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American Mineralogist; February 2006; v. 91; no. 2-3; p. 404-412; DOI: 10.2138/am.2005.1929
© 2006 Mineralogical Society of America
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An experimental determination of the effect of pressure on the Fe3+/{sum}Fe ratio of an anhydrous silicate melt to 3.0 GPa

Hugh St.C. O’Neill1, Andrew J. Berry1, Catherine C. McCammon1,2, Kasthuri D. Jayasuriya3,*, Stewart J. Campbell3 and Garry Foran4,5

1 Research School of Earth Sciences, Australian National University, Canberra, ACT 0200, Australia
2 Bayerisches Geoinstitut, Universität Bayreuth, D-95440, Germany
3 School of Physical, Environmental and Mathematical Sciences, University of New South Wales, Australian Defence Force Academy, Canberra, ACT 2600, Australia
4 Australian Synchrotron Research Program, Australian Nuclear Science and Technology Organisation, PMB 1, Menai, NSW 2234, Australia
5 Australian National Beamline Facility, KEK, Photon Factory, Oho 1-1, Tsukuba-shi, Ibaraki-ken 305-0801, Japan

The effect of pressure on the Fe3+/{sum}Fe ratio of an anhydrous andesitic melt was determined from 0.4 to 3.0 GPa at 1400 °C with oxygen fugacity controlled internally by the Ru + RuO2 buffer. Values of Fe3+/{sum}Fe were determined by Mössbauer spectroscopy on quenched glasses with a precision of ±0.01, one standard deviation. This precision was verified independently by XANES spectroscopy of the same samples. The XANES spectra show a systematic increase in energy and decrease in intensity of the 1s -> 3d transition with increasing pressure. The results to 2.0 GPa are in good agreement with predictions from density and compressibility measurements fitted to a Murnaghan equation of state, but the datum at 3.0 GPa has higher Fe3+/{sum}Fe than predicted from the trend established by the lower-pressure data. This might be due to a coordination change in Fe3+ at high pressure; although there is no evidence for this in the Mössbauer spectra, such a change could account for the change in intensity of the 1s -> 3d transition in the XANES spectra with pressure.

Key Words: redox ratio • silicate melt • XANES • Mössbauer • experimental petrology




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