摘 要

依據環保署台灣空氣品質監測網監測統計資料，高屏空品區懸浮微粒有逐年下降趨勢，但臭氧卻有逐年上升、惡化現象，顯示臭氧問題已成為高屏空品區待解決的問題。

對流層臭氧的生成，主要與NOx 與VOC 有關，因此此二物種被認為是臭氧的主要前驅物。然而臭氧的濃度與NOx、VOC卻不呈線性關係，有鑑於大氣中臭氧濃度，乃受多種前驅物及相關物種的影響，因此近來學者便進一步發展光化指標（photochemical indicators）。即以數種臭氧前驅物或相關物種之比值，決定臭氧敏感性。

本研究以國外學者所界定之光化指標界定比值(Sillman, 1995；Sillman, 1997)，對照實地採樣臭氧敏感性物種(H2O2、HNO3及NOy)製作而成的光化指標，對高雄地區之臭氧前驅物進行敏感性分析。以實地採樣方式在高雄市北部的楠梓區、橋頭鄉以及高雄市南部的小港區、林園鄉進行光化指標的建立，採樣結果比對相關研究之界定比值，以判斷控制臭氧形成之主要前驅物種為何；並且以SPM模擬各採樣日，以提供比較分析。

由光化指標對臭氧前驅物種敏感性分析的結果顯示，楠梓站、小港站、林園站以及橋頭站在春、夏、秋、冬四季是以VOC為主要控制物種。

由SPM對臭氧前驅物敏感性分析結果顯示，楠梓、小港、林園、橋頭四站在四個季節都顯示為VOC控制。

ABSTRACT

According to the data of the Taiwan Air Quality Monitoring Network (TAQMN), the suspenden particulates decreases gradually with year at the Kao-Ping Air Quality Area, but the ozone increases with year and deteriorates. Therefore, the problem of the ozone is wating for solving at Kao-Ping Air Quality Area.

Because the ground-level ozone has a relationship with NOx and VOC, they are thought to be the major precursors of the ozone. The concentration of the ozone is not linearly related with concentrations NOx and VOC. The precursors of the ozone affect the ground-level ozone, so the photochemical indicators are further developed in recent years.

The photochemical indicators H2O2,HNO3 and NOy in this study in Kaohsiung area are analysed by criteria values (Sillman,1995 and 1997) and on-site sampling. The sampling sites are at Nan-Zih, Siao-Gang, Lin-Yuan and Chiao-Tou. The results can determine the major precursors forming ozone. In addition Smog Production Model (SPM) is also used to analyze the results.

According to the analyses of the photochemical indicators, Nan-Zih, Siao-Gang, Lin-Yuan and Chiao-Tou are VOC-limited in the spring, summer, fall and winter.According to the analysis result of SPM, the four sites are also VOC-limited in four seasons.

目 錄
謝 誌…………………………………………………………Ⅰ
摘 要…………………………………………………………Ⅱ
Abstract………………………………………………………Ⅲ
目 錄…………………………………………………………Ⅳ
表目錄…………………………………………………………Ⅵ
圖目錄…………………………………………………………Ⅷ
第一章 前言…………………………………………………1-1
1.1 研究動機……………………………………………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 高雄地區近年空氣品質趨勢及污染量概述………2-1
2.1.1 高雄地區歷年氣象概述…………………………2-1
2.1.2 各空氣污染物濃度變化趨勢……………………2-4
2.1.3 高雄市各類污染物排放放量推估………………2-18
2.1.4 高雄縣各類污染物排放放量推估………………2-19
2.2 對流層臭氧之形成…………………………………2-20
2.3 臭氧的影響…………………………………………2-23
2.3.1 對人體健康之影響………………………………2-24
2.3.2 對農業之影響……………………………………2-24
2.3.3 對物體之影響……………………………………2-25
2.4 光化煙霧產量模式之發展…………………………2-26
2.4.1 光化指標…………………………………………2-26
2.4.2 光化指標之原理…………………………………2-27
2.4.3 Johnson光化煙霧產量模式 ……………………2-30
2.4.4 Blanchard光化煙霧產量模式 …………………2-31
2.4.5 Chang光化煙霧產量模式 ………………………2-33
2.4.6 本土化光化煙霧產量模式………………………2-35
第三章 研究方法……………………………………………3-1
3.1 大氣光化指標之採樣規劃…………………………3-1
3.2 實驗方法……………………………………………3-3
3.3 採樣方法及分析……………………………………3-5
3.3.1 大氣中H2O2採樣…………………………………3-5
3.3.2 大氣中HNO3採樣…………………………………3-7
3.3.3 大氣中NOy採樣 …………………………………3-8
3.3.4 H2O2與HNO3檢量線………………………………3-9
3.4 光化指標分析………………………………………3-10
3.5 光化煙霧產量模式之研究方法……………………3-11
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 高雄市（楠梓站、小港站）濃度分析討論……4-6
4.1.2 高雄縣（林園站、橋頭站）濃度分析討論……4-8
4.2 光化指標分析之結果………………………………4-11
4.2.1 楠梓站光化指標分析之結果……………………4-12
4.2.2 小港站光化指標分析之結果 ……………………4-18
4.2.3 林園站光化指標分析之結果 ……………………4-24
4.2.4 橋頭站光化指標分析之結果 ……………………4-30
4.3 SPM模式模擬之結果 ………………………………4-36
4.3.1 楠梓站SPM模式模擬之結果………………………4-36
4.3.2 小港站SPM模式模擬之結果………………………4-42
4.3.3 林園站SPM模式模擬之結果………………………4-47
4.3.4 橋頭站SPM模式模擬之結果………………………4-52
4.4 光化指標與SPM模式之綜合討論 …………………4-57
第五章 結論與建議…………………………………………5-1
5.1 結論…………………………………………………5-1
5.2 建議…………………………………………………5-2
參考文獻……………………………………………………參-1
附錄A 高雄縣市各污染源排放量總量表………………附A-1
附錄B H2O2採樣分析方法………………………………附B-1
附錄C HNO3採樣分析方法………………………………附C-1
附錄D NOx採樣分析方法 ………………………………附D-1
附錄E 大氣臭氧敏感物種（H2O2、HNO3、NOy）採樣分析
結果………………………………………………附E-1

