Skip to main content

Advertisement

SpringerLink
Log in

Crystal chemistry of wadsleyite II and water in the Earth’s interior

  • Original Paper
  • Published:
Physics and Chemistry of Minerals Aims and scope Submit manuscript

Abstract

Wadsleyite II is a variably hydrous magnesium-iron silicate phase similar to spinelloid IV and a potential host for H in the Transition Zone of the Earth’s mantle. Two separate samples of wadsleyite II synthesized at 17.5 GPa and 1400°C and at 18 GPa and 1350°C have been characterized by electron microprobe, single-crystal X-ray diffraction, visible, IR, Raman, and Mössbauer spectroscopies, and transmission electron microscopy including electron energy-loss spectroscopy. The two samples have the following chemical formulae: Mg1.71Fe0.18Al0.01H0.33Si0.96O4 and Mg1.60Fe0.22Al0.01 H0.44Si0.97O4. Mössbauer spectroscopy and electron energy loss spectroscopy (EELS) indicate that about half of the iron present is ferric. Refinement of the structures shows them to be essentially the same as spinelloid IV. Calculated X-ray powder diffraction patterns show only subtle differences between wadsleyite and wadsleyite II. The hydration mechanism appears to be protonation of the non-silicate oxygen (O2) and possibly the oxygens surrounding the partially vacant tetrahedral site Si2, charge-balanced by cation vacancies in Si2, M5 and M6. The unit cell volume of this phase and its synthesis conditions indicate that it may be an intermediate phase occurring between the fields of wadsleyite and ringwoodite, if sufficient trivalent cations are available. The unit cell parameters have been refined at pressures up to 10.6 GPa by single-crystal X-ray diffraction in the diamond anvil cell. The refined bulk modulus for the sample containing 2.8 wt% H2O is 145.6 ± 2.8 GPa with a K’ of 6.1 ± 0.7. Similar to wadsleyite and ringwoodite, hydration has a large effect on the bulk modulus. The presence of this phase in the mantle could serve to obscure the seismic expression of the phase boundary between wadsleyite and ringwoodite near 525 km. The large apparent effect of hydration on bulk modulus is consistent with hydration having a larger effect on seismic velocities than temperature in the Transition Zone.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11
Fig. 12

Similar content being viewed by others

References

  • Akaogi M, Akimoto S., Horioka H, Takahashi K, Horiuchi H (1982) The system NiAl2O4-Ni2SiO4 at high pressures ad high temperatures: spinelloids with spinel-related structures. J Solid State Chem 44:257–267

    Article  Google Scholar 

  • Amthauer G, Rossman GR (1984) Mixed valence of iron in minerals with cation clusters. Phys Chem Minerals 11:37–51.

    Article  Google Scholar 

  • Angel RJ, Allan DR, Miletich R, Finger LW (1997). The use of quartz as an internal pressure standard in high pressure crystallography. J Appl Cryst 30:461–466

    Article  Google Scholar 

  • Crichton WA, Ross NL, Frost D, Kung J (1999) Comparative compressibilities of anhydrous and hydrous wadsleyites. Journal of Conference Abstracts (EUG) 657

  • Cromer DT, Mann J (1968) X-ray scattering factors computed from numerical Hartree-Fock wave functions. Acta Cryst A24:321–325

    Google Scholar 

  • Deuss A, Woodhouse J (2001) Seismic observations of splitting of the mid-transition zone discontinuity in Earth’s mantle. Science 294:354–357

    Article  Google Scholar 

  • Downs RT, Bartelmehs KL, Gibbs GV, Boisen M B (1993) Interactive software for calculating and displaying X-ray or neutron diffraction patterns of crystalline material. Am Mineral 78:1104–1107

    Google Scholar 

  • Drake MJ, Righter K. (2002) Determining the composition of the Earth. Nature 416:39–44

    Article  Google Scholar 

  • Egerton RF (1996) Electron energy-loss spectroscopy in the electron microscope. 2nd edition, Plenum Press, New York

  • Ferrugia LJ, (1999) WinGX suite for small-molecule single-crystal crystallography. J Appl Cryst 32:837–838

    Article  Google Scholar 

  • Finger LW, Hazen RM, Yagi T (1979) Crystal structures and electron densities of nickel and iron silicate spinels at elevated temperature or pressure. Am Mineral 64:1002–1009

    Google Scholar 

  • Finger LW, Hazen RM, Zhang J, Ko J, Navrotsky A (1993) The effect of Fe on the crystal structure of wadsleyite β-(Mg1-xFex)2SiO4, 0.00<x<0.40. Physics and Chemistry of Minerals 19: 361–368

