本研究探討高雄市臭氧敏感物種與光化指標之研究探討，以易發生臭氧事件日之高雄區為研究區域，量測民國91年至92年間大氣中秋季、冬季與春季之H2O2與HNO3濃度且計算光化指標H2O2/HNO3 與O3/HNO3比值，並配合光化煙霧產量模式(SPM)，來判斷高雄市區臭氧之生成屬於VOC控制或NOX控制。
H2O2與HNO3濃度逐時濃度量測結果顯示，H2O2濃度以中午時段(12：00~15：00)達最高值，HNO3濃度則以中午時段(12：00~15：00)達最低值。在季節變化上以秋季濃度最高，其次為春季和冬季。經由統計分析顯示，臭氧濃度與溫度及日照強度呈正相關，但與NOX、NO及NO2呈負相關。
本研究以實地採樣分析H2O2/HNO3和O3/HNO3兩組光化指標，以Silman(1997)所建立之界定比值( H2O2/HNO3=0.3~0.6； O3/HNO3=12-16)，高雄市秋季小港VOC控制比例為62.5﹪、58.3﹪，秋季楠梓VOC控制比例為47.8﹪、69.6﹪，秋季前金VOC控制比例為33.3﹪、70.8﹪。高雄市冬季小港VOC控制比例為80.9﹪、66.7﹪，冬季楠梓VOC控制比例為54.2﹪、41.7﹪，冬季前金VOC控制比例為70.8﹪、45.8﹪。高雄市春季小港VOC控制比例為52.4﹪、80.9﹪，春季楠梓VOC控制比例為50.0﹪、66.7﹪，春季前金VOC控制比例為35.7﹪、28.6﹪。
另外利用Blanchard (1994)之SPM中的反應程度參數臨界值(Ecritical=0.7)分析，小港測站和楠梓測站在秋季、冬季及春季以VOC為主要控制物種(100%)；前金站在秋季、冬季以VOC為主要控制物種(100%)，在春季以VOC為主要控制物種(91.7%)。
比對實地採樣與SPM模擬結果顯示兩者在小港測站及楠梓測站秋季、冬季及春季敏感性物種判定上一致；前金測站在秋季、冬季敏感性物種判定上一致，而春季敏感性判定較不一致。根據相關文獻研究顯示界定比值會隨不同排放特徵、氣象因素等影響，本研究建議未來可以利用相關模式搭配實地量測更精確判定高雄市臭氧敏感性物種。

Ground-level ozone (O3) is a secondary pollutant produced by its precursors, such as volatile organic compounds (VOC) and nitrogen oxides (NOx) through complex photochemical reactions in sunlight. This study was aimed to investigate the relationships of surface ozone with its precursors in urban locations. Atmospheric measurements of hydrogen peroxide (H2O2) and nitric acid (HNO3) were conducted at the three sites, namely Nan-Tze, Chien-Chin and Hsiung-Kong, in Kaohsiung City during three consecutive days of fall, winter and spring seasons in 2002-2003, from which the ozone-VOC-NOx sensitive regimes were derived using two methods, namely the indicator ratios of H2O2/HNO3 and O3/HNO3 developed by Sillman (1997), and the extent parameter, E, of SPM (Smog Production Model) developed by Blanchard (1994).
Measurements indicate that H2O2 reaches its peak concentration approximately at noon to afternoon (12:00 to 15:00); meanwhile HNO3 reaches its lowest concentration. In general, fall season has highest concentrations on H2O2 and HNO3, followed by spring and winter. The correlation analyses indicate that ozone has positive relationships with temperature and solar insolation, while it has negative relationships with NOx, NO and NO2.
According to the indicator ratios of H2O2/HNO3 = 0.3 – 0.6, O3/HNO3 = 12 -16 (Sillman, 1997), results show that VOC-limited regimes occupy about 62.5% and 58.3% at the Hsiung-Kong site, 47.8% and 69.6% at the Nan-Tze site, and 33.3% and 70.8% at the Chien-Chin site in the fall season. Results also show that VOC-limited regimes occupy about 80.9% and 66.7% at the Hsiung-Kong site, 54.2% and 41.7% at the Nan-Tze site, and 70.8% and 45.8% at the Chien-Chin site in the winter, while it is 52.4﹪and 80.9﹪at the Hsiung-Kong site, 50.0﹪and 66.7﹪at the Nan-Tze site, and 35.7﹪and 28.6﹪at the Chien-Chin site in the spring.
According to the critical value of extent parameter, Ecrit = 0.7 (Blanchard, 1994),
IV
results show that VOC-limited regimes pre-dominate at three sites in autumn, winter and spring, all occupying 100% except in that a VOC-limited regime occupies about 91.7% at the Chien-Chin site in spring.
In summary, the ozone-VOC-NOx sensitivity results derived from indicator ratios agree fairly well with SPM results, except for the Chien-Chin site in spring. The indicator ratios and Ecrit are frequently considered to be universal under given assumptions. However, these values may vary with meteorology and topography. Further studies are needed to characterize these parameters locally.

