Equation of State and Spin Crossover of (Al, Fe)–Phase H

Strozewski, Benjamin; Buchen, Johannes; Sturhahn, Wolfgang; Ishii, Takayuki; Ohira, Itaru; Chariton, Stella; Lavina, Barbara; Zhao, Jiyong; Toellner, Thomas S.; Jackson, Jennifer M.

doi:10.1029/2022jb026291

Equation of State and Spin Crossover of (Al, Fe)–Phase H

Journal Article · Sat Mar 25 00:00:00 EDT 2023 · Journal of Geophysical Research. Solid Earth

DOI:https://doi.org/10.1029/2022jb026291· OSTI ID:2228906

^[1]; ^[2]; ^[1]; ^[3]; ^[4]; Chariton, Stella ^[5]; ^[6]; Zhao, Jiyong ^[7]; Toellner, Thomas S. ^[7]; ^[1]

California Institute of Technology (CalTech), Pasadena, CA (United States)
California Institute of Technology (CalTech), Pasadena, CA (United States); Univ. of Oxford (United Kingdom)
Univ. of Bayreuth (Germany); Center for High Pressure Science and Technology Advanced Research (HPSTAR), Beijing (China)
Gakushuin University, Tokyo (Japan)
Univ. of Chicago, IL (United States). Center for Advanced Radiation Sources (CARS)
Univ. of Chicago, IL (United States). Center for Advanced Radiation Sources (CARS); Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

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 phases δ-AlOOH (delta phase), MgSiO₂(OH)₂ (phase H), and ε-FeOOH at high temperatures and pressures, their solid solutions may transport significant amounts of hydrogen as deep as the core-mantle boundary. Here 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 and δ-(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 with δ-(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.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-06CH11357; FG02-94ER14466

OSTI ID:: 2228906

Journal Information:: Journal of Geophysical Research. Solid Earth, Journal Name: Journal of Geophysical Research. Solid Earth Journal Issue: 4 Vol. 128; ISSN 2169-9313

Publisher:: American Geophysical UnionCopyright Statement

Country of Publication:: United States

Language:: English

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Crystal chemistry of dense hydrous magnesium silicates: The structure of phase H, MgSiH2O4, synthesized at 45 GPa and 1000 C Bindi, L.; Nishi, M.; Tsuchiya, J. American Mineralogist, Vol. 99, Issue 8-9 https://doi.org/10.2138/am.2014.4994	journal	August 2014
Equations of State Angel, R. J. Reviews in Mineralogy and Geochemistry, Vol. 41, Issue 1 https://doi.org/10.2138/rmg.2000.41.2	journal	January 2000
Vibrational anisotropy of δ-(Al,Fe)OOH single crystals as probed by nuclear resonant inelastic X-ray scattering Buchen, Johannes; Sturhahn, Wolfgang; Ishii, Takayuki European Journal of Mineralogy, Vol. 33, Issue 4 https://doi.org/10.5194/ejm-33-485-2021	journal	August 2021

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