    Article  Google Scholar 

  • Horioka K, Takahashi K, Morimoto N, Horiuchi H, Akaogi M, Akimoto S (1981) Structure of nickel aluminosilicate (Phase IV): A high pressure phase related to spinel. Acta Cryst B37:635–638

    Google Scholar 

  • Inoue T, Yurimoto H, Kudoh Y. (1995) Hydrous modified spinel, Mg1.75SiH0.5O4: a new water reservoir in the mantle transition region. Geophys Res Lett 22:117–120

    Article  Google Scholar 

  • Jacobsen SD, Smyth JR, Spetzler HA, Holl CM, Frost DJ (2004a) Sound velocities and elastic constants of iron-bearing hydrous ringwoodite. Phys Earth Planet Int 143–144:47–56

    Google Scholar 

  • Jacobsen SD, Demouchy S, Frost DJ, Boffa-Ballaran T, Kung J (2004b) New insight on hydrous wadsleyite from polarized FTIR spectroscopy. Am Mineral (in press)

  • Kawamoto T (2004) Hydrous phase stability and partial melt chemistry of H2O-saturated KLB-1 peridotite up to the uppermost lower mantle conditions. Phys Earth Planet Int (in press)

  • Kleppe, AK, Jephcoat AP, Olijnyk H, Slesinger AE, Kohn SC, and Wood BJ (2001) Raman spectroscopic study of hydrous wadsleyite (β-Mg2SiO4) to 50 GPa, Phys Chem Minerals 28:232-241

    Google Scholar 

  • Koch M, Woodland AB, Angel RJ (2004) Stability of spinelloid phases in the system Mg2SiO4-Fe2SiO4-Fe3O4 at 1100°C and up to 10.5 GPa. Phys Earth Planet Int 143–144:171–183

    Google Scholar 

  • Kohlstedt DL, Keppler H, Rubie DC (1996) The solubility of water in α, β and γ phases of (Mg,Fe)2SiO4. Contr Mineral and Petrol 123:345–357

    Article  Google Scholar 

  • Kudoh Y, Kuribayashi T, Mizohata H, Ohtani E. (2000) Structure and cation disorder of hydrous ringwoodite, γ-Mg1.89Si0.97H0.34O4. Phys Chem Minerals 27:474–479

    Article  Google Scholar 

  • Li D, Bancroft GM, Kasrai M, Fleet ME, Feng XH, Tan KH, Yang BX (1993) High-resolution Si K- and L 2,3 -edge XANES of α-quartz and stishovite. Sol State Comm 87:613–617

    Article  Google Scholar 

  • Li D, Bancroft GM, Kasrai M, Fleet ME, Secco RA, Feng XH, Tan KH, Yang BX (1994) X-ray absorption spectroscopy of silicon dioxide (SiO2) polymorphs: The structural characterization of opal. Am. Mineral. 79: 622–632

    Google Scholar 

  • Libowitzky E (1999) Correlation of O-H stretching frequencies and O-H. . .O hydrogen bond lengths in minerals. Monatsh Chemie 130:1047–1059

    Google Scholar 

  • Mao HK, Xu J, Bell PM (1986) Calibration of the ruby pressure gauge to 800 kbar under quasi-hydrostatic conditions. J Geophys Res 91:4673–4676

    Google Scholar 

  • McCammon CA (1994) A Mössbauer milliprobe: Practical considerations. Hyper. Int. 92: 1235–1239

    Google Scholar 

  • McCammon CA, Chaskar V, Richards GG (1991) A technique for spatially resolved Mössbauer spectroscopy applied to metallurgical slags. Meas. Sci. Technol. 2: 657–662

    Google Scholar 

  • McCammon CA, Frost DJ, Smyth JR, Lausten HMS, Kawamoto T, Ross NL, van Aken PA (2004) Oxidation state of iron in hydrous mantle phases: Implications for subduction and mantle oxygen fugacity. Phys Earth Planet Int 143–144:157–169

    Google Scholar 

  • Poe B, Seifert F, Sharp T, Wu Z (1997) ELNES spectroscopy of mixed Si coordination in minerals. Phys. Chem. Minerals 24:477–487

    Article  Google Scholar 

  • Piermarini GJS, Block S, Barnet JD, Forman RA (1975) Calibration of the pressure dependence of the R1 ruby fluorescence line to 195 kbar. J Appl Phys 46:2774–2780

    Article  Google Scholar 

  • Rossman GR, Smyth JR (1990) Hydroxyl and ammonia contents of accessory minerals in mantle eclogites and related rocks. Am Mineral 75:775–780

    Google Scholar 

  • Sheldrick GM (1997) SHELXL-97 A program for crystal structure refinement. University of Goettingen, Germany, Release 97–2

