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Licensed Unlicensed Requires Authentication Published by De Gruyter March 1, 2020

Seismic detectability of carbonates in the deep Earth: A nuclear inelastic scattering study

  • Stella Chariton , Catherine McCammon ORCID logo , Denis M. Vasiukov , Michal Stekiel , Anastasia Kantor , Valerio Cerantola , Ilya Kupenko , Timofey Fedotenko , Egor Koemets , Michael Hanfland , Alexandr I. Chumakov and Leonid Dubrovinsky
From the journal American Mineralogist


Carbonates play an important role in the transport and storage of carbon in the Earth’s mantle. However, the abundance of carbon and carbonates in subduction zones is still an unknown quantity. To determine the most abundant accessory phases and how they influence the dynamical processes that operate within the Earth, investigations on the vibrational, elastic, and thermodynamic properties of these phases are crucial for interpreting seismological observations. Recently, the nuclear inelastic scattering (NIS) method has proved to be a useful tool to access information on the lattice dynamics, as well as to determine Debye sound velocities of Fe-bearing materials. Here we derive the acoustic velocities from two carbonate compositions in the FeCO3-MgCO3 binary system up to ~70 GPa using the NIS method. We conclude that more Mg-rich samples, in this case (Fe0.26Mg0.74)CO3, have ~19% higher sound velocities than the pure end-member Fe composition. In addition, we observed a significant velocity increase after the Fe2+ spin transition was complete. After laser heating of FeCO3 at lower mantle conditions, we observed a dramatic velocity drop, which is probably associated with thermal decomposition to another phase. Parallel to our NIS experiments, we conducted a single-crystal X‑ray diffraction (SCXRD) study to derive the equation of states of FeCO3 and (Fe0.26Mg0.74)CO3. The combined information from NIS (i.e., Debye velocities) and SCXRD (i.e., densities and bulk moduli) experiments enabled us to derive the primary and shear wave velocities of our samples. Our results are consistent with results obtained by other methods in previous studies, including Brillouin spectroscopy, inelastic X‑ray scattering, and DFT calculations, supporting NIS as a reliable alternative method for studying the elastic properties of Fe-bearing systems at high pressures and temperatures. Finally, we discuss the seismic detectability of carbonates. We determine that nearly 22 wt% CO2 must be present in the subduction slab to detect a 1% shear wave velocity decrease compared to non-carbonated lithologies at the transition zone to lower mantle boundary depths.

Acknowledgments and Funding

We thank the European Synchrotron Radiation Facility for provision of synchrotron radiation (ID18, ID15b). The project was supported by funds from the German Science Foundation (DFG) through the CarboPaT Research Unit FOR2125 (Mc3/20, Du393/9) and the German Federal Ministry for Education (BMBF).

References cited

Achterhold, K., Keppler, C., Ostermann, A., van Bürck, U., Sturhahn, W., Alp, E.E., and Parak, F.G. (2002) Vibrational dynamics of myoglobin determined by the phonon-assisted Mössbauer effect. Physical Review E, 65, 051916.10.1103/PhysRevE.65.051916Search in Google Scholar

Angel, J.R., Alvaro, M., and Gonzalez-Platas, J. (2014) EosFit7c and a Fortran module (library) for equation of state calculations. Zeitschrift für Kristallographie: Crystalline Matters, 229, 405–419.10.1515/zkri-2013-1711Search in Google Scholar

Aprilis, C., Strohm, C., Kupenko, I., Linhardt, S., Laskin, A., Vasiukov, D.M., Cerantola, C., Koemets, E.G., McCammon, C., Kurnosov, A., and others. (2017) Portable double-sided pulsed laser heating system for time-resolved geoscience and materials science applications. Review of Scientific Instruments, 88, 084501.10.1063/1.4998985Search in Google Scholar

Becker, H., and Altherr, R. (1992) Evidence from ultra-high pressure marbles for recycling of sediments into the mantle. Nature, 358, 745–748.10.1038/358745a0Search in Google Scholar

