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Control of oxygen fugacity during high-temperature phase equilibrium experiments is required to simulate the conditions that exist in natural systems. At high pressures, oxygen fugacity may be imposed using solid buffer equilibria via the classic "double capsule" technique. This design becomes untenable, however, at temperatures above the melting points of commonly used noble metal capsule materials and/or where buffer assemblages may alloy with the capsule or contaminate the sample. Here we introduce and test a modified double capsule approach that includes a solid metal-oxide buffer in close proximity to but separate from the sample of interest. Buffers used include (in order of most oxidized to reduced) Ni-NiO, Co-CoO, W-WO3, Fe-FeO, Mo-MoO2, Cr-Cr2O3, V-V2O3, Ta-Ta2O5, and Nb-NbO. At a fixed temperature, these buffers span a wide range—up to 10 log fO2 units. To demonstrate the buffering capacity of this double capsule approach, secondary redox equilibria and V-doped CaO-MgO-Al2O3-SiO2 system glasses were studied in experiments using the double capsule geometry. The secondary equilibria provide an independent verification of the oxygen fugacity established in the double capsule environment. The glasses proved difficult to interpret, and our results provide guidance to future efforts to utilize the glass oxybarometer at reducing conditions. Application of this modified double capsule technique to studies of V valence in MgAl2O4 spinels led to the recognition of several factors that will affect V valence in this system: temperature of equilibration, duration of experiment, and spinel bulk composition. We have synthesized V-bearing MgAl2O4 spinel at the reduced conditions of the Cr-Cr2O3, (IW-3.51), Ta-Ta2O5, (IW-5.37), and Nb-NbO buffers (IW-5.44). This spinel exhibits a very small V3+ pre-edge peak consistent with its reduced nature. The absence of evidence for V2+ suggests that MgAl2O4 spinel excludes V2+ due to the preference of V for octahedral sites. This finding is supported by DFT calculations for spinels of variable composition, and in agreement with some other indirect evidence for preference for V3+ in aluminous spinels (Bosi et al. 2016,; Paque et al. 2013,). [ABSTRACT FROM AUTHOR]

Carbonaceous chondrites of the Vigarano group (CV) are primitive (nearly un‐metamorphosed) meteorites that provide a wealth of information about the early solar system, including constraints on chondrule formation, origin of calcium‐aluminum inclusions, stability of organic compounds, and redox conditions. The US Antarctic meteorite collection contains 119 CV samples from 15 dense collection areas (DCAs) from the TransAntarctic Mountains; these samples have been assigned a preliminary classification as CVs, but not to the subgroups oxidized A, oxidized B, and reduced. Furthermore, variation in petrologic grade can be determined non‐destructively using Raman spectroscopy. To update the classification of both subgroups and petrologic types in the collection, we have acquired magnetic susceptibility, metal and sulfide compositions, and Raman spectra. Overall, there are 55 oxidized A samples, 18 oxidized B samples, and 46 reduced samples. Several of the CVs are quite primitive (Lewis Cliffs Ice Tongue and MacAlpine Hills) but are also very small. Multiple pairing groups have been identified in the Miller Range (MIL), Queen Alexandra Range, and Larkman Nunatak DCAs, including all of the subgroups. In MIL 090981, there is evidence for multiple lithologies. We make suggested updates for all the samples, knowing that this information will help to better guide researchers interested in studying the CV chondrites in the US Antarctic meteorite collection. [ABSTRACT FROM AUTHOR]