多環芳香烴(polycyclic aromatic hydrocarbons,PAHs)是環境中常見的有機汙染物，會透過海氣交換的機制進行傳輸；本研究的主旨在於量化高屏海域地區，海水及近岸空氣中的多環芳香烴濃度，再套用Whitman’s two-film模式計算交換通量，並藉由採樣策略來得到時間和空間的變化趨勢。此外，研究中亦利用空氣中顆粒相濃度來推估乾沉降通量。
高屏海域的季節性通量介於-2020 ~ +320 ng/m2day之間，除了小琉球皆為吸收通量之外，在高雄港、壽山近岸、高屏溪河口的交換通量呈現8、11、3月為吸收，5月為揮發的趨勢，而比對區-蘭嶼的交換趨勢則與高屏海域截然不同，皆是呈現揮發通量，範圍介於+121 ~ +1020 ng/m2day之間；低分子量的acenapthylene、acenapthene、fluorene是較偏向揮發，其餘分子量較高的化合物則是以吸收為主，其中又以phenanthrene的吸收通量最大，主導了整體的交換趨勢。
各地區的淨交換通量，以小琉球為最高(-1650 ng /m2day)，其次為高屏溪河口(-932 ng /m2day)、高雄港(-824 ng /m2day)、壽山近岸(-523 ng /m2day)，蘭嶼地區則為揮發通量(+358 ng/m2day)；在乾沉降的通量部份，季節性變化是以11、3月較高，而化合物則是以容易附著於顆粒上的高分子量化合物為主；若再加上濕沉降的影響，兩者總和仍遠低於交換通量，因此整體而言，多環芳香烴進入高屏海域的方式是以交換吸收為主。
利用各樣品的化合物組成分析，溶解相樣品的來源多數為交通排放，而高雄港有較多的石油及工業污染來源，蘭嶼則偏向植物燃燒及石油來源；氣相方面則多數屬於燃燒來源，包含交通和柴油來源；而透過大氣逆軌跡的路線可以得知在蘭嶼及高屏海域的8、5月是以地區性的汙染源為主，而高屏海域的11、3月則有受到本島內陸的影響，長程傳輸則發生在3月的高屏海域和蘭嶼。

Polycyclic aromatic hydrocarbons(PAHs) are one of major classes of organic pollutants that transport through air-sea exchange in the environment. The objectives of this study were to quantify the PAHs concentrations in air and seawater and calcu-late the exchange fluxes by using Whitman’s two-film mode. Spatial and temporal distributions were also determined through the sampling strategy of this study. In ad-dition, particulate concentrations in the ambient air were used to estimate the dry de-position fluxes of PAHs.
Seasonal fluxes of PAHs in Gao-Ping coastal areas ranged from -2020 to +320 ng/m2day. The net gas exchange fluxes were negative (net absorption) in August, No-vember and March but positive (net volatilization) in May at Kaohsiung Harbor (KH), Off Shore (OFS) and Gao-ping River Estuary (GRE). Howerer negative exchange fluxes were found in each sampling month at Liu-Chiu Isle (LCI). In contrast, Lanyu Isle (LI) showed a different tend in exchange fluxes. It’s exchange fluxes were all positive in each sampling month and ranged from the +121 to +1020 ng/m2day. Mostly the net fluxes of low molecular weight PAHs were volatile; while high molecular weight PAHs were absorptive. The compound with highest flux was mostly phenanthrene, therefore, it dominates the gas exchange fluxes in Gao-Ping coastal areas.
The highest average net gas exchange fluxes among stations were observed at LCI (-1650 ng/m2day) and decreased in the following order: GRE (-932 ng/m2day), KH (-824 ng/m2day), OFS (-523 ng/m2day), LI (+358 ng/m2day). Dry particle deposi-tion fluxes were higher in November and March. The high molecular weight PAHs were found predominant in these particles. Even adding up with the wet deposition, the magnitude of total deposition fluxes(dry+wet) were still lower than those of gas exchange. Therefor, gas exchange is the main transport pathway for PAHs in Gao-Ping coastal areas.
By identifying composition patterns of PAHs in each sample, source of PAHs in dissolved phase were mainly from traffic emission. However, KH is indicative of in-dustrial and petrogenic souces; while grass and wood combustion and petrogenic might be the dominant source of PAHs at LI. In gas phase, sources of PAHs were mostly from combustion, including traffic emission and diesel combustion. Finally, the transport pathway of the airflow was analyzed through back trajectory analysis. The results show that the PAH concentrations in gas phase might be affected by re-gional pollution in August and May, and long-rang atmospheric transport in March at Gao-Ping coastal areas and LI. Local origin was suggested for PAHs from Gao-Ping coastal areas in November and March.

論文審定書i
謝誌ii
摘要iii
Abstract iv
目錄vi
圖目錄ix
表目錄xi
附錄xii
第一章 前言 1
1.1 研究動機 1
1.2 研究目的2
第二章 文獻回顧 3
2.1 多環芳香烴之特性3
2.2 多環芳香烴之來源 6
2.3 化學指紋鑑定 6
2.4 傳輸特性 7
2.5 水氣交換通量8
2.6 高屏海域背景8
第三章 研究方法 10
3.1 研究流程 10
3.2 採樣設計 11
3.3 材料與儀器14
3.3.1 材料14
3.3.2 儀器14
3.4 樣品之採樣與保存15
3.4.1 空氣樣品 15
3.4.2 海水樣品 15
3.5 分析方法 16
3.5.1 樣品分析 16
3.5.2 量化 19
3.6 品保及品管(QA/QC) 19
3.7 水氣交換通量模式20
3.7.1 雙膜模式 20
3.7.2 通量計算 21
3.7.3 亨利常數 22
3.7.4 通量計算之衍生誤差 23
3.8 主成分及群集分析24
3.9 大氣逆軌跡模式25
第四章 研究結果 26
4.1 海水溶解相多環芳香烴濃度 26
4.2 空氣氣相多環芳香烴濃度31
4.3 空氣與海水中顆粒相濃度分佈33
4.4 來源判斷分析37
4.4.1 化學指紋特徵37
4.4.2 主成分及群集分析42
4.4.3 大氣逆軌跡55
4.5 海氣交換通量58
4.5.1 通量趨勢58
4.5.2 敏感度分析67
4.5.3 乾沉降通量67
4.5.4 通量比較72
4.6 計算參數之影響75
4.6.1 質量傳輸係數75
4.6.2 亨利常數78
第五章 結論及建議 80
5.1 結論 80
5.2 建議82
參考文獻83

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中央氣象局，2010，中央氣象局 氣候統計資料.

方孟德，2007，多環芳香烴、多氯聯苯及六氯苯化合物於高雄港區海氣交換通量之研究，國立中山大學海洋環境及工程研究所博士論文。

巫思佩，2006，高屏河海系統多環芳香碳氫化合物之分佈及通量研究，國立中山大學海
洋環境及工程研究所碩士論文。

陳凱亭，2010，高雄港內水域多環芳香烴與多氯聯苯含量分佈，國立中山大學海洋環境
及工程研究所碩士論文。

陳健民，2007，環境毒物學，新文京開發，台北縣

陳鎮東，1994，海洋化學，茂昌圖書有限公司

經濟部水利署，2010，高屏溪基本資料

蔡詠安，2002，氣象條件與臭氧事件日相關性之探討:以高高屏地區為例，國立中山大
學環境工程研究所碩士論文