Theoretical and modeling studies of the atmospheric chemistry of sulfur oxide and hydroxyl radical systems

Models are the tools that integrate our understanding of the atmospheric processes. Box models are utilized frequently and used to simulate the fates and transformation of atmospheric pollutants. The results from models are usually used to produce one integrated system and further help the policy makers to develop control strategies.;We have investigated the atmospheric chemistry of the SOx and HOx systems. The results of 15 laboratory experiments that involved the studies of the HO-SO2, reaction have been analyzed. Mixtures of HONO, NO, NO2, H2O, SO2 and CO were photolyzed in synthetic air or in nitrogen containing approximately 50 ppm oxygen. Upon analyzing the data we have found that a very large amount of the observed SO2 oxidation (70.0 +/- 9.1%) can not be explained through the gas phase reaction of HO + SO2 reaction alone. The Regional Atmospheric Chemistry Mechanism, Version 2 (RACM2) was used to investigate additional chemical pathways for the oxidation of SO2. The results indicate that a mechanism(s) involving photochemical heterogeneous reactions could account for the observed additional sulfur dioxide oxidation not accounted for by gas phase oxidation alone.;We have also investigated the distribution of the hydroxyl radical in different urban and rural areas. Photolysis of ozone and its reactions with nitrogen oxides and organic compounds, including both anthropogenic and biogenic volatile organic compounds (VOCs), control the mixing ratios of the hydroxyl radical (HO). Measurements of ozone, nitrogen oxides and volatile hydrocarbons from a deciduous forest in July 1999 and six sites located in the San Joaquin Valley obtained during the Central California Ozone Study (CCOS) measured in July 2000 and September 2000 were used to estimate the hydroxyl radical concentrations. Two methods were employed to determine the concentrations: (1) box model simulations and (2) steady state approximation of the species concentrations (Production-Loss Method). The results indicate that the concentrations observed here in this study are comparable with the HO concentrations measured and/or modeled from other studies.;HO concentrations produced from ozone, formaldehyde and isoprene were by far the most important sources for HO production but the HO removal processes greatly differs between the urban and rural areas. Hydroxyl radical concentrations vary by location, time of the day, season and meteorological conditions. Comparing the HO concentrations from our study with other studies from different urban, rural and marine environments shows that hydroxyl radical concentrations in the urban areas can be lower than some pristine environments.