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A new path for hydroxyl radical formation via photo-excitation of nitrogen dioxide (NO2) and the reaction of photo-excited NO2 with water is evaluated using the UCI-CIT model for the South Coast Air Basin of California (SoCAB). Two separate studies predict different reaction rates, which differ by nearly an order of magnitude, for the reaction of photo-excited NO2 with water. Impacts of this new chemical mechanism on ozone and particulate matter formation, while utilizing both reaction rates, are quantified by simulating two summer episodes. First, sensitivity simulations are conducted to evaluate the uncertainty in the rate of reaction of photo-excited NO2 with water reported in the literature. Results indicate that the addition of photo-excited NO2 chemistry increases peak 8-h average ozone and particulate matter concentrations. The importance of this new chemistry is then evaluated in the context of pollution control strategies. A series of simulations are conducted to generate isopleths for ozone and particulate matter concentrations, varying baseline nitrogen oxides (NOx) and volatile organic compounds (VOC) emissions. Isopleths are obtained using 1987 emissions, to represent past conditions, and 2005, to represent current conditions in the SoCAB. Results show that the sensitivity of modeled pollutant control strategies due to photoexcitation decreases with the decrease in baseline emissions from 1987 to 2005. Results show that including NO2 photo-excitation, increases the sensitivity of ozone concentration with respect to changes in NOx emissions for both years. In particular, decreasing NOx emissions in 2005 when NO2 photo-excitation is included, while utilizing the higher reaction rate, leads to ozone relative reduction factors that are 15% lower than in a case without photo-excited NO2. This implies that photoexcitation increases the effectiveness in reducing ozone through NOx emissions reductions alone, which has implications for the assessment of future e

A new path for hydroxyl radical formation via photo-excitation of nitrogen dioxide (NO2) and the reaction of photo-excited NO2 with water is evaluated using the UCI-CIT model for the South Coast Air Basin of California (SoCAB). Two separate studies predict different reaction rates, which differ by nearly an order of magnitude, for the reaction of photo-excited NO2 with water. Impacts of this new chemical mechanism on ozone and particulate matter formation, while utilizing both reaction rates, are quantified by simulating two summer episodes. First, sensitivity simulations are conducted to evaluate the uncertainty in the rate of reaction of photo-excited NO2 with water reported in the literature. Results indicate that the addition of photo-excited NO2 chemistry increases peak 8-h average ozone and particulate matter concentrations. The importance of this new chemistry is then evaluated in the context of pollution control strategies. A series of simulations are conducted to generate isopleths for ozone and particulate matter concentrations, varying baseline nitrogen oxides (NOx) and volatile organic compounds (VOC) emissions. Isopleths are obtained using 1987 emissions, to represent past conditions, and 2005, to represent current conditions in the SoCAB. Results show that the sensitivity of modeled pollutant control strategies due to photoexcitation decreases with the decrease in baseline emissions from 1987 to 2005. Results show that including NO2 photo-excitation, increases the sensitivity of ozone concentration with respect to changes in NOx emissions for both years. In particular, decreasing NOx emissions in 2005 when NO2 photo-excitation is included, while utilizing the higher reaction rate, leads to ozone relative reduction factors that are 15% lower than in a case without photo-excited NO2. This implies that photoexcitation increases the effectiveness in reducing ozone through NOx emissions reductions alone, which has implications for the assessment of future e

Refractory black carbon (rBC) mass and number concentrations were quantified by a Single Particle Soot Photometer (SP2) in the CalNex 2010 field study on board the Center for Interdisciplinary Remotely-Piloted Aircraft Studies (CIRPAS) Twin Otter in the Los Angeles (LA) Basin in May, 2010. The mass concentrations of rBC in the LA Basin ranged from 0.002 0.530 micro g m(expn -3), with an average of 0.172 micro g m(expn -3). Lower concentrations were measured in the Basin outflow regions and above the inversion layer. The SP2 afforded a quantification of the mixing state of rBC aerosols through modeling the scattering cross-section with a core-and-shell Mie model to determine coating thickness. The rBC particles above the inversion layer were more thickly coated by a light-scattering substance than those below, indicating a more aged aerosol in the free troposphere. Near the surface, as the LA plume is advected from west to east with the sea breeze, a coating of scattering material grows on rBC particles, coincident with a clear growth of ammonium nitrate within the LA Basin and the persistence of water-soluble organic compounds as the plume travels through the outflow regions. Detailed analysis of the rBC mixing state reveals two modes of coated rBC particles; a mode with smaller rBC core diameters (90 nm) but thick (200 nm) coating diameters and a mode with larger rBC cores (145 nm) with a thin (75 nm) coating. The weekend effect in the LA Basin results in more thickly coated rBC particles, coinciding with more secondary formation of aerosol., Published in the Journal of Geophysical Research, v117 article ID D00V13, 20 Apr 2012. Prepared in cooperation with the Division of Engineering and Applied Science, California Institute of Technology, Pasadena, the Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, the Chemical Sciences Division, NOAA Earth System Research Laboratory, Boulder, CO, the Department of Chemical and Environmental Engineering, University of Arizona, Tucson, and the Department of Atmospheric Sciences, University of Arizona, Tucson.