Biellmann, C., Gillet, P., Guyot, F., Peyronneau, J., and Reynard, B. (1993) Experimental evidence for carbonate stability in the Earth’s lower mantle. Earth and Planetary Science Letters, 118, 31–41.10.1016/0012-821X(93)90157-5Search in Google Scholar

Buchen, J., Marquardt, H., Speziale, S., Kawazoe, T., Boffa Ballaran, T., and Kurnosov, A. (2018) High-pressure single-crystal elasticity of wadsleyite and the seismic signature of water in the shallow transition zone. Earth and Planetary Science Letters, 498, 77–87.10.1016/j.epsl.2018.06.027Search in Google Scholar

Cerantola, V., McCammon, C., Kupenko, I., Kantor, I., Marini, C., Wilke, M., Ismailova, L., Solopova, N., Chumakov, A.I., Pascarelli, S., and others. (2015) High-pressure spectroscopic study of siderite (FeCO3) with focus on spin crossover. American Mineralogist, 100, 2670–2681.10.2138/am-2015-5319Search in Google Scholar

Cerantola, V., Bykova, E., Kupenko, I., Merlini, M., Ismailova, L., McCammon, C., Bykov, M., Chumakov, A.I., Petitgirard, S., Kantor, I., and others. (2017) Stability of iron-bearing carbonates in the deep Earth’s interior. Nature Communications, 8, 15960.10.1038/ncomms15960Search in Google Scholar PubMed PubMed Central

Chen, C., Zhao, D., Tian, Y., Wu, S., Hasegawa, A., Lei, J., Park, J-H., and Kang, I-B. (2017) Mantle transition zone, stagnant slab and intraplate volcanism in Northeast Asia. Geophysical Journal International, 209, 68–85.10.1093/gji/ggw491Search in Google Scholar

Chumakov, A.I., and Rüffer, R. (1998) Nuclear inelastic scattering. Hyperfine Interactions, 113, 59–79.10.1023/A:1012659229533Search in Google Scholar

Chumakov, A.I., Rüffer, R., Baron, A.Q.R., Grünsteudel, H., and Grünsteudel, H.F. (1996) Temperature dependence of nuclear inelastic absorption of synchrotron radiation in α-57Fe. Physical Review B, 44, R9599.Search in Google Scholar

Chumakov, A.I., Rüffer, R., Baron, A.Q.R., Grünsteudel, H., Grünsteudel, H.F., and Kohn, V.G. (1997) Anisotropic inelastic nuclear absorption. Physical Review B, 56, 10758.10.1103/PhysRevB.56.10758Search in Google Scholar

Dasgupta, R., and Hirschmann, M.M. (2010) The deep carbon cycle and melting in Earth’s interior. Earth and Planetary Science Letters, 298, 1–13.10.1016/j.epsl.2010.06.039Search in Google Scholar

Dasgupta, R., Hirschmann, M.M., and Withers, A.C. (2004) Deep global cycling of carbon constrained by solidus of anhydrous, carbonated eclogite under upper mantle conditions. Earth and Planetary Science Letters, 227, 73–85.10.1016/j.epsl.2004.08.004Search in Google Scholar

Dewaele, A., Datchi, F., Loubeyre, P., and Mezouar, M. (2008) High pressure–high temperature equations of state of neon and diamond. Physical Review B, 77, 094106.10.1103/PhysRevB.77.094106Search in Google Scholar

Dziewonski, A.M., and Anderson, D.L. (1981) Preliminary Reference Earth Model. Physics of the Earth and Planetary Interiors, 25, 297–356.10.1016/0031-9201(81)90046-7Search in Google Scholar

Fei, Y., Ricolleau, A., Frank, M., Mibe, K., Shen, G., and Prakapenka, V. (2007) Toward an internally consistent pressure scale. Proceedings of the National Academy of Sciences, 104, 9182–9186.10.1073/pnas.0609013104Search in Google Scholar PubMed PubMed Central

