skip to main content


Title: Single-crystal elasticity of phase Egg AlSiO3OH and δ-AlOOH by Brillouin spectroscopy
Abstract Phase Egg and δ-AlOOH are two typical hydrous phases that might exist in the wet sedimentary layer of subducted slabs under mantle conditions. They are thus regarded as potential water carriers to Earth’s deep mantle. In this report, we report the full elastic constants of both phases determined by Brillouin scattering and X-ray diffraction measurements under ambient conditions. Our results indicate that the hydrogen-bond configurations in the crystal structures of the two phases have a profound effect on their principal elastic constants. The adiabatic bulk modulus (KS) and shear modulus (G) calculated from the obtained elastic constants using the Voigt-Reuss-Hill averaging scheme are 158.3(201) GPa and 123.0(60) GPa for phase Egg and 162.9(31) GPa and 145.2(13) GPa for δ-AlOOH, respectively. These results allow us to evaluate elastic moduli and sound velocities of hydrous minerals in the Al2O3-H2O-SiO2 ternary system (simplified composition of subducted wet sedimentary layer) at ambient conditions, including the contrast of the acoustic velocities VP and VS for the reaction AlSi3OH = δ-AlOOH + SiO2 (stishovite) and the evolution in the elastic moduli and sound velocities of hydrous minerals as a function of density.  more » « less
Award ID(s):
1916941
NSF-PAR ID:
10317880
Author(s) / Creator(s):
; ; ; ; ; ; ;
Date Published:
Journal Name:
American Mineralogist
Volume:
107
Issue:
1
ISSN:
0003-004X
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. 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. 
    more » « less
  2. null (Ed.)
    Abstract The high-pressure phases of oxyhydroxides (δ-AlOOH, ε-FeOOH, and their solid solution), candidate components of subducted slabs, have wide stability fields, thus potentially influencing volatile circulation and dynamics in the Earth’s lower mantle. Here, we report the elastic wave velocities of δ-(Al,Fe)OOH (Fe/(Al + Fe) = 0.13, δ-Fe13) to 79 GPa, determined by nuclear resonant inelastic X-ray scattering. At pressures below 20 GPa, a softening of the phonon spectra is observed. With increasing pressure up to the Fe 3+ spin crossover (~ 45 GPa), the Debye sound velocity ( v D ) increases. At higher pressures, the low spin δ-Fe13 is characterized by a pressure-invariant v D . Using the equation of state for the same sample, the shear-, compressional-, and bulk-velocities ( v S , v P , and v Φ ) are calculated and extrapolated to deep mantle conditions. The obtained velocity data show that δ-(Al,Fe)OOH may cause low- v Φ and low- v P anomalies in the shallow lower mantle. At deeper depths, we find that this hydrous phase reproduces the anti-correlation between v S and v Φ reported for the large low seismic velocity provinces, thus serving as a potential seismic signature of hydrous circulation in the lower mantle. 
    more » « less
  3. Abstract

    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: Al0.84Fe3+0.07Mg0.02Si0.06OOH, 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.

     
    more » « less
  4. Abstract

    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.

     
    more » « less
  5. 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. 
    more » « less