ACPD Atmospheric Chemistry and Physics Discussions ACPD 1680-7375 Copernicus GmbH Göttingen, Germany 10.5194/acpd-12-5851-2012 Modeling nitrous acid and its impact on ozone and hydroxyl radical during the Texas Air Quality Study 2006 Czader B. H. 1 Rappenglück B. 1 Percell P. 1 Byun D. W. 1 2 5 Ngan F. 3 Kim S. 4 University of Houston, Department of Earth and Atmospheric Sciences, 4800 Calhoun Rd, TX 77204-5007, Houston, USA Resources Laboratory, NOAA, Silver Spring, MD20910, USA present affiliation: Air Resources Laboratory,NOAA, Silver Spring, MD20910, USA now at: Ajou University, Suwon, South Korea author deceased 23 02 2012 12 2 5851 5880 This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. This article is available from http://www.atmos-chem-phys-discuss.net/12/5851/2012/acpd-12-5851-2012.html The full text article is available as a PDF file from http://www.atmos-chem-phys-discuss.net/12/5851/2012/acpd-12-5851-2012.pdf

Nitrous acid (HONO) mixing ratios for the Houston metropolitan area were simulated with the Community Multiscale Air Quality (CMAQ) model for an episode during the Texas Air Quality Study (TexAQS) II in August/September 2006 and compared to in-situ MC/IC (mist-chamber/ion chromatograph) and long path DOAS (Differential Optical Absorption Spectroscopy) measurements at three different altitudes. Several HONO sources were accounted for in simulations, such as gas phase formation, direct emissions, nitrogen dioxide (NO<sub>2</sub><sup>*</sup>) hydrolysis, photo-induced formation from excited NO<sub>2</sub><sup>*</sup> and photo-induced conversion of NO<sub>2</sub> into HONO on surfaces covered with organic materials. Compared to the gas-phase HONO formation there was about a tenfold increase in HONO mixing ratios when additional HONO sources were taken into account, which improved the correlation between modeled and measured values. Concentrations of HONO simulated with only gas phase chemistry did not change with altitude, while measured HONO concentrations decrease with height. A trend of decreasing HONO concentration with altitude was well captured with CMAQ predicted concentrations when heterogeneous chemistry and photolytic sources of HONO were taken into account. Heterogeneous HONO production mainly accelerated morning ozone formation, albeit slightly. Also HONO formation from excited NO<sub>2</sub> only slightly affected HONO and ozone (O<sub>3</sub>) concentrations. Photo-induced conversion of NO<sub>2</sub> into HONO on surfaces covered with organic materials turned out to be a strong source of daytime HONO. Since HONO immediately photo-dissociates during daytime its ambient mixing ratios were only marginally altered (up to 0.5 ppbv), but significant increase in the hydroxyl radical (OH) and ozone concentration was obtained. In contrast to heterogeneous HONO formation that mainly accelerated morning ozone formation, inclusion of photo-induced surface chemistry influenced ozone throughout the day.

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