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Complex seismic, thermal, and chemical features have been reported in Earth's lowermost mantle. In particular, possible iron enrichments in the large low shear-wave velocity provinces (LLSVPs) could influence thermal transport properties of the constituting minerals in this region, altering the lower mantle dynamics and heat flux across core-mantle boundary (CMB). Thermal conductivity of bridgmanite is expected to partially control the thermal evolution and dynamics of Earth's lower mantle. Importantly, the pressure-induced lattice distortion and iron spin and valence states in bridgmanite could affect its lattice thermal conductivity, but these effects remain largely unknown. Here we precisely measured the lattice thermal conductivity of Fe-bearing bridgmanite to 120 gigapascals using optical pump-probe spectroscopy. The conductivity of Fe-bearing bridgmanite increases monotonically with pressure, but drops significantly around 45 gigapascals due to pressure-induced lattice distortion on iron sites. Our findings indicate that lattice thermal conductivity at lowermost mantle conditions is twice smaller than previously thought. The decrease in the thermal conductivity of bridgmanite in mid-lower mantle and below would promote mantle flow against a potential viscosity barrier, facilitating slabs crossing over the 1000-km depth. Modeling of our results applied to LLSVPs shows that variations in iron and bridgmanite fractions induce a significant thermal conductivity decrease, which would enhance internal convective flow. Our CMB heat flux modeling indicates that, while heat flux variations are dominated by thermal effects, variations in thermal conductivity also play a significant role. The CMB heat flux map we obtained is substantially different from those assumed so far, which may influence our understanding of the geodynamo.

Deciphering the origin of seismic heterogeneity has been one of the major challenges in understanding the geochemistry and geodynamics of the deep mantle. Fully anisotropic elastic properties of constituent minerals at relevant pressure-temperature conditions of the lower mantle can be used to calculate seismic heterogeneity parameters in order to better understand chemically- and thermally-induced seismic heterogeneities. In this study, the single-crystal elastic properties of ferropericlase (Mg0.94Fe0.06)O were measured using Brillouin spectroscopy and X-ray diffraction at conditions up to 50 GPa and 900 K. The velocity-density results were modeled using third-order finite-strain theory and thermoelastic equations along a representative geotherm to investigate high pressure-temperature and compositional effects on the seismic heterogeneity parameters. Our results demonstrate that from 660 to 2000 km, compressional wave anisotropy of ferropericlase increased from 4% to 9.7% while shear wave anisotropy increased from 9% to as high as 22.5%. The thermally-induced lateral heterogeneity ratio (RS/P = ∂lnVS/∂lnVP) of ferropericlase was calculated to be 1.48 at ambient pressure but decreased to 1.43 at 40 GPa along a representative geotherm. The RS/P of a simplified pyrolite model consisting of 80% bridgmanite and 20% ferropericlase was approximately 1.5, consistent with seismic models at depths from 670 to 1500 km, but showed an increased mismatch at lower mantle depths below ~1500 km. This discrepancy below mid-lower mantle could be due to either a contribution from chemically-induced heterogeneity or the effects of the Fe spin transition in the deeper parts of the Earth's lower mantle.

Hydrous magnesium silicate phase D plays a key role in the transport of water from the upper to the lower mantle via subducted slabs. Here we report pressure dependence hyperfine and lattice parameters of FeAl-bearing phase D up to megabar pressures using synchrotron nuclear forward scattering and X-ray diffraction in a diamond anvil cell at room temperature. FeAl-bearing phase D undergoes a two-stage high-spin to low-spin transition of iron for Fe2+ at 37–41 GPa and for Fe3+ at 64–68 GPa. These transitions are accompanied by an increase in density and a significant softening in the bulk modulus and bulk velocity at their respective pressure range. The occurrence of the dense low-spin FeAl-bearing phase D with relatively high velocity anisotropies in deep-subducted slabs can potentially contribute to small-scale seismic heterogeneities in the middle-lower mantle beneath the circum-Pacific area.

