為瞭解台灣南部地區大氣中戴奧辛／呋喃及多氯聯苯之分佈特性，本研究分別選定一處工業區、兩處都會區以及一處郊區等三種不同性質之地區進行戴奧辛／呋喃及多氯聯苯之採樣分析，並利用氣固相分佈模式及乾沉降模式進行模擬，進一步得到大氣中戴奧辛／呋喃及多氯聯苯之氣固相分佈、乾沉降通量與乾沉降速度。研究結果顯示，大氣中戴奧辛／呋喃及多氯聯苯之濃度及毒性當量濃度皆以都會區為最高，其次是工業區及郊區，且多氯聯苯之濃度在四個地區中皆高於戴奧辛／呋喃，但若以毒性觀點論之，多氯聯苯之毒性當量濃度遠低於戴奧辛／呋喃，表示大氣中有害空氣汙染物之毒性主要是由戴奧辛／呋喃所主導。分別繪製兩種汙染物的特徵剖面可看出兩種汙染物分別以1,2,3,4,6,7,8-HpCDD, OCDD, 1,2,3,4,6,7,8-HpCDF, OCDF 以及PCB#77 (4CL), PCB#105 (5CL), PCB#118 (5CL)等異構物所含的比例較高。進一步研究大氣中兩種汙染物之氣固相分佈發現，除了少數較低氯數取代之異構物(4-5Cl PCDD/Fs)，固相之戴奧辛／呋喃在實測值與模擬值中皆佔有較高之比例，平均約72.68-75.03%。反觀多氯聯苯，於實測值中由氣相之異構物較佔優勢，但於模擬值中，少數較高氯數取代之異構物如PCB#169 (6CL)以及PCB#189 (7CL)卻在固相佔有極高的比例，平均約65.86-74.15%。此外，根據模擬值與實測值比較之結果，採樣分析時的人為誤差有顯著之影響，以致無法忽略。在乾沉降通量的部分，秋季中戴奧辛／呋喃之乾沉降通量以及估算之逐月乾沉降通量皆高於春季，顯示乾沉降通量與氣溫呈現負相關，而多氯聯苯之乾沉降通量也有相同的趨勢，推測為兩者之物化特性相似所造成。此外，兩種汙染物之乾沉降通量主要由粒狀物沉降為主，推測主要原因為兩種汙染物之粒狀物相乾沉降速度(戴奧辛／呋喃為0.506-0.571 cm/s，多氯聯苯為2.83-5.49 cm/s)遠大於兩者之氣相乾沉降速度(0.010 cm/s)。分別計算個別異構物之乾沉降速度可發現，個別異構物之乾沉降速度在秋季與春季均隨著異構物之氯取代數的增加而增加，且較高氯數取代之異構物與較低氯數取代之異構物間有明顯之速度差異(戴奧辛／呋喃平均相差約3.9-4.8 倍，多氯聯苯則平均相差約7.7-9.3 倍)。

This study investigates the characteristics of polychlorinated dibenzo-p-dioxins, dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs) in the atmosphere of southern Taiwan. The ambient air was collected seasonally in four areas including industrial area, urban area A, urban area B as well as rural area to determine the concentrations of PCDD/Fs and PCBs. Gaseous and particulate
concentrations were both obtained by measurement and simulation, and dry deposition fluxes and velocities were also developed. PCDD/F, PCB and their I-TEQ concentrations in urban area B were both the highest of all areas in fall and spring, followed by urban area A, industrial area and rural area. All PCB concentrations were higher than PCDD/Fs, but all the I-TEQ concentrations of PCBs were 10 times lower than PCDD/Fs. This result shows that PCDD/Fs
dominated the toxicity in the atmosphere. The PCDD/F and PCB congener profiles of four different areas all show that 1,2,3,4,6,7,8-HpCDD, OCDD, 1,2,3,4,6,7,8-HpCDF and OCDF; PCB#77 (4CL), PCB#105 (5CL) and PCB#118 (5CL) were dominant respectively. The particle-phase PCDD/Fs dominated the partition in both measured and simulated data (average of 72.68-75.03%) except the lowly chlorinated congeners (4-5Cl PCDD/Fs). In terms of PCBs, the particle-phase PCBs contributed little in measured data, but the congeners which were highly chlorinated such as PCB#169 (6CL) and PCB#189 (7CL) were dominant in simulated data (average of 65.86-74.15%). The results form PCBs were quite different with PCDD/Fs. Additionally, the artifacts during sampling work due to the adsorption and blow-off mechanism were not fewer enough to neglect. The total dry deposition flux and estimated monthly dry deposition flux of PCDD/Fs in fall were both higher than in spring. It demonstrates that the dry deposition flux of PCDD/Fs decrease as the temperature increase. The trend of PCBs was the same as PCDD/Fs. It might due to the similar physical and chemical properties of PCDD/Fs and PCBs. Moreover, the dry deposition of PCDD/Fs and PCBs were mainly contributed by particle-phase compounds. This is probably due to the significantly higher
deposition velocity of particle-phase PCDD/Fs (0.506-0.571 cm/s) and PCBs (2.83-5.49 cm/s) than the gas-phase (0.010 cm/s). Dry deposition velocities of individual congeners increased as the chlorine number increased in both fall and
spring, and there was a significant difference between highly and lowly chlorinated congeners (differences of PCDD/Fs and PCBs were 3.9-4.8 and 7.7-9.3 times respectively).

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