本研究針對高高屏地區空氣污染問題，在地表處利用環保署自動監測站之監測數據、光化學污染物(HCHO、H2O2與HNO3)之採樣及氣象條件(溫度、濕度、日照強度與NO2之光解速率常數(J-NO2))之觀測；在高空中利用釋放氣球(radiosonde)、繫留氣球(tethersonde、ozonesonde及採樣袋)與輕航機(GPS與O3 monitor)進行採樣，藉以了解高高屏地區空氣污染物在三度空間中垂直與水平之分佈現象。 在採樣期間(民國92年10/25~11/1與93年5/12~5/15)發現，高高屏地區在這十二天中之指標污染物幾乎均為臭氧，且在10/28、10/30、10/31與11/1均有數個測站之臭氧最大小時濃度超過120 ppb，所以將這四天稱為臭氧事件日。從氣象條件中發現，溫度、J-NO2、[HNO3]與[NO2+O3]在出現臭氧事件日之四天中比其他四天高，且radiosonde之結果顯示，發生事件日的四天中，混合層高度明顯較低。在繫留氣球採樣中發現，事件日發生當天晚上與隔日清晨，混合層之上發現較高濃度之殘留臭氧，高達80~110 ppb ，且高高屏地區高空中有時會有高污染煙流經過，其中高濃度之NO常對臭氧產生消耗的作用(NO titration)。因此，高高屏地區發生之臭氧事件日 應可歸因於：高濃度之臭氧前驅污染物、強烈之光化學反應、混和層上之高濃度殘留臭氧與混和層高度較低。反觀高高屏內陸地區城市(美濃與 里港)，在輕航機之盤旋結果中並未發現混和層上之高濃度殘留臭氧，僅30~60 ppb，卻頻頻出現臭氧事件日，顯然高高屏沿海與內陸地區臭氧事件日之形成原因應略有不同。 本研究並應用radical budget預測由光化學反應產生之臭氧生成速率，並藉此推估傳輸作用對臭氧生成速率之貢獻量，但結果顯示模式明顯較實測值高出許多，原因應為模式預測之過氧自由基濃度偏高，應用chemical amplification於里港進行過氧自由基之實測修正後，臭氧生成速率較實測值差小，此差距應來自於臭氧濃度水平與垂直傳輸效應下之結果，其貢獻量為20~90%，六點至七點時，達90%以上，七點至十點時，下降至20~70% ，近午時，又上升至85%，若配合從繫留氣球觀察出之海陸風效應，海風對臭氧與其前驅污染物之水平傳輸作用，應對內陸鄉鎮(美濃、里港)常發生臭氧事件日地區具有一定之貢獻量。

　　The purpose of this study is to characterize the three-dimensional spatial distribution of gaseous pollutants at the Kao-Ping air basin, which is the worst air quality area in Taiwan. On the ground, the photochemical pollutants including HCHO, H2O2, and HNO3 and the meteorological factors, including temperature, relative humidity, radiation intensity and photolysis rate constant of NO2 were measured simultaneously. In aloft, radiosonde, tethersonde, ozonesonde, and tethered balloon with sampling bag and personal pump were used to measure the vertical concentration profile at fixed location. The light-aircraft was used to measure the horizontal and vertical concentration profiles.
　　There were four ozone episode days, that is the maximum hourly O3 concentration greater than 120 ppb, during 10/25~11/1, 2003 based on the Taiwan EPA air quality monitoring network. In the episodic days, the temperature, J-NO2, HNO3, and [NO2 + O3] were greater than those in the other days; but RH and mixing height were smaller. The results of tethered balloon indicated that the reserved ozone concentration above mixing layer were 80~110 ppb in ozone episode days and sometimes the reserved ozone was titrated by NO in polluted plume. The effect of sea-land breeze was significant on the air quality in Kao-Ping air basin based on the results from tethersonde. The high ozone concentrations in Kao-Ping air basin were attributed to the strong photochemical reaction, the high concentration of reserved ozone aloft, and the low mixing height.
　　The radical budget method was used to estimate the ozone production rates in the polluted Kao-Ping air basin. The calculated results were much greater than the observed. The differences were due to the calculation of peroxide radical, which was not suitable for polluted area. Therefore, observed peroxide radical concentrations by the chemical amplification method were used in the radical budget method. The modified ozone production rate was less than the observed and the magnitude of difference should be from transportation of ozone including horizontal and vertical transportation. The contributions of transportation to the ozone production rate were 20~90%.

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