skip to main content

Title: Metallic iron limits silicate hydration in Earth’s transition zone
The Earth’s mantle transition zone (MTZ) is often considered an internal reservoir for water because its major minerals wadsleyite and ringwoodite can store several oceans of structural water. Whether it is a hydrous layer or an empty reservoir is still under debate. Previous studies suggested the MTZ may be saturated with iron metal. Here we show that metallic iron reacts with hydrous wadsleyite under the pressure and temperature conditions of the MTZ to form iron hydride or molecular hydrogen and silicate with less than tens of parts per million (ppm) water, implying that water enrichment is incompatible with iron saturation in the MTZ. With the current estimate of water flux to the MTZ, the iron metal preserved from early Earth could transform a significant fraction of subducted water into reduced hydrogen species, thus limiting the hydration of silicates in the bulk MTZ. Meanwhile, the MTZ would become gradually oxidized and metal depleted. As a result, water-rich region can still exist near modern active slabs where iron metal was consumed by reaction with subducted water. Heterogeneous water distribution resolves the apparent contradiction between the extreme water enrichment indicated by the occurrence of hydrous ringwoodite and ice VII in superdeep diamonds and more » the relatively low water content in bulk MTZ silicates inferred from electrical conductivity studies. « less
Authors:
; ; ; ;
Award ID(s):
1763189
Publication Date:
NSF-PAR ID:
10142625
Journal Name:
Proceedings of the National Academy of Sciences
Volume:
116
Issue:
45
Page Range or eLocation-ID:
22526 to 22530
ISSN:
0027-8424
Sponsoring Org:
National Science Foundation
More Like this
  1. The distribution and transportation of water in Earth’s interior depends on the stability of water-bearing phases. The transition zone in Earth’s mantle is generally accepted as an important potential water reservoir because its main constituents, wadsleyite and ringwoodite, can incorporate weight percent levels of H2O in their structures at mantle temperatures. The extent to which water can be transported beyond the transition zone deeper into the mantle depends on the water carrying capacity of minerals stable in subducted lithosphere. Stishovite is one of the major mineral components in subducting oceanic crust, yet the capacity of stishovite to incorporate water beyond at lower mantle conditions remains speculative. In this study, we combine in situ laser heating with synchrotron X-ray diffraction to show that the unit cell volume of stishovite synthesized under hydrous conditions is ∼2.3 to 5.0% greater than that of anhydrous stishovite at pressures of ∼27 to 58 GPa and temperatures of 1,240 to 1,835 K. Our results indicate that stishovite, even at temperatures along a mantle geotherm, can potentially incorporate weight percent levels of H2O in its crystal structure and has the potential to be a key phase for transporting and storing water in the lower mantle.

  2. 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.
  3. 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 enhancesmore »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.« less
  4. 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% atmore »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.« less
  5. Abstract As the reaction product of subducted water and the iron core, FeO2 with more oxygen than hematite (Fe2O3) has been recently recognized as an important component in the D” layer just above the Earth's core-mantle boundary. Here, we report a new oxygen-excess phase (Mg, Fe)2O3+δ (0 < δ < 1, denoted as “OE-phase”). It forms at pressures greater than 40gigapascals when (Mg, Fe)-bearing hydrous materials are heated over 1,500 kelvin. The OE-phase is fully recoverable to ambient conditions for ex-situ investigation using transmission electron microscopy, which indicates that the OE-phase contains ferric iron (Fe3+) as in Fe2O3 but holds excess oxygen through interactions between oxygen atoms. The new OE-phase provides strong evidence that H2O has extraordinary oxidation power at high pressure. Unlike the formation of pyrite-type FeO2Hx which usually requires saturated water, the OE-phase can be formed with under-saturated water at mid-mantle conditions, and is expected to be more ubiquitous at depths greater than 1,000 km in Earth's mantle. The emergence of oxygen-excess reservoirs out of primordial and subducted (Mg, Fe)-bearing hydrous materials may revise our view on the deep-mantle redox chemistry.