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1. Equation of State and Spin Crossover of (Al, Fe)‐Phase H

   https://doi.org/10.1029/2022JB026291  

   Strozewski, Benjamin ; Buchen, Johannes ; Sturhahn, Wolfgang ; Ishii, Takayuki ; Ohira, Itaru ; Chariton, Stella ; Lavina, Barbara ; Zhao, Jiyong ; Toellner, Thomas S. ; Jackson, Jennifer M. ( April 2023 , Journal of Geophysical Research: Solid Earth)

   The transport of hydrogen into Earth's deep interior may have an impact on lower mantle dynamics as well as on the seismic signature of subducted material. Due to the stability of the hydrous phasesδ‐AlOOH (delta phase), MgSiO₂(OH)₂(phase H), andε‐FeOOH at high temperatures and pressures, their solid solutions may transport significant amounts of hydrogen as deep as the core‐mantle boundary. We have constrained the equation of state, including the effects of a spin crossover in the Fe³⁺atoms, of (Al, Fe)‐phase H: Al_0.84Fe³⁺_0.07Mg_0.02Si_0.06OOH, using powder X‐ray diffraction measurements to 125 GPa, supported by synchrotron Mössbauer spectroscopy measurements on (Al, Fe)‐phase H andδ‐(Al, Fe)OOH. The changes in spin state of Fe³⁺in (Al, Fe)‐phase H results in a significant decrease in bulk sound velocity and occurs over a different pressure range (48–62 GPa) compared withδ‐(Al, Fe)OOH (32–40 GPa). Changes in axial compressibilities indicate a decrease in the compressibility of hydrogen bonds in (Al, Fe)‐phase H near 30 GPa, which may be associated with hydrogen bond symmetrization. The formation of (Al, Fe)‐phase H in subducted oceanic crust may contribute to scattering of seismic waves in the mid‐lower mantle (∼1,100–1,550 km). Accumulation of 1–4 wt.% (Al, Fe)‐phase H could reproduce some of the seismic signatures of large, low seismic‐velocity provinces. Our results suggest that changes in the electronic structure of phases in the (δ‐AlOOH)‐(MgSiO₂(OH)₂)‐(ε‐FeOOH) solid solution are sensitive to composition and that the presence of these phases in subducted oceanic crust could be seismically detectable throughout the lower mantle.

    

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2. Elastic Properties of the Pyrite‐Type FeOOH‐AlOOH System From First‐Principles Calculations

   https://doi.org/10.1029/2021GC009703  

   Thompson, Elizabeth C. ; Campbell, Andrew J. ; Tsuchiya, Jun ( May 2021 , Geochemistry, Geophysics, Geosystems)

   The stability, structure, and elastic properties of pyrite‐type (FeS₂structured) FeO₂H were determined using density functional theory‐based computations with an internally consistent Coulombic self‐interaction term (U_eff). The properties of pyrite‐type FeO₂H are compared to that of pyrite‐type AlO₂H, with which it likely forms a solid solution at high temperature, as well as the respective lower pressure CaCl₂‐type polymorphs of both endmembers:ϵ‐FeOOH andδ‐AlOOH. Due to substantial differences in the CaCl₂‐type → pyrite‐type structural transition pressures of these endmembers, the stabilities of the (Al,Fe)O₂H solid solution polymorphs are anticipated to be compositionally driven at lower mantle pressures. As the geophysical properties of (Al,Fe)OOH are structurally dependant, interpretations regarding the contribution of pyrite‐type FeO₂H to seismically observed features must take into account the importance of this broad phase loop. With this in mind, Fe‐rich pyrite‐type (Al,Fe)OOH may coexist with Al‐dominant CaCl₂‐typeδ‐(Al,Fe)OOH in the deep Earth. Furthermore, pyrite‐type (Al_0.5–0.6,Fe_0.4–0.5)O₂H can reproduce the reduced compressional and shear velocities characteristic of seismically observed ultra low velocity zones in the Earth's lowermost mantle while Al‐dominant but Fe‐bearing CaCl₂‐typeδ‐(Al,Fe)OOH may contribute to large low shear velocity provinces.

