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Ultra-reducing conditions in average mantle peridotites and in podiform chromitites: a thermodynamic model for moissanite (SiC) formation

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Abstract

Natural moissanite (SiC) is reported from mantle-derived samples ranging from lithospheric mantle keel diamonds to serpentinites to podiform chromitites in ophiolites related to suprasubduction zone settings (Luobusa, Dongqiao, Semail, and Ray-Iz). To simulate ultra-reducing conditions and the formation of moissanite, we compiled thermodynamic data for alloys (Fe–Si–C and Fe–Cr), carbides (Fe3C, Fe7C3, SiC), and Fe-silicides; these data were augmented by commonly used thermodynamic data for silicates and oxides. Computed phase diagram sections then constrain the P–T–fO2 conditions of SiC stability in the upper mantle. Our results demonstrate that: Moissanite only occurs at oxygen fugacities 6.5–7.5 log units below the iron–wustite buffer; moissanite and chromite cannot stably coexist; increasing pressure does not lead to the stability of this mineral pair; and silicates that coexist with moissanite have X Mg > 0.99. At upper mantle conditions, chromite reduces to Fe–Cr alloy at fO2 values 3.7–5.3 log units above the moissanite-olivine-(ortho)pyroxene-carbon (graphite or diamond) buffer (MOOC). The occurrence of SiC in chromitites and the absence of domains with almost Fe-free silicates suggest that ultra-reducing conditions allowing for SiC are confined to grain scale microenvironments. In contrast to previous ultra-high-pressure and/or temperature hypotheses for SiC origin, we postulate a low to moderate temperature mechanism, which operates via ultra-reducing fluids. In this model, graphite-/diamond-saturated moderately reducing fluids evolve in chemical isolation from the bulk rock to ultra-reducing methane-dominated fluids by sequestering H2O into hydrous phases (serpentine, brucite, phase A). Carbon isotope compositions of moissanite are consistent with an origin of such fluids from sediments originally rich in organic compounds. Findings of SiC within rocks mostly comprised by hydrous phases (serpentine + brucite) support this model. Both the hydrous phases and the limited diffusive equilibration of SiC with most minerals in the rocks indicate temperatures below 700–800 °C. Moissanite from mantle environments is hence a mineral that does not inform on pressure but on a low to moderate temperature environment involving ultra-reduced fluids. Any mineral in equilibrium with SiC could only contain traces of Fe2+ or Cr3+.

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Acknowledgments

This study was financed through Grants 200020-140541/1 and 200020-153112/1 by the Swiss National Science Foundation. We thank L. Dobrzhinitskaya, M.F. Zhou, and an anonymous reviewer for critical remarks that helped very much sharpening the manuscript.

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  1. Institute of Geochemistry and Petrology, ETH Zurich, Clausiusstrasse 25, 8092, Zurich, Switzerland

    Anastasia Golubkova, Max W. Schmidt & James A. D. Connolly

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  1. Anastasia Golubkova
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Golubkova, A., Schmidt, M.W. & Connolly, J.A.D. Ultra-reducing conditions in average mantle peridotites and in podiform chromitites: a thermodynamic model for moissanite (SiC) formation. Contrib Mineral Petrol 171, 41 (2016). https://doi.org/10.1007/s00410-016-1253-9

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