skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Dry (Mg,Fe)SiO 3 perovskite in the Earth's lower mantle

Abstract

Combined synthesis experiments and first-principles calculations show that MgSiO 3-perovskite with minor Al or Fe does not incorporate significant OH under lower mantle conditions. Perovskite, stishovite, and residual melt were synthesized from natural Bamble enstatite samples (Mg/(Fe+Mg) = 0.89 and 0.93; Al 2O 3 < 0.1 wt% with 35 and 2065 ppm wt H 2O, respectively) in the laser-heated diamond anvil cell at 1600-2000 K and 25-65 GPa. Combined Fourier transform infrared (FTIR) spectroscopy, x-ray diffraction, and ex-situ transmission electron microscopy (TEM) analysis demonstrates little difference in the resulting perovskite as a function of initial water content. Four distinct OH vibrational stretching bands are evident upon cooling below 100 K (3576, 3378, 3274, and 3078 cm -1), suggesting 4 potential bonding sites for OH in perovskite with a maximum water content of 220 ppm wt H 2O, and likely no more than 10 ppm wt H 2O. Complementary, Fe-free, first-principles calculations predict multiple potential bonding sites for hydrogen in perovskite, each with significant solution enthalpy (0.2 eV/defect). We calculate that perovskite can dissolve less than 37 ppm wt H 2O (400 ppm H/Si) at the top of the lower mantle, decreasing to 31 ppm wt H 2O (340 ppm H/Si)more » at 125 GPa and 3000 K in the absence of a melt or fluid phase. Here, we propose that these results resolve a long-standing debate of the perovskite melting curve and explain the order of magnitude increase in viscosity from upper to lower mantle.« less

Authors:
 [1];  [1];  [2];  [1];  [3]
  1. The Ohio State Univ., Columbus, OH (United States)
  2. U.S. Army Research Lab., RDRL-WMRD, Aberdeen, MD (United States)
  3. Carnegie Institution of Washington, Washington, D.C. (United States)
Publication Date:
Research Org.:
Carnegie Institution of Washington, Washington, D.C. (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1335876
Grant/Contract Number:  
NA0002006
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Geophysical Research. Solid Earth
Additional Journal Information:
Journal Volume: 120; Journal Issue: 2; Journal ID: ISSN 2169-9313
Publisher:
American Geophysical Union
Country of Publication:
United States
Language:
English
Subject:
58 GEOSCIENCES

Citation Formats

Panero, Wendy R., Pigott, Jeffrey S., Reaman, Daniel M., Kabbes, Jason E., and Liu, Zhenxian. Dry (Mg,Fe)SiO3 perovskite in the Earth's lower mantle. United States: N. p., 2015. Web. doi:10.1002/2014JB011397.
Panero, Wendy R., Pigott, Jeffrey S., Reaman, Daniel M., Kabbes, Jason E., & Liu, Zhenxian. Dry (Mg,Fe)SiO3 perovskite in the Earth's lower mantle. United States. doi:10.1002/2014JB011397.
Panero, Wendy R., Pigott, Jeffrey S., Reaman, Daniel M., Kabbes, Jason E., and Liu, Zhenxian. Thu . "Dry (Mg,Fe)SiO3 perovskite in the Earth's lower mantle". United States. doi:10.1002/2014JB011397. https://www.osti.gov/servlets/purl/1335876.
@article{osti_1335876,
title = {Dry (Mg,Fe)SiO3 perovskite in the Earth's lower mantle},
author = {Panero, Wendy R. and Pigott, Jeffrey S. and Reaman, Daniel M. and Kabbes, Jason E. and Liu, Zhenxian},
abstractNote = {Combined synthesis experiments and first-principles calculations show that MgSiO3-perovskite with minor Al or Fe does not incorporate significant OH under lower mantle conditions. Perovskite, stishovite, and residual melt were synthesized from natural Bamble enstatite samples (Mg/(Fe+Mg) = 0.89 and 0.93; Al2O3 < 0.1 wt% with 35 and 2065 ppm wt H2O, respectively) in the laser-heated diamond anvil cell at 1600-2000 K and 25-65 GPa. Combined Fourier transform infrared (FTIR) spectroscopy, x-ray diffraction, and ex-situ transmission electron microscopy (TEM) analysis demonstrates little difference in the resulting perovskite as a function of initial water content. Four distinct OH vibrational stretching bands are evident upon cooling below 100 K (3576, 3378, 3274, and 3078 cm-1), suggesting 4 potential bonding sites for OH in perovskite with a maximum water content of 220 ppm wt H2O, and likely no more than 10 ppm wt H2O. Complementary, Fe-free, first-principles calculations predict multiple potential bonding sites for hydrogen in perovskite, each with significant solution enthalpy (0.2 eV/defect). We calculate that perovskite can dissolve less than 37 ppm wt H2O (400 ppm H/Si) at the top of the lower mantle, decreasing to 31 ppm wt H2O (340 ppm H/Si) at 125 GPa and 3000 K in the absence of a melt or fluid phase. Here, we propose that these results resolve a long-standing debate of the perovskite melting curve and explain the order of magnitude increase in viscosity from upper to lower mantle.},
doi = {10.1002/2014JB011397},
journal = {Journal of Geophysical Research. Solid Earth},
number = 2,
volume = 120,
place = {United States},
year = {2015},
month = {2}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 14 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