    

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3. Synthesis, Elasticity, and Spin State of an Intermediate MgSiO 3 ‐FeAlO 3 Bridgmanite: Implications for Iron in Earth's Lower Mantle

   https://doi.org/10.1029/2020JB019964  

   Zhu, Feng ; Liu, Jiachao ; Lai, Xiaojing ; Xiao, Yuming ; Prakapenka, Vitali ; Bi, Wenli ; Alp, E. Ercan ; Dera, Przemyslaw ; Chen, Bin ; Li, Jie ( July 2020 , Journal of Geophysical Research: Solid Earth)

   Fe‐Al‐bearing bridgmanite may be the dominant host for ferric iron in Earth's lower mantle. Here we report the synthesis of (Mg_0.5Fe³⁺_0.5)(Al_0.5Si_0.5)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 yieldsV₀ = 172.1(4) ų,K₀ = 229(4) GPa withK₀′ = 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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4. High P‐T Sound Velocities of Amphiboles: Implications for Low‐Velocity Anomalies in Metasomatized Upper Mantle

   https://doi.org/10.1029/2023GL106583  

   Zhou, Wen‐Yi ; Hao, Ming ; Zhang, Dongzhou ; Dera, Przemyslaw ; Charin, Soisiri ; Zhang, Jin S ( March 2024 , Geophysical Research Letters)

   Metasomatized mantle xenoliths containing hydrous minerals, such as amphiboles, serpentine, and phlogopite, likely represent the potential mineralogical compositions of the metasomatized upper mantle, where low seismic velocities are commonly observed. This study presents the first experimentally determined single‐crystal elasticity model of an Fe‐free near Ca, Mg‐endmember amphibole tremolite at high pressure and/or temperature conditions (maximum pressure 7.3(1) GPa, maximum temperature 700 K) using Brillouin spectroscopy. We found that sound velocities of amphiboles strongly depend on the Fe content. We then calculated the sound velocities of 441 hydrous‐mineral‐bearing mantle xenoliths collected around the globe, and quantitatively evaluated the roles that amphiboles, phlogopite and serpentine played in producing the low velocity anomalies in the metasomatized upper mantle.

    

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5. Effects of composition and pressure on electronic states of iron in bridgmanite

   https://doi.org/10.2138/am-2020-7309  

   Dorfman, Susannah M. ; Potapkin, Vasily ; Lv, Mingda ; Greenberg, Eran ; Kupenko, Ilya ; Chumakov, Aleksandr I. ; Bi, Wenli ; Alp, E. Ercan ; Liu, Jiachao ; Magrez, Arnaud ; et al ( July 2020 , American Mineralogist)

   null (Ed.)

   Abstract Electronic states of iron in the lower mantle's dominant mineral, (Mg,Fe,Al)(Fe,Al,Si)O3 bridgmanite, control physical properties of the mantle including density, elasticity, and electrical and thermal conductivity. However, the determination of electronic states of iron has been controversial, in part due to different interpretations of Mössbauer spectroscopy results used to identify spin state, valence state, and site occupancy of iron. We applied energy-domain Mössbauer spectroscopy to a set of four bridgmanite samples spanning a wide range of compositions: 10–50% Fe/total cations, 0–25% Al/total cations, 12–100% Fe3+/total Fe. Measurements performed in the diamond-anvil cell at pressures up to 76 GPa below and above the high to low spin transition in Fe3+ provide a Mössbauer reference library for bridgmanite and demonstrate the effects of pressure and composition on electronic states of iron. Results indicate that although the spin transition in Fe3+ in the bridgmanite B-site occurs as predicted, it does not strongly affect the observed quadrupole splitting of 1.4 mm/s, and only decreases center shift for this site to 0 mm/s at ~70 GPa. Thus center shift can easily distinguish Fe3+ from Fe2+ at high pressure, which exhibits two distinct Mössbauer sites with center shift ~1 mm/s and quadrupole splitting 2.4–3.1 and 3.9 mm/s at ~70 GPa. Correct quantification of Fe3+/total Fe in bridgmanite is required to constrain the effects of composition and redox states in experimental measurements of seismic properties of bridgmanite. In Fe-rich, mixed-valence bridgmanite at deep-mantle-relevant pressures, up to ~20% of the Fe may be a Fe2.5+ charge transfer component, which should enhance electrical and thermal conductivity in Fe-rich heterogeneities at the base of Earth's mantle. 

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