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

Smyth, J. R. and Holl, C. M. and Langenhorst, F. and Laustsen, H. M. S. and Rossman, G. R. and Kleppe, A. and McCammon, C. A. and Kawamoto, T. and van Aken, P. A. (2005) Crystal chemistry of wadsleyite II and water in the Earth’s interior. Physics and Chemistry of Minerals, 31 (10). pp. 691-705. ISSN 0342-1791. doi:10.1007/s00269-004-0431-x.

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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: Mg_(1.71)Fe_(0.18)Al_(0.01)H_(0.33)Si_(0.96)O_4 and Mg_(1.60)Fe_(0.22)Al_(0.01) H_(0.44)Si_(0.97)O_4. 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% H_(2)O 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.

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Rossman, G. R.0000-0002-4571-6884
Additional Information:© 2005 Springer-Verlag. Received: 30 March 2004; Accepted: 30 August 2004; Published online: 19 January 2005. 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.
Funding AgencyGrant Number
NSFEAR 02-29315
NSFEAR 03–37611
NSFEAR 94–05438
NSFEAR 01-25767
Bayerisches Geoinstitut Visitors ProgramUNSPECIFIED
Alexander von Humboldt FoundationUNSPECIFIED
Deutsche Forschungsgemeinschaft (DFG)AK 26/2–1,2
Subject Keywords:Wadsleyite; Spinelloid; Mantle; Water; Transition zone; Bulk modulus; TEM; FTIR; Mössbauer; ELNES; EELS
Issue or Number:10
Record Number:CaltechAUTHORS:20130417-104531830
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Official Citation:Smyth, J. R., C. M. Holl, et al. (2005). "Crystal chemistry of wadsleyite II and water in the Earth’s interior." Physics and Chemistry of Minerals 31(10): 691-705.
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:37987
Deposited On:22 Apr 2013 23:59
Last Modified:09 Nov 2021 23:32

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