Iron-titanium oxyhydroxides as water carriers in the Earth’s deep mantle

Yu Nishihara; Kyoko N. Matsukage

doi:10.2138/am-2016-5517

Article

Iron-titanium oxyhydroxides as water carriers in the Earth’s deep mantle

Yu Nishihara and Kyoko N. Matsukage

Published/Copyright: April 5, 2016

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From the journal American Mineralogist Volume 101 Issue 4

Abstract

We experimentally explored phase relations in the System FeOOH-TiO₂ at pressures of 16 GPa and temperatures of 1000–1600 °C, which corresponds to conditions of the Earth’s mantle transition zone. Analyses of the recovered samples revealed that, in the studied conditions, there are two stable iron-titanium oxyhydroxide phases whose estimated composition is expressed by (FeH)_1-x, Ti_xO₂. One is the Fe-rich solid solution (x < 0.23) with ε-FeOOH type crystal structure (orthorhombic, P2₁nm), and the other is the more Ti-rich solid solution (x > 0.35) with α-PbO₂ type structure (orthorhombic. Pbcn). The ε-FeOOH phase is stable up to -1100 °C irrespective of chemical composition, whereas the α-PbO₂ type phase is stable up to 1500 °C for a composition of x = 0.5 and at least to 1600 °C for x = 0.75, and thus the α-PbO₂ type phase is stable at average mantle temperature in the Earth’s mantle transition zone. Iron-titanium-rich phases found previously in basalt + H₂O System are estimated to be the ε-FeOOH and α-PbO₂ type phases where the phase with iron-rich composition found at relatively low temperature (< 1100 °C) is ε-FeOOH phase and the phase with titanium-rich composition is α-PbO₂ type phase. The α-PbO₂ type and ε-FeOOH phases may be stable in the subducted basaltic crust at pressures in the mantle transition zone under water-rich conditions.

Keywords: Mantle transition zone; water, titanium; hydrous mineral; basaltic crust

^†These authors contributed equally to this work

Acknowledgments

We thank Y. Seto for his technical assistance in analyses using scanning electron microscope, and M. Hashimoto, K. Fuke, T. Shinmei, and T. Inoue for their assistance in sample preparation and high-pressure and high-temperature experiments. This work was supported by Grant-in-Aid for Scientific Research (B) (22340161) and for Scientific Research on Innovative Areas (21109004), and Women’s Future Development Center in Ehime University. Constructive comments by G. Bromiley and T. Kawamoto are appreciated. Author Contributions: Y.N. performed the high-pressure experiments, X-ray diffraction, and FTIR measurements. K.N.M. discovered the iron-titanium oxyhydroxides in basalt + H₂O System, and performed SEM-EDS analysis. Both authors designed the research methodology, wrote the paper, and approved the final manuscript.

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Appendix Iron-titanium mineral in basalt + H₂O composition

In our recent experimental study on the Connectivity of H₂O-rich fluids, we identified iron-titanium-rich phases in a basalt + 3.5 wt% H₂O System at P = 10 and 12 GPa and T = 1000 °C (Matsukage et al. in review; Hashimoto and Matsukage 2013). The high-pressure and high-temperature experiments were car-ried out based on the similar method as that used in this study. The starting material of the basalt + 3.5 wt% H₂O were prepared

by mixing JB-2 basalt powder (geochemical reference material, Geological Survey of Japan) and a reagent grade of Mg(OH)₂. The basalt + 3.5 wt% H₂O was packed in an Au capsule (OD: 1.5 mm, ID: 1.3 mm), and the Au capsule was further packed in a Pt capsule (OD: 1.8 mm, ID: 1.6 mm) together withNi + NiO + Ni(OH)₂mixture(withweightratio of 10:3:3)to control oxygen fugacity (f_Ol) during experiments. Both the Au and Pt capsules were sealed by welding. Experimental duration was 24 h.

The SEM-EDS analy ses revealed that both samples at 10 and 12 GPa consist of garnet, clinopyroxene, coesite or stishovite, FeTi-phase(s) and fluid (Fig. la). Presence of both Ni and NiO in the recovered/Jj₂ buffer material were observed suggesting that sample/^ was controlled by the Ni-NiO reaction throughout experiments. Weight total of the FeTi-rich minerals determined by chemical analyses using SEM-EDS turned out to be signifi-cantly lower than 100%, suggesting high water content of the phase (Table AI). Two chemically distinct FeTi-phases were observed in the sample at 12 GPa suggesting coexistence of s-FeOOH and <x-PbO₂ type phases (Table AI).

Received: 2015-7-30

Accepted: 2015-11-14

Published Online: 2016-4-5

Published in Print: 2016-4-1

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https://doi.org/10.2138/am-2016-5517

Keywords for this article

Mantle transition zone; water, titanium; hydrous mineral; basaltic crust

Iron-titanium oxyhydroxides as water carriers in the Earth’s deep mantle

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Abstract

Acknowledgments

References cited

Appendix Iron-titanium mineral in basalt + H2O composition

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Appendix Iron-titanium mineral in basalt + H₂O composition