謝 誌 Ⅰ
摘 要……………………………………………………….Ⅱ
ABSTRACT…………………………………………………..Ⅳ
目 錄……………………………………………………….Ⅵ
表目錄……………………………………………………….Ⅷ
圖目錄……………………………………………………….Ⅸ

第一章 前 言 1-1
1.1研究緣起 1-1
1.2研究目的 1-2
第二章 文獻回顧及相關研究 2-1
2.1高雄市空氣品質回顧 .2-1
2.1.1 PSI趨勢 2-1
2.1.2 空氣品質與氣象關聯 2-8
2.2各類污染物排放放量推估 2-11
2.3對流層臭氧之生成 2-12
2.3.1對流層H2O2與HNO3之生成 2-13
2.4臭氧敏感性 2-16
2.4.1臭氧敏感性介紹 2-16
2.4.2光化指標 2-17
2.5光化煙霧產物模式 2-22
2.5.1Johnson光化煙霧產量模式 2-22
2.5.2Blanchard光化煙霧產量模式 2-23
2.5.3 Chang光化煙霧產量模式 2-25
2.5.4本土化光化煙霧產量模式 2-26
2.6採樣分析方法回顧 2-26
2.6.1硝酸（HNO3）採樣分析方法 2-26
2.6.2過氧化氫(H2O2)採樣分析方法 2-27
2.7臭氧管制策略 2-28
第三章 研究方法 3-1
3.1大氣實際監測採樣規劃 3-3
3.1.1採樣時間 3-3
3.1.2採樣地點 3-5
3.2大氣中硝酸與過氧化氫採樣分析方法 3-5
3.2.1硝酸(HNO3)採樣方法 3-6
3.2.2 過氧化氫 (H2O2)採樣方法 3-8
3.3 藥品來源與用途 3-10
3.4品保品管 3-11
3.5品保與品管結果 3-12
3.6光化指標分析 3-14
3.7光化煙霧產量模式 3-14
3.7.1前處理程序 3-15
3.7.2光化煙霧產量模式反應程度分析 3-15
第四章 結果與討論 .4-1
4.1臭氧前驅物質分析 4-1
4.1.1過氧化氫(H2O2)濃度分析 4-1
4.1.2硝酸 (HNO3)濃度分析 4-9
4.1.3 季節性大氣總HNO3與H2O2濃度變化 4-16
4.2氣象條件對污染物影響 4-17
4.3 氣象影響因子相關性分析 4-30
4.4高雄市光化指標應用與探討 4-35
4.5高雄市光化煙霧產量模式應用 4-48
4.6高雄市臭氧敏感性物種分析結果 4-49
第五章 結論及建議…………………..……………………5-1
5.1 結論 5-1
5.2 建議 5-2
參考文獻……………………………………………………參-1

附錄A 高雄市各污染源排放量總量表…………..………..附A-1

表 目 錄

表2-1-1 高雄測候站近十年各月份平均氣象資料統計表 2-9
表2-4-1 過去研究提出之光化指標與界定比值整理 2-18
表2-4-2 各光化指標之特性比較 2-19
表2-5-1 Johnson、Blanchard和Chang三種光化煙霧產量模式之比 2-25
表2-6-2 過氧化氫不同採樣方法比較表 2-27
表3-1-1 採樣時間表 .3-3
表3-3-1 藥品來源與用途 3-10
表3-6-1 過去提出各光化指標與界定比值整理 3-13
表4-1-1 秋季前金、楠梓與小港站大氣H2O2濃度 .4-3
表4-1-2 冬季前金、楠梓與小港站大氣H2O2濃度 4-4
表4-1-3 春季前金、楠梓與小港站大氣H2O2濃度 .4-5
表4-1-4 秋季前金、楠梓與小港站大氣HNO3濃度 .4-10
表4-1-5 冬季前金、楠梓與小港站大氣HNO3濃度 .4-11
表4-1-6 春季前金、楠梓與小港站大氣HNO3濃度 .4-12
表4-3-1 高雄市秋季相關性分析 4-32
表4-3-2 高雄市冬季相關性分析 4-33
表4-3-3 高雄市春季相關性分析 4-34
表4-4-1 2002年10月28-30日(秋季)高雄市小港測站採樣結果分析 4-39
表4-4-2 2002年10月28-30日(秋季)高雄市楠梓測站採樣結果分析 4-40
表4-4-3 2002年10月28-30日(秋季)高雄市小港測站採樣結果分析 4-41

