Characterization of gas chemistry and noble-gas isotope ratios of inclusion fluids in magmatic-hydrothermal and magmatic-steam alunite

Chemical and isotope data were obtained for the active gas and noble gas of inclusion fluids in coarse-grained samples of magmatic-hydrothermal and magmatic-steam alunite from well-studied deposits (Marysvale, Utah; Tambo, Chile; Tapajós, Brazil; Cactus, California; Pierina, Peru), most of which are discussed in this Volume. Primary fluid inclusions in the alunite typically are less than 0.2 μm but range up to several micrometers. Analyses of the active-gas composition of these alunite-hosted inclusion fluids released in vacuo by both crushing and heating indicate consistent differences in the compositions of magmatic-hydrothermal and magmatic-steam fluids. The compositions of fluids released by crushing were influenced by contributions from significant populations of secondary inclusions that trapped largely postdepositional hydrothermal fluids. Thermally released fluids gave the best representation of the fluids that formed primary alunite. The data are consistent with current models for the evolution of magmatic-hydrothermal and magmatic-steam fluids. Magmatic-steam fluids are vapor-dominant, average about 49 mol% H 2O, and contain N 2, H 2, CH 4, CO, Ar, He, HF, and HCl, with SO 2 the dominant sulfur gas (average SO 2/H 2S=202). In contrast, magmatic-hydrothermal fluids are liquid-dominant, average about 88 mol% H 2O, and contain N 2, H 2, CO 2, and HF, with H 2S about as abundant as SO 2 (average SO 2/H 2S=0.7). The low SO 2/H 2S and N 2/Ar ratios, and the near-absence of He in magmatic-hydrothermal fluids, are consistent with their derivation from degassed condensed magmatic fluids whose evolution from reduced-to-oxidized aqueous sulfur species was governed first by rock and then by fluid buffers. The high SO 2/H 2S and N 2/Ar with significant concentrations of He in magmatic-steam fluids are consistent with derivation directly from a magma. None of the data supports the entrainment of atmospheric gases or mixing of air-saturated gases in meteoric water in either magmatic-hydrothermal or magmatic-steam fluids. Thus, the oxidation of SO 2 to aqueous sulfate in the magmatic-steam fluids did not result from mixing with atmospheric oxygen. Both of the fluid types are characterized by high H 2 contents that range from 0.2 mol% to the extraordinarily large amounts (66 mol%) observed in some magmatic-steam fluids. Modeling of gas speciation using SOLVGAS requires most of the gas species to have been in disequilibrium at the time of their trapping in the flu