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1. Anomalous elastic behavior of phase egg, AlSiO3(OH), at high pressures

   Mookherjee, Mainak; Panero, Wendy R.; Wunder, Bernd; Jahn, Sandro (January 2019, The American mineralogist)

   Phase egg, [AlSiO3(OH)], is an aluminosilicate hydrous mineral that is thermodynamically stable in lithological compositions represented by Al2O3-SiO2-H2O (ASH) ternary, i.e., a simplified ternary for the mineralogy of subducted sediments and continental crustal rocks. High-pressure and high-temperature experiments on lithological compositions resembling hydrated sedimentary layers in subducting slabs show that phase egg is stable up to pressures of 20–30 GPa, which translates to the transition zone to lower mantle depths. Thus, phase egg is a potential candidate for transporting water into the Earth’s mantle transition zone. In this study, we use first-principles simulations based on density functional theory to explore the pressure dependence of crystal structure and how it influences energetics and elasticity. Our results indicate that phase egg exhibits anomalous behavior of the pressure dependence of the elasticity at mantle transition zone depths (~15 GPa). Such anomalous behavior in the elasticity is related to changes in the hydrogen bonding O-H···O configurations, which we delineate as a transition from a low-pressure to a high-pressure structure of phase egg. Full elastic constant tensors indicate that phase egg is very anisotropic resulting in a maximum anisotropy of compressional wave velocity, AvP ≈ 30% and of shear wave velocity, AvS ≈ 17% at zero pressures. Our results also indicate that the phase egg has one of the fastest bulk sound velocities (vP and vS) compared to other hydrous aluminous phases in the ASH ternary, which include topaz-OH, phase Pi, and d-AlOOH. However, the bulk sound velocity of phase egg is slower than that of stishovite. At depths corresponding to the base of mantle transition zone, phase egg decomposes to a mixture of d-AlOOH and stishovite. The changes in compressional DvP and shear DvS velocity associated with the decomposition is ~0.42% and –1.23%, respectively. Although phase egg may be limited to subducted sediments, it could hold several weight percentages of water along a normal mantle geotherm. 

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2. Atomistic Mechanism of Al Substitution Effects on the Ferroelastic Post-stishovite Transition by High-Pressure Single-Crystal X-Ray Diffraction

   https://doi.org/10.2138/am-2023-9257  

   Zhang, Yanyao; Chariton, Stella; Prakapenka, Vitali B; Okuchi, Takuo; Lin, Jung-Fu (October 2024, American Mineralogist)

   Abstract The influence of Al substitution on the elastic properties of stishovite and its transition to post-stishovite is of great importance for interpreting the seismic wave velocities of subducted mid-ocean ridge basalt (MORB) within the mantle transition zone and the lower mantle. However, atomistic mechanisms of Al substitution effects on the transition and its associated elasticity remain debated. Here synchrotron single-crystal X-ray diffraction measurements have been performed at room temperature on Al1.3-SiO2 (1.3 mol% Al in the chemical formula of Si0.965(3)Al0.041(1)O2H0.017(4)) and Al2.1-SiO2 (2.1 mol% Al in Si0.948(2)Al0.064(1)O2H 0.018(3)) crystals in diamond anvil cells with Boehler-Almax designed anvils up to 38.0 GPa and 28.5 GPa, respectively. Refinements of the diffraction patterns show that a transformation from stishovite (space group P42/mnm; No. 136) to CaCl2-typed post-stishovite (space group Pnnm; No. 58) is accompanied by splitting of O coordinates. The Al substitution in stishovite results in a faster decrease in the O coordinate, softer apical (Si,Al)-O bonds, and a softer and less distorted (Si,Al)O6 octahedron under compression. This leads to reduced adiabatic bulk modulus (KS), shear modulus (G), shear wave velocity (VS), and compressional wave velocity (VP) in the stishovite phase, explaining seismic wave perturbations in the mantle transition zone. Together with Raman data, Landau theory modeling shows that Al substitution increases the order parameter and excess free energy, stabilizing the post-stishovite phase at lower pressures. Correlation between elasticity and octahedral distortion index (D) reveals that at certain D, the Al substitution reduces KS, G, VS, and VP of the stishovite phase while increasing G, VS, and VP of the post-stishovite phase. Importantly, the maximum shear reduction is slightly enhanced at D = 0.00620(9) at the transition point. Our results help explain the seismically observed small-scale VS anomalies beneath subduction regions in the shallow lower mantle where Al,H-bearing stishovite undergoes the post-stishovite transition. 