Fischer, T.P., Burnard, P., Marty, B., Hilton, D.R., Füri, E., Palhol, F., Sharp, Z.D., and Mangasini, F. (2009) Upper-mantle volatile chemistry at Oldoinyo Lengai volcano and the origin of carbonatites. Nature Letters, 459, 07977.10.1038/nature07977Search in Google Scholar PubMed

Fu, S., Yang, J, and Lin, J-F. (2017) Abnormal elasticity of single-crystal magnesiosiderite across the spin transition in Earth’s lower mantle. Physical Review Letters, 118, 036402.10.1103/PhysRevLett.118.036402Search in Google Scholar PubMed

Fukao, Y., and Obayashi, M. (2013) Subducted slabs stagnant above, penetrating through, and trapped below the 660 km discontinuity. Journal of Geophysical Research: Solid Earth, 118, 5920–5938.10.1002/2013JB010466Search in Google Scholar

Gonzalez-Platas, J., Alvaro, M., Nestola, F., and Angel, R.J. (2016) EosFit7-GUI: A new GUI tool for equation of state calculations, analyses and teaching. Journal of Applied Crystallography, 49, 1377–1382.10.1107/S1600576716008050Search in Google Scholar

Hu, M.Y., Sturhahn, W., Toellner, T.S., Mannheim, P.D., Brown, D.E., Zhao, J., and Alp, E.E. (2003) Measuring velocity of sound with nuclear resonant inelastic X‑ray scattering. Physical Review B, 67, 094304.10.1103/PhysRevB.67.094304Search 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 PubMed

Kaminsky, F. (2012) Mineralogy of the lower mantle: A review of ‘super-deep’ mineral inclusions in diamond. Earth-Science Reviews, 110, 127–147.10.1016/j.earscirev.2011.10.005Search in Google Scholar

Kantor, A., Kantor, I., Kurnosov, A., Dubrovinsky, L., Krisch, M., Bossak, A., and Jacobsen, S. (2008) Anelasticity of FexO at high pressure. Applied Physics Letters, 93, 034106.10.1063/1.2952274Search in Google Scholar

Kantor, I., Prakapenka, V., Kantor, A., Dera, P., Kurnosov, A., Sinogeikin, S., Dubrovinskaia, N., and Dubrovinsky, L. (2012) BX90: A new diamond anvil cell design for X‑ray diffraction and optical measurements. Review of Scientific Instruments, 83, 125102.10.1063/1.4768541Search in Google Scholar PubMed

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, 3997–4006.10.1073/pnas.1507889112Search in Google Scholar PubMed PubMed Central

Kennett, B.L.N., Engdahl, E.R., and Buland, R. (1995) Constraints on seismic velocities in the earth from travel times. Geophysical Journal International, 122, 108–124.10.1111/j.1365-246X.1995.tb03540.xSearch in Google Scholar

Kohn, V.G., and Chumakov, A.I. (2000) DOS: Evaluation of phonon density of states from nuclear resonant inelastic absorption. Hyperfine Interactions, 125, 205–221.10.1023/A:1012689705503Search in Google Scholar

Kupenko, I., Dubrovinsky, L., Dubrovinskaia, N., McCammon, C., Glazyrin, K., Bykova, E., Boffa Ballaran, T., Sinmyo, R., Chumakov, A., Potapkin, V., and others. (2012) Portable double-sided laser-heating system for Mössbauer spectroscopy and X‑ray diffraction experiments at synchrotron facilities with diamond anvil cells. Review of Scientific Instruments, 83, 124501.10.1063/1.4772458Search in Google Scholar PubMed

