Previous work has shown that Mo isotopes measurably fractionate between metal and silicate liquids, even at temperatures appropriate for core formation. However, the effect of variations in the structural environment of Mo in the silicate liquid, especially as a function of valence state, on Mo isotope fractionation remained poorly explored. We have investigated the role of valence state in metal-silicate experiments in a gas-controlled furnace at 1400 degrees C and at oxygen fugacities between 10(-12.7) and 10(-9.9), i.e. between three and 0.2 log units below the iron-wustite buffer. Two sets of experiments were performed, both with a silicate liquid in the CaO-Al2O3-SiO2 system. One set used molybdenum metal wire loops as the metal source, the other liquid gold alloyed with 2.5 wt % Mo contained in silica glass tubes. X-ray absorption near-edge spectroscopy analysis indicates that Mo6+/Sigma Mo in the silicate glasses varies between 0.24 and 0.77 at oxygen fugacities of 10-(12.0) and 10(-9.9) in the wire loop experiments and between 0.15 and 0.48 at 10(-11.4) and 10(-9.9) in the experiments with Au-Mo alloys. Double spiked analysis of Mo isotope compositions furthermore shows that Mo isotope fractionation between metal and silicate is a linear function of Mo6+/Sigma Mo in the silicate glasses, with a difference of 0.51 parts per thousand in Mo-98/Mo-95 between purely Mo4+-bearing and purely Mo6+-bearing silicate liquid. The former is octahedrally and the latter tetrahedrally coordinated. Our study implies that previous experimental work contained a mixture of Mo4+ and Mo6+ species in the silicate liquid. Our refined parameterisation for Mo isotope fractionation between metal and silicate can be described as

In this article, the specification and application of the new double-sided YAG laser-heating system built on beamline I15 at Diamond Light Source are presented. This system, combined with diamond anvil cell and X-ray diffraction techniques, allows in situ and ex situ characterization of material properties at extremes of pressure and temperature. In order to demonstrate the reliability and stability of this experimental setup over a wide range of pressure and temperature, a case study was performed and the phase diagram of lead was investigated up to 80GPa and 3300K. The obtained results agree with previously published experimental and theoretical data, underlining the quality and reliability of the installed setup.

We report on laser-heated diamond anvil cell (LHDAC) experiments in the FeO-MgO-SiO2-CO2 (FMSC) and CaO-MgO-SiO2-CO2 (CMSC) systems at lower mantle pressures designed to test for decarbonation and diamond forming reactions. Sub-solidus phase relations based on synthesis experiments are reported in the pressure range of similar to 35 to 90 GPa at temperatures of similar to 1600 to 2200 K. Ternary bulk compositions comprised of mixtures of carbonate and silica are constructed such that decarbonation reactions produce non-ternary phases (e.g. bridgmanite, Ca-perovskite, diamond, CO2-V), and synchrotron X-ray diffraction and micro-Raman spectroscopy are used to identify the appearance of reaction products. We find that carbonate phases in these two systems react with silica to form bridgmanite +/- Ca-perovskite + CO2 at pressures in the range of similar to 40 to 70 GPa and 1600 to 1900 K in decarbonation reactions with negative Clapeyron slopes. Our results show that decarbonation reactions form an impenetrable barrier to subduction of carbonate in oceanic crust to depths in the mantle greater than similar to 1500 km. We also identify carbonate and CO2-V dissociation reactions that form diamond plus oxygen. On the basis of the observed decarbonation reactions we predict that the ultimate fate of carbonate in oceanic crust subducted into the deep lower mantle is in the form of refractory diamond in the deepest lower mantle along a slab geotherm and throughout the lower mantle along a mantle geotherm. Diamond produced in oceanic crust by subsolidus decarbonation is refractory and immobile and can be stored at the base of the mantle over long timescales, potentially returning to the surface in OIB magmas associated with deep mantle plumes. (C) 2019 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license.

