High‐quality single‐crystals of (Al,Fe)‐bearing bridgmanite, Mg0.88Fe3+0.065Fe2+0.035Al0.14Si0.90O3, of hundreds of micrometer size were synthesized at 24 GPa and 1800 °C in a Kawai‐type apparatus from the starting hydrous melt containing ~6.7 wt% water. Analyses of synthesized bridgmanite using petrographic microscopy, scanning electron microscopy, and transmission electron microscopy show that the crystals are chemically homogeneous and inclusion free in micrometer‐ to nanometer‐spatial resolutions. Nanosecondary ion mass spectrometry (NanoSIMS) analyses on selected platelets show ~1,020(±70) ppm wt water (hydrogen). The high water concentration in the structure of bridgmanite was further confirmed using polarized and unpolarized Fourier‐transform infrared spectroscopy (FTIR) analyses with two pronounced OH‐stretching bands at ~3,230 and ~3,460 cm−1. Our results indicate that lower‐mantle bridgmanite can accommodate relatively high amount of water. Therefore, dehydration melting at the topmost lower mantle by downward flow of transition zone materials would require water content exceeding ~0.1 wt%.
High pressure and temperature experiments were carried out on the oxide mixtures corresponding to the bridgmanite stoichiometry under the hydrous shallow lower mantle conditions (24–25 GPa and 1673–1873 K with 5–10 wt. % of water in the starting material). Oxide mixtures investigated correspond to MgSiO3, (Mg, Fe)SiO3, (Mg, Al, Si)O3, and (Mg, Fe, Al, Si)O3. Melting was observed in all runs. Partitioning of various elements, including Mg, Fe, Si, and H is investigated. Melting under hydrous lower mantle conditions leads to increased (Mg + Fe)O/SiO2in the melt compared to the residual solids. The residual solids often contain a large amount of stishovite, and the melt contains higher (Mg,Fe)O/SiO2ratio than the initial material. (Mg + Fe)O‐rich hydrous melt could explain the low‐velocity anomalies observed in the shallow lower mantle and a large amount of stishovite in the residual solid may be responsible for the scattering of seismic waves in the mid‐lower mantle and may explain the “stishovite paradox. Since stishovite‐rich materials are formed only when silica‐rich source rock (MORB) is melted (not a typical peridotitic rock [bulk silicate Earth]), seismic scattering in the lower mantle provides a clue on the circulation of subducted MORB materials. To estimate hydrogen content, we use a new method of estimating the water content of unquenchable melts, and also propose a new interpretation of the significance of superhydrous phase B inclusions in bridgmanite. The results provide revised values of water partitioning between solid minerals and hydrous melts that are substantially higher than previous estimates.
more » « less- Award ID(s):
- 2001339
- NSF-PAR ID:
- 10366998
- Publisher / Repository:
- DOI PREFIX: 10.1029
- Date Published:
- Journal Name:
- Journal of Geophysical Research: Solid Earth
- Volume:
- 126
- Issue:
- 9
- ISSN:
- 2169-9313
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract Fe‐Al‐bearing bridgmanite may be the dominant host for ferric iron in Earth's lower mantle. Here we report the synthesis of (Mg0.5Fe3+0.5)(Al0.5Si0.5)O3bridgmanite (FA50) with the highest Fe3+‐Al3+coupled substitution known to date. X‐ray diffraction measurements showed that at ambient conditions, the FA50 adopted the LiNbO3structure. Upon compression at room temperature to 18 GPa, it transformed back into the bridgmanite structure, which remained stable up to 102 GPa and 2,600 K. Fitting Birch‐Murnaghan equation of state of FA50 bridgmanite yields
V 0 = 172.1(4) Å3,K 0 = 229(4) GPa withK 0′ = 4(fixed). The calculated bulk sound velocity of the FA50 bridgmanite is ~7.7% lower than MgSiO3bridgmanite, mainly because the presence of ferric iron increases the unit‐cell mass by 15.5%. This difference likely represents the upper limit of sound velocity anomaly introduced by Fe3+‐Al3+substitution. X‐ray emission and synchrotron Mössbauer spectroscopy measurements showed that after laser annealing, ~6% of Fe3+cations exchanged with Al3+and underwent the high‐ to low‐spin transition at 59 GPa. The low‐spin proportion of Fe3+increased gradually with pressure and reached 17–31% at 80 GPa. Since the cation exchange and spin transition in this Fe3+‐Al3+‐enriched bridgmanite do not cause resolvable unit‐cell volume reduction, and the increase of low‐spin Fe3+fraction with pressure occurs gradually, the spin transition would not produce a distinct seismic signature in the lower mantle. However, it may influence iron partitioning and isotopic fractionation, thus introducing chemical heterogeneity in the lower mantle.