The energetics of aluminum solubility into MgSiO3 perovskite at lower mantle conditions
journal, April 2004


Equation of state of lower mantle (Al,Fe)-MgSiO3 perovskite
journal, December 2001

  • Andrault, Denis; Bolfan-Casanova, Nathalie; Guignot, Nicolas
  • Earth and Planetary Science Letters, Vol. 193, Issue 3-4
  • DOI: 10.1016/S0012-821X(01)00506-4

Water in Earth's Mantle: The Role of Nominally Anhydrous Minerals
journal, March 1992


Hydroxide in olivine: A quantitative determination of the absolute amount and calibration of the IR spectrum: HYDROXIDE IN OLIVINE
journal, February 2003

  • Bell, David R.; Rossman, George R.; Maldener, Joachim
  • Journal of Geophysical Research: Solid Earth, Vol. 108, Issue B2
  • DOI: 10.1029/2001JB000679

Whole-mantle convection and the transition-zone water filter
journal, September 2003


Water partitioning at 660 km depth and evidence for very low water solubility in magnesium silicate perovskite: WATER PARTITIONING
journal, September 2003

  • Bolfan-Casanova, Nathalie; Keppler, Hans; Rubie, David C.
  • Geophysical Research Letters, Vol. 30, Issue 17
  • DOI: 10.1029/2003GL017182

Pressure-induced changes in the compression mechanism of aluminous perovskite in the Earth's mantle
journal, October 2000


A sensitivity study of three-dimensional spherical mantle convection at 10 8 Rayleigh number: Effects of depth-dependent viscosity, heating mode, and an endothermic phase change
journal, June 1997

  • Bunge, Hans-Peter; Richards, Mark A.; Baumgardner, John R.
  • Journal of Geophysical Research: Solid Earth, Vol. 102, Issue B6
  • DOI: 10.1029/96JB03806

Thermodynamic properties and hydrogen speciation from vibrational spectra of dense hydrous magnesium silicates
journal, August 1996

  • Cynn, H.; Hofmeister, A. M.; Burnley, P. C.
  • Physics and Chemistry of Minerals, Vol. 23, Issue 6
  • DOI: 10.1007/BF00199502

Equation of state of Al-bearing perovskite to lower mantle pressure conditions
journal, October 2001

  • Daniel, Isabelle; Cardon, Hervé; Fiquet, Guillaume
  • Geophysical Research Letters, Vol. 28, Issue 19
  • DOI: 10.1029/2001GL013011

Pressure and temperature-dependence of water solubility in Fe-free wadsleyite
journal, July 2005


Linked magma ocean solidification and atmospheric growth for Earth and Mars
journal, July 2008


Metasomatism of gabbro - mineral replacement and element mobilization during the Sveconorwegian metamorphic event: METASOMATISM OF GABBRO
journal, December 2010


Water storage capacity in olivine and pyroxene to 14GPa: Implications for the water content of the Earth's upper mantle and nature of seismic discontinuities
journal, October 2012


Deep-mantle high-viscosity flow and thermochemical structure inferred from seismic and geodynamic data
journal, April 2001

  • Forte, Alessandro M.; Mitrovica, Jerry X.
  • Nature, Vol. 410, Issue 6832
  • DOI: 10.1038/35074000

The effect of Al 2 O 3 on Fe–Mg partitioning between magnesiowüstite and magnesium silicate perovskite
journal, May 2002


Preserving noble gases in a convecting mantle
journal, May 2009

  • Gonnermann, Helge M.; Mukhopadhyay, Sujoy
  • Nature, Vol. 459, Issue 7246
  • DOI: 10.1038/nature08018