  • Sharp T, Wu Z, Seifert F, Poe B, Doerr M, Paris E (1996) Distinction between six- and fourfold-coordinated silicon in SiO2 polymorphs via electron loss near edge structure (ELNES) spectroscopy. Phys Chem Minerals 23:17–24

    Article  Google Scholar 

  • Smyth JR (1987) Beta-Mg2SiO4: a potential host for water in the mantle? American Mineralogist 72: 1051–1055

    Google Scholar 

  • Smyth JR (1989) Electrostatic characterization of oxygen sites in minerals. Geochim Cosmochim Acta 53:1101–1110

    Article  Google Scholar 

  • Smyth JR (1994) A crystallographic model for hydrous wadsleyite (β-Mg2SiO4) An ocean in the Earth’s interior? Am Mineral 79:1021–1025

    Google Scholar 

  • Smyth JR, Kawamoto T (1997) Wadsleyite II: a new high pressure hydrous phase in the peridotite-H2O system. Earth Planet Sci Lett 146: E9-E16

    Article  Google Scholar 

  • Smyth JR, Bell DR, Rossman GR (1991) Hydrous clinopyroxenes from the upper mantle. Nature 351:732–735

    Article  Google Scholar 

  • Smyth JR, Holl CM, Frost DJ, Jacobsen SD, Langenhorst F, McCammon CA (2003) Structural systematics of hydrous ringwoodite and water in the Earth’s interior. Am Mineral 88:1402–1407

    Google Scholar 

  • Smyth JR, Holl CM, Frost DJ, Jacobsen SD (2004) High-pressure crystal chemistry of hydrous ringwoodite and water in the Earth’s interior. Phys Earth Planet Int 143–144:271–278

    Google Scholar 

  • Tokonami M. (1965) Atomic scattering factor for O2-. Acta Cryst 19:486

    Article  Google Scholar 

  • van Aken PA, Liebscher B, Styrsa VJ (1998a) Quantitative determination of iron oxidation states in minerals using Fe L 2,3 -edge electron energy-loss near edge structure spectroscopy. Phys. Chem. Minerals 25: 323–327

    Article  Google Scholar 

  • van Aken PA, Sharp TG, Seifert F (1998b) : Electron-beam induced amorphization of stishovite : silicon-coordination change observed using Si K-edge extended electron energy-loss fine structure. Phys Chem Minerals 25:83–93

    Article  Google Scholar 

  • van Aken PA, Liebscher B (2002) Quantitative of ferrous/ferric ratios in minerals: new evaluation schemes of Fe L 2,3 electron energy-loss near-edge spectra. Phys. Chem. Minerals 29:188–200

    Article  Google Scholar 

  • Yusa H, Inoue T, Ohishi Y. (2000) Isothermal compressibililty of hydrous ringwoodite and its relation to mantle discontinuities. Geophys Res Lett 27:1831–1834

    Article  Google Scholar 

Download references

Acknowledgments

The authors thank Drs. S. D. Jacobsen and S. Demouchy for useful discussions and access to polarized FTIR spectra of hydrous wadsleyite. This work was supported by NSF grants EAR 02–29315 and 03–37611 to JRS; EAR 94–05438 and EAR-0125767 to GRR, the Bayerisches Geoinstitut Visitors Program, the Alexander von Humboldt Foundation, and the Deutsche Forschungsgemeinschaft (Bonn, Germany) under project number AK 26/2–1,2.

Author information

Authors and Affiliations

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

    J. R. Smyth, C. M. Holl & H. M. S. Laustsen

  2. Bayerisches Geoinstitut, Universität Bayreuth, D-95440, Bayreuth, Germany

    F. Langenhorst & C. A. McCammon

  3. Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA 91125, USA

    G. R. Rossman

  4. Department of Earth Sciences, University of Oxford, Parks Road, Oxford, OX1 3PR, UK

    A. Kleppe

  5. Institute for Geothermal Sciences, Kyoto University, 874-0903, Beppu, Japan

    T. Kawamoto

  6. Institut für Angewandte Geowissenschaften, Technische Universität Darmstadt, D-64287, Darmstadt, Germany

    P. A. van Aken

Authors
  1. J. R. Smyth
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. C. M. Holl
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. F. Langenhorst
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. H. M. S. Laustsen
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. G. R. Rossman
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. A. Kleppe
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. C. A. McCammon
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. T. Kawamoto
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. P. A. van Aken
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to J. R. Smyth.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Smyth, J.R., Holl, C.M., Langenhorst, F. et al. Crystal chemistry of wadsleyite II and water in the Earth’s interior. Phys Chem Minerals 31, 691–705 (2005). https://doi.org/10.1007/s00269-004-0431-x

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00269-004-0431-x

Keywords

Search

Navigation