高雄地區人口密集，兼具國際港埠，並為我國工業重鎮，石化、鋼鐵等產業密集，汽機車密度亦高。由於南部地區日照強度大，各類污染源所排放之揮發性有機物易產生光化反應，而造成高臭氧濃度之問題。

本研究於高雄市2004年冬季選定3天在楠梓及小港站同步測量上午(07-10)、下午(13-16)及傍晚(18-21)時段之大氣63種碳氫化合物(HC) 。結果顯示高雄大氣中以甲苯濃度最高平均濃度(43.01-60.95 μg/m3)，其次是異戊烷(i-pentane)、1,2,4-三甲基苯(1,2,4-trimethylbenzene)、苯(benzene)、正丁烷(n-butane)、丙烷(propane)及乙炔(acetylene)等物種，其濃度為9.55 -16.93 μg/m3，其中鹵素類碳氫化合物(halocarbons)濃度約為0.17-4.12 μg/m3。若以有機物成分(重量百分比)來區分則以烷類(44.7-45.9%)比例最高，其次為芳香族(35.4-36.8%)、烯類(10.5-10.9%)及鹵素類(3.6-3.9%)。

大氣中各HC物種之臭氧生成潛勢分析(OFP)以最大增量反應進行推估，結果顯示芳香族(45.9-54.3%)臭氧潛勢最高，其次為烯類(17.7-37.5%)及烷類(16.5-23.6%)。以因子分析來探討高雄市區大氣揮發性有機物可能來源，結果顯示移動源排放、工業源、表面塗裝/溶劑揮發等、燃燒、石化燃料等為主要污染來源。

Kaohsiung is a densely populated harbor city, in which the density of motor vehicles is also high. Since the temperature and sunlight is also relatively high in Southern Taiwan, tending to transform ambient volatile organic compounds to ozone thus causes high ozone events.

This study measured the concentrations of 63 hydrocarbon (HC) species from C2 to C15 simultaneously at the Nan-Chie and Hsiung-Kong sites in Kaohsiung city during the morning (07-10), the afternoon (13-16), and the evening (18-21) periods on three successive days in winter 2004. Results show that the most abundant species of Kaohsiung’s air is toluene (43.01-60.95 μg/m3), followed by i-pentane, 1,2,4-trimethylbenzene, benzene, n-butane, propane, and acetylene, in the range 9.55-16.93 μg/m3, while the concentrations of halocarbons is 0.17-4.12 μg/m3. Alkanes (44.7-45.9%) represent the largest proportion of the total HC, followed by aromatics (35.4-36.8%), alkenes (10.5-10.9%) and halocarbons (3.6-3.9 %).

The OFP (ozone formation potential) of HC species were evaluated based on the MIR (maximum incremental reactivity). Results show that aromatics (45.9-54.3%) represent the largest proportion of the OFP, followed by alkenes (17.7-37.5%), and alkanes (16.5-23.6%). The results from the factor analyses show the major sources of ambient HC in Kaohsiung city are the vehicle exhausts, industrial processes, solvent evaporations, combustion exhausts, and petrochemical processes.

目 錄
謝誌 I
摘要 II
ABSTRACT III
目錄 IV
表目錄 VI
圖目錄 VII
附表目錄 VIII


第一章 前言 1-1
1.1 研究動機 1-1
1.2 研究內容 1-1
第二章 高雄市近年空氣品質趨勢及氣象背景資料述 2-1
2.1 空氣品質PSI變化趨勢 2-1
2.2 各空氣污染物濃度變化趨勢 2-2
2.3高雄市空氣污染物排放量概估 2-7
2.4 高雄地區歷年氣象概述 2-9
第三章 文獻回顧 3-1
3.1 大氣中揮發性有機物(VOC) 來源及排放特性 3-1
3.1.1固定源揮發性有機物排放特性 3-2
3.1.2移動源揮發性有機物排放特性 3-5
3.1.3自然源揮發性有機物排放特性 3-6
3.2大氣中揮發性有機物之影響 3-8
3.2.1揮發性有機物之危害性 3-8
3.2.2揮發性有機物與光化學煙霧之聯 3-13
3.2.3揮發性有機物光化反應性度量 3-15

3.2.4最大增量反應性 (Maximum Incremental Reactivities, MIR) 3-18
3.3 揮發性有機物監測分析 3-21
3.3.1 測站位置之選定 3-21
3.3.2 揮發性有機物監測物種 3-22
3.4主成分/因子分析 3-23
第四章 研究方法與步驟 4-1
4.1 研究架構與流程 4-1
4.2 現場採樣及分析 4-2
4.2.1大氣揮發性有機物採樣規劃 4-2
4.2.2採樣設備與程序 4-4
4.2.3 分析儀器與條件 4-6
4.3 品保及品管結果 4-8
4.3.1品保及品管作業 4-8
4.3.2 檢量線之品保及品管結果 4-10
4.4 因子分析之理論基礎 4-14
第五章 結果與討論 5-1
5.1大氣NMHC、臭氧及NOX濃度變化趨勢 5-1
5.1.1 監測站之氣象條件 5-1
5.1.2監測站污染源及地理位置分布概況 5-4
5.1.3監測站NMHC、臭氧及NOX監測值之變化趨勢 5-6
5.2大氣中揮發性有機物濃度及成分特徵分析 5-8
5.2.1大氣揮發性有機物濃度之變化 5-8
5.2.2大氣揮發性有機物成分特徵結構之變化 5-14
5.3楠梓站及小港站臭氧生成潛勢分析 (Ozone Formation Potential,OFP) 5-17
5.4 因子分析推估高雄市VOC污染來源 5-21