The solid-state flow of polymineralic rocks
journal, January 1990


Partitioning of water during melting of the Earth's upper mantle at H2O-undersaturated conditions
journal, August 2006


Measurement of the melting curve of Mg 0.9 Fe 0.1 SiO 3 at lower mantle conditions and its geophysical implications
journal, October 1987

  • Heinz, Dion L.; Jeanloz, Raymond
  • Journal of Geophysical Research: Solid Earth, Vol. 92, Issue B11
  • DOI: 10.1029/JB092iB11p11437

The incorporation of water into lower-mantle perovskites: A first-principles study
journal, February 2013


WATER, MELTING, AND THE DEEP EARTH H 2 O CYCLE
journal, May 2006


Storage capacity of H2O in nominally anhydrous minerals in the upper mantle
journal, July 2005

  • Hirschmann, Marc M.; Aubaud, Cyril; Withers, Anthony C.
  • Earth and Planetary Science Letters, Vol. 236, Issue 1-2
  • DOI: 10.1016/j.epsl.2005.04.022

Water content in the transition zone from electrical conductivity of wadsleyite and ringwoodite
journal, April 2005

  • Huang, Xiaoge; Xu, Yousheng; Karato, Shun-ichiro
  • Nature, Vol. 434, Issue 7034
  • DOI: 10.1038/nature03426

Elastic properties of hydrous ringwoodite (γ-phase) in Mg2SiO4
journal, July 1998


Water partitioning in the Earth's mantle
journal, November 2010

  • Inoue, Toru; Wada, Tomoyuki; Sasaki, Rumi
  • Physics of the Earth and Planetary Interiors, Vol. 183, Issue 1-2
  • DOI: 10.1016/j.pepi.2010.08.003

Alteration of oceanic crust and geologic cycling of chlorine and water
journal, September 1983


Sound velocities and elastic constants of iron-bearing hydrous ringwoodite
journal, June 2004

  • Jacobsen, Steven D.; Smyth, Joseph R.; Spetzler, Hartmut
  • Physics of the Earth and Planetary Interiors, Vol. 143-144
  • DOI: 10.1016/j.pepi.2003.07.019

Water-Induced Fabric Transitions in Olivine
journal, August 2001


Rheology of the Upper Mantle: A Synthesis
journal, May 1993


Elasticity and strength of hydrous ringwoodite at high pressure
journal, September 2003


Garnet yield strength at high pressures and implications for upper mantle and transition zone rheology
journal, January 2007


Synthesis and Equation of State of (Mg,Fe) SiO3 Perovskite to Over 100 Gigapascals
journal, February 1987


Simulating the core-mantle boundary: An experimental study of high-pressure reactions between silicates and liquid iron
journal, July 1989


Hydrogen concentration analyses using SIMS and FTIR: Comparison and calibration for nominally anhydrous minerals: HYDROGEN CONCENTRATION ANALYSES
journal, February 2003

  • Koga, Kenneth; Hauri, Erik; Hirschmann, Marc
  • Geochemistry, Geophysics, Geosystems, Vol. 4, Issue 2
  • DOI: 10.1029/2002GC000378

Solubility of water in the α, β and γ phases of (Mg,Fe) 2 SiO 4
journal, May 1996

  • Kohlstedt, D. L.; Keppler, H.; Rubie, D. C.
  • Contributions to Mineralogy and Petrology, Vol. 123, Issue 4
  • DOI: 10.1007/s004100050161

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Proton-Conducting Oxides
journal, August 2003


Experimental investigation of the ?-? transformation of San Carlos olivine single crystal
journal, November 1998

  • Kubo, T.; Ohtani, E.; Kato, T.
  • Physics and Chemistry of Minerals, Vol. 26, Issue 1
  • DOI: 10.1007/s002690050155

Mössbauer and ELNES spectroscopy of (Mg,Fe)(Si,Al)O3 perovskite: a highly oxidised component of the lower mantle
journal, January 2000

  • Lauterbach, S.; McCammon, C. A.; van Aken, P.
  • Contributions to Mineralogy and Petrology, Vol. 138, Issue 1
  • DOI: 10.1007/PL00007658

Equations of state of the high-pressure phases of a natural peridotite and implications for the Earth's lower mantle
journal, July 2004