Velocity and density jumps across the 410-km seismic discontinuity generally indicate olivine contents of similar to 30 to 50 vol.% on the basis of the elastic properties of anhydrous olivine and wadsleyite, which is considerably less than the similar to 60% olivine in the widely accepted pyrolite model for the upper mantle. A possible explanation for this discrepancy is that water dissolved in olivine and wadsleyite affects their elastic properties in ways that can reconcile the pyrolitic model with seismic observations. In order to more fully constrain the olivine content of the upper mantle near the 410-km discontinuity, and to place constraints on the mantle water content at this depth, we determined the full elasticity of hydrous wadsleyite at the P-T conditions of the discontinuity based on density functional theory calculations. Together with previous determinations for the effect of water on olivine elasticity, we simultaneously modeled the density and seismic velocity jumps (Delta(rho), Delta V-p, Delta V-S) across the olivine-wadsleyite transition. Our models allow for several scenarios that can well reproduce the density and seismic velocity jumps across the 410-km discontinuity when compared to globally averaged seismic models. When the water content of olivine and wadsleyite is assumed to be equal as in a simple binary system, our modeling indicates a best fit for low water contents (<0.1 wt.%) with an olivine proportion of similar to 50%, suggesting a relatively dry, non-pyrolitic mantle at depths of the 410-km discontinuity. However, our modeling can be reconciled with a pyrolitic mantle if the water content in wadsleyite is similar to 0.9 wt.% and that in olivine is at its storage capacity of similar to 500-1500 ppm. The result would be consistent with a hydrous melt phase produced at depths just above the phase transition. (C) 2019 Elsevier B.V. All rights reserved.

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 sub-ducted 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 similar to 2.3 to 5.0% greater than that of anhydrous stishovite at pressures of similar to 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.

Diamonds are unrivalled in their ability to record the mantle carbon cycle and mantle fO(2) over a vast portion of Earth's history. Diamonds' inertness and antiquity means their carbon isotopic characteristics directly reflect their growth environment within the mantle as far back as similar to 3.5 Ga. This paper reports the results of a thorough secondary ion mass spectrometry (SIMS) carbon isotope and nitrogen concentration study, carried out on fragments of 144 diamond samples from various locations, from similar to 3.5 to 1.4 Ga for P [peridotitic]-type diamonds and 3.0 to 1.0 Ga for E [eclogitic]-type diamonds. The majority of the studied samples were from diamonds used to establish formation ages and thus provide a direct connection between the carbon isotope values, nitrogen contents and the formation ages. In total, 908 carbon isotope and nitrogen concentration measurements were obtained. The total delta C-13 data range from -17.1 to -1.9 parts per thousand (P = -8.4 to -1.9 parts per thousand; E = -17.1 to -2.1 parts per thousand) and N contents range from 0 to 3073 at. ppm (P 0 to 3073 at. ppm; E = 1 to 2661 at. ppm). In general, there is no systematic variation with time in the mantle carbon isotope record since > 3 Ga. The mode in delta C-13 of peridotitic diamonds has been at similar to 5 (+/- 2) parts per thousand since the earliest diamond growth similar to 3.5 Ga, and this mode is also observed in the eclogitic diamond record since similar to 3 Ga. The skewness of eclogitic diamonds' delta C-13 distributions to more negative values, which the data establishes began around 3 Ga, is also consistent through time, with no global trends apparent.

A new diamond-anvil cell apparatus for in situ synchrotron X-ray diffraction measurements of liquids and glasses, at pressures from ambient to 5 GPa and temperatures from ambient to 1300 K, is reported. This portable setup enables in situ monitoring of the melting of complex compounds and the determination of the structure and properties of melts under moderately high pressure and high temperature conditions relevant to industrial processes and magmatic processes in the Earth's crust and shallow mantle. The device was constructed according to a modified Bassett-type hydrothermal diamond-anvil cell design with a large angular opening (theta = 95 degrees). This paper reports the successful application of this device to record in situ synchrotron X-ray diffraction of liquid Ga and synthetic PbSiO3 glass to 1100 K and 3 GPa.

We present a theoretical model of the stability and migration of carbonate-rich melts to test whether they can explain seismic low-velocity layers (LVLs) observed above stalled slabs in several convergent tectonic settings. The LVLs, located atop the mantle transition zone, contain small (similar to 1 vol%) amounts of partial melt, possibly derived from melting of subducted carbonate-bearing oceanic crust. Petrological and geochemical evidence from inclusions in superdeep diamonds supports the existence of slab-derived carbonate melt, which may potentially explain the origin of the observed melt in the LVL. However, the presumptive reducing nature of the ambient mantle can be an impediment to the stability of carbonated melt. To reconcile this apparent contradiction, we test the stability and migration rates of carbonate-rich melts atop a stalled slab as a function of melt percolation, redox freezing, amount of carbon supplied by subduction, and the metallic Fe concentration in the mantle. Our results demonstrate that carbonaterich melts in the LVL can potentially survive redox freezing over long geological time scales. We also show that the amount of subducted carbon exerts a stronger influence on the stability of carbonate melt than does the mantle redox condition. Concentration dependent melt density leads to rapid melt propagation through channels while a constant melt density causes melt to migrate as a planar front. Our calculations suggest that the LVLs can sequester significant fractions of carbon transported to the mantle by subduction. (C) 2019 Elsevier B.V. All rights reserved.