Modelling Atmospheric Mineral Aerosol Chemistry to Predict Heterogeneous Photooxidation of SO2
Zechen Yu, Myoseon Jang, and Jiyeon Park
P. O. Box 116450, Department of Environmental Engineering Sciences, Engineering School of Sustainable Infrastructure and Environment, University of Florida, Gainesville, FL, USA, 32611
Received: 08 Feb 2017 – Accepted for review: 01 Mar 2017 – Discussion started: 09 Mar 2017
Abstract. The photocatalytic ability of airborne mineral dust particles is known to heterogeneously promote SO2 oxidation, but prediction of this phenomenon is not fully taken into account by current models. In this study, the Atmospheric Mineral Aerosol Reaction (AMAR) model was developed to capture the influence of air-suspended mineral dust particles on sulfate formation in various environments. In the model, SO2 oxidation proceeds in three phases including the gas phase, the inorganic-salted aqueous phase (non-dust phase), and the dust phase. Dust chemistry is described as the adsorption-desorption kinetics (gas-particle partitioning) of SO2 and NOx. The reaction of adsorbed SO2 on dust particles occurs via two major paths: autoxidation of SO2 in open air and photocatalytic mechanisms under UV light. The kinetic mechanism of autoxidation was first leveraged using controlled indoor chamber data in the presence of Arizona Test Dust (ATD) particles without UV light, and then extended to photochemistry. With UV light, SO2 photooxidation was promoted by surface oxidants (OH radicals) that are generated via the photocatalysis of semiconducting metal oxides (electron–hole theory) of ATD particles. This photocatalytic rate constant was derived from the integration of the combinational product of the dust absorbance spectrum and wave-dependent actinic flux for the full range of wavelengths of the light source. The predicted concentrations of sulfate and nitrate using the AMAR model agreed well with outdoor chamber data that were produced under natural sunlight. For seven consecutive hours of photooxidation of SO2 in an outdoor chamber, dust chemistry at the low NOx level was attributed to 70 % of total sulfate (60 ppb SO2, 290 μg m−3 ATD, and NOx less than 5 ppb). At high NOx (> 50 ppb of NOx with low hydrocarbons), sulfate formation was also greatly promoted by dust chemistry, but it was significantly suppressed by the competition between NO2 and SO2 that both consume the dust-surface oxidants (OH radicals or ozone). The AMAR model, derived in this study with ATD particles, will provide a platform for predicting sulfate formation in the presence of authentic dust particles (e.g. Gobi and Saharan dust).
Yu, Z., Jang, M., and Park, J.: Modelling Atmospheric Mineral Aerosol Chemistry to Predict Heterogeneous Photooxidation of SO2, Atmos. Chem. Phys. Discuss., doi:10.5194/acp-2017-120, in review, 2017.