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This study shows how the composition of gases released from a single magmatic source may be modified during their ascending path. The main processes that influence the composition of the gases in these high temperature fumarolic environments, are: 1) interactions with wallrocks during gas ascent, which change the fugacities of the metal volatile species and affect the equilibrium between major species (fH2S/fSO2; fH2/fH2O); 2) mixing with meteoric water with consequent Cl adsorption, which may account for the Cl depletion of the gases; 3) remobilisation of previously formed sublimates and/or incrustation deposits. Comparison between the thermochemical models and the mineralogical composition of the silica tubes at Kudryavy and Satsuma-Iwojima volcanoes suggests that high fO2 due to the mixing of the gases with air during their injection into the atmosphere significantly reduces the volatility of several trace elements (As, Sb, Sn, Na, K, Tl, Te, Se and Cd). Comparisons between the enriched metals in aerosols and in the gases suggest that Mo, Pb, Bi, Na, K, Cu, Zn or Fe, which are enriched in the gases, are preferentially deposited in the gas conduits and vents whereas the highly volatile metals (Te, Tl, Sb, As and Se) and Cd condense in the plume. This study determines the reactions that may occur during the alteration of rocks in high temperature fumarolic environments. Three different processes of alteration prevail: (1) Acidic alteration which is characterized by the complete absence of clays, because the constant supply of gases to these systems allows for the pH values of the acidic fluids to be maintained low enough to prevent the precipitation of clay minerals. Complete leaching of all cations, except Si, from the primary silicates leads to important "silicification" of the wall rock. The primary mineral cations are leached in the following order: K, Na > Ca > Fe, Mg > Al > Si, Ti. The fluids enriched in these cations circulate in microcracks at different temperatures and different redox conditions and lead to the precipitation of secondary incrustations. At Kudryavy the incrustations are mainly sulfates. At Usu the lower sulfur/fluoride ratio of the gases allows the occurrence of aluminum fluoride incrustations. The order of primary minerals dissolution (olivine > plagioclase > pyroxene > matrix glass > Fe-Ti oxides) is established for both sites studied. (2) Alteration by an oxidized volcanic gas, resulting from mixing with the atmosphere (500 to 300°C). At Kudryavy, thermochemical modeling suggests that anhydrite and anhydrous sulfates, which occur at intermediate temperatures, are formed by interactions of the rock with oxidized gas. (3) The most important outcome of this work is the identification of the features of alteration by the volcanic gas that directly reacts with the rock at high temperatures (T > 500°C). The Kudryavy rocks show evidences for mineral transformations, which occur in the presence of the volcanic gas phase. Volcanic gas directly reacts with rocks at high temperatures (T > 500°C). The gas destabilizes the primary minerals, remobilizes the rock-bearing cations, and leads to the formation of second mineral assemblages. These transformations occur in situ, without significant mobility (gain or loss) of the cations. The high temperature secondary associations are characterized by the presence of andradite, hedenbergite, hercynite, tridymite/cristobalite. Anhydrite and anhydrous Al sulfate may occur within these mineral assemblages if the gas is oxidized. |
