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Crystal structure, Raman and FTIR spectroscopy, and equations of state of OH-bearing MgSiO3 akimotoite

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Abstract

MgSiO3 akimotoite is stable relative to majorite-garnet under low-temperature geotherms within steeply or rapidly subducting slabs. Two compositions of Mg–akimotoite were synthesized under similar conditions: Z674 (containing about 550 ppm wt H2O) was synthesized at 22 GPa and 1,500 °C and SH1101 (nominally anhydrous) was synthesized at 22 GPa and 1,250 °C. Crystal structures of both samples differ significantly from previous studies to give slightly smaller Si sites and larger Mg sites. The bulk thermal expansion coefficients of Z674 are (153–839 K) of a 1 = 20(3) × 10−9 K−2 and a 0 = 17(2) × 10−6 K−1, with an average of α 0 = 27.1(6) × 10−6 K−1. Compressibility at ambient temperature of Z674 was measured up to 34.6 GPa at Sector 13 (GSECARS) at Advanced Photon Source Argonne National Laboratory. The second-order Birch–Murnaghan equation of state (BM2 EoS) fitting yields: V 0 = 263.7(2) Å3, K T0 = 217(3) GPa (K′ fixed at 4). The anisotropies of axial thermal expansivities and compressibilities are similar: α a  = 8.2(3) and α c  = 10.68(9) (10−6 K−1); β a  = 11.4(3) and β c  = 15.9(3) (10−4 GPa). Hydration increases both the bulk thermal expansivity and compressibility, but decreases the anisotropy of structural expansion and compression. Complementary Raman and Fourier transform infrared (FTIR) spectroscopy shows multiple structural hydration sites. Low-temperature and high-pressure FTIR spectroscopy (15–300 K and 0–28 GPa) confirms that the multiple sites are structurally unique, with zero-pressure intrinsic anharmonic mode parameters between −1.02 × 10−5 and +1.7 × 10−5 K−1, indicating both weak hydrogen bonds (O–H···O) and strong OH bonding due to long O···O distances.

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Acknowledgments

This work was supported by US National Science Foundation Grants EAR 11-13369 to JRS, EAR-0748707 (CAREER) to SDJ, and EAR-0955647 (CAREER) to WRP. We also acknowledge the support from Carnegie/DOE Alliance Center (CDAC) and the David and Lucile Packard Foundation. Synthesis was carried out at Bayerisches Geoinstitut (BGI), through support of the BGI Visitors Program. Neal Blair is acknowledged for access to the FTIR microscope at Northwestern University. GeoSoilEnviroCARS was supported by the NSF (EAR-0622171), the Department of Energy (DOE) DE-FG02-94ER14466, and the State of Illinois. Use of the Advanced Photon Source was supported by the DOE Office of Science, Office of Basic Energy Sciences, Under Contract No. DE-AC02-06CH11357. The use of the U2A beamline at the National Synchrotron Light Source beamline was supported by COMPRES, through the NSF Cooperative Agreement EAR 06-49658 and by the DOE, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-98CH10886.

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  1. Yu Ye

    Present address: School of Earth and Space Exploration, Arizona State University, Tempe, AZ, 85287, USA

Authors and Affiliations

  1. Department of Physics, University of Colorado, Boulder, CO, 80309, USA

    Yu Ye

  2. Department of Geological Sciences, University of Colorado, Boulder, CO, 80309, USA

    Joseph R. Smyth & David A. Brown

  3. Department of Earth and Planetary Sciences, Northwestern University, Evanston, IL, 60208, USA

    Steven D. Jacobsen, Yun-Yuan Chang & Joshua P. Townsend

  4. School of Earth Sciences, Ohio State University, Columbus, OH, 43210, USA

    Wendy R. Panero & Cayman Unterborn

  5. Bayerisches Geoinstitut, Universität Bayreuth, 95440, Bayreuth, Germany

    Tomoo Katsura

  6. Center for Advanced Radiation Sources, University of Chicago, Argonne National Laboratory, Argonne, IL, 60439, USA

    Przemyslaw Dera & Sergey Tkachev

  7. Geophysical Laboratory, Carnegie Institution of Washington, Washington, DC, 20015, USA

    Zhenxian Liu

  8. Institut Néel, CNRS and Université Joseph Fourier, BP 166, 38042, Grenoble Cedex 9, France

    Céline Goujon

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Correspondence to Yu Ye.

Additional information

Communicated by T. L. Grove.

Appendices

Appendix 1

See Table 7.

Table 7 OH frequencies (cm−1) for akimotoite Z674 at pressures and temperatures
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Appendix 2

See Table 8.

Table 8 Unit-cell parameters of akimotoite Z674 as functions of temperature
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Appendix 3

See Table 9.

Table 9 Unit-cell parameters of akimotoite Z674 as functions of pressure
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Ye, Y., Smyth, J.R., Jacobsen, S.D. et al. Crystal structure, Raman and FTIR spectroscopy, and equations of state of OH-bearing MgSiO3 akimotoite. Contrib Mineral Petrol 166, 1375–1388 (2013). https://doi.org/10.1007/s00410-013-0933-y

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