Melting of Fe–Ni–Si and Fe–Ni–S alloys at megabar pressures: implications for the core–mantle boundary temperature

High pressure melting behavior of three Fe-alloys containing 5 wt% Ni and (1) 10 wt% Si, (2) 15 wt% Si or (3) 12 wt% S was investigated up to megabar pressures by in situ X-ray diffraction and laser-heated diamond anvil cell techniques. We observe a decrease in melting temperature with increasing Si content over the entire investigated pressure range. This trend is used to discuss the melting curve of pure Fe. Moreover, our measurements of eutectic melting in the Fe–Fe₃S system show a change in slope around 50 GPa concomitant with the fcc–hcp phase transition in pure solid iron. Extrapolations of our melting curve up to the core–mantle boundary pressure yield values of 3,600–3,750 K for the freezing temperature of plausible outer core compositions.     

The great sulfur depletion of Earth’s mantle is not a signature of mantle–core equilibration

The extreme depletion of the Earth’s mantle in sulfur is commonly seen as a signature of metal segregation from Earth’s mantle to Earth’s core. However, in addition to S, the mantle contains other elements as volatile as S that are hardly depleted relative to the lithophile volatility trend although they are potentially as siderophile as sulfur. We report experiments in metal-sulfide–silicate systems to show that the CI normalized abundances of S, Pb, and Sn in Earth’s mantle cannot be reproduced by element partitioning in Fe ± S–silicate systems, neither at low nor at high pressure. Much of the volatile inventory of the Earth’s mantle must have been added late in the accretion history, when metal melt segregation to the core had become largely inactive. The great depletion in S is attributed to the selective segregation of a late sulfide matte from an oxidized and largely crystalline mantle. Apparently, the volatile abundances of Earth’s mantle are not in redox equilibrium with Earth’s core.     

Equation of state of iron–silicon alloys to megabar pressure

The stability and pressure–volume equation of state of iron–silicon alloys, Fe-8.7 wt% Si and Fe-17.8 wt% Si, have been investigated using diamond-anvil cell techniques up to 196 and 124 GPa, respectively. Angular–dispersive X-ray diffractions of iron–silicon alloys were measured at room temperature using monochromatic synchrotron radiation and an imaging plate (IP). A bcc–Fe-8.7 wt% Si transformed to hcp structure at around 1636 GPa. The high-pressure phase of Fe-8.7 wt% Si with hexagonal close-packed (hcp) structure was found to be stable up to 196 GPa and no phase transition of bcc–Fe-17.8 wt% Si was observed up to 124 GPa. The pressure–volume data were fitted to a third-order Birch–Murnaghan equation of state (BM EOS) with zero–pressure parameters: V₀=22.2(8) ų, K₀=198(9) GPa, and K₀=4.7(3) for hcp–Fe-8.7 wt% Si and V₀=179.41(45) ų, K₀=207(15) GPa and K₀=5.1(6) for Fe-17.8 wt% Si. The density and bulk sound velocity of hcp–Fe-8.7 wt% Si indicate that the inner core could contain 3–5 wt% Si.     

Long-term electromagnetic core–mantle coupling and the Earth’s rotation acceleration in the Mesozoic Era