Kupenko, I., Strohm, C., McCammon, C., Cerantola, V., Glazyrin, K., Petitgirard, S., Vasiukov, D., Aprilis, G., Chumakov, A.I., Rüffer, R., and Dubrovinsky, L. (2015) differentiated nuclear resonance spectroscopy coupled with pulsed laser heating in diamond anvil cells. Review of Scientific Instruments, 86, 114501.10.1063/1.4935304Search in Google Scholar PubMed

Kurnosov, A., Kantor, I., Boffa Ballaran, T., Lindhardt, S., Dubrovisnky, L., Kuznetsov, A., and Zehnder, B.H. (2008) A novel gas-loading system for mechanically closing of various types of diamond anvil cells. Review of Scientific Instruments, 79, 045110.10.1063/1.2902506Search in Google Scholar

Lavina, B., Dera, P., Downs, R.T., Yang, W., Sinogeikin, S., Meng, Y., Shenand, G., and Schiferl, D. (2010) Structure of siderite FeCO3 to 56 GPa and hysteresis of its spin-pairing transition. Physical Review B, 82, 064110.10.1103/PhysRevB.82.064110Search in Google Scholar

Liu, Y., He, D., Gao, C., Foley, S., Gao, S., Hu, Z., Zong, K., and Chen, H. (2015) First direct evidence of sedimentary carbonate recycling in subduction-related xenoliths. Scientific Reports, 11547.10.1038/srep11547Search in Google Scholar

Mao, H.K., Xu, J., and Bell, P.M. (1986) Calibration of the ruby pressure gauge to 800 kbar under quasi-hydrostatic conditions. Journal of Geophysical Research, 91, 4673–7676.10.1029/JB091iB05p04673Search in Google Scholar

McCammon, C., Caracas, R., Glazyrin, K., Potapkin, V., Kantor, A., Sinmyo, R., Prescher, C., Kupenko, I., Chumakov, A.I., and Dubrovinsky, L. (2016) Sound velocities of bridgmanite from density of states determined by nuclear inelastic scattering and first-principles calculations. Progress in Earth and Planetary Science, doi:10.1186/s40645-016-0089-2.10.1186/s40645-016-0089-2Search in Google Scholar

McDonough, W.F., and Sun, S.S. (1995) The composition of the Earth. Chemical Geology, 120, 223–253.10.1016/S0074-6142(01)80077-2Search 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 PubMed PubMed Central

Müller, J., Speziale, S., Efthimiopoulos, I., Jahn, S., and Koch-Müller, M. (2016) Raman spectroscopy of siderite at high pressure: Evidence for a sharp spin transition. American Mineralogy, 101, 2638–2644.10.2138/am-2016-5708Search in Google Scholar

Nowacki, A., Kendall, J.-M., Wookey, J., and Pemberton, A. (2015) Mid-mantle an-isotropy in subduction zones and deep water transport. Geochemistry, Geophysics, Geosystems, 16, 764–784.10.1002/2014GC005667Search in Google Scholar

Parlinski, K., Lażewski, J., Jochym, P.T., Chumakov, A., Rüffer, R., and Kresse, G. (2001) Influence of magnetic interaction on lattice dynamics of FeBO3. Europhysics Letters, 56, 275–281.10.1209/epl/i2001-00517-6Search in Google Scholar

Petricek, V., Dusek, M., and Palatinus, L. (2014) Crystallographic Computing System JANA2006: General features. Zeitschrift für Kristallographie: Crystalline Materials, 229, 345–352.10.1515/zkri-2014-1737Search in Google Scholar

Plank, T., and Langmuir, C.H. (1998) The chemical composition of subducting sediment and its consequences for the crust and mantle. Chemical Geology, 145, 325–394.10.1016/S0009-2541(97)00150-2Search in Google Scholar

Rigaku Oxford Diffraction (2015) CrysAlisPRO software system, ver. 1.171. Rigaku Corporation, Oxford, U.K.Search in Google Scholar