參考文獻

Blachard, C. L., and. Roth P. M, ”Spatial mapping of preferred strategies for reducing ambient ozone concentrations nationwide”,U.S.EPA, Research Triangle Park, NC.(1994)

Blachard, C. L., and Lurmann F. W., Kore M., and Roth P. M., “The use of ambient data to corroborate analysis of ozone control strategies” finalreport, Research Triangle Park, NC.(1994)

Blanchard, C. L., Lurmann, F. W., Kore, M., Roth, P. M. and Jeffries, H.E. and Korc, M. “The use of ambient data to corroborate analysis of ozone control strategies” Atmospheric Environment, Vol.33, pp. 369-381.(1999)

Blanchard, C. L.,”Ozone process insights from field experiments-Part III: extent of reaction and ozone formation”,Atmospheric Environment, Vol.34, pp.2035-2043.(2000)

Blanchard, C.L. and Stoeckenius, T. “Ozone response to precursor controls：comparison of data analysis methods with the predication of photochemical air quality simulation models ”, Atmospheric Environment, Vol.35, pp. 1203-1215.(2001)

Chang, T. Y. and Suzio M. J., “Assessing Ozone-Precursor Relationships Based on a Smog Production Model and Ambient Data”, Air & Waste Management Association, Vol.45, pp.20-28.(1995)

Chang, T. Y. and Suzio M. J., “A Smog Production Model and an Assessment of Ozone Control Strategies”, Air & Waste Management Association (1994)

Chang, T. Y. and Rudy S. J., “Ozone-Precursor Relationships: A Modeling Study of Semiempirical Relationships”, Environmental. Science & Technology, Vol.27, No.10, pp.2213-2219 (1993)

Chu,S.H “Meteorological considerations in siting photochemical pollutant monitor.”Atmospheric Environment, Vol.29, pp. 2905~2913.(1995)

Chang, T. Y. and Suzio, M. J. “Assessing Ozone-Precursor Relationships Based on a Smog Production Model and Ambient Data”, Air & Waste Management Association, Vol.45, pp.20-28.(1995)

Chang, T. Y. and Rudy, S. J. “On the indivator-based approach to assess ozone sensitivities and emissions feature”, Journal Of Geophysical Research, Vol.3, pp.3453-3462.(1998)

Chen,K.S., Ho,Y.T. and Chou,Y. M.“Photochemical modeling and analysis of meteorological parameters during ozone episodes in Kaohsiung, Taiwan”, Atmospheric Environment, Vol.37, pp. 1811-1823.(2003)

David, P. C., Chang ,T. Y., Winkler, S. L. and Nance, B. I “The impact of an 8h ozone air quality standard on ROG and NOx controls in Southern California”, Atmospheric Environment, Vol.33, pp. 2471-2485.(1999)

Duenas, C., Fernandez, M. C., Canete, S., Carretero, J. and Liger, E. “Assessment of ozone variation and meteorological effects in an urban in the Mediterranean Coast”, the Science of Total Environment pp. 299.(2002)

