Hostname: page-component-cd9895bd7-hc48f Total loading time: 0 Render date: 2024-12-24T00:35:15.841Z Has data issue: false hasContentIssue false

Hydrogen incorporation in a ringwoodite analogue: Mg2GeO4 spinel

Published online by Cambridge University Press:  05 July 2018

B. Hertweck*
Affiliation:
Laboratoire Mécanismes de Transferts en Géologie, CNRS, UMR 5563, Université Paul Sabatier, 14 avenue Edouard Belin, 31400 Toulouse, France
J. Ingrin
Affiliation:
Laboratoire Mécanismes de Transferts en Géologie, CNRS, UMR 5563, Université Paul Sabatier, 14 avenue Edouard Belin, 31400 Toulouse, France
*

Abstract

Single crystals of Mg2GeO4 spinel, a stable analogue to mantle ringwoodite at atmospheric pressure up to 800°C, were synthesized from Mg2GeO4 olivine in hydrous conditions at 1.9 GPa and ∼1000°C. Infrared (IR) spectra show OH-stretching peaks at 3531 and 3502 cm–1. Quantification of IR spectra reveals hydrogen in the order of 5 to 10 ppm wt. H2O. A complete hydrogen/deuterium exchange was achieved at 700°C leading to a diffusion coefficient of deuterium of ∼3x10–14 m2/s. This value is of the same order as diffusion coefficients observed in other mantle minerals, such as garnet and diopside.

The O–O distance of ∽ 2.9 Å calculated from the spectra of Mg2GeO4 spinel is consistent with the GeO4 tetrahedra edge length known from crystal-structure data. Whereas the hydration mechanism and the site occupancies involved are still in discussion for mantle spinel, the IR measurements on Mg2GeO4 confirm the idea of protonation at the tetrahedral edges.

Type
Research Article
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2005

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

Bell, D.R. and Rossman, G.R. (1992) Water in the earth's mantle: The role of nominally anhydrous minerals. Science, 255, 13911397.CrossRefGoogle ScholarPubMed
Blanchard, M. and Ingrin, J. (2004) Kinetics of deuteration in pyrope. European Journal of Mineralogy, 16, 567576.CrossRefGoogle Scholar
Bolfan-Casanova, N., Keppler, H. and Rubie, D.C. (2000) Water partitioning between nominally anhydrous minerals in the MgO-SiO2-H2O system up to 24 GPa: implications for the distribution of water in the Earth's mantle. Earth and Planetary Science Letters, 182, 209.CrossRefGoogle Scholar
Carslaw, H.S. and Jaeger, J.C. (1959) Conduction of Heat in Solids, 2nd edition. Oxford, UK, 510 pp.Google Scholar
Drake, M.J. and Righter, K. (2002) Determining the composition of the earth. Nature, 416, 3944.CrossRefGoogle Scholar
Dreele, R.B. and Navrotsky, A. (1954) Refinement of the crystal structure of Mg2GeO4 spinel. American Mineralogist, 39, 957–97.Google Scholar
Dupas-Bruzek, C, Tingle, T.N., Green II, H.W., Doukhan, N. and Doukhan, J.C. (1998) The rheology of olivine and spinel magnesium germanate (Mg2GeO4). TEM study of the defect microstructure. Physics and Chemistry of Minerals, 25, 501514.CrossRefGoogle Scholar
Hercule, S. and Ingrin, J. (1999) Hydrogen in diopside: Diffusion, extraction-incorporation, and solubility. American Mineralogist, 84, 15771588.CrossRefGoogle Scholar
Ingrin, J. and Skogby, H. (2000) Hydrogen in nominally anhydrous upper mantle minerals: Concentration levels and implications.. European Journal of Mineralogy, 12, 543570.CrossRefGoogle Scholar
Ingrin, J., Hercule, S. and Charton, T. (1995) Diffusion of hydrogen in diopside: Results of dehydration experiments. Journal of Geophysical Research, 100, 489499.CrossRefGoogle Scholar
Jeanloz, R. (1980) Infrared spectra of olivine polymorphs: α, β-phase and spinel.. Physics and Chemistry of Minerals, 5, 327339.CrossRefGoogle Scholar
Kohlstedt, D.L., Keppler, H. and Rubie, D.C. (1996) Solubility of water in the α, β and γ phases of (Mg,Fe)2SiO4 . Mineralogy and Petrology, 123, 345357.CrossRefGoogle Scholar
Kudoh, Y., Kuribayashi, T., Mizobata, H. and Ohtani, E. (2000) Structure and cation disorder of hydrous ringwoodite, y-Mg1.89Si0.98H0.30O4.. Physics and Chemistry of Minerals, 27, 474479.CrossRefGoogle Scholar
Kurka, A., Blanchard, M. and Ingrin, J. (2005) Kinetics of hydrogen extraction and deuteration in grossular. Mineralogical Magazine, 69, 359371.CrossRefGoogle Scholar
Libowitzky, E. (1999) Correlation of O-H stretching frequencies and O-H···O hydrogen bond lengths in minerals. Monatshefte für Chemie/Chemical Monthly, 130, 10471059.CrossRefGoogle Scholar
Libowitzky, E. and Rossman, G.R. (1997) An IR absorption calibration for water in minerals. American Mineralogist, 82, 1111 — 1115.CrossRefGoogle Scholar
Ohtani, E., Toma, M., Litasov, K., Kubo, T. and Suzuki, A. (2001) Stability of dense hydrous magnesium silicate phases and water storage capacity in the transition zone and lower mantle. Physics of the Earth and Planetary Interiors, 124, 105117.CrossRefGoogle Scholar
Ross, N.L. and Navrotsky, A. (1987) The Mg2GeO4 olivine-spinel phase transition. Physics and Chemistry of Minerals, 14, 473481.CrossRefGoogle Scholar
Sasaki, S., Prewitt, C.T., Saito, Y. and Ito, E. (1982) Single crystal X-ray study of γ-Mg2SiO4 . Journal of Geophysical Research, 87, 78297832.CrossRefGoogle Scholar
Smyth, J.R. (1987) Beta-Mg2SiO4: a potential host for water in the mantle. American Mineralogist, 72, 10511055.Google Scholar
Smyth, J.R. and Frost, D.J. (2002) The effect of water on the 410-km discontinuity: An experimental study. Geophysical Research Letters 2002GL014418.CrossRefGoogle Scholar
Smyth, J.R., Holl, CM., Frost, D.J., Jacobsen, S.D., Langenhorst, F. and McCammon, C.A. (2003) Structural systematics of hydrous ringwoodite and water in earth's interior. American Mineralogist, 88, 14021407.CrossRefGoogle Scholar
Truckenbrodt, J. and Johannes, W. (1999) H2O loss during piston-cylinder experiments. American Mineralogist, 84, 13331335.CrossRefGoogle Scholar
Williams, Q. and Hemley, R.J. (2001) Hydrogen in the deep earth. Annual Review of Earth and Planetary Sciences, 29, 365418.CrossRefGoogle Scholar
Woods, S.C., Mackwell, S. and Dyar, D. (2000) Hydrogen in diopside: Diffusion profiles. American Mineralogist, 85, 480487.CrossRefGoogle Scholar