Modelling SO₂conversion into sulfates in the mid-troposphere with a 3D chemistry transport model: the case of Mount Etna's eruption on 12 April 2012

Volcanic activity is an important source of atmospheric sulfur dioxide (SO2), which, after conversion into sulfuric acid, induces impacts on rain acidity, human health, meteorology and the radiative balance of the atmosphere, among others. This work focuses on the conversion of SO2 into sulfates (SO4(p)2-, S(+VI)) in the mid-tropospheric volcanic plume emitted by the explosive eruption of Mount Etna (Italy) on 12 April 2012, using the CHIMERE chemistry transport model. As the volcanic plume location and composition depend on several often poorly constrained parameters, using a chemistry transport model allows us to study the sensitivity of SO2 oxidation to multiple aspects, such as volcanic water emissions, transition metal emissions, plume diffusion and plume altitude. Our results show that two pathways contribute to sulfate production in the mid-troposphere: (1) the oxidation of SO2 by OH in the gaseous phase (70 %) and (2) aqueous oxidation by O2 catalysed by Mn2+ and Fe3+ ions (25 %). Oxidation in the aqueous phase is the faster process, but liquid water is scarce in the mid-troposphere; therefore, the relative share of gaseous oxidation can be important. After 1 d in the mid-troposphere, about 0.5 % of the volcanic SO2 was converted to sulfates via the gaseous process. Because of the nonlinear dependency of the kinetics in the aqueous phase on the amount of volcanic water emitted and on the availability of transition metals in the aqueous phase, several experiments have been designed to determine the prominence of different parameters. Our simulations show that, during the short time that liquid water remains in the plume, around 0.4 % of sulfates manage to quickly enter the liquid phase. Sensitivity tests regarding the advection scheme have shown that this scheme must be chosen wisely, as dispersion will impact both of the oxidation pathways explained above.