The Redox State of Earth's Mantle
Abstract
Oxygen thermobarometry measurements on spinel peridotite rocks indicate that the oxygen fugacity at the top of the upper mantle falls within ±2 log units of the fayalite-magnetite-quartz (FMQ) oxygen buffer. Measurements on garnet peridotites from cratonic lithosphere reveal a general decrease in fo 2 with depth, which appears to result principally from the effect of pressure on the controlling Fe 3+/Fe 2+ equilibria. Modeling of experimental data indicates that at approximately 8 GPa, mantle fo 2 will be 5 log units below FMQ and at a level where Ni-Fe metal becomes stable. Fe-Ni alloy and an Fe 2 O 3-garnet component will be formed as a result of the disproportionation of FeO, which is experimentally demonstrated through observations of high Fe 3+/ΣFe ratios in minerals in equilibrium with metallic Fe. In the lower mantle, the favorable coupled substitution of Al and Fe 3+ into (Fe,Mg)SiO 3 perovskite results in very high perovskite Fe 3+/ΣFe ratios in equilibrium with metallic Fe. As a result, the lower mantle should contain approximately 1 weight% metallic Fe formed through FeO disproportionation, if the bulk oxygen content is the same as the upper mantle. Loss of disproportionated metallic Fe from the lower mantle during core formation could explain the higher Fe 3+/ΣFe ratio of the present-day upper mantle when compared to that expected during core formation. The influence of pressure on mantle fo 2 has important implications for the speciation of C-O-H-S volatile phases in Earth today and during its early evolution.
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The Hadean atmosphere and mantle were probably initially highly reducing, before subsequent oxidation either by hydrogen escape or disproportionation of mantle FeO accompanied by Fe loss to the core.
“Therefore, the Hadean atmosphere and mantle were probably initially highly reducing, before subsequent oxidation either by hydrogen escape (29) or disproportionation of mantle FeO accompanied by Fe loss to the core (30, 31).”
From The Archean atmosphere (2020) · cites this paper as [30]
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Litvin, Y. А., Бутвина, В. Г., Bobrov, A. V., et al. (2002) · Doklady Earth Sciences · Cited by 35 · see citing works
Canil, D., Johnston, S. T., & Mihalynuk, M. G. (2006) · Earth and Planetary Science Letters · doi:10.1016/j.epsl.2006.04.038 · Cited by 33 · see citing works
Chapter 11.OXYGEN BAROMETRY OF SPINEL PERIDOTITES
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Redox control during mantle/melt interaction
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The oxidation state of Hadean magmas and implications for early Earth’s atmosphere
Trail, D., Watson, E. B., & Tailby, N. D. (2011) · Nature · doi:10.1038/nature10655 · Cited by 613 · see citing works
Catling, D. C., & Zahnle, K. J. (2020) · Science Advances · doi:10.1126/sciadv.aax1420 · Cited by 568 · see citing works
“Therefore, the Hadean atmosphere and mantle were probably initially highly reducing, before subsequent oxidation either by hydrogen escape (29) or disproportionation of mantle FeO accompanied by Fe loss to the core (30, 31).”
