Skip to content
Licensed Unlicensed Requires Authentication Published by De Gruyter January 3, 2017

Ab initio study of the structure and stability of CaMg(CO3)2 at high pressure

  • Natalia V. Solomatova EMAIL logo and Paul D. Asimow
From the journal American Mineralogist


Dolomite is one of the major mineral forms in which carbon is subducted into the Earth’s mantle. End-member CaMg(CO3)2 dolomite typically breaks down upon compression into two carbonates at 5–6 GPa in the temperature range of 800–1200 K (Shirasaka et al. 2002). However, high-pressure X-ray diffraction experiments have shown that dense high-pressure polymorphs of dolomite may be favored over single-cation carbonates (Santillán et al. 2003; Mao et al. 2011; Merlini et al. 2012). Here we compare calculated dolomite structures to experimentally observed phases. Using density functional theory interfaced with a genetic algorithm that predicts crystal structures (USPEX), a monoclinic phase with space group C2/c was found to have lower energy at pressures above 15 GPa than all previously reported dolomite structures. It is possible that this phase is not observed experimentally due to a large activation energy of transition from dolomite I, resulting in the observed second-order phase transition to a metastable dolomite II. Due to the complex energy landscape for candidate high-pressure dolomite structures, several structurally unique metastable polymorphs exist. We calculate the equation of state of a set of lowest-energy dolomite polymorphs with space groups P1¯, P2/c, and C2/c up to 80 GPa. Our results demonstrate a need for calculations and experiments on Fe-Mn bearing high-pressure carbonate phases to extend our understanding of Earth’s deep carbon cycle and test whether high-pressure polymorphs of double-cation carbonates represent the main reservoir for carbon storage within downwelling regions of Earth’s mantle.


We thank E.A. Schauble, A. Kavner, M. Merlini, G.F. Finkelstein, A.R. Oganov, and O. Hellman for valuable discussions and insights. We are thankful to N. Near-Ansari for assistance with technical aspects using FRAM, the high-performance computing cluster at Caltech. This work is supported by the U.S. National Science Foundation through award EAR-1551433.

References cited

Blöchl, P.E. (1994) Projector augmented-wave method. Physical Review B, 50, 17953.10.1103/PhysRevB.50.17953Search in Google Scholar

Boulard, E., Menguy, N., Auzende, A.L., Benzerara, K., Bureau, H., Antonangeli, D., Corgne, A., Morard, G., Siebert, J., Perrillat, J.P, and Guyot, F. (2012) Experimental investigation of the stability of Fe-rich carbonates in the lower mantle. Journal of Geophysical Research: Solid Earth, 117, B02208.10.1029/2011JB008733Search in Google Scholar

Boulard, E., Pan, D., Galli, G., Liu, Z., and Mao, W.L. (2015) Tetrahedrally coordinated carbonates in Earth’s lower mantle. Nature Communications, 6, 6311.10.1038/ncomms7311Search in Google Scholar

Brenker, F.E., Vollmer, C., Vincze, L., Vekemans, B., Szymanski, A., Janssens, K., and Kaminsky, F. (2006) CO2-recycling to the deep convecting mantle. Geochimica et Cosmochimica Acta, 70, A66.10.1016/j.gca.2006.06.236Search in Google Scholar

Brenker, F.E., Vollmer, C., Vincze, L., Vekemans, B., Szymanski, A., Janssens, K., Szaloki, I., Nasdala, L., Joswig, W., and Kaminsky, F. (2007) Carbonates from the lower part of transition zone or even the lower mantle. Earth and Planetary Science Letters, 260, 1–9.10.1016/j.epsl.2007.02.038Search in Google Scholar

Eggler, D.H. (1976) Does CO2 cause partial melting in the low-velocity layer of the mantle? Geology, 4, 69–72.10.1130/0091-7613(1976)4<69:DCCPMI>2.0.CO;2Search in Google Scholar

——— (1987) Solubility of major and trace elements in mantle metasomatic fluids: Experimental constraints. Mantle Metasomatism, Academic Press London, 21–41.Search in Google Scholar

Hazen, R.M., Jones, A.P., and Baross, J.A., Eds. (2013) Carbon in Earth. Reviews in Mineralogy and Geochemistry, 75, 698 p.10.1515/9781501508318Search in Google Scholar

Isshiki, M., Irifune, T., Hirose, K., Ono, S., Ohishi, Y., Watanuki, T., Nishibori, E., Takata, M., and Sakata, M. (2004) Stability of magnesite and its high-pressure form in the lowermost mantle. Nature, 427, 60–63.10.1038/nature02181Search in Google Scholar

Kelemen, P.B., and Manning, C.E. (2015) Reevaluating carbon fluxes in subduction zones, what goes down, mostly comes up. Proceedings of the National Academy of Sciences, 112, E3997–E4006.10.1073/pnas.1507889112Search in Google Scholar

Kresse, G., and Furthmüller, J. (1996) Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Computational Materials Science, 6(1), 15–50.10.1016/0927-0256(96)00008-0Search in Google Scholar

Mao, Z., Armentrout, M., Rainey, E., Manning, C.E., Dera, P., Prakapenka, V.B., and Kavner, A. (2011) Dolomite III: A new candidate lower mantle carbonate. Geophysical Research Letters, 38, L22303.10.1029/2011GL049519Search in Google Scholar

