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Dolomite-IV: Candidate structure for a carbonate in the Earth’s lower mantle

  • Marco Merlini EMAIL logo , Valerio Cerantola , G. Diego Gatta , Mauro Gemmi , Michael Hanfland , Ilya Kupenko , Paolo Lotti , Harald Müller and Li Zhang
Published/Copyright: July 31, 2017
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American Mineralogist
From the journal American Mineralogist Volume 102 Issue 8

Abstract

We report the crystal structure of dolomite-IV, a high-pressure polymorph of Fe-dolomite stabilized at 115 GPa and 2500 K. It is orthorhombic, space group Pnma, a =10.091(3), b = 8.090(7), c = 4.533(3) Å, V = 370.1(4) Å3 at 115.2 GPa and ambient temperature. The structure is based on the presence of threefold C3O9 carbonate rings, with carbon in tetrahedral coordination. The starting Fe-dolomite single crystal during compression up to 115 GPa transforms into dolomite-II (at 17 GPa) and dolomite-IIIb (at 36 GPa). The dolomite-IIIb, observed in this study, is rhombohedral, space group R3, a =11.956(3), c =13.626(5) Å, V =1686.9(5) Å3 at 39.4 GPa. It is different from a previously determined dolomite-III structure, but topologically similar. The density increase from dolomite-IIIb to dolomite IV is ca. 3%. The structure of dolomite-IV has not been predicted, but it presents similarities with the structural models proposed for the high-pressure polymorphs of magnesite, MgCO3. A ring-carbonate structure match with spectroscopic analysis of high-pressure forms of magnesite-siderite reported in the literature, and, therefore, is a likely candidate structure for a carbonate at the bottom of the Earth’s mantle, at least for magnesitic and dolomitic compositions.

Keywords: Carbonate; high-pressure structure; tetrahedral ring-carbonate; single-crystal X-ray diffraction

Acknowledgments

We acknowledge ESRF for provision of beamtime (experiments HS-4720 and ES-142). Andrea Risplendente is acknowledged for microprobe analysis in Milan. We acknowledge the Deep Carbon Observatory (DCO) for supporting the research. Simon Redfern and two anonymous reviewers are acknowledged for helpful comments.

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Received: 2017-4-13
Accepted: 2017-5-22
Published Online: 2017-7-31
Published in Print: 2017-8-28

© 2017 by Walter de Gruyter Berlin/Boston

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https://doi.org/10.2138/am-2017-6161
Keywords for this article
Carbonate; high-pressure structure; tetrahedral ring-carbonate; single-crystal X-ray diffraction

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