Growth lines in the mineralized tissues of living and fossil organisms often exhibit regular patterns that record daily, monthly, or annual cycles. Growth laminations in fossil corals and other marine invertebrates indicate long-term deceleration of the Earth’s rotation, probably largely due to tidal friction, resulting in a decline in the number of days per year over the Earth’s history. Fossils suggest the rate of decline has not been uniform, with the trend between the late Carboniferous and Cretaceous in particular departing from preceding and subsequent periods. However, insufficient data have obscured the nature and cause of the apparent halt in despinning within this time interval. Here we present new fossil geochronometer data that reveal a sustained acceleration in the Earth’s rotation in the early Mesozoic Era, lasting about 90 million years and producing a decrease in the length of day (LOD) at an average rate of about 3 ms/cy. The coincidence of this acceleration with certain geophysical events including the final assembly of Pangaea and a change in the intensity and stability of the geomagnetic field strongly suggests that its cause is rooted in the deep interior of the Earth. A similar explanation has been proposed for observed decadal variations in the Earth’s rotation. Our results suggest large-scale linkage of rotational variation, tectonics, and the geomagnetic field to core–mantle boundary (CMB) dynamics. Furthermore the newly identified acceleration in the Earth’s rotation which began at the end of the Paleozoic, and the geophysical factors that are associated with it, can ultimately bear on the causal mechanisms behind the Permo-Triassic mass extinction.     

Gravitational interactions of the solid core and the Earth’s mantle and variations in the length of the day

A simple mechanical model explaining the long-period (about 100-year) variations in the Earth’s rotational velocity is proposed. This model takes into account the gravitational interaction of the mantle with the solid core of the Earth and the fact that the core rotation leads that of the mantle. Well-known Earth parameters provide estimates of the gravitational torque that support the proposed model. The mathematical problem involved reduces to the classical problem of a nonlinear oscillator exposed to a constant torque. The well-known parameters of the core-mantle system result in a stable equilibrium and a stable limiting cycle on the phase cylinder of this oscillator. This equilibrium corresponds to a single angular velocity for the mantle and solid core, with no long-period oscillations in the length of the day. The limiting cycle corresponds to the core rotation leading the mantle rotation. In this case, the ellipsoidality of the gravitationally interacting bodies provides a periodic interchange of kinetic angular momentum between the mantle and solid core that results in long-period variations in the length of the day. The proposed model does not support the formerly widespread opinion that the core rotates more slowly than the mantle.     

Fluorine and chlorine in mantle minerals and the halogen budget of the Earth’s mantle

The fluorine (F) and chlorine (Cl) contents of arc magmas have been used to track the composition of subducted components, and the F and Cl contents of MORB have been used to estimate the halogen content of depleted MORB mantle (DMM). Yet, the F and Cl budget of the Earth’s upper mantle and their distribution in peridotite minerals remain to be constrained. Here, we developed a method to measure low concentrations of halogens (≥0.4 µg/g F and ≥0.3 µg/g Cl) in minerals by secondary ion mass spectroscopy. We present a comprehensive study of F and Cl in co-existing natural olivine, orthopyroxene, clinopyroxene, and amphibole in seventeen samples from different tectonic settings. We support the hypothesis that F in olivine is controlled by melt polymerization, and that F in pyroxene is controlled by their Na and Al contents, with some effect of melt polymerization. We infer that Cl compatibility ranks as follows: amphibole > clinopyroxene > olivine ~ orthopyroxene, while F compatibility ranks as follows: amphibole > clinopyroxene > orthopyroxene ≥ olivine, depending on the tectonic context. In addition, we show that F, Cl, Be and B are correlated in pyroxenes and amphibole. F and Cl variations suggest that interaction with slab melts and fluids can significantly alter the halogen content of mantle minerals. In particular, F in oceanic peridotites is mostly hosted in pyroxenes, and proportionally increases in olivine in subduction-related peridotites. The mantle wedge is likely enriched in F compared to un-metasomatized mantle, while Cl is always low (<1 µg/g) in all tectonic settings studied here. The bulk anhydrous peridotite mantle contains 1.4–31 µg/g F and 0.14–0.38 µg/g Cl. The bulk F content of oceanic-like peridotites (2.1–9.4 µg/g) is lower than DMM estimates, consistent with F-rich eclogite in the source of MORB. Furthermore, the bulk Cl budget of all anhydrous peridotites studied here is lower than previous DMM estimates. Our results indicate that nearly all MORB may be somewhat contaminated by seawater-rich material and that the Cl content of DMM could be overestimated. With this study, we demonstrate that the halogen contents of natural peridotite minerals are a unique tool to understand the cycling of halogens, from ridge settings to subduction zones.     