  • Lee, Kanani K. M.; O'Neill, Bridget; Panero, Wendy R.
  • Earth and Planetary Science Letters, Vol. 223, Issue 3-4
  • DOI: 10.1016/j.epsl.2004.04.033

Water solubility in Mg-perovskites and water storage capacity in the lower mantle
journal, June 2003

  • Litasov, Konstantin; Ohtani, Eiji; Langenhorst, Falko
  • Earth and Planetary Science Letters, Vol. 211, Issue 1-2
  • DOI: 10.1016/S0012-821X(03)00200-0

Numerical study of creep in two-phase aggregates with a large rheology contrast: Implications for the lower mantle
journal, August 2005

  • Madi, Kamel; Forest, Samuel; Cordier, Patrick
  • Earth and Planetary Science Letters, Vol. 237, Issue 1-2
  • DOI: 10.1016/j.epsl.2005.06.027

Synchrotron Infrared Absorbance Measurements of Hydrogen in MgSiO3 Perovskite
journal, June 1994


Influence of water on plastic deformation of olivine aggregates: 1. Diffusion creep regime
journal, September 2000

  • Mei, S.; Kohlstedt, D. L.
  • Journal of Geophysical Research: Solid Earth, Vol. 105, Issue B9
  • DOI: 10.1029/2000JB900179

Strength of (Mg,Fe)2SiO4 wadsleyite determined by relaxation of transformation stress
journal, June 2000

  • Mosenfelder, Jed L.; Connolly, James A. D.; Rubie, David C.
  • Physics of the Earth and Planetary Interiors, Vol. 120, Issue 1-2
  • DOI: 10.1016/S0031-9201(00)00142-4

Water in Earth's Lower Mantle
journal, March 2002


Aluminum in magnesium silicate perovskite: Formation, structure, and energetics of magnesium-rich defect solid solutions: ALUMINUM IN SILICATE PEROVSKITE
journal, July 2003

  • Navrotsky, Alexandra; Schoenitz, Mirko; Kojitani, Hiroshi
  • Journal of Geophysical Research: Solid Earth, Vol. 108, Issue B7
  • DOI: 10.1029/2002JB002055

Stability of a hydrous δ-phase, AlOOH–MgSiO2(OH)2, and a mechanism for water transport into the base of lower mantle
journal, September 2014


Stability of dense hydrous magnesium silicate phases in the systems Mg 2 SiO 4 -H 2 O and MgSiO 3 -H 2 O at pressures up to 27 GPa
journal, September 2000

  • Ohtani, E.; Mizobata, H.; Yurimoto, H.
  • Physics and Chemistry of Minerals, Vol. 27, Issue 8
  • DOI: 10.1007/s002690000097

Hydrogen incorporation in stishovite at high pressure and symmetric hydrogen bonding in δ-AlOOH
journal, April 2004


Transport of water into the lower mantle: Role of stishovite: TRANSPORT OF WATER INTO THE LOWER MANTLE
journal, January 2003

  • Panero, Wendy R.; Benedetti, Laura Robin; Jeanloz, Raymond
  • Journal of Geophysical Research: Solid Earth, Vol. 108, Issue B1
  • DOI: 10.1029/2002JB002053

Al2O3 incorporation in MgSiO3 perovskite and ilmenite
journal, November 2006

  • Panero, Wendy R.; Akber-Knutson, Sofia; Stixrude, Lars
  • Earth and Planetary Science Letters, Vol. 252, Issue 1-2
  • DOI: 10.1016/j.epsl.2006.09.036

Hydrous ringwoodite to 5 K and 35 GPa: Multiple hydrogen bonding sites resolved with FTIR spectroscopy
journal, March 2013

  • Panero, W. R.; Smyth, J. R.; Pigott, J. S.
  • American Mineralogist, Vol. 98, Issue 4
  • DOI: 10.2138/am.2013.3978

Hydrogen in Stishovite, with Implications for Mantle Water Content
journal, August 1993


Hydrous mantle transition zone indicated by ringwoodite included within diamond
journal, March 2014

  • Pearson, D. G.; Brenker, F. E.; Nestola, F.
  • Nature, Vol. 507, Issue 7491
  • DOI: 10.1038/nature13080

Single crystal X-ray diffraction study of MgSiO3 perovskite from 77 to 400 K
journal, April 1989

  • Ross, NancyL.; Hazen, RobertM.
  • Physics and Chemistry of Minerals, Vol. 16, Issue 5
  • DOI: 10.1007/BF00197010

