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Investigation of the Heterogeneous Formation Mechanisms of Nitrous Acid in the Highly Polluted Urban Air
|關鍵字:||high pollution;高污染;nitrous acid;heterogeneous reactions;OH radical;亞硝酸;異相反應;OH 自由基||出版社:||環境工程學系所||引用:||1. Acker, K., G. Spindler and E. Bruggemann, “Nitrous and Nitric Acid Measurements During the INTERCOMP2000 Campaign in Melpitz,” Atmospheric Environment, Vol. 38, No. 38, pp. 6497-6505 (2004). 2. Acker, K., D. Moller, R. Auel, W. Wieprecht and D. Kalab, “Concentration of Nitrous Acid, Nitrite and Nitrate in the Gas and Aerosol Phase at a Site in the Emission Zone During ESCOMPTE 2001 Experiment,” Atmospheric Research, Vol. 74, No. 1/4, pp. 507-524 (2005). 3. Acker, K., A. Febo, S. Trick, C. Perrino, P. Bruno, P. Wiesen, D. Moller, W. Wieprecht, R. Auel, M. Giusto, A. Geyer, U. Platt and I. Allegrini, “Nitrous Acid in the Urban Area of Rome,” Atmospheric Environment, Vol. 40, No. 17, pp. 3123-3133 (2006). 4. Alicke, B. and U. 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亞硝酸濃度在0.1 ~ 4.8 ppb之間，其中高污染(PM2.5 > 65 μg/m3)和夜間濃度分別為平日和日間的2倍，所量測之夜間HONO/NO2與PM2.5也較平日有較佳的相關性。理論推估之日間亞硝酸主要來自同相機制，夜間則以微粒表面上之異相機制為主，此結果除顯示夜間和高污染期間亞硝酸異相反應的重要性外，也可提供光解以生成較多的OH，進而影響日間的光化反應。理論推估之亞硝酸光解產生的OH相較於臭氧在秋季、冬季和各季節清晨顯得更為重要，且凌晨亞硝酸和當日正午臭氧最大值呈高度相關，顯示無法忽略亞硝酸對日間光化反應的重要性。進一步利用多元線性迴歸分析，其日間和夜間之亞硝酸濃度經驗模式分別為:
[亞硝酸]日間 = 0.034 [NOx] - 0.010 [O3-MAX] + 0.759
[亞硝酸]夜間 = 0.046 [NOx] + 0.015 [PM2.5]
Nitrous acid is an important source of OH radicals which act to enhance photochemical reactions. Accordingly, it is necessary to understand its formation mechanisms. However, the heterogeneous formation mechanisms of nitrous acid are still not completely understood, and to date, few studies have addressed the characteristics of such mechanisms under high pollution conditions and their coupling with the added the importance of OH to photochemical reactions. Hence, in this study we collected air pollutants in Taichung city every 4 hours during August 2006 - March 2007, in order to investigate the importance of heterogeneous mechanisms and photochemical reactions of nitrous acid.
Nitrous acid concentration ranged between 0.1 - 4.8 ppb. Concentration during high pollution episodes (PM2.5 > 65 μg/m3) and during the night were twice as high as those during normal air quality condition and during the day, respectively. There was a strong correlation between HONO/NO2 and PM2.5 during high pollution episodes. Nitrous acid was predominantly formed by homogeneous mechanism during the day, and NO2 reduced aerosol reaction was main source of nitrous acid during the night by the theoretical evaluations. These results suggest that nitrous acid is formed by heterogeneous reactions during the night and during high pollution episodes, and nitrous acid is also accounted for OH by photolysis. During autumn, winter and the early mornings of each season, nitrous acid photolysis was by far a greater source of OH than ozone. Furthermore, nitrous acid concentration was found to be highly correlated with maximum ozone, which demonstrates that the impact of nitrous acid photochemistry should not be neglected. Models for nitrous acid concentration obtained using multiple linear regression analysis are:
[Nitrous acid] day = 0.034 [NOx] - 0.010 [O3-MAX] + 0.759;
[Nitrous acid] night = 0.046 [NOx] + 0.015 [PM2.5],
Where nitrous acid, NOx, and O3-MAX concentration are measured in ppb, and the units of PM2.5 are μg/m3. The main factors influencing nitrous acid were found to be NOx and PM2.5, so controlling traffic emissions is expected to indirectly abate O3 formation in urban areas.
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