Physics and Chemistry of Minerals

, Volume 33, Issue 8–9, pp 613–621 | Cite as

On the mechanisms for H and Al incorporation in stishovite

  • Geoffrey D. Bromiley
  • Fiona A. Bromiley
  • David W. Bromiley
Original Paper


The solubility and incorporation mechanisms of hydrogen in synthetic stishovite as a function of Al2O3 content have been investigated. Mechanisms for H incorporation in stishovite are more complex than previously thought. Most H in stishovite is incorporated via the Smyth et al. (Am Mineral 80:454–456, 1995) model, where H docks close to one of the shared O–O edges, giving rise to an OH stretching band in infrared (IR) spectra at 3,111–3,117 cm−1. However, careful examination of IR spectra from Al-stishovite reveals the presence of an additional OH band at 3,157–3,170 cm−1. All H is present on one site, with interstitial H both coupled to Al3+ substitutional defects on adjacent octahedral (Si4+) sites, and decoupled from other defects, giving rise to two distinct absorption bands. Trends in IR data as a function of composition are consistent with a change in Al incorporation mechanism in stishovite, with Al3+ substitution for Si4+ charge-balanced by oxygen vacancies at low bulk Al2O3 contents, and coupled substitution of Al3+ onto octahedral (Si4+) and interstitial sites at high bulk Al2O3 contents. Trends in OH stretching frequencies as a function of Al2O3 content suggest that any such change in Al incorporation mechanism could alter the effect that Al incorporation has on the compressibility of stishovite, as noted by Ono et al. (Am Mineral 87:1486–1489, 2002).


  1. Asimov P, Stein L, Mosenfelder J, Rossman G (2006) Quantitative polarized infrared analysis of trace OH in populations of randomly oriented mineral grains. Am Mineral 86:147–158Google Scholar
  2. Bromiley GD, Hilairet N (2005) An investigation of hydrogen and minor element incorporation in synthetic rutile. Mineral Mag 69(3):345–358CrossRefGoogle Scholar
  3. Bromiley GD, Keppler H (2004) An experimental investigation of hydroxyl solubility in jadeite and Na-rich pyroxenes. Contrib Mineral Petrol 147:189–200CrossRefGoogle Scholar
  4. Bromiley GD, Shiryaev AA (2006) Neutron irradiation and post-irradiation annealing of rutile (TiO2−x): effect on hydrogen incorporation and optical absorption. Phys Chem Miner 33:426–434CrossRefGoogle Scholar
  5. Bromiley GD, Hilairet N, McCammon C (2004) Solubility of hydrogen and ferric iron in rutile and TiO2 (II): implications for phase assemblages during ultrahigh-pressure metamorphism and for the stability of silica polymorphs in the lower mantle. Geophys Res Lett 31:L04610CrossRefGoogle Scholar
  6. Chung J, Kagi H (2002) High concentration of water in stishovite in the MORB system. Geophys Res Lett 29(21). DOI 10.1029/2002GL015579Google Scholar
  7. Demouchy S, Deloule E, Frost D, Keppler H (2005) Pressure and temperature-dependence of water solubility in Fe-free wadsleyite. Am Mineral 90:1084–1091CrossRefGoogle Scholar
  8. Gesenhues U, Rentschler T (1999) Crystal growth and defect structure of Al3+-doped rutile. J Solid State Chem 143:210–218CrossRefGoogle Scholar
  9. Gibbs G, Cox D, Ross N (2004) A modeling of the structure and favourable H-docking sites and defects for the high-pressure silica polymorph stishovite. Phys Chem Miner 31:232–239CrossRefGoogle Scholar
  10. Hirose K, Takafuji N, Sata N, Ohishi Y (2005) Phase transition and density of subducted MORB crust in the lower mantle. Earth Planet Sci Lett 23(1–2):239–251CrossRefGoogle Scholar
  11. Khomenko V, Langer K, Rager H, Fett A (1998) Electronic absorption by Ti3+ ions and electronic delocalization in synthetic blue rutile. Phys Chem Miner 25:338–346CrossRefGoogle Scholar
  12. Kröger FA, Vink HJ (1956) Relations between the concentrations of imperfections in crystalline solids. In: Seitz F, Turnball D (eds) Solid state physics: advances and applications, vol 3. Academic, New York, pp. 307–435Google Scholar
  13. Libowitzky E (1999) Correlation of O–H stretching frequencies and O–H···O hydrogen bond lengths in minerals. Monatsh Chem 130(8):1047–1059Google Scholar
  14. Libowitzky E, Rossman G (1996) Principles of quantitative absorbance measurements in anisotropic crystals. Phys Chem Miner 23:319–327CrossRefGoogle Scholar
  15. Mierdel K, Keppler H (2004) The temperature dependence of water solubility in enstatite. Contrib Mineral Petrol 148(3):305–311CrossRefGoogle Scholar
  16. Ono S (1999) High temperature stability limit of phase egg, AlSiO3(OH). Contrib Mineral Petrol 137:83–89CrossRefGoogle Scholar
  17. Ono S, Ito E, Katsura T (2001) Mineralogy of subducted basaltic crust (MORB) from 25 to 37 GPa, and chemical heterogeneity of the lower mantle. Earth Planet Sci Lett 190:57–63CrossRefGoogle Scholar
  18. Ono S, Suto T, Hirose K, Kuwayama Y, Komabayashi T, Kikegawa T (2002) Equation of state of Al-bearing stishovite to 40 GPa at 300 K. Am Mineral 87(10):1486–1489Google Scholar
  19. Panero W, Benedetti L, Jeanloz R (2003) Transport of water into the lower mantle: role of stishovite. J Geophy Res 108(B1). DOI 10.1029/2002JB002053Google Scholar
  20. Pawley A, McMillan P, Holloway J (1993) Hydrogen in stishovite, with implications for mantle water-content. Science 261(5124):1024–1026CrossRefGoogle Scholar
  21. Smyth J, Bell D, Rossman G (1991) Incorporation of hydroxyl in upper-mantle clinopyroxenes. Nature 351:732–735CrossRefGoogle Scholar
  22. Smyth J, Swope R, Pawley A (1995) H in rutile-type compounds: II. Crystal chemistry of Al substitution in H-bearing stishovite. Am Mineral 80:454–456Google Scholar
  23. Swope R, Smyth J, Larson A (1995) H in rutile compounds: I. Single-crystal neutron and X-ray diffraction study of H in rutile. Am Mineral 80:448–453Google Scholar
  24. Vlassopoulos D, Rossman G, Haggerty S (1993) Coupled substitution of H and minor elements in rutile and the implications of high OH contents in Nb- and Cr-rich rutile from the upper mantle. Am Mineral 78:1181–1191Google Scholar

Copyright information

© Springer-Verlag 2006

Authors and Affiliations

  • Geoffrey D. Bromiley
    • 1
    • 2
  • Fiona A. Bromiley
    • 2
  • David W. Bromiley
    • 3
  1. 1.Department of Earth SciencesUniversity of CambridgeCambridgeUK
  2. 2.Bayerisches GeoinstitutUniversität BayreuthBayreuthGermany
  3. 3.Department of Earth SciencesUniversity of BristolBristolUK

Personalised recommendations