BackgroundOrigins of building blocks of life: A review
Kitadai, N., & Maruyama, S. (2018) · Geoscience Frontiers · doi:10.1016/j.gsf.2017.07.007 · Cited by 464 · see citing works
Laboratory Simulations of Abiotic Hydrocarbon Formation in Earth's Deep Subsurface
McCollom, T. M. (2013) · Reviews in Mineralogy and Geochemistry · doi:10.2138/rmg.2013.75.15 · Cited by 285 · see citing works
Johnson, B., & Goldblatt, C. (2015) · Earth-Science Reviews · doi:10.1016/j.earscirev.2015.05.006 · Cited by 224 · see citing works
Deep magma ocean formation set the oxidation state of Earth’s mantle
Armstrong, K., Frost, D. J., McCammon, C. A., Rubie, D. C., & Boffa Ballaran, T. (2019) · Science · doi:10.1126/science.aax8376 · Cited by 197 · see citing works
Self-citationCartigny, P., & Marty, B. (2013) · Elements · doi:10.2113/gselements.9.5.359 · Cited by 192 · see citing works
Nitrogen speciation in upper mantle fluids and the origin of Earth's nitrogen-rich atmosphere
Mikhail, S., & Sverjensky, D. A. (2014) · Nature Geoscience · doi:10.1038/ngeo2271 · Cited by 185 · see citing works
Strange messenger: a new history of hydrogen on Earth, as told by xenon
Zahnle, K. J., Gacesa, M., & Catling, D. C. (2019) · Geochimica et Cosmochimica Acta · doi:10.1016/j.gca.2018.09.017 · Cited by 175 · see citing works
A hydrogen-based oxidation mechanism relevant to planetary formation
Sharp, Z. D., McCubbin, F. M., & Shearer, C. K. (2013) · Earth and Planetary Science Letters · doi:10.1016/j.epsl.2013.08.015 · Cited by 147 · see citing works
Early Archaean tectonics and mantle redox recorded in Witwatersrand diamonds
Smart, K. A., Tappe, S., Stern, R. A., Webb, S. J., & Ashwal, L. D. (2016) · Nature Geoscience · doi:10.1038/ngeo2628 · Cited by 131 · see citing works
Ammonium-bearing clinopyroxene: A potential nitrogen reservoir in the Earth's mantle
Watenphul, A., Wunder, B., Wirth, R., & Heinrich, W. (2010) · Chemical Geology · doi:10.1016/j.chemgeo.2009.12.003 · Cited by 109 · see citing works
Nitrogen solubility in the deep mantle and the origin of Earth's primordial nitrogen budget
Yoshioka, T., Wiedenbeck, M., Shcheka, S., & Keppler, H. (2018) · Earth and Planetary Science Letters · doi:10.1016/j.epsl.2018.02.021 · Cited by 64 · see citing works
EarthN: A New Earth System Nitrogen Model
Johnson, B. W., & Goldblatt, C. (2018) · Geochemistry, Geophysics, Geosystems · doi:10.1029/2017gc007392 · Cited by 51 · see citing works
High-pressure compressibility and vibrational properties of (Ca,Mn)CO <sub>3</sub>
Liu, J., Caracas, R., Fan, D., Bobocioiu, E., Zhang, D., & Mao, W. L. (2016) · American Mineralogist · doi:10.2138/am-2016-5742 · Cited by 38 · see citing works
- Authors
- Frost, D. J., & McCammon, C. A.
- Affiliations
- University of Bayreuth (DE)
- Venue
- Annual Review of Earth and Planetary Sciences
- Publisher
- Annual Reviews
- Published
- 2008-05-01
- Volume
- 36
- Issue
- 1
- Pages
- 389-420
- ISSN
- 0084-6597 (ISSN-L)
- 1545-4495
- OpenAlex
- W2171968174
- Cited by
- 1,134
- References
- 124
- Citations by year
- 2026: 65 · 2025: 91 · 2024: 72 · 2023: 67 · 2022: 78 · 2021: 93 · 2020: 84 · 2019: 77 · 2018: 81 · 2017: 70 · 2016: 64 · 2015: 55 · 2014: 56 · 2013: 61 · 2012: 29
- FWCI
- 5.72
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Annual Review of Earth and Planetary Sciences (publishedVersion)
- Topics
- Physical Sciences › Earth and Planetary Sciences › Geophysics › High-pressure geophysics and materials
- Physical Sciences › Earth and Planetary Sciences › Geophysics › Geological and Geochemical Analysis
- Physical Sciences › Physics and Astronomy › Astronomy and Astrophysics › Astro and Planetary Science
- Keywords
- mantle redox state, oxygen fugacity, spinel peridotite, garnet peridotite, metallic iron, perovskite, core formation, cratonic lithosphere, early Earth evolution
About these checks
Registry, retraction, Cites and statistics results are computed, not judged, with one exception: a printed reference that no index lists is read once by a model before it counts as a citation error. Claims are extracted by a model and kept only when their quote appears verbatim in the text; each cited source is then checked, with a model’s help, for whether it says what the claim relies on. Those verdicts can be wrong — read the claim’s quote and the cited source before relying on one.
Statistics and arithmetic are recomputed, not judged.
Confidence bands are shown only for fields calibrated on our annotated test set. None is calibrated yet, so no band is shown.
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