第六章 結論與建議 6-1
6-1結論 6-1
6-2建議 6-2

參考文獻 參-1
附錄A 大氣揮發性有機物採樣原始濃度數據 附A-1
附錄B 國內臭氧防制經驗及相關法規附 附B-1




表 目 錄

表2.3-1 民國89年高雄市各污染源排放總表 2-8
表2.4-1 高雄地區近十年各月份平均氣象資料統計表 2-11
表3.1-1 揮發性有機物(VOC)排放源 3-3
表3.1-2 高屏空品區固定與移動污染源排放量 3-4
表3.2-1 有害空物污染物(Hazardous air pollutants, HAPs) (1/4) 3-9
表3.2-1 有害空物污染物(Hazardous air pollutants, HAPs) (2/4)...... 3-10
表3.2-1 有害空物污染物(Hazardous air pollutants, HAPs) (3/4)….. 3-11
表3.2-1 有害空物污染物(Hazardous air pollutants, HAPs) (4/4)........3-12
表3.2-2 依據VOC參與光化學反應活性分類(HMSO,1991).............3-17
表3.2-3 最大增量反應性(MIR)反應尺度資料表(1/2)…………........3-19
表3.2-3 最大增量反應性(MIR)反應尺度資料表(2/2)…………........3-20
表3.3-1 美國環保署PAMS監測物種………………………………..3-22
表4.2-1 大氣HC分析物種 (63種)………………….…………….….4-3
表4.2-2 吸附管之組成及特性…………………………………….…...4-5
表4.2-3 氣相層析儀(GC/FID)之操作條件…………………………....4-6
表4.3-1 標準品檢量線 (大氣HC) (1/3)……………………….……..4-11
表4.3-1 標準品檢量線 (大氣HC) (2/3)……………..…………….....4-12
表4.3-1 標準品檢量線 (大氣HC) (3/3)…………..……………........4-13
表5.1-1 採樣期間楠梓站及小港站之氣象條件………………………5-2
表5.1-2 高雄市區空氣品質監測網測站環境資料一覽表……………5-5
表5.2-1 2004年冬季楠梓站及小港站之63種HC平均濃度及標準偏差(1/2)………………………………………………………………….…5-10
表5.2-1 2004年冬季楠梓站及小港站之63種HC平均濃度及標準偏差(2/2)…………………………………………………………………….5-11
表5.3-1 楠梓測站及小港測站之臭氧生成潛勢量(OFP) 5-19
表5.4-1 高雄市2001年NMHC 之排放量 (噸/年) (DEP, 2002) 5-21
表5.4-2 高雄市列管石化廠之VOC排放量 (慧群，2001)………….5-22
表5.4-3 楠梓站之HC平均濃度因子分析結果(1/2)…………………5-26
表5.4-3 楠梓站之HC平均濃度因子分析結果(2/2)…………………5-27
表5.4-4 小港站之HC平均濃度因子分析結果(1/2)…………………5-28
表5.4-4 小港站之HC平均濃度因子分析結果(2/2)…………………5-29

圖 目 錄

圖2.1-1 高屏地區空氣品質現況(84-93年) 2-1
圖2.1-2 高雄市一般測站84年至93年PSI＞100指標污染物逐月變圖……………………………………………………...............2-2
圖 2.2-1 高屏地區84-93年逐月PM10濃度變化…………………....2-2
圖 2.2-2 高屏地區84-93年逐月SO2濃度變化 2-3
圖 2.2-3 高屏地區84-93年逐月NO2濃度變化 2-3
圖 2.2-4 高屏地區84-93年逐月O3濃度變化 2-4
圖 2.2-5 高屏地區84-93年逐月CO濃度變化 2-4
圖 2.2-6 高雄市各測站PM10逐月濃度變化趨勢 (1/2) 2-5
圖2.2-7 高雄市各測站PM10逐月濃度變化趨勢 (2/2) 2-6
圖3.1-1 民國89年高屏空品區固定與移動源NMHC排放百分比 3-4
圖3.2-1 光化反應流程圖 3-14
圖3.3-1 美國環保署之光化評估監測站之示意圖 3-21
圖4.1-1 研究架構與流程 4-1
圖4.2-1 採樣設備示意圖(a)多層吸附管(b)濃度穿透實驗 4-4
圖4.2-2 氣相層析質譜儀升溫程式示意圖 4-6
圖5.1-1 (a)楠梓站及(b)小港站於2004年12月21-23日之上午(07-10時)、下午 (13-16時) 及傍晚(18-21時)風花圖 5-3
圖5.1-2 高雄市區VOC監測站及周界環境示意圖 5-5
圖5.1-3楠梓監測站NMHC、臭氧及NOX變化圖 5-7
圖5.1-4小港監測站NMHC、臭氧及NOX變化圖 5-7
圖5.2-1 (a) 楠梓(b) 小港站之THC日濃度變化圖 5-12
圖5.2-2 楠梓站主要20種VOCs成分特徵 5-13
圖5.2-3 小港站主要20種VOCs成分特徵 5-13
圖5.2-4 2004年12月21-23日C2-C15 不同時段之濃度變化圖(a)楠梓站(b)小港站 5-15
圖5.2-5 2004年冬季之ethylene,i-pentane,benzene and toluene與acetylene 濃度之關係圖(a)楠梓站(b)小港站(實現為迴歸分析線) 5-16
圖5.3-1 採樣期間16種物種實測濃度與臭氧生成潛勢量之關係圖(a)楠梓站(b)小港站 5-20
5-25
附 表 目 錄
附表A-1 楠梓大氣揮發性有機物原始濃度數據 附A-1
附表A-2 小港大氣揮發性有機物原始濃度數據 附A-2

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