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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. Behavior and properties of water in silicate melts under deep mantle conditions

   https://doi.org/https://doi.org/10.1038/s41598-021-90124-7  

   Karki, Bijaya B ; Ghosh, Dipta B ; Karato, Shun-ichiro ( May 2021 , Scientific reports)

   null (Ed.)

   Water (H2O) as one of the most abundant fluids present in Earth plays crucial role in the generation and transport of magmas in the interior. Though hydrous silicate melts have been studied extensively, the experimental data are confined to relatively low pressures and the computational results are still rare. Moreover, these studies imply large differences in the way water influences the physical properties of silicate magmas, such as density and electrical conductivity. Here, we investigate the equation of state, speciation, and transport properties of water dissolved in Mg1-xFexSiO3 and Mg2(1-x)Fe2xSiO4 melts (for x = 0 and 0.25) as well as in its bulk (pure) fluid state over the entire mantle pressure regime at 2000 to 4000 K using first-principles molecular dynamics. The simulation results allow us to constrain the partial molar volume of the water component in melts along with the molar volume of pure water. The predicted volume of silicate melt+water solution is negative at low pressures and becomes zero above 15 GPa. Consequently, the hydrous component tends to lower the melt density to similar extent over much of the mantle pressure regime irrespective of composition. Our results also show that hydrogen diffuses fast in silicate melts and enhances the melt electrical conductivity in a way that differs from electrical conduction in the bulk water. The speciation of the water component varies considerably from the bulk water structure as well. Water is dissolved in melts mostly as hydroxyls at low pressure and as -O-H-O-, -O-H-O-H- and other extended species with increasing pressure. On the other hand, the pure water behaves as a molecular fluid below 15 GPa, gradually becoming a dissociated fluid with further compression. On the basis of modeled density and conductivity results, we suggest that partial melts containing a few percent of water may be gravitationally trapped both above and below the upper mantle-transition region. Moreover, such hydrous melts can give rise to detectable electrical conductance by means of electromagnetic sounding observations. 

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3. Nonlinear effects of hydration on high-pressure sound velocities of rhyolitic glasses

   https://doi.org/10.2138/am-2021-7597  

   Gu, Jesse T. ; Fu, Suyu ; Gardner, James E. ; Yamashita, Shigeru ; Okuchi, Takuo ; Lin, Jung-Fu ( July 2021 , American Mineralogist)

   Abstract Acoustic compressional and shear wave velocities (VP, VS) of anhydrous (AHRG) and hydrous rhyolitic glasses (HRG) containing 3.28 wt% (HRG-3) and 5.90 wt% (HRG-6) total water concentration (H2Ot) have been measured using Brillouin light scattering (BLS) spectroscopy up to 3 GPa in a diamond-anvil cell at ambient temperature. In addition, Fourier-transform infrared (FTIR) spectroscopy was used to measure the speciation of H2O in the glasses up to 3 GPa. At ambient pressure, HRG-3 contains 1.58 (6) wt% hydroxyl groups (OH–) and 1.70 (7) wt% molecular water (H2Om) while HRG-6 contains 1.67 (10) wt% OH– and 4.23 (17) wt% H2Om where the numbers in parentheses are ±1σ. With increasing pressure, very little H2Om, if any, converts to OH– within uncertainties in hydrous rhyolitic glasses such that HRG-6 contains much more H2Om than HRG-3 at all experimental pressures. We observe a nonlinear relationship between high-pressure sound velocities and H2Ot, which is attributed to the distinct effects of each water species on acoustic velocities and elastic moduli of hydrous glasses. Near ambient pressure, depolymerization due to OH– reduces VS and G more than VP and KS. VP and KS in both anhydrous and hydrous glasses decrease with increasing pressure up to ~1–2 GPa before increasing with pressure. Above ~1–2 GPa, VP and KS in both hydrous glasses converge with those in AHRG. In particular, VP in HRG-6 crosses over and becomes higher than VP in AHRG. HRG-6 displays lower VS and G than HRG-3 near ambient pressure, but VS and G in these glasses converge above ~2 GPa. Our results show that hydrous rhyolitic glasses with ~2–4 wt% H2Om can be as incompressible as their anhydrous counterpart above ~1.5 GPa. The nonlinear effects of hydration on high-pressure acoustic velocities and elastic moduli of rhyolitic glasses observed here may provide some insight into the behavior of hydrous silicate melts in felsic magma chambers at depth. 

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4. Non-linear Effects of Hydration on Sound Velocities of Rhyolitic Glasses up to 3 GPa.

