Lachatre, Mathieu

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 (SO2􀀀 4(p), S(CVI)) in the midtropospheric 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 Mn2C and Fe3C 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 midtroposphere, 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.

We developed a new retrieval algorithm based on the Infrared Atmospheric Sounding Interferometer (IASI) observations, called AEROIASI-H2SO4, to measure the extinction and mass concentration of sulphate aerosols (binary solution droplets of sulphuric acid and water), with moderate random uncertainties (typically 35% total uncertainty for column mass concentration estimations). The algorithm is based on a self-adapting Tikhonov–Phillips regularization method. It is here tested over a moderate-intensity eruption of Mount Etna volcano (18 March 2012), Italy, and is used to characterise this event in terms of the spatial distribution of the retrieved plume. Comparisons with simultaneous and independent aerosol optical depth observations from MODIS (Moderate Resolution Imaging Spectroradiometer), SO2 plume observations from IASI and simulations with the CHIMERE chemistry/transport model show that AEROIASI-H2SO4 correctly identifies the volcanic plume horizontal morphology, thus providing crucial new information towards the study of volcanic emissions, volcanic sulphur cycle in the atmosphere, plume evolution processes, and their impacts. Insights are given on the possible spectroscopic evidence of the presence in the plume of larger-sized particles than previously reported for secondary sulphate aerosols from volcanic eruptions.

Excessive numerical diffusion is one of the major limitations in the representation of long-range transport by chemistry transport models. In the present study, we focus on excessive diffusion in the vertical direction, which has been shown to be a major issue, and we explore three possible ways of addressing this problem: increasing the vertical resolution, using an advection scheme with anti-diffusive properties and more accurately representing the vertical wind. This study was carried out using the CHIMERE chemistry transport model for the 18 March 2012 eruption of Mount Etna, which released about 3 kt of sulfur dioxide into the atmosphere in a plume that was observed by satellite instruments (the Infrared Atmospheric Sounding Interferometer instrument, IASI, and the Ozone Monitoring Instrument, OMI) for several days. The change from the classical Van Leer (1977) scheme to the Després and Lagoutière (1999) anti-diffusive scheme in the vertical direction was shown to provide the largest improvement to model outputs in terms of preserving the thin plume emitted by the volcano. To a lesser extent, the improved representation of the vertical wind field was also shown to reduce plume dispersion. Both of these changes helped to reduce vertical diffusion in the model as much as a brute-force approach (increasing vertical resolution).