Potential docking sites and positions of hydrogen in high-pressure silicates
journal, October 2003

  • Ross, Nancy L.; Gibbs, G. V.; Rosso, Kevin M.
  • American Mineralogist, Vol. 88, Issue 10
  • DOI: 10.2138/am-2003-1009

Aluminous hydrous mineral δ -AlOOH as a carrier of hydrogen into the core-mantle boundary
journal, January 2008

  • Sano, Asami; Ohtani, Eiji; Kondo, Tadashi
  • Geophysical Research Letters, Vol. 35, Issue 3
  • DOI: 10.1029/2007GL031718

Dehydration melting at the top of the lower mantle
journal, June 2014


High-pressure infrared spectroscopy of the dense hydrous magnesium silicates phase D and phase E
journal, July 2009

  • Shieh, Sean R.; Duffy, Thomas S.; Liu, Zhenxian
  • Physics of the Earth and Planetary Interiors, Vol. 175, Issue 3-4
  • DOI: 10.1016/j.pepi.2009.02.002

Structural systematics of hydrous ringwoodite and water in Earth’s interior
journal, October 2003

  • Smyth, Joseph R.; Holl, Christopher M.; Frost, Daniel J.
  • American Mineralogist, Vol. 88, Issue 10
  • DOI: 10.2138/am-2003-1001

Melting of iron-magnesium-silicate perovskite
journal, May 1993

  • Sweeney, Jeffrey S.; Heinz, Dion L.
  • Geophysical Research Letters, Vol. 20, Issue 9
  • DOI: 10.1029/93GL00556

Seismic evidence for a global low-velocity layer within the Earth’s upper mantle
journal, September 2010

  • Tauzin, Benoît; Debayle, Eric; Wittlinger, Gérard
  • Nature Geoscience, Vol. 3, Issue 10
  • DOI: 10.1038/ngeo969

H2O storage capacity of olivine and low-Ca pyroxene from 10 to 13 GPa: consequences for dehydration melting above the transition zone
journal, August 2011

  • Tenner, Travis J.; Hirschmann, Marc M.; Withers, Anthony C.
  • Contributions to Mineralogy and Petrology, Vol. 163, Issue 2
  • DOI: 10.1007/s00410-011-0675-7

Mantle transition zone structure along a profile in the SW Pacific: thermal and compositional variations
journal, January 2009


Postperovskite phase equilibria in the MgSiO3-Al2O3 system
journal, November 2008

  • Tsuchiya, J.; Tsuchiya, T.
  • Proceedings of the National Academy of Sciences, Vol. 105, Issue 49
  • DOI: 10.1073/pnas.0805660105

Low S velocity atop the 410-km discontinuity and mantle plumes
journal, October 2007


Influence of temperature, composition, silica activity and oxygen fugacity on the H2O storage capacity of olivine at 8 GPa
journal, April 2008

  • Withers, Anthony C.; Hirschmann, Marc M.
  • Contributions to Mineralogy and Petrology, Vol. 156, Issue 5
  • DOI: 10.1007/s00410-008-0303-3

Substitution mechanism of Al ions in MgSiO3 perovskite under high pressure conditions from first-principles calculations
journal, February 2003

  • Yamamoto, Tomoyuki; Yuen, David A.; Ebisuzaki, Toshikazu
  • Earth and Planetary Science Letters, Vol. 206, Issue 3-4
  • DOI: 10.1016/S0012-821X(02)01099-3

Some mineral physics constraints on the rheology and geothermal structure of Earth’s lower mantle
journal, April 2001

  • Yamazaki, Daisuke; Karato, Shun-ichiro
  • American Mineralogist, Vol. 86, Issue 4
  • DOI: 10.2138/am-2001-0401

Dry mantle transition zone inferred from the conductivity of wadsleyite and ringwoodite
journal, January 2008

  • Yoshino, Takashi; Manthilake, Geeth; Matsuzaki, Takuya
  • Nature, Vol. 451, Issue 7176
  • DOI: 10.1038/nature06427

    Works referencing / citing this record:

    Water Concentration in Single‐Crystal (Al,Fe)‐Bearing Bridgmanite Grown From the Hydrous Melt: Implications for Dehydration Melting at the Topmost Lower Mantle
    journal, September 2019

    • Fu, Suyu; Yang, Jing; Karato, Shun‐ichiro
    • Geophysical Research Letters, Vol. 46, Issue 17-18
    • DOI: 10.1029/2019gl084630