We investigated the combined effect of pressure and temperature on the elasticity of single-crystal superhydrous phase B (Shy-B) using Brillouin scattering and X-ray diffraction up to 12 GPa and 700 K. Using the obtained elasticity, we modeled the anisotropy of Shy-B along slab geotherms, showing that Shy-B has a low anisotropy and cannot be the major cause of the observed anisotropy in the region. Modeled velocities of Shy-B show that Shy-B will be shown as positive velocity anomalies at the bottom transition zone. Once Shy-B is transported to the topmost lower mantle, it will exhibit a seismic signature of lower velocities than topmost lower mantle. We speculate that an accumulation of hydrous phases, such as Shy-B, at the topmost lower mantle with a weight percentage of ~17–26% in the peridotite layer as subduction progresses could help explain the observed 2–3% low shear velocity anomalies in the region.

The new hexagonal aluminous phase, named the NAL phase, is expected to be stable at depths of

Spin and valence states of iron in single-crystal bridgmanite (Mg0.89Fe0.12Al0.11Si0.89O3) are investigated using X-ray emission and Mossbauer spectroscopies with laser annealing up to 115 GPa. The results show that Fe predominantly substitutes for Mg2+ in the pseudo-dodecahedral A site, in which 80% of the iron is Fe3+ that enters the lattice via the charge-coupled substitution with Al3+ in the octahedral B site. The total spin momentum and hyperfine parameters indicate that these ions remain in the high-spin state with Fe2+ having extremely high quadrupole splitting due to lattice distortion. (Al,Fe)-bearing bridgmanite is expected to contain mostly high-spin, A-site Fe3+, together with a smaller amount of A-site Fe2+, that remains stable throughout the region. Even though the spin transition of B-site Fe3+ in bridgmanite was reported to cause changes in its elasticity at high pressures, (Fe,Al)-bearing bridgmanite with predominantly A-site Fe will not exhibit elastic anomalies associated with the spin transition.

In this study, we have examined the lower mantle composition and mineralogy by modeling the density (ρ), bulk sound velocity (VΦ), and dlnρ/dlnVΦ profiles of candidate lower mantle minerals using literature and new experimental equation of state (EoS) results. For CaSiO3 perovskite, complimentary synchrotron X-ray diffraction measurements in a laser-heated diamond anvil cell were conducted up to 156 GPa between 1200 K and 2600 K to provide more reliable constraints on the thermal EoS parameters. These new experimental results as well as literature P-V-T data sets are systematically analyzed using an internally self-consistent pressure scale. We have modeled ρ, VΦ, and dlnρ/dlnVΦ profiles of the lower mantle with representative pyrolitic and chondritic compositional models in which the effect of Fe spin transition in ferropericlase is also taken into account. Our modeling results show that a pyrolitic lower mantle with an aggregate mineralogy of 75 vol % bridgmanite, 17 vol % ferropericlase, and 8 vol % CaSiO3 perovskite produces ρ and VΦ profiles in better agreement with preliminary reference Earth model than a lower mantle with a chondritic composition. The modeled ρ, VΦ, and dlnρ/dlnVΦ are mainly affected by the relative ratio of bridgmanite and ferropericlase but are not sensitive to the variation of the CaSiO3 perovskite content. In addition, the spin crossover of Fe in ferropericlase can greatly raise the value of dlnρ/dlnVΦ in the middle lower mantle, which is useful in detecting the presence of ferropericlase in the region. Based on these new mineral physical constraints and radial seismic structure, our study suggests the lower mantle is pyrolitic, which is chemically indistinguishable from the upper mantle.