Martinez, I., Zhang, J., and Reeder, R.J. (1996) In situ X-ray diffraction of aragonite and dolomite at high pressure and high temperature; evidence for dolomite breakdown to aragonite and magnesite. American Mineralogist, 81, 611–624.10.2138/am-1996-5-608Search in Google Scholar

Merlini, M., Crichton, W.A., Hanfland, M., Gemmi, M., Müller, H., Kupenko, I., and Dubrovinsky, L. (2012) Structures of dolomite at ultrahigh pressure and their influence on the deep carbon cycle. Proceedings of the National Academy of Sciences, 109, 13509–13514.10.1073/pnas.1201336109Search in Google Scholar

Momma, K., and Izumi, F. (2008) VESTA: A three-dimensional visualization system for electronic and structural analysis. Journal of Applied Crystallography, 41, 653–658.10.1107/S0021889808012016Search in Google Scholar

Mörner, N.A., and Etiope, G. (2002) Carbon degassing from the lithosphere. Global and Planetary Change, 33, 185–203.10.1016/S0921-8181(02)00070-XSearch in Google Scholar

Murakami, M., Hirose, K., Kawamura, K., Sata, N., and Ohishi, Y. (2004) Postperovskite phase transition in MgSiO3. Science, 304, 855–858.10.1126/science.1095932Search in Google Scholar PubMed

Oganov, A.R., and Glass, C.W. (2006) Crystal structure prediction using ab initio evolutionary techniques: Principles and applications. The Journal of Chemical Physics, 124, 244704.10.1063/1.2210932Search in Google Scholar PubMed

Oganov, A.R., and Ono, S. (2004) Theoretical and experimental evidence for a post-perovskite phase of MgSiO3 in Earth’s D” layer. Nature, 430, 445–448.10.1038/nature02701Search in Google Scholar PubMed

Oganov, A.R., Glass, C.W., and Ono, S. (2006) High-pressure phases of CaCO3: Crystal structure prediction and experiment. Earth and Planetary Science Letters, 241, 95–103.10.1016/j.epsl.2005.10.014Search in Google Scholar

Oganov, A.R., Ono, S., Ma, Y., Glass, C.W., and Garcia, A. (2008) Novel high-pressure structures of MgCO3, CaCO3 and CO2 and their role in Earth’s lower mantle. Earth and Planetary Science Letters, 273, 38–47.10.1016/j.epsl.2008.06.005Search in Google Scholar

Oganov, A.R., Hemley, R.J., Hazen, R.M., and Jones, A.P. (2013) Structure, bonding, and mineralogy of carbon at extreme conditions. Reviews in Mineralogy and Geochemistry, 75, 47–77.10.1515/9781501508318-005Search in Google Scholar

Ono, S., Kikegawa, T., Ohishi, Y., and Tsuchiya, J. (2005) Post-aragonite phase transformation in CaCO3 at 40 GPa. American Mineralogist, 90, 667–671.10.2138/am.2005.1610Search in Google Scholar

Perdew, J.P., Burke, K., and Ernzerhof, M. (1996) Generalized gradient approximation made simple. Physical Review Letters, 77, 3865.10.1103/PhysRevLett.77.3865Search in Google Scholar

Ross, N.L., and Reeder, R.J. (1992) High-pressure structural study of dolomite and ankerite. American Mineralogist, 77, 412–421.Search in Google Scholar

Santillán, J., Williams, Q., and Knittle, E. (2003) Dolomite-II: A high-pressure polymorph of CaMg(CO3)2. Geophysical Research Letters, 30, 1054.10.1029/2002GL016018Search in Google Scholar

Shcheka, S.S., Wiedenbeck, M., Frost, D.J., and Keppler, H. (2006) Carbon solubility in mantle minerals. Earth and Planetary Science Letters, 245, 730–742.10.1016/j.epsl.2006.03.036Search in Google Scholar

Shirasaka, M., Takahashi, E., Nishihara, Y., Matsukage, K., and Kikegawa, T. (2002) In situ X-ray observation of the reaction dolomite = aragonite + magnesite at 900–1300 K. American Mineralogist, 87, 922–930.10.2138/am-2002-0715Search in Google Scholar

Skorodumova, N.V., Belonoshko, A.B., Huang, L., Ahuja, R., and Johansson, B. (2005) Stability of the MgCO3 structures under lower mantle conditions. American Mineralogist, 90, 1008–1011.10.2138/am.2005.1685Search in Google Scholar

Smyth, J.R., and Ahrens, T.J. (1997) The crystal structure of calcite III. Geophysical Research Letters, 24, 1595–1598.10.1029/97GL01603Search in Google Scholar

Sobolev, N.V., and Shatsky, V.S. (1990) Diamond inclusions in garnets from metamorphic rocks: A new environment for diamond formation. Nature, 343, 742–746.10.1038/343742a0Search in Google Scholar

Sturhahn, W. (2015) MINUTI open source software, ver. 1.1.2, Accessed on March 2015.Search in Google Scholar

Wyllie, P.J., Baker, M.B., and White, B.S. (1990) Experimental boundaries for the origin and evolution of carbonatites. Lithos, 26, 3–19.10.1016/0024-4937(90)90037-2Search in Google Scholar

Received: 2016-4-26
Accepted: 2016-8-24
Published Online: 2017-1-3
Published in Print: 2017-1-1

© 2017 by Walter de Gruyter Berlin/Boston

Downloaded on 5.2.2023 from
Scroll Up Arrow