Geyer, A., Ackermann, R., Dubois, R., Muller, T. and Platt, U.“The Long-term observation nitrate radicals in the continental boundary layer near Berlin”, Atmospheric Environment, Vol.35, pp. 3619-3631.(2001)

Helen, W. Y. and Chan, L.Y. “Surface ozone trends in Hong Kong in 1985-1995”, Environment International Vol.26, pp. 213-222 (2001)

Johnson, G. M. ,”A Simple Model for Predicting the Ozone Concentration of Ambient Air”, In Proc. 8th Int. Clean Air Conf., Clean Air Soc. Of Australia and New Zealand Vol.2, pp.715-731 (1984)

Johnson, G. M., and M. Azzi, ”Notes on the derivation : the integrated empirical rate model(V2.2)” Report prepared by CSIRO Division of Coal and Energy Technology, North Ryde,NSW,Australia.(1992)

Johnson, G. M., S. M. Quigley, and J. G. Smith, “Management of photochemical smog using the AIRTRAK apporch” 10th International Conference of the Energy Society of Australia and New Zealand, March, pp.209-214.(1990)

K.S. Chen, Y.T. Ho, C.H. Lai, Youn-Min Chou, “Photochemical modeling and analysis of meteorological parameters during ozone episodes in Kaohsiung, Taiwan”, Atmospheric Environment, Vol.37, pp.1811-1823 (2003)

Lurmann, F. W., W. P. L. Cater, and L. A. Coyner, ”A surrigate species chemical mechanism for urban-scale air quality modeling.” Report prepared for U.S. Environment Protection Agency, Research Triangle Park, NC,.EPA-600/3-87-014.(1987)

Lu,C.H., ”On the Indicator-based Approach to Assess Ozone Sensitivities and Emission Features ” Journal Of Geophysical Research, V.103, pp.3453-3462 (1998)

Milford, J. B., D. Gao, S. Sillman, P. Blosse, and A. G. Russell, “Total reactivity nitrogen (NOy) as an indicator for the sensitivity of ozone to NOX and hydrocarbons”,
Journal of Geophysical Research, Vol.99, pp.3533-3542 (1994)

Russell, A., J. Milford, M. S. Bergin, S. McBride, L. McNair, Y. Yang, W. R. stockwell, and B. Croes, “Urban ozone control and atmospheric reactivity of organic gases”, American Assoc. for the Advencement of Science, p.491(1995)

Seinfeld, J. H., “Atmospheric Chemistry and Physics of Air Pollution”, John Wiley & Sons, Inc. pp.738,(1996)

Sillman S., F. A. Logan, and S.C. Wofsy, “The sensitivity of ozone to nitrogen oxides and hydrocarbons in regional ozone episodes”, Journal of Geophysical Research, Vol.95 (D2), pp.1837-1851 (1990)

Sillman, S., “Evaluating the Relation Between Ozone, NOX and hydrocarbons: The Method of Photochemical Incators”, EPA/600/R-98/022, USEPA, Research Triangle Park, NC. (1998)

Sillman, S., J. A. Logan, and S. C. Wofsy, “The Sensitivity of Ozone to Nitrogen and Hydrocarbons in Regional Ozone Episodes”, Journal of Geophysical Research, Vol.100, N. D7, pp.14175-14188 (1995)

沈信旭，「大氣光化煙霧產量模式之應用研究」，國立雲林科技大學環境與安全工程系，碩士論文，中華民國八十七年。

蔣志剛，「光化煙霧產量模式本土化之研究」，國立雲林科技大學環境與安全工程系，碩士論文，中華民國八十八年。

周明顯、樓基中、袁中新，「高雄市臭氧生成前驅物控制及減量策略研擬」，高雄市政府環境保護局，中華民國九十年。

莊桓齊、鄭福田，「台灣地區臭氧敏感性光化指標方法之建立與探討」，國立台灣大學環境工程研究所，碩士論文，中華民國九十年。

吳義林、林清和，「台南縣臭氧防治策略規劃－敏感性物種之調查研究」，台南縣環境保護局，中華民國九十一年三月。

陳幸芬、李俊璋、吳義林，「台南縣臭氧敏感性物種之調查研究」，國立成功大學環境醫學研究所，碩士論文，中華民國九十一年。

陳瑞仁、陳康興，「屏東地區空氣品質劣化原因探究及改善策略研擬」，屏東縣環境保護局，中華民國九十一年十二月。

陳康興，「高雄市大氣臭氧形成敏感性物種(H2O2, HNO3)之調查研究」，2002區域臭氧污染與防制就數研討會論文集，高雄市環境保護局，中華民國九十一年十二月。

陳康興、謝連德，「屏東地區揮發性有機物空氣污染調查檢測計畫」，屏東縣環境保護局，中華民國九十二年。