Iron alloyed with Ni and Si has been suggested to be a major component of the Earth’s inner core. High-pressure results on the combined alloying effects of Ni and Si on seismic parameters of iron are thus essential for establishing satisfactory geophysical and geochemical models of the region. Here we have investigated the compressional (VP) and shear (Vs) wave velocity-density (ρ) relations, Poisson’s ratio (ν), and seismic heterogeneity ratios (dlnρ/dlnVP, dlnρ/dlnVS, and dlnVP/dlnVS) of hcp-Fe and hcp-Fe86.8Ni8.6Si4.6 alloy up to 206GPa and 136GPa, respectively, using multiple complementary techniques. Compared with the literature velocity values for hcp-Fe and Fe-Ni-Si alloys, our results show that the combined addition of 9.0wt% Ni and 2.3wt% Si slightly increases the VP but significantly decreases the VS of hcp-Fe at a given density relevant to the inner core. Such distinct alloying effects on velocities of hcp-Fe produce a high ν of about 0.40 for the alloy at inner core densities, which is approximately 20% higher than that for hcp-Fe. Analysis of the literature high P-T results on VP and VS of Fe alloyed with light elements shows that high temperature can further enhance the ν of hcp-Fe alloyed with Ni and Si. Most significantly, the derived seismic heterogeneity ratios of this hcp alloy present a better match with global seismic observations. Our results provide a multifactored geophysical constraint on the compositional model of the inner core which is consistent with silicon being a major light element alloyed with Fe and 5wt% Ni.

We have investigated the equation of state of Fe-bearing bridgmanite, (Mg0.9Fe0.1)SiO3, using synchrotron X-ray diffraction in diamond anvil cells up to 125 GPa and 300 K. Combined with previous synchrotron Mossbauer spectroscopy results, we have found that the occurrence of the low-spin Fe3+ in the octahedral sites (B site) of bridgmanite has produced a 0.5(±0.1)% reduction in the unit cell volume at 18–25 GPa and has increased the isothermal bulk modulus to 284(±4) GPa, consistent with recent theoretical calculations. Together with literature results, we note that the addition of Fe can cause an increase in the density, bulk modulus, and bulk sound velocity in both Al-free and Al-bearing bridgmanite at lower mantle pressures. The presence of Fe3+ in the B site of bridgmanite can further enhance this increase. The observed spin transition of B site Fe3+ in bridgmanite is thus important for understanding the density and velocity structures of the lower mantle.

We have measured acoustic VP and VS velocities of (Fe,Al)-bearing MgSiO3 silicate glasses and an Icelandic basalt glass up to 25 GPa. The velocity profiles of the (Fe,Al)-bearing and basaltic silicate glasses display decreased VP and VS with minima at approximately 5 and 2 GPa, respectively, which could be explained by the mode softening in the aluminosilicate networks. Our results represent the first observation of such velocity softening extending into the chemically complex basaltic glass at a relatively low transition pressure, which is likely due to its degree of polymerization, while the Fe and Al substitutions reduce sound velocities in MgSiO3 glass. If the velocity softening in the basaltic and silicate glasses can be used as analogs for understanding melts in Earth's interior, these observations suggest that the melt fraction needed to account for the velocity reduction in the upper mantle low-velocity zone may be smaller than previously thought.

Much of the lunar crust is monomineralic, comprising >98% plagioclase. The prevailing model argues the crust accumulated as plagioclase floated to the surface of a solidifying lunar magma ocean (LMO). Whether >98% pure anorthosites can form in a flotation scenario is debated. An important determinant of the efficiency of plagioclase fractionation is the viscosity of the LMO liquid, which was unconstrained. Here we present results from new experiments conducted on a late LMO-relevant ferrobasaltic melt. The liquid has an exceptionally low viscosity of 0.22−0.19+0.11 to 1.45−0.82+0.46 Pa s at experimental conditions (1,300–1,600°C; 0.1–4.4 GPa) and can be modeled by an Arrhenius relation. Extrapolating to LMO-relevant temperatures, our analysis suggests a low viscosity LMO would form a stratified flotation crust, with the oldest units containing a mafic component and with very pure younger units. Old, impure crust may have been buried by lower crustal diapirs of pure anorthosite in a serial magmatism scenario.