Rüffer, R., and Chumakov, A.I. (1996) Nuclear Resonance Beamline at ESRF. Hyperfine Interactions, 97/98, 589–604.10.1007/BF02150199Search in Google Scholar

Sanchez-Valle, C., Ghosh, S., and Rosa, A.D. (2011) Sound velocities of ferromagnesian carbonates and the seismic detection of carbonates in eclogites and the mantle. Geophysical Research Letters, 38, L24315.10.1029/2011GL049981Search in Google Scholar

Shcheka, 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

Shen, G., Sturhahn, W., Alp, E.E., Zhao, J., Toellner, T.S., Prakapenka, V.B., Meng, Y., and Mao, H-R. (2004) Phonon density of states in iron at high pressures and high temperatures. Physics and Chemistry of Minerals, 31, 353–359.10.1007/s00269-004-0403-lSearch in Google Scholar

Shi, H., Luo, W., Johansson, B., and Ahuja, R. (2008) First-principles calculations of the electronic structure and pressure-induced magnetic transition in siderite FeCO3. Physical Review B, 78, 155119.10.1103/PhysRevB.78.155119Search in Google Scholar

Sinmyo, R., Glazyrin, K., McCammon, C., Kupenko, I., Kantor, I., Potapkin, V., Chumakov, A.I., Rüffer, R., and Dubrovinsky, L. (2014) The influence of solid solution on elastic wave velocity determination in (Mg,Fe)O using nuclear inelastic scattering. Physics of the Earth and Planetary Interiors, 229, 16–23.10.1016/j.pepi.2013.12.002Search in Google Scholar

Stekiel, M., Nguyen-Thanh, T., Chariton, S., McCammon, C., Bosak, A., Morgenroth, W., Milman, V., Refson, K., and Winkler, B. (2017) High pressure elasticity of FeCO3-MgCO3 carbonates. Physics of the Earth and Planetary Interiors, 271, 57–63.10.1016/j.pepi.2017.08.004Search in Google Scholar

Sturhahn, W., and Jackson, J.M. (2007) Geophysical applications of nuclear resonant spectroscopy. Geological Society of America, 421, 157–174.10.1130/2007.2421(09)Search in Google Scholar

Vasiukov, D.M., Ismailova, L., Kupenko, I., Cerantola, V., Sinmyo, R., Glazyrin, K., McCammon, C., Chumakov, A.I., Dubrovinsky, L., and Dubrovinskaia, N. (2018) Sound velocities of skiagite–iron–majorite solid solution to 56 GPa probed by nuclear inelastic scattering. Physics and Chemistry of Minerals, 45, 397–404.10.1007/s00269-017-0928-8Search in Google Scholar

Weis, C., Sternemann, C., Cerantola, V., Sahle, C.J., Spiekermann, G., Harder, M., Forov, Y., Kononov, A., Sakrowski, R., Yavas, H., and others (2017) Pressure driven spin transition in siderite and magnesiosiderite single crystals. Scientific Reports, 7, 16526.10.1038/s41598-017-16733-3Search in Google Scholar PubMed PubMed Central

Winkler, B., and Milman, V. (2014) Density functional theory based calculations for high pressure research. Zeitschrift für Kristallographie, 229, 112–122.10.1515/zkri-2013-1650Search in Google Scholar

Yang, J., Mao, Z., Lin, J-F., and Prakapenka, V.B. (2014) Single-crystal elasticity of the deep-mantle magnesite at high pressure and temperature. Earth and Planetary Science Letters, 392, 292–299.10.1016/j.epsl.2014.01.027Search in Google Scholar

Zhang, J., Martinez, I., Guyot, F., and Reeder, R. J. (1998) Effects of Mg-Fe2+ substitution in calcite-structure carbonates: Thermoelastic properties. American Mineralogist, 83, 280–287.10.2138/am-1998-3-411Search in Google Scholar

Received: 2018-11-19
Accepted: 2019-10-19
Published Online: 2020-03-01
Published in Print: 2020-03-26

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