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Abstract: Impact of the excited nitrogen dioxide (NO2 ∗) chemistry on air quality in the U.S. is examined using the Community Multiscale Air Quality (CMAQ) model for a summer month. Model simulations were conducted with and without the NO2 ∗ chemistry. The largest impact of the NO2 ∗ chemistry in the eastern U.S. occurred in the northeast and in the western U.S. occurred in Los Angeles. While the single largest daily maximum 8-h ozone (O3) increased by 9 ppbv in eastern U.S. and 6 ppbv in western U.S., increases on most days were much lower. No appreciable change in model performance statistics for surface-level O3 predictions relative to measurements is noted between simulations with and without the NO2 ∗ chemistry. Based on model calculations using current estimates of tropospheric emission burden, the NO2 ∗ chemistry can increase the monthly mean daytime hydroxyl radicals (OH) and nitrous acid (HONO) by a maximum of 28% and 100 pptv, respectively. [Copyright &y& Elsevier]

The oceans are the main source of natural halogen and sulfur compounds, which have a significant influence on the oxidizing capacity of the marine atmosphere; however, their impact on the air quality of coastal cities is currently unknown. We explore the effect of marine halogens (Cl, Br and I) and dimethyl sulfide (DMS) on the air quality of a large coastal city through a set of high-resolution (4-km) air quality simulations for the urban area of Los Angeles, US, using the Community Multiscale Air Quality (CMAQ model). The results indicate that marine halogen emissions decrease ozone and nitrogen dioxide levels up to 5 ppbv and 2.5 ppbv, respectively, in the city of Los Angeles. Previous studies suggested that the inclusion of chlorine in air quality models leads to the generation of ozone in urban areas through photolysis of nitryl chloride (ClNO 2 ). However, we find that when considering the chemistry of Cl, Br and I together the net effect is a reduction of surface ozone concentrations. Furthermore, combined ocean emissions of halogens and DMS cause substantial changes in the levels of key urban atmospheric oxidants such as OH, HO 2 and NO 3 , and in the composition and mass of fine particles. Although the levels of ozone, NO 3 and HO x are reduced, we find a 10% increase in secondary organic aerosol (SOA) mean concentration, attributed to the increase in aerosol acidity and sulfate aerosol formation when combining DMS and bromine. Therefore, this new pathway for enhanced SOA formation may potentially help with current model under predictions of urban SOA. Although further observations and research are needed to establish these preliminary conclusions, this first city-scale investigation suggests that the inclusion of oceanic halogens and DMS in air quality models may improve regional air quality predictions over coastal cities around the world. [ABSTRACT FROM AUTHOR]