We have investigated phase relations and melting behavior of Fe3C and Fe7C3 using X-ray diffraction in a laser-heated diamond cell up to 185 GPa and 5200 K. Our results show that the starting Fe3C sample decomposes into a mixture of solid orthorhombic Fe7C3 and hcp-Fe at above 145 GPa upon laser heating and then transforms into Fe-C liquid and solid Fe7C3 at temperatures above 3400 K. Using the intensity of the diffuse scattering as a primary criteria for detecting melting, the experimentally derived liquidus for a bulk composition of Fe3C fitted with the Simon-Glatzel equation is Tm(K) = 1800 × [1 + (Pm − 5.7)/15.10 ± 2.55]1/2.41 ± 0.17 at 24–185 GPa, which is ~500 K higher than the melting curve of iron reported by Anzellini et al. (2013) at Earth's core pressures. The higher melting point and relative stability of Fe7C3 in Fe-rich Fe-C system at Earth's core conditions indicate that Fe7C3 could solidify out of the early Earth's molten core to become a constituent of the innermost inner core.

[1] We have critically reviewed and discussed currently available information regarding the spin and valence states of iron in lower mantle minerals and the associated effects of the spin transitions on physical, chemical, and transport properties of the deep Earth. A high-spin to low-spin crossover of Fe2+ in ferropericlase has been observed to occur at pressure-temperature conditions corresponding to the middle part of the lower mantle. In contrast, recent studies consistently show that Fe2+ predominantly exhibits extremely high quadrupole splitting values in the pseudo-dodecahedral site (A site) of perovskite and post-perovskite, indicative of a strong lattice distortion. Fe3+ in the A site of these structures likely remains in the high-spin state, while a high-spin to low-spin transition of Fe3+ in the octahedral site of perovskite occurs at pressures of 15–50 GPa. In post-perovskite, the octahedral-site Fe3+ remains in the low-spin state at the pressure conditions of the lowermost mantle. These changes in the spin and valence states of iron as a function of pressure and temperature have been reported to affect physical, chemical, rheological, and transport properties of the lower mantle minerals. The spin crossover of Fe2+ in ferropericlase has been documented to affect these properties and is discussed in depth here, whereas the effects of the spin transition of iron in perovskite and post-perovskite are much more complex and remain debated. The consequences of the transitions are evaluated in terms of their implications to deep Earth geophysics, geochemistry, and geodynamics including elasticity, element partitioning, fractionation and diffusion, and rheological and transport properties.

The thermal equation of state of ferropericlase [(Mg{sub 0.75}Fe{sub 0.25})O] has been investigated by synchrotron X-ray diffraction up to 140 GPa and 2000 K in a laser-heated diamond anvil cell. Based on results at high pressure-temperature conditions, the derived phase diagram shows that the spin crossover widens at elevated temperatures. Along the lower-mantle geotherm, the spin crossover occurs between 1700 km and 2700 km depth. Compared to the high-spin state, thermoelastic modeling of the data shows a {approx}1.2% increase in density, a factor of two increase in thermal expansion coefficient over a range of 1000 km, and a maximum decrease of 37% and 13% in bulk modulus and bulk sound velocity, respectively, at {approx}2180 km depth across the spin crossover. These anomalous behaviors in the thermoelastic properties of ferropericlase across the spin crossover must be taken into account in order to understand the seismic signatures and geodynamics of the lower mantle.

