Local structural variation with oxygen fugacity in Fe2SiO4+x fayalitic iron silicate melts

ALDERMAN, O. L. G., LAZAREVA, L., WILDING, Martin, BENMORE, C. J., HEALD, M., JOHNSON, C. E., JOHNSON, J. A., HAH, H. Y., SENDELBACH, S., TAMALONIS, A., SKINNER, L. B., PARISE, J. B. and WEBER, J. K. R. (2017). Local structural variation with oxygen fugacity in Fe2SiO4+x fayalitic iron silicate melts. Geochimica et Cosmochimica Acta, 203, 15-36.

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Abstract

The structure of molten Fe2SiO4+x has been studied using both high-energy X-ray diffraction and Fe K-edge X-ray absorption near-edge structure (XANES) spectroscopy, combined with aerodynamic levitation and laser beam heating. A wide range of Fe3+ contents were accessed by varying the levitation and atmospheric gas composition. Diffraction measurements were made in the temperature (T) and oxygen partial pressure ranges 1624(21) < T < 2183(94) K (uncertainties in parentheses) and -5.6(3) < DFMQ < +2.8(5) log units (relative to the Fayalite-Magnetite-Quartz buffer). Iron K-edge XANES measurements covered the ranges 1557(33) < T < 1994(36) K and -2.1(3) < DFMQ < +4.4(3) log units. Fe3+ contents, x = Fe3+/RFe, estimated directly from the pre-edge peaks of the XANES spectra varied between 0.15(1) and 0.40(2). While these agree in some cases with semi-empirical models, notable discrepancies are discussed in the context of the redox kinetics and the limitations in both the models and in the calibrations used to derive oxidation state from XANES spectra. XANES pre-edge peak areas imply average Fe–O coordination numbers, nFeO, close to 5 for all Fe3+/RFe. Diffraction measurements yielded values of 4.4(2) < nFeO < 4.7(1). There is limited evidence for a linear trend nFeO(x) = 4.46(3) + 0.4(1)x. Asymmetric Fe–O bond length distributions peak at around 1.96A and have a shoulder arising from longer interatomic distances. Mean rFeO lie close to 2.06A , consistent with nFeO close to 5. These observations suggest that Fe2+ is less efficient at stabilizing tetrahedral Fe3+ compared to large monovalent alkali cations. Comparison of in-situ XANES estimates of Fe3+/RFe in the melts to those of the quenched solids obtained from XANES as well as Mo¨ssbauer spectroscopy indicate rapid oxidation during cooling, enabled by stirring of the melt by the levitation gas flow. As such, the oxidation state of hot komatiitic and other highly fluid melts may not be retained, even during rapid cooling, as it is for cooler basaltic and more silicic magmas.

Item Type:	Article
Research Institute, Centre or Group - Does NOT include content added after October 2018:	Materials and Engineering Research Institute > Engineering Research
Departments - Does NOT include content added after October 2018:	Faculty of Science, Technology and Arts > Department of Engineering and Mathematics
Identification Number:	https://doi.org/10.1016/j.gca.2016.12.038
Page Range:	15-36
Depositing User:	Martin Wilding
Date Deposited:	07 Jun 2018 13:26
Last Modified:	18 Mar 2021 12:17
URI:	https://shura.shu.ac.uk/id/eprint/21463

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