Rainwater Chemistry at Mt. Etna (Italy): Natural and Anthropogenic Sources of Major Ions

Major ion content of 37 wet-only rainwater samples collected on the southern flank of Mount Etna volcano was investigated. Measured pH values range from 3.80 to 7.22 and display a positive correlation with Ca²⁺ and an inverse correlation with NO₃^–, suggesting that anthropogenic NO_x are the most effective acidifying agents while Ca, likely as solid CaCO₃, is the prevailing proton acceptor. Na/Cl ratios indicate a dominant marine origin for both species, while K, mg and Ca contents point to additional sources (soil dust, fertilisers etc.). Nitrate and sulphate concentrations display a nearly constant ratio indicating a common anthropogenic origin, and only a few samples are characterised by sulphate excess. The analysis of time series reveals a good correlation between the excess sulphate in rainwater and SO₂ fluxes from the summit craters plume. Non sea salt chloride contents show also a significant correlation with volcanic activity indicating a magmatic sulphur and chloride contribution to rainwater. Meteoric flux estimations point to a prevailing magmatic origin for sulphur in the collected rainwaters while sea spray is the main source of chlorine.