We report here the very first assessment of volatile flux emissions from Gorely, an actively degassing volcano in Kamchatka. Using a variety of in situ and remote sensing techniques, we determined the bulk plume concentrations of major volatiles (H2O 93.5%, CO2, 2.6%, SO2 2.2%, HCl 1.1%, HF 0.3%, H2 0.2%) and trace-halogens (Br, I), therefore estimating a total gas release of 11,000 tons·day−1 during September 2011, at which time the target was non-eruptively degassing at 900°C. Gorely is a typical arc emitter, contributing 0.3% and 1.6% of the total global fluxes from arc volcanism for CO2 and HCl, respectively. We show that Gorely's volcanic gas (H2O/SO2 43, CO2/SO2 1.2, HCl/SO2 0.5) is a representative mean end-member for arc magmatism in the north-west Pacific region. On this basis we derive new constraints for the abundances and origins of volatiles in the subduction-modified mantle source which feeds magmatism in Kamchatka
Sphalerite is the main source of In – a ‘critical’ metal widely used in high-tech electronics. In this mineral the concentration of In is commonly correlated directly with Cu content. Here we use X-ray absorption spectroscopy of synthetic compounds and natural crystals in order to investigate the substitution mechanisms in sphalerites where In is present, together with the group 11 metals. All the admixtures (Au, Cu, In) are distributed homogeneously within the sphalerite matrix, but their structural and chemical states are different. In all the samples investigated In3+ replaces Zn in the structure of sphalerite. The In ligand distance increases by 0.12 Å and 0.09–0.10 Å for the 1st and 2nd coordination shells, respectively, in comparison with pure sphalerite. The In–S distance in the 3rd coordination shell is close to the one of pure sphalerite. Gold in synthetic sphalerites is coordinated with sulfur (NS = 2.4–2.5, RAu–S = 2.35 ± 0.01 Å). Our data suggest that at high Au concentrations (0.03–0.5 wt.%) the Au2S clusters predominate, with a small admixture of the Au+ solid solution with an Au–S distance of 2.5 Å. Therefore, the homogeneous character of a trace-element distribution, which is commonly observed in natural sulfides, does not confirm formation of a solid solution. In contrast to Au, the presence of Cu+ with In exists only in the solid-solution state, where it is tetrahedrally coordinated with S atoms at a distance of 2.30 ± 0.03 Å. The distant coordination shells of Cu are disordered. These results demonstrate that the group 11 metals (Cu, Ag and Au) can exist in sphalerite in the metastable solid-solution state. The solid solution forms at high temperature via the charge compensation scheme 2Zn2+↔Me++Me3+. The final state of the trace elements at ambient temperature is governed by the difference in ionic radii with the main component (Zn), and concentration of admixtures.
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