Synthesis, Elasticity, and Spin State of an Intermediate MgSiO3‐FeAlO3 Bridgmanite: Implications for Iron in Earth’s Lower Mantle

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)O3 bridgmanite (FA50) with the highest Fe3+‐Al3+ coupled substitution known to date. X‐ray diffraction measurements showed that at ambient conditions, the FA50 adopted the LiNbO3 structure. 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 V0 = 172.1(4) Å3, K0 = 229(4) GPa with K0′ = 4(fixed). The calculated bulk sound velocity of the FA50 bridgmanite is ~7.7% lower than MgSiO3 bridgmanite, 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.Plain Language SummaryFe‐Al‐bearing bridgmanite may be the dominant mineral in the lower mantle, which occupies more than half of Earth’s volume. A subject of much debate is whether spin transition of Fe in bridgmanite produces an observable influence on the physics and chemistry of the lower mantle. In this study, we synthesized a new (Mg0.5Fe3+0.5)(Al0.5Si0.5)O3 bridgmanite with the highest Fe3+‐Al3+ coupled substitution known to date. We studied its structure, elasticity, and spin state by multiple experimental and theoretical methods. The high Fe content allowed us to better resolve a pressure‐induced spin transition of Fe3+ caused by Fe‐Al cation exchange at high temperature. Our results suggest that the spin transition is enabled by cation exchange but has a minor effect on the seismic velocity, although it may introduce chemical heterogeneity in the lower mantle. Our study helps resolve existing discrepancies on the nature of spin transition of Fe‐Al bridgmanite and its influence on the physics and chemistry of the lower mantle.Key PointsBridgmanite may contain 50% trivalent cations through Fe3+‐Al3+ coupled substitutionThe bulk sound velocity of (Mg0.5Fe3+0.5)(Al0.5Si0.5)O3 bridgmanite is 7.7% lower than MgSiO3Through Fe‐Al cation exchange, Fe3+ in (Mg0.5Fe3+0.5)(Al0.5Si0.5)O3 bridgmanite undergoes gradual spin transition at lower mantle conditionsPeer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/156245/3/jgrb54280-sup-0001-2020JB019964-SI.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/156245/2/jgrb54280.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/156245/1/jgrb54280_am.pd

Crystal structure of hydrous wadsleyite with 2.8% H 2 O and compressibility to 60 GPa

ABSTRACT Hydrous wadsleyite (β-Mg 2 SiO 4 ) with 2.8 wt% water content has been synthesized at 15 GPa and 1250 °C in a multi-anvil press. The unit-cell parameters are: a = 5.6686(8), b = 11.569(1), c = 8.2449(9) Å, β = 90.14(1)°, and V = 540.7(1) Å 3 , and the space group is I2/m. The structure was refined in space groups Imma and I2/m. The room-pressure structure differs from that of anhydrous wadsleyite principally in the increased cation distances around O1, the non-silicate oxygen. The compression of a single crystal of this wadsleyite was measured up to 61.3(7) GPa at room temperature in a diamond anvil cell with neon as pressure medium by X-ray diffraction at Sector 13 at the Advanced Photon Source, Argonne National Laboratory. The experimental pressure range was far beyond the wadsleyite-ringwoodite phase-transition pressure at 525 km depth (17

Magneto‐elastic coupling in compressed Fe 7 C 3 supports carbon in Earth's inner core

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/94986/1/grl29522.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/94986/2/grl29522-sup-0002-txts01.pd

Spin transition of Fe 3+ in Al-bearing phase D: An alternative explanation for small-scale seismic scatterers in the mid-lower mantle

. An equation of state over the entire pressure range was calculated using the observed variation in low-spin fraction with pressure and a low-spin bulk modulus of K T0 = 253(30) GPa, derived from the data above 65 GPa. Pronounced softening in the bulk modulus occurs during the spin transition, reaching a minimum at 50 GPa (∼1500 km) where the bulk modulus of Fe-Al phase D is about 35% lower than Fe-Al-bearing silicate perovskite. Recovery of the bulk modulus at 50-65 GPa results in a structure that has a similar incompressibility as silicate perovskite above 65 GPa. Similarly, the bulk sound velocity of Fe-Al phase D reaches a minimum at ∼50 GPa, being about 10% slower than silicate perovskite. The potential association of Fe-Al phase D with subducted slabs entering the lower mantle, along with its elastic properties through the Fe 3+ spin transition predicted at 1200-1800 km, suggests that phase D may provide an alternative explanation for small-scale mid-lower mantle seismic scatterers and supports the presence of deeply recycled sediments in the lower mantle