Abstract
Seismological studies have revealed that a complex texture or heterogeneity exists in the Earth's inner core and at the boundary between core and mantle1,2,3,4. These studies highlight the importance of understanding the properties of iron when modelling the composition and dynamics of the core and the interaction of the core with the lowermost mantle5,6,7. One of the main problems in inferring the composition of the lowermost mantle is our lack of knowledge of the high-pressure and high-temperature chemical reactions that occur between iron and the complex Mg–Fe–Si–Al-oxides which are thought to form the bulk of the Earth's lower mantle. A number of studies6,8,9,10,11,12 have demonstrated that iron can react with MgSiO3-perovskite at high pressures and high temperatures, and it was proposed6,8 that the chemical nature of this process involves the reduction of silicon by the more electropositive iron. Here we present a study of the interaction between iron and corundum (Al2O3) in electrically- and laser-heated diamond anvil cells at 2,000–2,200 K and pressures up to 70 GPa, simulating conditions in the Earth's deep interior. We found that at pressures above 60 GPa and temperatures of 2,200 K, iron and corundum react to form iron oxide and an iron–aluminium alloy. Our results demonstrate that iron is able to reduce aluminium out of oxides at core–mantle boundary conditions, which could provide an additional source of light elements in the Earth's core and produce significant heterogeneity at the core–mantle boundary.
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Acknowledgements
We thank D. C. Rubie for comments and discussions. This work was supported by the Swedish Science Foundation (NFR), the Wallenberg and Göran Gustafssons Stiftelse Funds.
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Figure 1a
(JPG 72.4 KB)
Diffraction pattern of the sample electrically heated at 59(2) GPa and 1450(50) K processed with GSAS program. The pattern is completely explained as a mixture of two phases – corundum (lower ticks, a=4.4966(6) Å, c=12.286(2) Å) and e -Fe (upper ticks, a=2.3606(3) Å, c=3.7719(4) Å). Background is subtracted.

Figure 1b
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Diffraction pattern of the sample electrically heated at 63(5) GPa and 2200(50) K processed with GSAS program. The pattern could not be described just as a mixture (b) of corundum and e -Fe, but a mixture (c) of corundum (lower ticks, a=4.4915(6) Å, c=12.256(2) Å), e -Fe (middle ticks, a=2.3533(2) Å, c=3.7564(4) Å), and rhombohedral wustite (upper ticks, a=2.843(1) Å, a =58.56(2)o) explain the pattern. Background is subtracted.

Figure 1c
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Diffraction pattern of the sample electrically heated at 63(5) GPa and 2200(50) K processed with GSAS program. The pattern could not be described just as a mixture (b) of corundum and e -Fe, but a mixture (c) of corundum (lower ticks, a=4.4915(6) Å, c=12.256(2) Å), e -Fe (middle ticks, a=2.3533(2) Å, c=3.7564(4) Å), and rhombohedral wustite (upper ticks, a=2.843(1) Å, a =58.56(2)o) explain the pattern. Background is subtracted.

Figure 1d
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Diffraction pattern of the sample laser-heated at 56(2) GPa and 2000(150) K, collected at ID30 beam line at ESRF. Blue bars show calculated intensities of the wustite reflections, and red ones - intensities of Fe3Al reflections.

Figure 2a
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Schematic diagram of the high-pressure assemblage used for microprobe analysis of the product of the reaction between iron and corundum. Specially shaped stainless steel gasket of 300 m m thickens was indented to 50 m m between diamonds with 300 m m culets. Pure corundum was loaded in to the indentation, covered by a 2 m m thick iron foil and NaCl with several small ruby chips were placed on the top. Pressure was measured by ruby fluorescence. The sample was heated by a Nd:YAG laser at pressures between 68 and 74 GPa and temperatures between 2200 and 2350 K. After complete decompression NaCl was washed out and the chemical composition of the heated foil was analysed.

Figure 2b
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Backscattered electron images of the recovered sample (dark color corresponds to iron-rich, and light area – to aluminum-rich parts). White circle marks indentation. Chemical composition of heated part of the foil varied from 2 wt.% Al to 10 wt.% Al in good agreement with X-ray data. White areas corresponds to higher Al content, and dark one to higher Fe content. Chemical analyses were obtained using the CAMECA SX-50 electron microprobe, employing a PAP correction program. The operating conditions were: accelerating voltage 20 kV, beam current 50 nA, and 1-2 m m beam diameter. Penetration depth of the beam is less than 2 m m. Counting times were 10 s. The following analyzing crystals were used: TAP for Al Ka and LiF for Fe Ka.
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Dubrovinsky, L., Annersten, H., Dubrovinskaia, N. et al. Chemical interaction of Fe and Al2O3 as a source of heterogeneity at the Earth's core–mantle boundary. Nature 412, 527–529 (2001). https://doi.org/10.1038/35087559
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DOI: https://doi.org/10.1038/35087559
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