Mineral–water reactions in Earth’s mantle:Predictions from Born theory and ab initio molecular dynamics

Recent studies present compelling evidence that a free aqueous fluid phase exists within the upper mantle. Fluid may be present at depths as great as the transition zone (410–660 km) and possibly beyond. The chemical reactivity of such deep fluids can be predicted from the Born model of solvation. To use the Born model, we need to know the dielectric constant of water under mantle conditions. We have used ab initio molecular dynamics simulations to determine the dielectric constant of water up to a pressure of 30 GPa and a temperature of 3000 K. Increased temperature lowers the dielectric constant and decreases ion solvation, but pressure overcomes this effect. The resulting high dielectric constant suggests that aqueous mantle fluids are highly reactive for ion solvation and mineral dissolution. We tested this by using the Helgeson–Kirkham–Flowers equation of state to estimate free energies of several mineral-solution and ion solvation reactions under mantle conditions. The results support previous estimates of carbonate solubility in the mantle. We also find that mantle fluids may play a key role in transporting ore metals: we evaluated the solubility of chalcopyrite and the complexation of Cu and Fe by Cl under mantle conditions and find that metal complexation is as significant as in ore-forming fluids in the crust. At reasonable conditions of pH and fH2, chalcopyrite is highly soluble. We tentatively hypothesize that exsolved fluids from subducted slabs may extract and mobilize primary sulfides in the mantle, implying potentially deep sources for porphyry copper deposits

The effect of potassium on aluminous phase stability in the lower mantle

The aluminous calcium-ferrite type phase (CF) and new aluminous phase (NAL) are thought to hold the excess alumina produced by the decomposition of garnet in MORB compositions in the lower mantle. The respective stabilities of CF and NAL in the nepheline-spinel binary (NaAlSiO4–MgAl2O4) are well established. However with the addition of further components the phase relations at lower mantle conditions remain unclear. Here we investigate a range of compositions around the nepheline apex of the nepheline-kalsilite-spinel compositional join (NaAlSiO4–KAlSiO4–MgAl2O4) at 28–78 GPa and 2000 K. Our experiments indicate that even small amounts of a kalsilite (KAlSiO4) component dramatically impact phase relations. We find NAL to be stable up to at least 71 GPa in potassium-bearing compositions. This demonstrates the stabilizing effect of potassium on NAL, because NAL is not observed at pressures above 48 GPa on the nepheline-spinel binary. We also observe a broadening of the CF stability field to incorporate larger amounts of potassium with increasing pressure. For pressures below 50 GPa only minor amounts ($$<0.011(1)\frac{K}{K+Na+Mg}$$) of potassium are soluble in CF, whereas at 68 GPa, we find a solubility in CF of at least $$0.088(3)\frac{K}{K+Na+Mg}$$. This indicates that CF and NAL are suitable hosts of the alkali content of MORB compositions at lower mantle conditions. For sedimentary compositions at lower mantle pressures, we expect K-Hollandite to be stable in addition to CF and NAL for pressures of 28–48 GPa, based on our simplified compositions

Fe–FeO and Fe–Fe₃C melting relations at Earth's core–mantle boundary conditions: Implications for a volatile-rich or oxygen-rich core

International audienceEutectic melting temperatures in the Fe–FeO and Fe–Fe3C systems have been determined up to 150 GPa. Melting criteria include observation of a diffuse scattering signal by in situ X-Ray diffraction, and textural characterisation of recovered samples. In addition, compositions of eutectic liquids have been established by combining in situ Rietveld analyses with ex situ chemical analyses. Gathering these new results together with previous reports on Fe–S and Fe–Si systems allow us to discuss the specific effect of each light element (Si, S, O, C) on the melting properties of the outer core. Crystallization temperatures of Si-rich core compositional models are too high to be compatible with the absence of extensive mantle melting at the core–mantle boundary (CMB) and significant amounts of volatile elements such as S and/or C (>5 at%, corresponding to >2 wt%), or a large amount of O (>15 at% corresponding to ∼5 wt%) are required to reduce the crystallisation temperature of the core material below that of a peridotitic lower mantle

X-ray absorption contrast images of binary chemical reactions

Low-divergence synchrotron-sourced X-rays enable a radiographic imaging scheme for full characterization of binary chemical reactions and characterization by type of more complex reactions, in situ, in diamond anvil cells (DAC). Spatially resolved reactants are induced to react by laser heating of their interface. The spatially intermediate products are observed through X-ray absorption contrast. Limits to the technique include the ability to maintain controlled experiment geometry during compression and the ability to resolve chemical differences between reactants and products by X-ray absorption. The ability to make in situ observations at experimental pressure and temperature obviates the problem with quenching techniques for capturing liquid compositions in experiments with dimensions smaller than the diffusion length during quenching time. Partially molten Fe-alloy systems, of poor quenchability, are examined at DAC pressures and temperatures for relevance to Earth's core constitution and evolution. Determinations of eutectic melting in Fe-FeS match known results. Of the probable light elements that may alloy with Fe in the Earth's liquid outer core, Fe-FeS experiments show only modest quenching problems, but C and Si alloy experiments are highly vulnerable to quenching artifacts. The observed reactivity of FeS, Fe₃C, FeSi, and FeO(OH) with Fe in DAC makes the observed non-reactivity between Fe and FeO more significant, reducing the probability that oxygen alone is the major alloy in Earth's molten outer core.10 page(s

Surface application and shallow injection of cattle slurry on grassland: nitrogen losses, herbage yields and nitrogen recoveries

An experiment was carried out over 2 years on grass and grass/clover swards in SW England to compare herbage yields and N recovery following surface application or shallow injection of cattle slurry at three different times of application. In the second year, losses of N via ammonia volatilization, denitrification and nitrate leaching were measured from applications to the grass sward. On the grass sward, there was no significant effect of time or method of application on dry-matter (DM) yield in the first year, although shallow injection reduced apparent N recovery (ANR) in the herbage by 45% when compared with surface application. In the second year, shallow injection reduced DM yields by 26% and ANR by 48%. On the grass/clover sward, there were no significant effects of time or method of application on DM yields or AWR in either year. Inclusion of dicyandiamide (DCD) in the October slurry applications had no significant effect in the first year, but in the second year on the grass sward increased DM yield by 31% and 14% and ANR by 156% and 42% for shallow injection and surface applications respectively. Measurements in the second year on the grass award showed a reduction in N loss by ammonia volatilization using shallow injection of 40% and 79% for March and June applications respectively. Losses due to denitrification were greatest following October application, Shallow injection increased denitrification losses following March application, but there were no significant differences following October or June applications. N losses due to leaching were small, with no significant difference between treatments. Reasons for the reductions in DM yield and ANR following shallow injection, despite the large reduction in N loss by ammonia volatilization. are discussed