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3. Crystallization of a hydrous magma ocean in the shallow lower mantle

   https://doi.org/10.1016/j.epsl.2024.118651  

   Xie, Longjian; Walter, Michael; Katsura, Tomoo; Xu, Fang; Wang, Jianhua; Fei, Yingwei (May 2024, Earth and Planetary Science Letters)

   The solidification of a deep magma ocean occurred early in Earth’s history. Although the initial amount of H2O in Earth’s magma ocean is predicted to be low (e.g., <3000 ppm), as an incompatible element it becomes highly enriched (e.g. >10 wt%) in the final few percent of crystallization. In order to understand how a hydrous magma ocean would crystallize at the top of the lower mantle, we determined liquidus phase relations in the MgO-FeOCaO-Al2O3-SiO2-H2O system at 24 GPa. We find that the bridgmanite (brg) + stishovite (st) + melt and bridgmanite (brg) + ferropericlase (fp) + melt cotectic boundary curves trend to Mg-rich melt compositions with decreasing temperature and extend to very high H2O contents (~80 mol% H2O). The brg+st+melt curve is a subtraction curve at < ~18 mol% H2O and a reaction curve at higher H2O contents, whereas the brg+fp+melt is a subtraction curve throughout its length. The density of melts along the two cotectics leads to neutral buoyancywith respect to shallow lower mantle and transition zone minerals at H2O contents up to ~25 mol%. A transient melt-rich layer can form at the top of the lower mantle during late-stage crystallization in a mushy magma ocean when melt percolation dominates. When crystallization exceeds ~98%, hydrous melts (>25 mol% H2O) become buoyant and can percolate into and hydrate the mantle transition zone. 

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4. Stability and Solid Solutions of Hydrous Alumino-Silicates in the Earth’s Mantle

   https://doi.org/10.3390/min10040330  

   Panero, Wendy R.; Caracas, Razvan (April 2020, Minerals)

   null (Ed.)

   The degree to which the Earth’s mantle stores and cycles water in excess of the storage capacity of nominally anhydrous minerals is dependent upon the stability of hydrous phases under mantle-relevant pressures, temperatures, and compositions. Two hydrous phases, phase D and phase H, are stable to the pressures and temperatures of the Earth’s lower mantle, suggesting that the Earth’s lower mantle may participate in the cycling of water. We build on our prior work of density functional theory calculations on phase H with the stability, structure, and bonding of hydrous phases D, and we predict the aluminum partitioning with H in the Al 2 O 3 -SiO 2 -MgO-H 2 O system. We address the solid solutions through a statistical sampling of site occupancy and calculation of the partition function from the grand canonical ensemble. We show that each phase has a wide solid solution series between MgSi 2 O 6 H 2 -Al 2 SiO 6 H 2 and MgSiO 4 H 2 -2 δ AlOOH + SiO 2 , in which phase H is more aluminum rich than phase D at a given bulk composition. We predict that the addition of Al to both phases D and H stabilizes each phase to higher temperatures through additional configurational entropy. While we have shown that phase H does not exhibit symmetric hydrogen bonding at high pressure, we report here that phase D undergoes a gradual increase in the number of symmetric H-bonds beginning at ∼30 GPa, and it is only ∼50% complete at 60 GPa. 

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5. Water in the crystal structure of CaSiO3 perovskite

   https://doi.org/10.2138/am-2022-8009  

   Shim, Sang-Heon; Chizmeshya, Andrew; Leinenweber, Kurt (April 2022, American Mineralogist)

   Abstract While the water storage capacities of the upper 700 km depths of the mantle have been constrained by high-pressure experiments and diamond inclusion studies, the storage capacity of the lower mantle remains controversial. A recent high-pressure experimental study on CaSiO3 perovskite, which is the third most abundant mineral in the lower mantle, reported possible storage of H2O up to a few weight percent. However, the substitution mechanism for H in this phase remains unknown. We have conducted a series of density functional theory calculations under static-lattice conditions and high pressures to elucidate hydration mechanisms at the atomic scale. All of the possible dodecahedral (Ca2+ → 2H+) and octahedral (Si4+ → 4H+) substitution configurations for a tetragonal perovskite lattice have very small energy differences, suggesting the coexistence of multiples of H configurations in CaSiO3 perovskite at mantle pressures and temperatures. The dodecahedral substitutions decrease the bulk modulus, resulting in a smaller unit-cell volume of hydrous CaSiO3 perovskite under pressure, consistent with the experimental observations. Although the octahedral substitutions also decrease the bulk modulus, they increase the unit-cell volume at 1 bar. The H atoms substituted in the dodecahedral sites develop much less hydrogen bonding with O atoms, leading to a large distortion in the neighboring SiO6 octahedra. Such distortion may be responsible for the non-cubic peak splittings observed in experiments on hydrous CaSiO3 perovskite. Our calculated infrared spectra suggest that the observed broad OH modes in CaSiO3 perovskite can result from the existence of multiples of H configurations in the phase. Combined with the recent experimental results, our study suggests that CaSiO3 can be an important mineral phase to consider for the H2O storage in the lower mantle. 

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