Lateral protrusions in the structure of the Earth’s lithosphere

The factual material and modeling results concerning the geology of specific structural elements defined as lateral protrusions, or flowing layers, are considered. The formation of such structural elements is a fundamental phenomenon that controls many features of the structural evolution and geodynamics of platform basement and foldbelts. A lateral protrusion, or flowing layer, is a spatially constrained, nearly horizontal geological body with attributes of 3D tectonic flow (rheid deformation) and lateral transport of rock masses. Flowing layers are large lateral protrusions that play important role in the structure of the continental and oceanic lithosphere. They embody the internal mobility of huge rock bodies and confirm the possibility of their lateral redistribution at different depths of the continental lithosphere. The lateral displacement of rocks within such assemblies may occur in the regime of cold deformation, heating, metamorphism, and ductile flow of rocks under subsolidus conditions or in the process of their partial melting.     

Equation of state of magnesite for the conditions of the Earth’s lower mantle

A semiempirical equation of state was derived for magnesite under the thermodynamic conditions of the Earth’s mantle. Within experimental uncertainties, it is consistent with thermochemical, ultrasonic, X-ray, and shock-wave data at temperatures from 15 K to the melting point and pressures of up to 100–130 GPa. The following values were recommended for the isothermal bulk modulus and its pressure derivative: K _T = 111.71 GPa and K′ = 4.08. Thermodynamic analysis showed that magnesite does not decompose to periclase and CO₂ under the thermodynamic conditions of the Earth’s lower mantle and outer core.     

Equation of state of silicate melts with densified intermediate-range order at the pressure condition of the Earth’s deep upper mantle

The knowledge from the compression behavior of densified SiO₂ glass suggests that SiO₂ melt may behave as a single phase having a densified network structure (intermediate-range order) at the pressure condition of the Earth’s deep upper mantle, including the transition zone. A simple and easy-to-use equation of state of silicate melts which is applicable to a wide range of chemical composition at the pressure condition of the deep upper mantle is proposed based on the assumption that SiO₂ component is in its densified state (or phase). The equation of state proposed in this study is consistent with all the available density data of silicate melts with an SiO₂ content of about 35–55 mol% measured with large-volume presses at pressures between 8 and 22 GPa. The equations of state in previous studies differ considerably from each other. The main reason for the discrepancies seems to be that the compression behavior of multiple states (or phases) of silicate melts has been described in most cases with a single equation of state. It is necessary to consider that silicate melts are in their densified states (or phases) in the deep upper mantle.     

Platinum group element (PGE) geochemistry to understand the chemical evolution of the Earth’s mantle

Platinum group elements (PGE: Os, Ir, Ru, Rh, Pt, Pd) are important geochemical and cosmochemical tracers. Depending on physical and chemical behaviour the PGEs are divided into two subgroups: IPGE (Ir, Os, Ru) and PPGE (Pd, Pt, Rh). Platinum group elements show strong siderophile and chalcophile affinity. Base metal sulfides control the PGE budget of the Earth’s mantle. Mantle xenoliths contain two types of sulfide populations: (1) enclosed within silicate minerals, and (2) interstitial to the silicate minerals. In terms of PGE characters the included variety shows IPGE enriched patterns — similar to the melt-depleted mantle harzburgite, whereas the interstitial variety shows PPGE enriched patterns — resembling the fractionated PGE patterns of the basalt. These PGE characters of the mantle sulfides have been interpreted to be representative of multi-stages melting process of the mantle that helped to shape the chemical evolution of the Earth.     

