The dependence of metal-silicate partitioning of moderately volatile elements on oxygen fugacity and Si contents of Fe metal: Implications for their valence states in silicate liquids

The volatile siderophile elements are important tracers of the delivery of volatile elements to the Earth. Their concentrations in the bulk silicate Earth are a function of the relative timing of their accretion and their sequestration into the core: a comprehensive understanding of their metal-silicate partitioning behaviour is therefore required in order to infer the volatile element accretion history. We present new partitioning data between liquid metal and liquid silicate at 11 GPa for a suite of volatile siderophile elements: Ag, As, Au, Cu, Ge, P, Pb, Sb, Sn. We focus particularly on determining their valence states and the effects of Si on partitioning, which are required in order to extrapolate from experimental conditions to core-formation conditions. It was found that all elements have weak to strong positive interaction parameters with Si. At low fO2, redox equilibria dictate that the siderophile elements should become more siderophile. However, at low fO2, Si also partitions more strongly into the metal. Given the repulsive nature of the interaction between Si and the elements of interest, the increased Si concentration at low fO2 will counteract the expected increase in the partition coefficient, making these elements less siderophile than expected at very reducing conditions. This causes the linear relationship between fO2 and log(D) to become non-linear at low fO2, which we account for by fitting an interaction parameter between Si and the elements of interest. This has implications for the interpretation of experimental results, because the valence cannot be determined from the slope of log(D) vs. logfO2 if low fO2, high Si metal compositions are employed without applying an activity correction. This also has implications for the extrapolation of experimental partitioning data to core-formation conditions: reducing conditions in the early stages of core formation do not necessarily result in complete or even strong depletion of siderophile elements when Si is present as a light element in the core-forming metal phase

SiO2 glass density to lower-mantle pressures

The convection or settling of matter in the deep Earth’s interior is mostly constrained by density variations between the different reservoirs. Knowledge of the density contrast between solid and molten silicates is thus of prime importance to understand and model the dynamic behavior of the past and present Earth. SiO2 is the main constituent of Earth’s mantle and is the reference model system for the behavior of silicate melts at high pressure. Here, we apply our recently developed x-ray absorption technique to the density of SiO2 glass up to 110 GPa, doubling the pressure range for such measurements. Our density data validate recent molecular dynamics simulations and are in good agreement with previous experimental studies conducted at lower pressure. Silica glass rapidly densifies up to 40 GPa, but the density trend then flattens to become asymptotic to the density of SiO2 minerals above 60 GPa. The density data present two discontinuities at ∼17 and ∼60  GPa that can be related to a silicon coordination increase from 4 to a mixed 5/6 coordination and from 5/6 to sixfold, respectively. SiO2 glass becomes denser than MgSiO3 glass at ∼40  GPa, and its density becomes identical to that of MgSiO3 glass above 80 GPa. Our results on SiO2 glass may suggest that a variation of SiO2 content in a basaltic or pyrolitic melt with pressure has at most a minor effect on the final melt density, and iron partitioning between the melts and residual solids is the predominant factor that controls melt buoyancy in the lowermost mantle

Can the multianvil apparatus really be used for high-pressure deformation experiments?

Past claims of the suitability of the MA-8 multianvil press as a deformation apparatus may have been overstated. On the basis of measurements of final octahedron size and of guide block displacement as a function of time, using the 10/5, 14/8, and 18/11 assemblies (octahedron edge length in mm/truncation edge length in mm) with MgO octahedra and pyrophyllite gasketing, it appears that at run conditions of interest to most researchers there is no appreciable time-dependent creep of gaskets and octahedra. All inelastic deformation occurs at rather low pressures: below about 10 GPa for the 10/5, 7 GPa for the 14/8, and 6 GPa for the 18/11 assemblies, with substantial uncertainties in these pressures. Above these limits all deformation of the pressure medium is elastic. Pressure stepping as a means of increasing the inelastic deformation rate of a sample is probably ineffective. Displacement measured at the guide blocks, previously believed to indicate deformation of the gaskets and octahedron, appears now to be unrelated to creep of these components. The calibrations have not been exhaustive and there is considerable scatter in some of the size measurements, so the above conclusions are not unequivocal. The calibrations do not exclude the possibility of deformation of a few tens of microns after the attainment of high pressure. Efforts to impose permanent shape change to samples at high pressure and temperature simply by relying on long run durations must be viewed with skepticism. There may be possibilities for deformation in the multianvil apparatus if materials of contrasting elastic modulus are used to differentially load a sample during pressure stepping

