Organic and inorganic geochemistry of low temperature gas discharges at the Baia di Levante beach, Vulcano Island, Italy

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Discharge from subaereal and submarine gas vents of the Baia di Levante beach gases from the Vulcano Island were sampled for major and trace gas components in May and November 1995.Chemical compositions and equilibrium calculations suggest three different groups of CO2-rich gas emissions depending on their distance from the La Fossa crater: (1) gas vents close to the Faraglione area are characterised by high H2S contents, high calculated equilibrium temperatures based on inorganic species and relatively high proportion of alkene compounds; (2) gas vents close to Vulcanello are characterised by low calculated equilibrium temperatures and low amounts of alkenes; and (3) Pontile sample has the highest equilibrium CO2 pressure (up to 68bars) which may account for the observed absence of benzene. The relative large variability of H2S in the Baia di Levante beach gas discharge may be attributed to either different interactions between iron sulphides and weakly acid waters or catalytic effect of elemental sulphur on the de-hydrogenation of cyclo-hexane. Thermodynamic calculations suggest that the main inorganic species and CH4 may have re-equilibrated at relatively shallow depth (10–200m b.s.l. and 30–600m b.s.l. for a lithostatic and hydrostatic pressure, respectively). The slow kinetics of reactions in the CnH2n/CnH2n+2 systems, with respect to that of CH4–CO–CO2, may explain the observed propene/propane ratios, which can only be reached at reaction temperatures of 300–350°C. This low speed of reactions can also explain the observed disequilibrium of C1–C4 alkanes.