Modelling Atmospheric Mineral Aerosol Chemistry to Predict Heterogeneous Photooxidation of SO<sub>2</sub>

Abstract

<p><strong>Abstract.</strong> The photocatalytic ability of airborne mineral dust particles is known to heterogeneously promote SO<sub>2</sub> 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, SO<sub>2</sub> 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 SO<sub>2</sub> and NO<sub>x</sub>. The reaction of adsorbed SO<sub>2</sub> on dust particles occurs via two major paths: autoxidation of SO<sub>2</sub> 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, SO<sub>2</sub> 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 SO<sub>2</sub> in an outdoor chamber, dust chemistry at the low NO<sub>x</sub> level was attributed to 70 % of total sulfate (60 ppb SO<sub>2</sub>, 290 μg m<sup>−3</sup> ATD, and NO<sub>x</sub> less than 5 ppb). At high NO<sub>x</sub> (> 50 ppb of NO<sub>x</sub> with low hydrocarbons), sulfate formation was also greatly promoted by dust chemistry, but it was significantly suppressed by the competition between NO<sub>2</sub> and SO<sub>2</sub> 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).</p>