The electronic spin and valence states of Fe in post-perovskite ((Mg{sub 0.75}Fe{sub 0.25})SiO{sub 3}) have been investigated by synchrotron X-ray diffraction, Moessbauer and X-ray emission spectroscopy at 142 GPa and 300 K. Rietveld refinement of the X-ray diffraction patterns revealed that our sample was dominated by CaIrO{sub 3}-type post-perovskite. Combined Moessbauer and X-ray emission results show that Fe in post-perovskite is predominantly Fe{sup 2+} (70%) in the intermediate-spin state with extremely high quadrupole splitting of 3.77(25) mm/s. The remaining 30% Fe can be assigned to two sites. Compared with recent studies, our results indicate that the intermediate-spin Fe{sup 2+} is stabilized in CaIrO{sub 3}-type post-perovskite over a wide range of Fe content, whereas the low-spin Fe{sup 3+} is more dominant in the 2 x 1 kinked post-perovskite structure. The characterization of these structural and compositional effects on the spin and valence states of Fe in post-perovskite can help in understanding the geochemical and geophysical behavior of the core-mantle region.

Phase relations of an Fe0.85Si0.15 alloy were investigated up to 240 GPa and 3000 K using in situ X-ray diffraction in a laser-heated diamond anvil cell. An alloy of this composition as starting material is found to result in a stabilized mixture of Si-rich bcc and Si-poor hcp Fe-Si phases up to at least 150 GPa and 3000 K, whereas only hcp-Fe0.85Si0.15 is found to be stable between approximately 170 GPa and 240 GPa at high temperatures. Our extended results indicate that Fe0.85Si0.15 alloy is likely to have the hcp structure in the inner core, instead of the previously proposed mixture of hcp and bcc phases. Due to the volumetric dominance of the hcp phase in the hcp + bcc coexistence region close to the outer-core conditions, the dense closest-packed Fe-Si liquid is more relevant to understanding the properties of the outer core.

High-pressure x-ray diffraction of (Mg{sub 0.8}Fe{sub 0.2})O at room temperature reveals a discontinuity in the bulk modulus at 40 ({+-}5) GPa, similar pressure at which an electronic spin-pairing transition of Fe{sup 2+} is also observed. In the x-ray diffraction experiments the transition is completed only at 80 GPa, possibly reflecting lack of equilibration. Combining recent measurements, we document anomalies in the compression curve of Mg-rich magnesiowuestites that are manifestations of the spin transition. The best fit to a third order Birch-Murnaghan equation for the low-spin phase of magnesiowuestite with 17-20 mol% FeO yields bulk modulus K{sub T0} = 190 ({+-}150) GPa, pressure derivative ({partial_derivative}K{sub T}/{partial_derivative}){sub T0} = 4.6 ({+-}2.7) and unit-cell volume V{sub 0} = 71 ({+-}5) {angstrom}{sup 3}, consistent with past estimates of the ionic radius of octahedrally-coordinated low-spin Fe{sup 2+} in oxides. A sharp spin transition at lower-mantle depths between 1100 and 1900 km (40-80 GPa) would cause a unit-cell volume decrease ({Delta}{nu}{sub {phi}}) of 3.7 ({+-}0.8) to 2.0 ({+-}0.2) percent and bulk sound velocity increase ({Delta}{nu}{sub {phi}}) of 8.1 ({+-}6-1.7) percent ({nu}{sub {phi}} = {radical}K{sub s}/{rho}). Even in the absence of a visible seismic discontinuity, we expect the Fe-spin transition to imply a correction to current compositionalmore » models of the lower mantle, with up to 10 mol percent increase of magnesiowuestite being required to match the seismological data.« less

[1] Electrical conductivity of the lower-mantle ferropericlase-(Mg0.75,Fe0.25)O has been studied using designer diamond anvils to pressures over one megabar and temperatures up to 500 K. The electrical conductivity of (Mg0.75,Fe0.25)O gradually rises by an order of magnitude up to 50 GPa but decreases by a factor of approximately three between 50 to 70 GPa. This decrease in the electrical conductivity is attributed to the isosymmetric high-spin to low-spin transition of iron in ferropericlase. That is, the electronic spin transition of iron results in a decrease in the mobility and/or density of the charge transfer carriers in the low-spin ferropericlase. The activation energy of the low-spin ferropericlase is 0.27 eV at 101 GPa, consistent with the small polaron conduction (electronic hopping, charge transfer). Our results indicate that low-spin ferropericlase exhibits lower electrical conductivity than high-spin ferropericlase, which needs to be considered in future geomagnetic models for the lower mantle.

