Super‐Earths ranging up to 10 Earth masses (ME) with Earth‐like density are common among the observed exoplanets thus far, but their measured masses and radii do not uniquely elucidate their internal structure. Exploring the phase transitions in the Mg‐silicates that define the mantle‐structure of super‐Earths is critical to characterizing their interiors, yet the relevant terapascal conditions are experimentally challenging for direct structural analysis. Here we investigated the crystal chemistry of Fe3O4as a low‐pressure analog to Mg2SiO4between 45–115 GPa and up to 3000 K using powder and single crystal X‐ray diffraction in the laser‐heated diamond anvil cell. Between 60–115 GPa and above 2000 K, Fe3O4adopts an 8‐fold coordinated Th3P4‐type structure (
The response of forsterite, Mg2SiO4, under dynamic compression is of fundamental importance for understanding its phase transformations and high‐pressure behavior. Here, we have carried out an in situ X‐ray diffraction study of laser‐shocked polycrystalline and single‐crystal forsterite (
- Award ID(s):
- 1725349
- NSF-PAR ID:
- 10450690
- Publisher / Repository:
- DOI PREFIX: 10.1029
- Date Published:
- Journal Name:
- Journal of Geophysical Research: Solid Earth
- Volume:
- 126
- Issue:
- 1
- ISSN:
- 2169-9313
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract I ‐43d,Z = 4) with disordered Fe2+and Fe3+into one metal site. This Fe‐oxide phase is isostructural with that predicted for Mg2SiO4above 500 GPa in super‐Earth mantles and suggests that Mg2SiO4can incorporate both ferric and ferrous iron at these conditions. The pressure‐volume behavior observed in this 8‐fold coordinated Fe3O4indicates a maximum 4% density increase across the 6‐ to 8‐fold coordination transition in the analog Mg‐silicate. Reassessment of the FeO—Fe3O4fugacity buffer considering the Fe3O4phase relationships identified in this study reveals that increasing pressure and temperature to 120 GPa and 3000 K in Earth and planetary mantles drives iron toward oxidation. -
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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. -
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Abstract The interplay between crystal–melt and grain boundary interfaces in partially melted polycrystalline aggregates controls many physical properties of mantle rocks. To understand this process at the fundamental level requires improved knowledge about the interfacial structures and energetics. Here, we report the results of first-principles molecular dynamics simulations of two grain boundaries of (0
l 1)/[100] type for tilt angles of 30.4° and 49.6° and the corresponding solid–liquid interfaces in Mg2SiO4forsterite at the conditions of the upper mantle. Our analysis of the simulated position time series shows that structural distortions at the solid–liquid interfacial region are stronger than intergranular interfacial distortions. The calculated formation enthalpy of the solid–solid interfaces increases nearly linearly from 1.0 to 1.4 J/m2for the 30.4° tilt and from 0.8 to 1.0 J/m2for the 49.6° tilt with pressure from 0 to 16 GPa at 1500 K, being consistent with the experimental data. The solid–liquid interfacial enthalpy takes comparable values in the range 0.9 to 1.5 J/m2over similar pressure interval. The dihedral angle of the forsterite–melt system estimated using these interfacial enthalpies takes values in the range of 67° to 146°, showing a decreasing trend with pressure. The predicted dihedral angle is found to be generally larger than the measured data for silicate systems, probably caused by compositional differences between the simulation and the measurements.
