms of PCDD/Fs in full scale incinerators by using the principal component analysis (PCA) to compare the congener profiles of PCDD/Fs in the stack flue gases. Finally, the influence by the emission of MSWIs on the atmosphere are assessed. The conclusions of this study are summarized as follows. 1. The emission factors of PCDD/Fs from the stack flue gases of MSWIs, MWIs, sinter plants with selective catalytic reduction (SCR), sinter plants without SCR, EAFs, secondary ALSs and crematories are 0.0961、20.0、0.970、3.13、1.82、21.5 μg I-TEQ/ton-(waste or feedstock) and 9.86 μg I-TEQ/body, respectively. 2. In Taiwan, the annual emissions of PCDD/Fs from MSWIs, MWIs, sinter plants, EAFs, secondary ALSs and crematories are 0.750、0.369、44.7、19.9、9.52 and 0.838 g I-TEQ/year; the estimated total annual emission of PCDD/Fs from these six important sources is 76.1 g I-TEQ/year. Considering that it represents 60-80% of the total PCDD/F emissions, the total PCDD/F emissions into the atmosphere in Taiwan is estimated as 95.1-127 g I-TEQ/year. These results reveal that the annual emissions of PCDD/Fs from MSWIs are very minor to those of metallurgical processes since strict emission limit have been applied to MSWIs in Taiwan. 3. PCDD/Fs are indeed decomposed (75.5% and 69% on ng and ng TEQ bases, respectively) by SCR and not only reduced in degree of chlorination. 4. The indicatory PCDD/Fs of MSWIs and MWIs are OCDD, 1,2,3,4,6,7,8-HpCDD, OCDF and 1,2,3,4,7,8,9-HpCDF, 1,2,3,7,8-PeCDF, OCDF, respectively; while those of metallurgical processes are 2,3,7,8-TeCDF, 1,2,3,7,8-PeCDF and 2,3,4,7,8- PeCDF. 5. When the chlorine level in the feeding waste is below the threshold value at 0.8% - 1.1%, the formation of PCDDs dominates. While the chlorine level in the feeding waste exceeds this threshold, the rates of formation of PCDFs increase faster than those of PCDDs, probably because when PCDD/Fs are formed from PAHs, the formation rates of PCDFs are higher than those of PCDDs. 6. The PCDD/Fs concentration in the atmosphere of background area is 0.00634 pg I-TEQ/Nm3. 7. The impact of the crematories to the surrounding environment was greater than that of MSWIs because the crematory had a low stack and installed without appropriate air pollution control devices. 8. The mean PCDD/Fs concentration of air quality monitoring stations was 0.0931 pg I-TEQ/Nm3, which was close to that of maximum ground concentrations of MSWIs and 15 times higher than that of background area. It revealed that PCDD/Fs emission sources existed in southern Taiwan. 9. By using PCA, cluster analysis and indicatory PCDD/Fs, the metallurgical processes were identified as the dominating PCDD/Fs emission sources in southern Taiwan, meanwhile, the influence of mobile sources can not be ignored.

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