Atmospheric oxidation chemistry and ozone production: Results from SHARP 2009 in Houston, Texas

Abstract

Ozone (O 3) and secondary fine particles come from the atmospheric oxidation chemistry that involves the hydroxyl radical (OH) and hydroperoxyl radical (HO 2), which are together called HO x. Radical precursors such as nitrous acid (HONO) and formaldehyde (HCHO) significantly affect the HO x budget in urban environments. These chemical processes connect surface anthropogenic and natural emissions to local and regional air pollution. Using the data collected during the Study of Houston Atmospheric Radical Precursors (SHARP) in spring 2009, we examine atmospheric oxidation chemistry and O 3 production in this polluted urban environment. A numerical box model with five different chemical mechanisms was used to simulate the oxidation processes and thus OH and HO 2 in this study. In general, the model reproduced the measured OH and HO 2 with all five chemical mechanisms producing similar levels of OH and HO 2, although midday OH was overpredicted and nighttime OH and HO 2 were underpredicted. The calculated HO x production was dominated by HONO photolysis in the early morning and by the photolysis of O 3 and oxygenated volatile organic compounds (OVOCs) in the midday. On average, the daily HO x production rate was 24.6 ppbv d -1, of which 30% was from O 3 photolysis, 22% from HONO photolysis, 15% from the photolysis of OVOCs (other than HCHO), 14% from HCHO photolysis, and 13% from O 3 reactions with alkenes. The O 3 production was sensitive to volatile organic compounds (VOCs) in the early morning but was sensitive to NO x for most of afternoon. This is similar to the behavior observed in two previous summertime studies in Houston: the Texas Air Quality Study in 2000 (TexAQS 2000) and the TexAQS II Radical and Aerosol Measurement Project in 2006 (TRAMP 2006). Ozone production in SHARP exhibits a longer NO x -sensitive period than TexAQS 2000 and TRAMP 2006, indicating that NO x control may be an efficient approach for the O 3 control in springtime for Houston. Results from this study provide additional support for regulatory actions to reduce NO x and reactive VOCs in Houston in order to reduce O 3 and other secondary pollutants. © 2013. American Geophysical Union. All Rights Reserved.