本研究探討大氣超細懸浮微粒水溶性離子成份濃度，與前驅氣體(SOx、NOx及NH3)及氣象因子（溫度、相對濕度）之關聯性，以瞭解南台灣微粒污染事件之大氣反應機制。現場調查觀測工作於大寮空氣品質監測站進行，以MOUDI/Nano-MOUDI、ADS(Annular Denuder System)分別採集大氣懸浮微粒及前驅氣體樣品，應用超微量天平及離子層析儀(IC)分析微粒質量、所含水溶性離子及前驅氣體濃度與成份。
研究結果顯示，高屏地區於懸浮微粒事件日與非事件日期間之大氣微粒粒徑分佈皆呈現三峰分佈型態，分別界於1.8~18 μm、0.18~1.8 μm及0.018~0.056 μm粒徑範圍。事件日與非事件日期間，日、夜粗微粒(1.8 µm <dp <18 µm)質量濃度差異不大；事件日夜間細微粒(0.1 µm <dp <1.8 µm)質量濃度則明顯高於其他時段濃度。研究結果顯示，發生粒狀物污染事件日與PM1濃度增高有密切關係。
研究觀測不同採樣條件微粒中和比（NR值）與粒徑關係顯示，當大氣微粒粒徑小於0.1 µm時呈現偏鹼性，大氣微粒粒徑大於2.5 µm時呈偏中性或微酸性，大氣微粒粒徑介於0.18 - 1 µm呈中性。整體而言，大氣微粒酸鹼性與微粒粒徑大小具強烈關連性。
研究結果顯示，高屏地區大氣衍生性氣膠（SO42-及NO3-）細粒徑波峰分佈主要界於0.18~1.8 μm；分析前驅氣體（SO2及NO2）於此粒徑範圍之氣固相轉化率顯示，夜間氮轉化率（Fn）於事件日為非事件日之4倍；夜間硫轉化率之（Fs）於事件日為非事件日之1.5倍。事件日期間夜間與日間之Fn及Fs皆隨大氣相對濕度增高而增加；非事件日期間之日間Fn與Fs隨大氣O3濃度增加呈升高現象。此結果與大氣高濕環境存在高濃度NO2、SO2及O3有關，亦說明大氣粒狀物污染事件日發生與氣固相轉換具密切關係。
以熱力學反應理論探討大氣硝酸銨生成機制，觀測HNO3(g)及NH3(g)濃度積(Km)高於理論值平衡常數(Ke)。大氣HNO3(g)及NH3(g)濃度高低為影響Km之重要因素，且較相對濕度或溫度之影響更為重要。當大氣PM10濃度高於90 µg/m3， Km高於Ke，微粒鹽類易形成NH4NO3形式。大氣呈高濕環境，易產生相對濕度高於潮解之相對濕度(Deliquescence relative humidity, DRH)狀況，當HNO3(g)及NH3(g)濃度升高時，觀測K值高於理論值，反應易生成NH4NO3，多致大氣微粒濃度明顯增高。

The purposes of this study built up the relationships among inorganic composition of aerosol, gas precursors and meteorological parameters. Furthermore, the ultrafine particle and gas precursor sampling technology are developed in this study. The sampling system used in this study, consisting of a MOUDI and a Nano-MOUDI, has been found useful in the previous studies. Ambient concentrations of gases were measured using an annular denuder system. A Dionex-120 ion chromatography unit was employed to analyze the inorganic ions under consideration. The filters were weighed using a high precision six digit electronic balance (Mettler MX5).
These particulate samples were analyzed for major water-soluble ionic species with an emphasis to characterize the mass concentrations and distributions of these ions in the ambient ultrafine (PM0.1, diameter < 0.1 µm) and nano mode (PMnano, diameter < 0.056 µm) particles. Particles collected at the sampling site (the Da-Liao station) on the whole exhibited a typical tri-modal size distribution on mass concentration. The fractions from the polluted days were higher than those from the normal days for particle size greater than 1 µm. This finding suggested that the PM1 (submicron aerosol particles) fraction played an important role in the ambient atmosphere on the polluted days. Overall, results from this study supported the notion that secondary aerosols played a significant role in the formation of ambient submicron particulates (PM0.1-1). Particles smaller than 0.1 µm were essentially basic, whereas those greater than 2.5 µm were neutral or slightly acidic. The neutralization ratio (NR) was close to unity for airborne particles with diameters ranging from 0.18 to 1 µm. The NRs of these airborne particles were found strongly correlated with their sizes, at least for samples taken during the aerosol episodes under study.
During the episode days, the average particulate nitrate mass of accumulation mode (0.18-1.8 µm) measured over nighttime was about 4 times higher than those measured during non-episode days. In addition, the SO42- mass of accumulation mode during episode days was about 1.5 times higher than those during the nighttime of the non-episode days. These results might be attributed to high NO2, SO2 and ozone concentrations in a humid atmosphere, and also the fact that the gas-to-particle conversion played an important role during episode days.
Under the thermodynamic theory to discuss the formation of NH4NO3, the measured concentration product (Km) was higher than calculated thermodynamical equilibrium constant (Ke). The ratio of Km/Ke increases with increasing Km, suggested that the levels of NH3 and HNO3, rather than the levels of temperature or RH. When there are high levels of gaseous ammonia and nitric acid in the atmosphere, the Km was higher than Ke during PM10 concentrations exceeded 90 µg/m3. Moreover, NH4NO3 was the probable chemical form of the nitrate present in the airborne fine particle, the level of relative humidity (RH) was above the deliquescence relative humidity (DRH) in a humid atmosphere.

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