表4-4-4 2002年10月31-11月2日(秋季)高雄市前金測站採樣結果分析 4-42

表4-4-5 2003年1月15-17日(冬季)高雄市小港測站採樣結果分析 4-43
表4-4-6 2003年1月15-17日(冬季)高雄市楠梓測站採樣結果分析 4-44
表4-4-7 2003年1月18-20日(冬季)高雄市前金測站採樣結果分析 4-45
表4-4-8 2003年4月7-10日(春季)高雄市小港測站採樣結果分析
4-46
表4-4-9 2003年4月7-10日(春季)高雄市楠梓測站採樣結果分析 4-47
表4-4-10 高雄市採樣期間光化指標與SPM百分比 4-50

圖 目 錄

圖1-1-1 空氣污染指標大於一百之指標分佈圖…………………….1-1
圖2-1-1 高屏地區品質現況………………..…………………………2-1
圖2-1-2 高雄市一般測站85年至92年PSI＞100指標污染物逐月變化圖………………………………………………………….2-2
圖2-1-3 高屏地區84-92年月平均PM10濃度變化………………...2-2
圖2-1-4 高屏地區84-92年月平均NO2濃度變化…………………2-3
圖2-1-5 高屏地區84-92年月平均O3濃度變化 2-3
圖2-1-6 高屏地區84-92年月平均CO濃度變化 2-4
圖2-1-7 高雄市各測站PM10逐月濃度變化趨勢 2-5
圖2-1-8 高雄市各測站O3逐月濃度變化趨勢 2-6
圖2-1-9 高雄市各測站NO2逐月濃度變化趨勢 2-7
圖2-4-1 EKMA臭氧等濃度 2-9
圖2-5-1 不同光化箱模式圖 2-22
圖3-1-1 研究架構流程圖 3-2
圖3-1-2 高雄市量測地點分佈圖 3-4
圖3-2-1 矽膠管剖面圖 3-6
圖3-2-2 H2O2採樣設備圖 3-9
圖4-1-1秋季楠梓、前金、小港三測站O3與H2O2濃度關係圖 4-6
圖4-1-2冬季楠梓、前金、小港三測站O3與H2O2濃度關係圖 4-7
圖4-1-3冬季楠梓、前金、小港三測站O3與H2O2濃度關係圖 4-8
圖4-1-4 秋季楠梓、前金、小港三測站O3與HNO3濃度關係圖4-13
圖4-1-5 冬季楠梓、前金、小港三測站O3與HNO3濃度關係圖4-14
圖4-1-6 春季楠梓、前金、小港三測站O3與HNO3濃度關係圖4-15
圖4-1-7 高雄市楠梓、小港及前金測站H2O2與HNO3濃度季節變化盒型圖 4-16
圖4-2-1 小港空品測站91年10月28-30日（秋季）污染物濃度值及氣象因子與採樣值趨勢比較 4-21
圖4-2-2 楠梓空品測站91年10月28-30日（秋季）污染物濃度值及氣象因子與採樣值趨勢比較 4-22
圖4-2-3 前金空品測站91年11月01-02日（秋季）污染物濃度值氣象因子與採樣值趨勢比較 4-23
圖4-2-4 小港空品測站92年1月15-17日（冬季）污染物濃度值及氣象因子與採樣值趨勢比較 4-24
圖4-2-5 梓空品測站92年1月15-17日（冬季）污染物濃度值及氣象因子與採樣值趨勢比較 4-25
圖4-2-6 前金空品測站92年1月18-20日（冬季）污染物濃度值及氣象因子與採樣值趨勢比較 4-26
圖4-2-7 小港空品測站92年4月7-10日（春季）污染物濃度值及氣象因子與採樣值趨勢比較 4-27
圖4-2-8 楠梓空品測站92年4月7-10日（春季）污染物濃度值及氣象因子與採樣值趨勢比較 4-28
圖4-2-9 前金空品測站92年3月30-31日（春季）污染物濃度值及氣象因子與採樣值趨勢比較 4-29
圖4-5-1 秋季高雄測站光化煙霧產量反應程度參數E(t)趨勢圖4-50
圖4-5-1 秋季高雄測站光化煙霧產量反應程度參數E(t)趨勢圖 4-51
圖4-5-1 秋季高雄測站光化煙霧產量反應程度參數E(t)趨勢圖 4-52
圖4-5-4 高雄市模擬Blanchard之SPM之E值分佈圖 4-54

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