[1] In the paper ‘‘Sound velocities of ferropericlase in the Earth’s lower mantle’’ by Jung-Fu Lin, Steven D. Jacobsen, Wolfgang Sturhahn, Jennifer M. Jackson, Jiyong Zhao, and Choong-Shik Yoo (Geophysical Research Letters, 33, L22304, doi:10.1029/2006GL028099, 2006), we regret that a factor of (1/2) was mistakenly unaccounted for in converting the Debye sound velocities to km/s unit. The correct figures of the derived Vp, Vs, and G are presented here. The derived Vp, Vs, and G at ambient conditions are now lower than that of ultrasonic measurements. The difference may arise from the choice of the energy range for deriving the Debye sound velocities, in combination with the energy resolution of the partial phonon density of states in our study. Further analyses to resolve the difference are forthcoming and will be presented elsewhere. Other parts of the original article, including the discussion, remain unchanged. Figure 2.

The spin state of Fe(II) and Fe(III) at temperatures and pressures typical for the Earth's lower mantle is discussed. We predict an extended high-spin to low-spin crossover region along the geotherm for Fe-dilute systems depending on crystal-field splitting, pairing energy, and cooperative interactions. In particular, spin transitions in ferromagnesium silicate perovskite and ferropericlase, the dominant lower mantle components, should occur in a wide temperature-pressure range. We also derive a gradual volume change associated with such transitions in the lower mantle. The gradual density changes and the wide spin crossover regions seem incompatible with lower mantle stratification resulting from a spin transition.

Water plays an important role in the physics and chemistry of planetary interiors. In situ high pressure-temperature Raman spectroscopy and synchrotron x-ray diffraction have been used to examine the phase diagram of H{sub 2}O. A discontinuous change in the melting curve of H{sub 2}O is observed at approximately 35 GPa and 1040 K, indicating a triple point on the melting line. The melting curve of H{sub 2}O increases significantly above the triple point and may intersect the isentropes of Neptune and Uranus. Solid ice could therefore form in stratified layers at depth within these icy planets. The extrapolated melting curve may also intersect with the geotherm of Earth's lower mantle above 60 GPa. The presence of solid H{sub 2}O would result in a jump in the viscosity of the mid-lower mantle and provides an additional explanation for the observed higher viscosity of the mid-lower mantle.

[1] The laser-heated diamond anvil cell has been widely used to study mineral physics under high pressure and temperature, and these studies have provided valuable information in understanding planetary interiors; however, use of the spectroradiometric method in the studies has raised concerns about the accuracy of obtained temperature values. We have built a laser-heating system coupled with nuclear resonant inelastic x-ray scattering to explore particular physical properties of deep-Earth materials. Energy spectra of iron were measured up to 58 GPa and 1700 K. The detailed balance principle applied to the inelastic x-ray scattering spectra provides absolute temperatures of the laser-heated sample. These temperatures are in very good agreement with values determined from the thermal radiation spectra fitted to the Planck radiation function up to 1700 K. Our data provide, for the first time, independent confirmation of the validity of temperatures determined from spectroradiometric method in the laser-heated diamond cell experiments.

lower the density of iron, but significantly changes its compressibility neither in the bcc phase, nor at high pressures in the hcp phase. Upon comparison with the Preliminary Reference Earth Model, the calculated equations of state (EOS) of hcp-Fe85Si15, using the Mie-Gruneisen EOS, indicate that an outer core containing about 8-10 wt.% Si and inner core containing about 4 wt.% Si in iron would satisfy the seismological constraints. Addition of silicon into iron increases the bulk sound velocity of iron, consistent with silicon being a light element in the Earth's core. INDEX TERMS: 1015 Geochemistry: Composition of the core; 3919 Mineral Physics: Equations of state; 3924 Mineral Physics: High-pressure behavior; 3954 Mineral Physics: X ray, neutron, and electron spectroscopy and diffraction; KEYWORDS: high pressure, light elements, iron-silicon alloy, Earth's core, X-ray diffraction, equation of state

