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Equations of state, phase relations, and oxygen fugacity of the Ru-RuO2 buffer at high pressures and temperatures

  • Katherine Armstrong ORCID logo , Nicki C. Siersch , Tiziana Boffa-Ballaran , Daniel J. Frost ORCID logo , Tony Yu and Yanbin Wang
Published/Copyright: March 1, 2020
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American Mineralogist
From the journal American Mineralogist Volume 105 Issue 3

Abstract

Experimental studies and measurements of inclusions in diamonds show that ferric iron components are increasingly stabilized with depth in the mantle. To determine the thermodynamic stability of such components, their concentration needs to be measured at known oxygen fugacities. The metal-oxide pair Ru and RuO2 are ideal as an internal oxygen fugacity buffer in high-pressure experiments. Both phases remain solid to high temperatures and react minimally with silicates, only exchanging oxygen. To calculate oxygen fugacities at high pressure and temperature, however, requires information on the phase relations and equation of state properties of the solid phases.

We have made in situ synchrotron X‑ray diffraction measurements in a multi-anvil press on mixtures of Ru and RuO2 to 19.4 GPa and 1473 K with which we have determined phase relations of the RuO2 phases and derived thermal equations of state (EoS) parameters for both Ru and RuO2. Rutile-structured RuO2 was found to undergo two phase transformations, first at ~7 GPa to an orthorhombic structure and then above 12 GPa to a cubic structure. The phase boundary of the cubic phase was constrained for the first time at high pressure and temperature. We have derived a continuous Gibbs free energy expression for the tetragonal and orthorhombic phases of RuO2 by fitting the second-order phase transition boundary and P-V-T data for both phases, using a model based on Landau theory. The transition between the orthorhombic and cubic phases was then used along with EoS terms derived for both phases to determine a Gibbs free energy expression for the cubic phase. We have used these data to calculate the oxygen fugacity of the Ru + O2 = RuO2 equilibrium, which we have parameterized as a single polynomial across the stability fields of all three phases of RuO2. The expression is log10fO2(Ru – RuO2) = (7.782 – 0.00996P + 0.001932P2 – 3.76 × 10–5P3) + (–13 763 + 592P – 3.955P2)/T + (–1.05 × 106 – 4622P)/T2, which should be valid from room pressure up to 25 GPa and 773–2500 K, with an estimated uncertainty of 0.2 log units. Our calculated fO2 is shown to be up to 1 log unit lower than estimates that use previous expressions or ignore EoS terms.

Keywords: Oxygen fugacity; ruthenium/ruthenium dioxide; experimental petrology; phase relations; equation of state

Acknowledgments and Funding

Raphael Njul and Alex Rother are thanked for sample preparation. Funding was provided within the DFG-SPP program 1833 “Building a Habitable Earth” through grant FR 1555/10-1.

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Received: 2019-03-20
Accepted: 2019-10-19
Published Online: 2020-03-01
Published in Print: 2020-03-26

© 2020 Walter de Gruyter GmbH, Berlin/Boston

Articles in the same Issue

  1. Heavy halogen geochemistry of martian shergottite meteorites and implications for the halogen composition of the depleted shergottite mantle source
  2. The distribution and abundance of halogens in eclogites: An in situ SIMS perspective of the Raspas Complex (Ecuador)
  3. Pressure dependence of Si diffusion in γ-Fe
  4. Seismic detectability of carbonates in the deep Earth: A nuclear inelastic scattering study
  5. Equations of state, phase relations, and oxygen fugacity of the Ru-RuO2 buffer at high pressures and temperatures
  6. Experimental determination of the phase relations of Pt and Pd antimonides and bismuthinides in the Fe-Ni-Cu sulfide systems between 1100 and 700 °C
  7. Layer stacking disorder in Mg-Fe chlorites based on powder X-ray diffraction data
  8. Elasticity of single-crystal Fe-enriched diopside at high-pressure conditions: Implications for the origin of upper mantle low-velocity zones
  9. XANES spectroscopy of sulfides stable under reducing conditions
  10. Zircon and apatite geochemical constraints on the formation of the Huojihe porphyry Mo deposit in the Lesser Xing’an Range, NE China
  11. Textural and compositional evolution of iron oxides at Mina Justa (Peru): Implications for mushketovite and formation of IOCG deposits
  12. Siwaqaite, Ca6Al2(CrO4)3(OH)12·26H2O, a new mineral of the ettringite group from the pyrometamorphic Daba-Siwaqa complex, Jordan
  13. Negevite, the pyrite-type NiP2, a new terrestrial phosphide
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https://doi.org/10.2138/am-2020-7060
Keywords for this article
Oxygen fugacity; ruthenium/ruthenium dioxide; experimental petrology; phase relations; equation of state

Articles in the same Issue

  1. Heavy halogen geochemistry of martian shergottite meteorites and implications for the halogen composition of the depleted shergottite mantle source
  2. The distribution and abundance of halogens in eclogites: An in situ SIMS perspective of the Raspas Complex (Ecuador)
  3. Pressure dependence of Si diffusion in γ-Fe
  4. Seismic detectability of carbonates in the deep Earth: A nuclear inelastic scattering study
  5. Equations of state, phase relations, and oxygen fugacity of the Ru-RuO2 buffer at high pressures and temperatures
  6. Experimental determination of the phase relations of Pt and Pd antimonides and bismuthinides in the Fe-Ni-Cu sulfide systems between 1100 and 700 °C
  7. Layer stacking disorder in Mg-Fe chlorites based on powder X-ray diffraction data
  8. Elasticity of single-crystal Fe-enriched diopside at high-pressure conditions: Implications for the origin of upper mantle low-velocity zones
  9. XANES spectroscopy of sulfides stable under reducing conditions
  10. Zircon and apatite geochemical constraints on the formation of the Huojihe porphyry Mo deposit in the Lesser Xing’an Range, NE China
  11. Textural and compositional evolution of iron oxides at Mina Justa (Peru): Implications for mushketovite and formation of IOCG deposits
  12. Siwaqaite, Ca6Al2(CrO4)3(OH)12·26H2O, a new mineral of the ettringite group from the pyrometamorphic Daba-Siwaqa complex, Jordan
  13. Negevite, the pyrite-type NiP2, a new terrestrial phosphide
  14. Transjordanite, Ni2P, a new terrestrial and meteoritic phosphide, and natural solid solutions barringerite-transjordanite (hexagonal Fe2P–Ni2P)
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