Abstract. 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 (mistchamber/ion chromatograph) and long path DOAS (Differential Optical Absorption Spectroscopy) measurements at three different altitude ranges. Several HONO sources were accounted for in simulations, such as gas phase formation, direct emissions, nitrogen dioxide (NO 2 ) hydrolysis, photoinduced formation from excited NO 2 and photo-induced conversion of NO 2 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 2 only slightly affected HONO and ozone (O 3 ) concentrations. Photo-induced conversion of NO 2 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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Modified local meteorology owing to heterogeneities in the urban–rural surface can affect urban air quality. In this study, the impacts of urban land-surface forcing on ozone air quality during a high ozone (O₃) episode in the Seoul metropolitan area, South Korea, are investigated using a high-resolution chemical transport model (CMAQ). Under fair weather conditions, the temperature excess (urban heat island) significantly modifies boundary layer characteristics/structures and local circulations. The modified boundary layer and local circulations result in an increase in O₃ levels in the urban area of 16 ppb in the nighttime and 13 ppb in the daytime. Enhanced turbulence in the deep urban boundary layer dilutes pollutants such as NO_x, and this contributes to the elevated O₃ levels through the reduced O₃ destruction by NO in the NO_x-rich environment. The advection of O₃ precursors over the mountains near Seoul by the prevailing valley-breeze circulation in the mid- to late morning results in the build-up of O₃ over the mountains in conjunction with biogenic volatile organic compound (BVOC) emissions there. As the prevailing local circulation in the afternoon changes to urban-breeze circulation, the O₃-rich air masses over the mountains are advected over the urban area. The urban-breeze circulation exerts significant influences on not only the advection of O₃ but also the chemical production of O₃ under the circumstances in which both anthropogenic and biogenic (natural) emissions play important roles in O₃ formation. As the air masses that are characterized by low NO_x and high BVOC levels and long OH chain length are advected over the urban area from the surroundings, the ozone production efficiency increases in the urban area. The relatively strong vertical mixing in the urban boundary layer embedded in the sea-breeze inflow layer reduces NO_x levels, thus contributing to the elevated O₃ levels in the urban area

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 (NO₂^*) hydrolysis, photo-induced formation from excited NO₂^* and photo-induced conversion of NO₂ 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 NO₂ only slightly affected HONO and ozone (O₃) concentrations. Photo-induced conversion of NO₂ 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

No abstract