Subsolar Al/Si and Mg/Si ratios of non-carbonaceous chondrites reveal planetesimal formation during early condensation in the protoplanetary disk

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High temperature measurements of hydrous albite liquid using in situ falling sphere viscometry at 2.5 Gpa

In-situ falling-sphere viscometry using shadow radiography in a multianvil apparatus was conducted on a series of samples along the NaAlSi3O8–H2O join up to 2.8 wt.% H2O at the Spring-8 synchrotron radiation facility (Hyogo, Japan). This allowed us to determine viscosities normally too low to be measured at ambient pressure for hydrous silicate melts at high temperatures due to rapid devolatilization. Pressure was fixed at 2.5 GPa for all experiments allowing us to gauge the effect of chemical composition on viscosity. In particular, the series of samples allowed us to vary the melt's degree of polymerization while maintaining a constant Al to Si ratio. Our results show that, for all samples, viscosity decreases as a function of pressure between 1 atm and 2.5 GPa at 1550 °C, indicating that the pressure anomaly can still be observed as depolymerization of the melt increases from nominally 0 (dry albite liquid) to NBO/T=0.8 (assuming water speciation entirely as hydroxyl groups at experimental conditions). We also find that the magnitude of the decrease in viscosity over this pressure interval does not appear to be dependent on the amount of water in the melt (i.e., NBO/T). An explanation for this behavior might be that the molar volume, at least over this limited compositional range, is nearly constant and the effects of compression of these melts, though different in degree of polymerization, are similar

Metal–silicate partitioning of W and Mo and the role of carbon in controlling their abundances in the Bulk Silicate Earth

The liquid metal–liquid silicate partitioning of molybdenum and tungsten during core formation must be well-constrained in order to understand the evolution of Earth and other planetary bodies, in particular because the Hf–W isotopic system is used to date early planetary evolution. The partition coefficients DMo and DW have been suggested to depend on pressure, temperature, silicate and metal compositions, although previous studies have produced varying and inconsistent models. Additionally, the high cationic charges of W and Mo in silicate melts make their partition coefficients particularly sensitive to oxygen fugacity. We combine 48 new high pressure and temperature experimental results with a comprehensive database of previous experiments to re-examine the systematics of Mo and W partitioning, and produce revised partitioning models from the large combined dataset. W partitioning is particularly sensitive to silicate and metallic melt compositions and becomes more siderophile with increasing temperature. We show that W has a 6+ oxidation state in silicate melts over the full experimental fO2 range of ΔIW -1.5 to -3.5. Mo has a 4+ oxidation state and its partitioning is less sensitive to silicate melt composition, but also depends on metallic melt composition. DMo stays approximately constant with increasing depth in Earth. Both W and Mo become more siderophile with increasing C content of the metal: we therefore performed experiments with varying C concentrations and fit epsilon interaction parameters: ε_"C" ^"Mo" = -7.03 ± 0.30 and ε_"C" ^"W" = -7.38 ± 0.57. W and Mo along with C are incorporated into a combined N-body accretion and core–mantle differentiation model, which already includes the major rock-forming elements as well as S, moderately and highly siderophile elements. In this model, oxidation and volatility gradients extend through the protoplanetary disk so that Earth accretes heterogeneously. These gradients, as well as the metal–silicate equilibration pressure, are fitted using a least squares optimisation so that the model Earth-like planet reproduces the composition of the Bulk Silicate Earth (BSE) across 17 simulated element concentrations (Mg, Fe, Si, Ni, Co, Nb, Ta, V, Cr, S, Pt, Pd, Ru, Ir, W, Mo, and C). The effects of the interaction of W and Mo with Si, S, O, and C in metal are included. Using this model with six separate terrestrial planet accretion simulations, we show that W and Mo require the early accreting Earth to be sulfur-depleted and carbon-enriched so that W and Mo are efficiently partitioned into Earth’s core and do not accumulate in the mantle. If this is the case, the produced Earth-like planets possess mantle compositions matching the BSE for all simulated elements. However, there are two distinct groups of estimates of the bulk mantle’s C abundance in the literature: low (~100 ppm), and high (~800 ppm), and all six models are consistent with the higher estimated carbon abundance. The low BSE C abundance would be achievable when the effects of the segregation of dispersed metal droplets produced in deep magma oceans by the disproportionation of Fe2+ to Fe3+ plus metallic Fe is considered

The timeline of the lunar bombardment: Revisited

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