On thermochemical mantle plumes with an intermediate thermal power that erupt on the Earth’s surface

The relative plume thermal power Ka = N/N₁ is used (N is the thermal power transferred from the plume base to its conduit and N₁ is the thermal power transferred from the plume conduit into the surrounding mantle in the steady-state heat conduction regime). Thermochemical mantle plumes with small (Ka < 1.15) and intermediate (1.15 < Ka < 1.9) thermal powers are formed at the core–mantle boundary beneath cratons in the absence of horizontal free-convection mantle flows beneath them, or in the presence of weak horizontal mantle flows. Thermochemical plumes reach the Earth’s surface when their relative thermal power is Ka > 1.15. The thermal and hydrodynamical structure of the plume conduit ascending from the core–mantle interface to the level from which the magmatic melt erupts on the Earth’s surface is presented. The model of two-stage eruption of the melt from the plume conduit to the surface is considered. The critical height of the massif above the plume roof, at which the eruption conduit supplying magmatic melt to the surface forms, is determined. The volume of melt erupting through the eruption conduit to the surface is estimated. The dependence of depth Δx from which the melt is transported to the surface on the plume diameter for a kinematic viscosity of ν = 0.5–2 m²/s is presented. In the case when the value Δx is larger than the depth starting from which diamond is stable (150 km), the melt from the plume conduit can transport diamonds to the Earth’s surface. The melt flow in the eruption conduit is considered as a turbulent flow in a cylindrical duct. The velocity of the melt flow in the eruption conduit and the time for the melt to be transported to the surface from a depth of Δx = 150 km for a kinematic viscosity of the melt in the eruption conduit ν_v = 0.01–1 m²/s are determined. Tangential stress on the eruption conduit sidewall is estimated in cases of melt flow both in smooth and rough conduits.     

Isotopic constraints on the age of the Earth’s core: Mutual consistency of the Hf-W and U-Pb systems

The estimation of the time of Earth??s core formation on the basis of isotopic systems with short-lived and long-lived parent nuclides gives significantly different results. Isotopic data for the ¹⁸²Hf-¹⁸²W system with a ¹⁸²Hf half-life of approximately 9 Myr can be interpreted in such a way that the core was formed 34 Myr after the origin of the solar system assuming complete core-mantle equilibrium. Similar estimates on the basis of the U-Pb isotopic system suggest a significantly longer mean time of core formation of approximately 120 Myr. If the Earth??s core were formed instantaneously, both isotopic systems would have shown identical values corresponding to the true age. The discrepancy between the U-Pb and Hf-W systems can be resolved assuming prolonged differentiation of prototerrestrial material into silicate and metallic phases, which occurred not simultaneously and uniformly in different parts of the mantle. This resulted in the isotopic heterogeneity of the mantle, and its subsequent isotopic homogenization occurred slowly. Under such conditions, the mean isotopic compositions of W and Pb in the mantle do not correspond to the mean time of the separation of silicate and metallic phases. This is related to the fact that the exponential function of radioactive decay is strongly nonlinear at high values of the argument, and its mean value does not correspond to the mean value of the function. There are compelling reasons to believe that the early mantle was heterogeneous with respect to W isotopic composition and was subsequently homogenized by convective mixing. This follows from the fact that the lifetime of isotopic heterogeneities in the mantle is close to 1.8 Gyr for various long-lived isotopic systems. There is also no equilibrium between the mantle and the core with respect to the contents of siderophile elements. Because of this, the mean isotopic ratios of W and Pb cannot be used for the direct computation of the time of metal-silicate differentiation in the Earth. Such estimation requires more sophisticated models accounting for the duration of the differentiation process using several isotope pairs. Given the prolonged core formation, which has probably continued up to now, the question about its age becomes ambiguous, and only the most probable growth rate of the core can be estimated. The combined use of the U-Pb and Hf-W systems constrains the time of formation of 90% of the core mass between 0.12 and 2.7 billion years. These model estimates could have been realistic under the condition of complete disequilibrium between the silicate and metallic phases, which is as improbable as the suggestion of complete equilibrium between them on the whole Earth scale.