An experimental determination of the effect of pressure on the Fe3+/ΣFe ratio of an anhydrous silicate melt to 3.0 GPa

The effect of pressure on the Fe3+/Sigma Fe ratio of an anhydrous andesitic melt was determined front 0.4 to 3.0 GPa at 1400 degrees C with oxygen fugacity controlled internally by the Ru + RuO2 buffer. Values of Fe3+/Sigma Fe were determined by Mossbauer 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+/Sigma 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 Mossbauer spectra, such a change Could account for the change in intensity of the 1s -> 3d transition in the XANES spectra with pressure.