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Oxybarometry of reduced silicate glasses: Using multivariate methods to constrain Cr oxidation states with application to lunar glasses

  • Molly C. McCanta ORCID logo EMAIL logo , M. Darby Dyar , Stephen R. Sutton ORCID logo , Sarah E. Roberts and Cai R. Ytsma
Published/Copyright: October 3, 2025
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American Mineralogist
From the journal American Mineralogist Volume 110 Issue 10

Abstract

Iron redox works well for constraining oxygen fugacity (fO2) in terrestrial igneous materials due to the relatively high fO2 of the Earth’s atmosphere, crust, and upper mantle [ fO2≥ quartz-fayalite-magnetite (QFM)], where there are large changes in Fe2+/Fe3+ with relatively small changes in fO2.  At  fO2 values <QFM, Fe redox becomes less sensitive, and analytical uncertainties may make it difficult to determine fO2 differences between samples. The valence change between Cr2+ and Cr3+ occurs at lower fO2 values than for iron, potentially making it a more sensitive oxybarometer for materials equilibrated under reducing conditions. The current approach to measuring fO2 from X-ray absorption (XAS) measurements derives Cr valence first from the 1s→4s transition and then uses that redox couple to estimate fO2 as a function of temperature and composition. Here, that method is compared to an alternate approach of predicting fO2 directly from the spectra of experimentally homogenized glasses of geological relevance without an intermediate step of attempting to discern Cr2+/Cr3+. In this study, partial least-squares (PLS) multivariate (MVA) regression models were trained on the whole XAS energy spectral range, and accuracy was quantified using root mean square error (RMSE). MVA results showed significantly higher accuracy (RMSE-C of ± 0.75 log units) for predicting fO2 ΔIW relative to known experimental conditions relative to the two-step method, which yielded RMSE-C of ±2.75 to ±7.65 log units for our data set vs. those of Berry and O’Neill (2004) and Berry et al. (2006), respectively. The MVA results calibrate a new Cr oxybarometer for use in low-fO2 glasses with a cross-validated (RMSE-CV) accuracy of ±0.84 log units fO2 relative to a standard oxygen buffer. Finally, the new Cr oxybarometer was applied to lunar glasses, both volcanic and impact metamorphosed, to assess the range in oxidation conditions the materials experienced during formation. Lunar volcanic glasses cluster ∼IW±1, close to that of previous studies while agglutinates and lunar impact melts record a wide range of fO2 values using Cr oxybarometry.

Keywords: Oxidation; XANES; chromium; lunar glasses

Acknowledgments and Funding

The authors thank Allen Patchen for his invaluable electron microprobe assistance and Tony Lanzirotti and Matt Newville for their help with XAS analysis at Argonne National Lab. The authors also express gratitude to A. Bell for placing complete analytical data from his 2021 study into a data repository. Finally, the authors thank the two reviewers for their constructive reviews that enhanced the clarity of this work. This study was supported by NASA Planetary Data Archiving, Restoration, and Tools grant NNX17AL07G (M.C.M.), NASA Apollo Next Generation Sample Analysis grant 80NSSC19K0802 (M.D.D.), NSF Petrology and Geochemistry grants EAR-1754261 (M.D.D.) and EAR-1754268 (M.C.M.), and RIS4E, SEEED, and VORTICES nodes of NASA SSERVI.

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Received: 2024-08-30
Accepted: 2025-02-23
Published Online: 2025-10-03
Published in Print: 2025-10-27

© 2025 Mineralogical Society of America

Articles in the same Issue

  1. Theoretical studies of thermodynamic and elastic properties of diamond under Earth’s mantle conditions
  2. Natrojarosite formed in the Matanomadh Formation, Kutch, India: A Na analog of jarosite on Mars
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  4. EBSD mapping of Cu-Fe-sulfides reveals microstructures enriched in critical/precious metals and resolves deformation histories
  5. The sulfate-bearing associations of fumarolic environments of Somma-Vesuvius volcano (Italy): A review from historical samples (Royal Mineralogical Museum of Naples)
  6. Snowball quartz in highly fractionated peraluminous granites: An indicator of multiple magma degassing
  7. Oxybarometry of reduced silicate glasses: Using multivariate methods to constrain Cr oxidation states with application to lunar glasses
  8. Nigelcookite, PbFe22+V23+(PO4)3(OH)3,and plumbojohntomaite, PbFe22+Fe23+(PO4)3(OH)3,two new members of the bjarebyite group from the Yushui Cu deposit, South China
  9. Rare occurrence of jarosite-alunite solid solutions with intermediate Al-Fe contents in the Jurassic Aztec Sandstone, Nevada, U.S.A
  10. Olgafrankite, Ni3Ge, a new mineral as the carrier of siderophile germanium in reduced systems
  11. Fuyuanite [Mg7Nb6O18(OH)8], a new hydrous magnesic-niobic oxide mineral from the Bayan Obo deposit, China
  12. Laboratory synthesis, spectroscopic characteristics, and thermal behavior of phoxite
  13. Sublattice disorder and Fe-Mg substitution in brucite: Implications for the subduction-zone water cycle
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  16. Book Review: Exoplanets: Compositions, Mineralogy, Evolution
https://doi.org/10.2138/am-2024-9602
Keywords for this article
Oxidation; XANES; chromium; lunar glasses

Articles in the same Issue

  1. Theoretical studies of thermodynamic and elastic properties of diamond under Earth’s mantle conditions
  2. Natrojarosite formed in the Matanomadh Formation, Kutch, India: A Na analog of jarosite on Mars
  3. Moxuanxueite, NaCa6Zr(Si2O7)2OF3, a new wöhlerite-group mineral from Gejiu alkaline complex, Yunnan Province, China
  4. EBSD mapping of Cu-Fe-sulfides reveals microstructures enriched in critical/precious metals and resolves deformation histories
  5. The sulfate-bearing associations of fumarolic environments of Somma-Vesuvius volcano (Italy): A review from historical samples (Royal Mineralogical Museum of Naples)
  6. Snowball quartz in highly fractionated peraluminous granites: An indicator of multiple magma degassing
  7. Oxybarometry of reduced silicate glasses: Using multivariate methods to constrain Cr oxidation states with application to lunar glasses
  8. Nigelcookite, PbFe22+V23+(PO4)3(OH)3,and plumbojohntomaite, PbFe22+Fe23+(PO4)3(OH)3,two new members of the bjarebyite group from the Yushui Cu deposit, South China
  9. Rare occurrence of jarosite-alunite solid solutions with intermediate Al-Fe contents in the Jurassic Aztec Sandstone, Nevada, U.S.A
  10. Olgafrankite, Ni3Ge, a new mineral as the carrier of siderophile germanium in reduced systems
  11. Fuyuanite [Mg7Nb6O18(OH)8], a new hydrous magnesic-niobic oxide mineral from the Bayan Obo deposit, China
  12. Laboratory synthesis, spectroscopic characteristics, and thermal behavior of phoxite
  13. Sublattice disorder and Fe-Mg substitution in brucite: Implications for the subduction-zone water cycle
  14. On the labyrinthine crystal-chemistry of boleite, a Pb-Ag-Cu hydroxyhalide
  15. Book Review
  16. Book Review: Exoplanets: Compositions, Mineralogy, Evolution
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