Dip CFTA, Univ. Palermo

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.

Helium isotope ratios of olivine and pyroxene phenocrysts from Plio-Quaternary volcanic rocks from southern Italy (seven Aeolian Islands, Mt. Vulture, Etna, Ustica, and Pantelleria) range from 2.3 to 7.1 Ra. Importantly, the phenocryst 3He/4He correlate well with whole rock Sr isotopic composition (0.70309– 0.70711), reflecting the mixing of two sources. A significant contribution of He from crustal contamination is recorded only occasionally (e.g., pyroxenes from Vulcano). When merged with data from the Roman Comagmatic Province, a remarkably strong near-linear He-Sr isotope correlation is apparent. The general northward decrease in 3He/4He corresponds to an increase in 87Sr/86Sr (and a decrease in 143Nd/144Nd and 206Pb/204Pb) that is due to increasing metasomatic enrichment of the mantle wedge via subduction of the Ionian-Adriatic plate. Calculations based on the ingrowth of 4He in the wedge and on the 4He content of the subducting crust show that mechanisms of enrichment in radiogenic He are effective only if the wedge is strongly depleted in He relative to best estimates of the depleted mantle. This can be accommodated if the process of metasomatism by the subduction fluids depletes the mantle wedge. The 3He/4He of Pantelleria, Etna, Iblei, Ustica, Alicudi, and Filicudi basalts (7.0 ± 0.6 Ra) define the mantle composition least affected by subduction-related metasomatism. Although these volcanoes are from a variety of tectonic regimes (subduction-related, intraplate, rifting), their similarities suggest a common origin of geochemical features. Their characteristics are consistent with a HIMU-type mantle that either is younger than the Cook- Austral island end-member or has a lower 238U/204Pb.