   Gu, J. ; Fu, S. ; Gardner, J. E. ; Yamashira, S. ; Okuchi, T. ; Lin, J. F. ( January 2021 , The American mineralogist)

   null (Ed.)

   Acoustic compressional and shear wave velocities (VP, VS) of anhydrous (AHRG) and hydrous rhyolitic glasses (HRG) containing 3.28 wt% (HRG-3) and 5.90 wt% (HRG-6) total water concentra- tion (H2Ot) have been measured using Brillouin light scattering (BLS) spectroscopy up to 3 GPa in a diamond-anvil cell at ambient temperature. In addition, Fourier-transform infrared (FTIR) spectroscopy was used to measure the speciation of H2O in the glasses up to 3 GPa. At ambient pressure, HRG-3 contains 1.58 (6) wt% hydroxyl groups (OH–) and 1.70 (7) wt% molecular water (H2Om) while HRG-6 contains 1.67 (10) wt% OH– and 4.23 (17) wt% H2Om where the numbers in parentheses are ±1σ. With increasing pressure, very little H2Om, if any, converts to OH– within uncertainties in hydrous rhyolitic glasses such that HRG-6 contains much more H2Om than HRG-3 at all experimental pressures. We observe a nonlinear relationship between high-pressure sound velocities and H2Ot, which is attributed to the distinct effects of each water species on acoustic velocities and elastic moduli of hydrous glasses. Near ambient pressure, depolymerization due to OH– reduces VS and G more than VP and KS. VP and KS in both anhydrous and hydrous glasses decrease with increasing pressure up to ~1–2 GPa before increasing with pressure. Above ~1–2 GPa, VP and KS in both hydrous glasses converge with those in AHRG. In particular, VP in HRG-6 crosses over and becomes higher than VP in AHRG. HRG-6 displays lower VS and G than HRG-3 near ambient pressure, but VS and G in these glasses converge above ~2 GPa. Our results show that hydrous rhyolitic glasses with ~2–4 wt% H2Om can be as incompressible as their anhydrous counterpart above ~1.5 GPa. The nonlinear effects of hydration on high-pressure acoustic velocities and elastic moduli of rhyolitic glasses observed here may provide some insight into the behavior of hydrous silicate melts in felsic magma chambers at depth. 

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5. Investigation of the crystal structure of a low water content hydrous olivine to 29.9 GPa: A high-pressure single-crystal X-ray diffraction study

   https://doi.org/10.2138/am-2020-7444  

   Xu, Jingui ; Fan, Dawei ; Zhang, Dongzhou ; Li, Bo ; Zhou, Wenge ; Dera, Przemyslaw K. ( December 2020 , American Mineralogist)

   null (Ed.)

   Abstract Olivine is the most abundant mineral in the Earth's upper mantle and subducting slabs. Studying the structural evolution and equation of state of olivine at high-pressure is of fundamental importance in constraining the composition and structure of these regions. Hydrogen can be incorporated into olivine and significantly influence its physical and chemical properties. Previous infrared and Raman spectroscopic studies indicated that local structural changes occur in Mg-rich hydrous olivine (Fo ≥ 95; 4883–9000 ppmw water) at high-pressure. Since water contents of natural olivine are commonly <1000 ppmw, it is inevitable to investigate the effects of such water contents on the equation of state (EoS) and structure of olivine at high-pressure. Here we synthesized a low water content hydrous olivine (Fo95; 1538 ppmw water) at low SiO2 activity and identified that the incorporated hydrogens are predominantly associated with the Si sites. We performed high-pressure single-crystal X-ray diffraction experiments on this olivine to 29.9 GPa. A third-order Birch-Murnaghan equation of state (BM3 EoS) was fit to the pressure-volume data, yielding the following EoS parameters: VT0 = 290.182(1) Å3, KT0 = 130.8(9) GPa, and K′T0 = 4.16(8). The KT0 is consistent with those of anhydrous Mg-rich olivine, which indicates that such low water content has negligible effects on the bulk modulus of olivine. Furthermore, we carried out the structural refinement of this hydrous olivine as a function of pressure to 29.9 GPa. The results indicate that, similar to the anhydrous olivine, the compression of the M1-O and M2-O bonds are comparable, which are larger than that of the Si-O bonds. The compression of M1-O and M2-O bonds of this hydrous olivine are comparable with those of anhydrous olivine, while the Si-O1 and Si-O2 bonds in the hydrous olivine are more compressible than those in the anhydrous olivine. Therefore, this study suggests that low water content has negligible effects on the EoS of olivine, though the incorporation of water softens the Si-O1 and Si-O2 bond. 

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