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Ti K-edge XANES study on the coordination number and oxidation state of Titanium in pyroxene, olivine, armalcolite, ilmenite, and silicate glass during mare basalt petrogenesis

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Abstract

Lunar mare basalts are a product of partial melting of the lunar mantle under more reducing conditions when compared to those expected for the Earth’s upper mantle. Alongside Fe, Ti can be a major redox sensitive element in lunar magmas, and it can be enriched by up to a factor of ten in lunar basaltic glasses when compared to their terrestrial counterparts. Therefore, to better constrain the oxidation state of Ti and its coordination chemistry during lunar magmatic processes, we report new X-ray absorption near edge structure (XANES) spectroscopy measurements for a wide range of minerals (pyroxene, olivine, Fe–Ti oxides) and basaltic melt compositions involved in partial melting of the lunar mantle. Experiments were conducted in 1 bar gas-mixing furnaces at temperatures between 1100 and 1300 °C and oxygen fugacities (fO2) that ranged from air to two orders of magnitude below the Fe–FeO redox equilibrium. Run products were analysed via electron microprobe and XANES Ti K-edge. Typical run products had large (> 100 µm) crystals in equilibrium with quenched silicate glass. Ti K-edge XANES spectra show a clear shift in energy of the absorption edge features from oxidizing to reducing conditions and yield an average valence for Fe–Ti oxides (armalcolite and ilmenite) of 3.6, i.e., a 40% of the overall Ti is Ti3+ under fO2 conditions relevant to lunar magmatism (IW − 1.5 to − 1.8). Pyroxenes and olivine have average Ti valence of 3.75 (i.e., 25% of the overall Ti is trivalent), while in silicate glasses Ti is exclusively tetravalent. Pre-edge peak intensities also indicate that the coordination number of Ti varies from an average V-fold in silicate glass to VI-fold in the Fe–Ti oxides and a mixture between IV and VI-fold coordination in the pyroxenes and olivine, with up to 82% [IV]Ti4+ in the pyroxene. In addition, our results can help to better constrain the Ti3+/∑Ti of the lunar mantle phases during magmatic processes and are applied to provide first insights into the mechanisms that may control Ti mass-dependent equilibrium isotope fractionation in lunar mare basalts.

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Acknowledgements

We thank all colleagues at the University of Bonn and University of Cologne, and at the ANKA Synchrotron facility in the Karlsruhe Institute of Technology, especially D. Lülsdorf, T. Schulz, N. Jung and H. Blanchard for the technical support. We are also grateful to C. Ballhaus and S. Aulbach for discussion of the results, as well as S. Sutton for valuable insights into the Ti valence determination. Editor J. Hoefs and the anonymous referees are acknowledge for their constructive input. F.P.L. was supported by a PhD. scholarship from the Brazilian National Council for Scientific and Technological Development (DAAD/CNPq-grant 248562/2013-4). R.F. acknowledges research funding from the Deutsche Forschungsgemeinschaft (DFG—Grants FO 698/5 and FO 698/6).

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  1. Steinmann-Institut für Geologie, Mineralogie und Paläontologie, Rheinische Friedrich-Wilhelms-Universität Bonn, Poppelsdorfer Schloss (Mineralogisches Museum), 53115, Bonn, Germany

    F. P. Leitzke, R. O. C. Fonseca & M. Lagos

  2. Institut für Geologie und Mineralogie, Universität zu Köln, 50674, Cologne, Germany

    R. O. C. Fonseca, S. Jahn & C. Prescher

  3. Institute for Photon Science and Synchrotron Radiation, Karlsruhe Institute für Technologie, 76021, Karlsruhe, Germany

    J. Göttlicher & R. Steininger

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  1. F. P. Leitzke
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Leitzke, F.P., Fonseca, R.O.C., Göttlicher, J. et al. Ti K-edge XANES study on the coordination number and oxidation state of Titanium in pyroxene, olivine, armalcolite, ilmenite, and silicate glass during mare basalt petrogenesis. Contrib Mineral Petrol 173, 103 (2018). https://doi.org/10.1007/s00410-018-1533-7

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