[1] Understanding the alloying effects of nickel and light element(s) on the physical properties of iron under core conditions is crucial for interpreting and constraining geophysical and geochemical models. We have studied two alloys, Fe0.92Ni0.08 and Fe0.85Si0.15, with nuclear resonant inelastic x-ray scattering up to 106 GPa and 70 GPa, respectively. The sound velocities of the alloys are obtained from the measured partial phonon density of states for 57Fe incorporated in the alloys. Addition of Ni slightly decreases the compression wave velocity and shear wave velocity of Fe under high pressures. Silicon alloyed with Fe increases the compressional wave velocity and shear wave velocity under high pressures, which provides a better match to seismological data of the Earth's core.

Because of its remoteness, together with pressures from 140 to 360 gigapascals and temperatures from 4000 to 7000 K, most direct observations of the Earth's core properties have come from teleseismic studies, requiring large earthquake sources and well-positioned seismometers to detect weak wave signals that have traversed the Earth's deepest interior. The decoding of geochemical signatures of the core—potentially carried to the surface in plumes originating at the core-mantle boundary—faces numerous challenges of the debated integrity of this hypothesis. For these reasons, understanding the Earth's core requires multidisciplinary efforts. In the past two decades, deep-Earth scientists have unveiled a number of unusual and enigmatic phenomena of the core, including inner core anisotropy, differential rotation of the inner core, fine-scale seismic heterogeneity, and the possible existence of the prefer-oriented hexagonal close packed (hcp, in which two closely packed layers stack alternately along a crystallographic axis) and/or body-centered cubic (bcc, in which eight atoms reside at the corners and one atom resides at the center of the cubic cell) iron/nickel/light element alloys in the inner core (Figure 1). In this feature article, we summarize recent new findings and frontiers about the nature of the core from mineral physics research.

Electronic spin is a quantum property of every electron, associated with its intrinsic angular momentum. Though there are no suitable physical analogies to describe the spin quantum number, there are two possibilities, called spin ‘up’ and spin ‘down.’ The electronic structure of iron in minerals is generally such that valence electrons will more abundantly occupy different spatial orbitals and maintain the same spin than occupy the same spatial orbital and assume opposite spin, called ‘spin-paired.’ To the astonishment of mineral physicists, pressure-induced electronic spin-pairing transitions of iron that were predicted nearly 50 years ago recently have been detected in major mantle-forming oxides and silicates in ultrahigh-pressure experiments at lower-mantle pressures [e.g., Badro et al., 2003, 2004; Lin et al., 2005]. If such a spin transition is occurring in the Earth's lower mantle, there may be profound geophysical implications.

[1] The phase relations of an Fe10wt%Ni alloy were investigated in a diamond anvil cell up to 86 GPa and 2382 K. Adding nickel into iron stabilizes the fcc phase to higher pressures and lower temperatures compared to pure iron, and a region of two-phase coexistence between fcc and hcp phases is observed. Iron with up to 10 wt% nickel is likely to be in the hcp structure under inner core conditions. The axial ratio (c/a) of hcp-Fe10wt%Ni has a weak pressure dependence, but it increases substantially with increasing temperature. The extrapolated c/a ratio at ∼5700 K and ∼86 GPa is approximately 1.64, lower than a theoretically predicted value of nearly 1.7 for hcp-Fe at 5700 K and inner-core pressure. A lower c/a ratio should have an effect on the longitudinal anisotropy of the hcp phase, and hence, may influence the interpretation of the seismic wave anisotropy of the inner core.