Monitoring of rainwater chemistry during the recent volcanic unrest at Vulcano Island (Italy)

Volcanoes are an important source of gas and particles into the atmosphere, during the eruptive periods or even during passive degassing activity. The study of volcanic gases is a robust geochemical tool to understand, monitor and predict the behaviour of volcano activity, but it is also important to evaluate the effects of volcanic emission on a local and regional scale. The study of the chemistry of atmospheric deposition can provide important information in this regard. Vulcano Island is a stratovolcano located in the southernmost sector of the Aeolian archipelago (Sicily). Since the last eruption occurred in 1888-1890, volcanic emissions are characterized by intense fumarolic activity localized on the northeastern rim of La Fossa crater. Several episodes of volcanic unrest have occurred over the past 130 years, and the most recent period of crisis was between 2021 and 2022. It was characterised by the increasing fumarole temperatures and gas fluxes, shallow long-period seismicity, and diffuse soil degassing around the main crater. This study reports on the chemical composition of rainwater samples collected from November 2021 to January 2023, during the last unrest period of Vulcano Island. Fifteen rainwater samples were collected through a network of three bulk collectors; two of them were placed inside the fumarolic field, and the last one was located near Vulcano Porto. Rainwater samples were analysed for major and trace element contents, and physicochemical parameters were also measured. The pH of rainwater collected near the summit area reaches very low pH values (min 1.63), with a mean value of 2.29, which is significantly lower respect to the mean value at Vulcano Porto (5.7). The concentrations of dissolved solutes in rainfall (expressed as Total Dissolved Solids) are inversely proportional to pH and reach extremely high values in the most acidic samples (up to 1133 mg/L). The most influenced samples by the volcanic emissions are strongly enriched in sulphate, chlorine and fluorine as a direct result of the dissolution of acid gases in rainwater. In addition to the major species, high concentrations of potentially toxic trace elements (Al, As, B, Cd, Fe, Pb, Sb, Te, Ti, Tl, and REE) were found. At the most distal site (Vulcano Porto) the impact of volcanic emissions on rainfall is much less pronounced and the dominant source is mainly related to marine aerosol. These preliminary results on trace element concentrations in rainfall at Vulcano highlight the importance of these studies to fully evaluate the potential impact of volcanic emissions on rainwater and consequently on other environmental matrices (e.g. soils and plants), especially during a period of intense outgassing.