Genesis of chlorine and sulphur in fumarolic emissions at Vulcano Island (Italy) : assessment of pH and redox conditions in the hydrothermal system

Abstract

Chlorine- and sulphur-bearing compounds in fumarole discharges of the La Fossa crater at Vulcano Island (Italy) can be modelled by a mixing process between magmatic gases and vapour from a boiling hydrothermal system. This allows estimating the compounds in both endmembers. Magma degassing cannot explain the time variation of sulphur and HCl concentrations in the deep endmember, which are more probably linked to reactions of solid phases at depth, before mixing with the hydrothermal vapours. Based on the P^T conditions and speciation of the boiling hydrothermal system below La Fossa, the HCl and Stot contents in the hydrothermal vapours were used to compute the redox conditions and pH of the aqueous solution. The results suggest that the haematite magnetite buffer controls the hydrothermal fO2 values, while the pH has increased since the end of the 1970s. The main processes affecting pH values may be linked to Na^Ca exchanges between evolved seawater, feeding the boiling hydrothermal system, and local rocks. While Na is removed from water, calcium enters the solution, undergoes hydrolysis and produces HCl,lowering the pH of the water. The increasing water^rock ratio within the hydrothermal system lowers the Ca availability, so the aqueous solution becomes less acidic. Seawater flowing towards the boiling hydrothermal brine dissolves a large quantity of pyrite along its path. In the boiling hydrothermal system, dissolved sulphur precipitates as pyrite and anhydrite, and becomes partitioned in vapour phase as H2S and SO2. These results are in agreement with the paragenesis of hydrothermal alteration minerals recovered in drilled wells at Vulcano and are also in agreement with the isotopic composition of sulphur emitted by the crater fumaroles.