skip to main content


Title: High‐Pressure Phase Stability and Thermoelastic Properties of Iron Carbonitrides and Nitrogen in the Deep Earth
Abstract

Iron‐dominant metallic phases are likely the primary hosts for nitrogen in the reduced deep Earth, hence the storage of nitrogen in the lower mantle and the core is governed by the behavior of the Fe‐N‐C system at high temperatures and pressures. In this study, phase transitions and thermoelastic properties of iron carbonitrides were investigated at high pressure‐temperature conditions by diamond anvil cell experiments and first‐principles calculations. Experimental data revealed no phase transition inε‐type Fe4(N0.6C0.4) or Fe7(N0.75C0.25)3up to 60 GPa at room temperature. At high temperature, Fe7(N0.75C0.25)3transforms into the Fe3C‐type phase at ∼27 GPa, and then into the Fe7C3‐type phase at ∼45 GPa, which is also corroborated by our theoretical calculations. We found that the phase stability of iron carbonitrides mainly depends on the N/C ratio, and the elastic properties of iron carbonitrides are dominantly affected by the Fe/(N+C) ratio. Iron carbonitrides with diverse structures may be the main host for nitrogen in the deep mantle. Some iron carbonitride inclusions in lower mantle diamonds could be the residue of the primordial mantle or originate from subducted nitrogen‐bearing materials, rather than iron‐enriched phases of the outer core. In addition, our experiments confirmed the existence of Fe7C3‐type Fe7C3‐Fe7N3solid solutions above 40 GPa. Fe7C3‐type Fe7(C, N)3has comparable density and thermoelastic properties to its isostructural endmembers and may be a promising candidate constituent of the Earth's inner core.

 
more » « less
Award ID(s):
1829273
NSF-PAR ID:
10367018
Author(s) / Creator(s):
 ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  
Publisher / Repository:
DOI PREFIX: 10.1029
Date Published:
Journal Name:
Journal of Geophysical Research: Solid Earth
Volume:
126
Issue:
6
ISSN:
2169-9313
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    We present ab initio (LDA + Usc) studies of high‐temperature and high‐pressure elastic properties of pure as well as iron‐bearing (ferrous, Fe2+, and ferric, Fe3+) and aluminum‐bearing MgSiO3postperovskite, the likely dominant phase in the deep lower mantle of the Earth. Thermal effects are addressed within the quasiharmonic approximation by combining vibrational density of states and static elastic coefficients. Aggregate elastic moduli and sound velocities for the Mg end members are successfully compared with scarce experimental data available. Effects of iron (Fe) and aluminum (Al) substitutions on elastic properties and their pressure and temperature dependence have been thoroughly investigated. At the observed perovskite to postperovskite transition (P = 125 GPa andT = 2,500 K), compressional and shear velocities increase by 0–1% and 1.5–3.75%, respectively. This observation is consistent with some seismic studies of the Ddiscontinuity beneath the Caribbean, which suggests that our robust estimates of elastic properties of the postperovskite phase will be very helpful to understand lateral velocity variations in the deep lower mantle region and to constrain its composition and thermal structure.

     
    more » « less
  2. Abstract

    Nitrogen is considered to be transported from Earth′s surface to the top of the lower mantle through subduction. However, little is known on the transportation and fate of subducted nitrogen to the Earth′s interior during slab‐mantle interactions. In this study, the stability of subducted sedimentary nitrogen in the reduced mantle was investigated to 35 GPa and 1600 K by laser‐heated diamond anvil cell experiments and first‐principles calculations. Our results showed that subducted nitrogen‐bearing silicates and fluids could not coexist with the metallic iron or iron‐rich alloys, and reacted with them to form different products at high pressure‐temperature conditions. Combining our results with previous data, we re‐determined the relative stability of iron‐light element binary compounds to 35 GPa and 1600 K to be Fe‐O > Fe‐N > Fe‐S > Fe‐C. This stability sequence contributes to explaining the observation that iron nitrides are trapped as inclusions in sulfur‐depleted lower‐mantle diamonds and are absent in sulfur‐rich ones. The recycling efficiency of subducted sedimentary nitrogen is strongly related to the availability of the metallic iron of the reduced mantle. Hydration of the metallic iron limits the storage of nitrogen in it and contributes to recycling nitrogen to Earth′s surface. Therefore, unlike subducted continental sediments, subducted marine sediments are unlikely to transport a large amount of surficial nitrogen to the metallic iron of the reduced mantle in which nitrogen could reside over long geologic periods.

     
    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

    The viscosity of iron alloy liquids is the key for the core dynamo and core‐mantle differentiation of terrestrial bodies. Here we measured the viscosity of Fe‐Ni‐C liquids up to 7 GPa using the floating sphere viscometry method and up to 330 GPa using first‐principles calculations. We found a viscosity increase at ∼3–5 GPa, coincident with a structural transition in the liquids. After the transition, the viscosity reaches ∼14–27 mPa·s, a factor of 2–4 higher than that of Fe and Fe‐S liquids. Our computational results from 5 to 330 GPa also indicate a high viscosity of the Fe‐Ni‐C liquids. For a carbon‐rich core in large terrestrial body, the level of turbulence in the outer core would be lessened approaching the inner core boundary. It is also anticipated that Fe‐Ni‐C liquids would percolate in Earth's deep silicate mantle at a much slower speed than Fe and Fe‐S liquids.

     
    more » « less
  5. Abstract

    Large Low Shear Velocity Provinces (LLSVPs) in the lowermost mantle are key to understanding the chemical composition and thermal structure of the deep Earth, but their origins have long been debated. Bridgmanite, the most abundant lower-mantle mineral, can incorporate extensive amounts of iron (Fe) with effects on various geophysical properties. Here our high-pressure experiments and ab initio calculations reveal that a ferric-iron-rich bridgmanite coexists with an Fe-poor bridgmanite in the 90 mol% MgSiO3–10 mol% Fe2O3system, rather than forming a homogeneous single phase. The Fe3+-rich bridgmanite has substantially lower velocities and a higherVP/VSratio than MgSiO3bridgmanite under lowermost-mantle conditions. Our modeling shows that the enrichment of Fe3+-rich bridgmanite in a pyrolitic composition can explain the observed features of the LLSVPs. The presence of Fe3+-rich materials within LLSVPs may have profound effects on the deep reservoirs of redox-sensitive elements and their isotopes.

     
    more » « less