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Mineralogical Magazine; June 2005; v. 69; no. 3; p. 345-358; DOI: 10.1180/0026461056930256
© 2005 Mineralogical Society of Great Britain and Ireland
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Hydrogen and minor element incorporation in synthetic rutile

G. D. Bromiley1,2,* and N. Hilairet3

1 Bayerisches Geoinstitut, Universität Bayreuth, 95440 Bayreuth, Germany
2 Department of Earth Sciences, University of Cambridge, Downing Street, Cambridge CB2 3EQ, UK
3 Laboratoire de Sciences de la Terre, ENS-Lyon, 46 Alleé d’Italie, 69364 Lyon, Cedex 07, France

* E-mail: gbro04{at}esc.cam.ac.uk

The solubility and incorporation mechanisms of H and various trivalent and divalent cations in synthetic rutile have been investigated. Experiments performed using different bulk Fe2O3 contents demonstrate that Fe3+ substitutes onto the main Ti site, charge-balanced by oxygen vacancies. Under more reducing conditions in Fe-poor systems, the concentration of Ti interstitials in rutile is increased, resulting in a decrease in H solubility. Variation in the solubility of different oxides in rutile as a function of ionic radius implies substitution onto the main Ti site, probably charge-balanced by oxygen vacancies. To a lesser degree, substitution of trivalent and divalent cations is locally charge-balanced by H incorporation. Variation in OH-stretching frequencies in infrared spectra as a function of composition implies that octahedral defects and structurally-incorporated H are coupled. However, in all samples, some of the H is also decoupled from substitutional impurities, as is evident from an OH-absorption band at 3279 cm–1. This band corresponds to the main OH band seen in spectra of many natural rutiles, implying that in most rutiles, H defects are decoupled from substitutional defects.

KEYWORDS: rutile, hydrogen, substitution, solubility, spectroscopy




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