Startseite Oxygen fugacity buffering in high-pressure solid media assemblies from IW-6.5 to IW+4.5 and application to the V K-edge oxybarometer
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Oxygen fugacity buffering in high-pressure solid media assemblies from IW-6.5 to IW+4.5 and application to the V K-edge oxybarometer

  • Kevin Righter ORCID logo , Anna L. Butterworth , Zack Gainsforth , Christine E. Jilly-Rehak ORCID logo , Subhayan Roychoudhury , Kayla Iacovino , Richard Rowland , Timmons M. Erickson , Kellye Pando , Daniel K. Ross , David Prendergast und Andrew J. Westphal
Veröffentlicht/Copyright: 2. März 2023
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American Mineralogist
Aus der Zeitschrift American Mineralogist Band 108 Heft 3

Abstract

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,).

Keywords: Oxygen fugacity; spinel; XANES; solar nebula

Funding statement: This research used resources of the Advanced Light Source and Molecular Foundry, which are DOE Office of Science User Facilities under contract no. DE-AC02-05CH11231. Research funding was provided by an award from the NASA Emerging Worlds program (A.J.W.) and the NASA Planetary Science Division (K.R.).

Acknowledgments

We thank Sirine Fakra, beamline scientist at ALS 10.3.2. We thank Roland Montes and Frank Cardenas for machining the Nb, Ta, and Cr buffer capsules, David Shapiro for additional computational support with the Phasis cluster at LBL, and Steve Sutton and an anonymous reviewer for very helpful reviews.

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Received: 2021-08-12
Accepted: 2022-03-02
Published Online: 2023-03-02
Published in Print: 2023-03-28

© 2023 by Mineralogical Society of America

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  13. Effects of thermal annealing on water content and δ18O in zircon
  14. Tourmaline and zircon trace the nature and timing of magmatic-hydrothermal episodes in granite-related Sn mineralization: Insights from the Libata Sn ore field
  15. Cation ordering, twinning, and pseudo-symmetry in silicate garnet: The study of a birefringent garnet with orthorhombic structure
  16. The occurrence of monoclinic jarosite in natural environments
  17. Niobium speciation in minerals revealed by L2,3-edges XANES spectroscopy
  18. The first occurrence of the carbide anion, C4–, in an oxide mineral: Mikecoxite, ideally (CHg4)OCl2, from the McDermitt open-pit mine, Humboldt County, Nevada, U.S.A
  19. Hydrothermal alteration of Ni-rich sulfides in peridotites of Abu Dahr, Eastern Desert, Egypt: Relationships among minerals in the Fe-Ni-Co-O-S system, fO2 and fS2
  20. New Mineral Names: Arsenic and Lead
https://doi.org/10.2138/am-2022-8301
Schlagwörter für diesen Artikel
Oxygen fugacity; spinel; XANES; solar nebula

Artikel in diesem Heft

  1. Mineralogy and bulk geochemistry of a fumarole at Hverir, Iceland: Analog for acid-sulfate leaching on Mars
  2. The crystal structure and chemistry of natural giniite and implications for Mars
  3. Solid solution of CaSiO3 and MgSiO3 perovskites in the lower mantle: The role of ferrous iron
  4. Secondary ion mass spectrometer analyses for trace elements in glass standards using variably charged silicon ions for normalization
  5. Raman shifts of c-BN as an ideal P-T sensor for studying water-rock interactions in a diamond-anvil cell
  6. Resetting of the U-Pb and Th-Pb systems in altered bastnäsite: Insight from the behavior of Pb at nanoscale
  7. X-ray diffraction reveals two structural transitions in szomolnokite
  8. Contamination of heterogeneous lower crust in Hannuoba tholeiite: Evidence from in situ trace elements and strontium isotopes of plagioclase
  9. Oxygen fugacity buffering in high-pressure solid media assemblies from IW-6.5 to IW+4.5 and application to the V K-edge oxybarometer
  10. Trace element partitioning between anhydrite, sulfate melt, and silicate melt
  11. Chemical reaction between ferropericlase (Mg,Fe)O and water under high pressure-temperature conditions of the deep lower mantle
  12. Composition-dependent thermal equation of state of B2 Fe-Si alloys at high pressure
  13. Effects of thermal annealing on water content and δ18O in zircon
  14. Tourmaline and zircon trace the nature and timing of magmatic-hydrothermal episodes in granite-related Sn mineralization: Insights from the Libata Sn ore field
  15. Cation ordering, twinning, and pseudo-symmetry in silicate garnet: The study of a birefringent garnet with orthorhombic structure
  16. The occurrence of monoclinic jarosite in natural environments
  17. Niobium speciation in minerals revealed by L2,3-edges XANES spectroscopy
  18. The first occurrence of the carbide anion, C4–, in an oxide mineral: Mikecoxite, ideally (CHg4)OCl2, from the McDermitt open-pit mine, Humboldt County, Nevada, U.S.A
  19. Hydrothermal alteration of Ni-rich sulfides in peridotites of Abu Dahr, Eastern Desert, Egypt: Relationships among minerals in the Fe-Ni-Co-O-S system, fO2 and fS2
  20. New Mineral Names: Arsenic and Lead
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Heruntergeladen am 10.9.2025 von https://www.degruyterbrill.com/document/doi/10.2138/am-2022-8301/html
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