Abstract Compression and decompression experiments on face-centered cubic (fcc) γ′-Fe4N to 77 GPa at room temperature were conducted in a diamond-anvil cell with in situ X-ray diffraction (XRD) to examine its stability under high pressure. In the investigated pressure range, γ′-Fe4N did not show any structural transitions. However, a peak broadening was observed in the XRD patterns above 60 GPa. The obtained pressure-volume data to 60 GPa were fitted to the third-order Birch-Murnaghan equation of state (EoS), which yielded the following elastic parameters: K0 = 169 (6) GPa, K′ = 4.1 (4), with a fixed V0 = 54.95 Å at 1 bar. A quantitative Schreinemakers' web was obtained at 15–60 GPa and 300–1600 K by combining the EoS for γ′-Fe4N with reported phase stability data at low pressures. The web indicates the existence of an invariant point at 41 GPa and 1000 K where γ′-Fe4N, hexagonal closed-packed (hcp) ε-Fe7N3, double hexagonal closed-packed β-Fe7N3, and hcp Fe phases are stable. From the invariant point, a reaction γ′-Fe4N = β-Fe7N3 + hcp Fe originates toward the high-pressure side, which determines the high-pressure stability of γ′-Fe4N at 56 GPa and 300 K. Therefore, the γ′-Fe4N phase observed in the experiments beyond this pressure must be metastable. The obtained results support the existing idea that β-Fe7N3 would be the most nitrogen-rich iron compound under core conditions. An iron carbonitride Fe7(C,N)3 found as a mantle-derived diamond inclusion implies that β-Fe7N3 and Fe7C3 may form a continuous solid solution in the mantle deeper than 1000 km depth. Diamond formation may be related to the presence of fluids in the mantle, and dehydration reactions of high-pressure hydrous phase D might have supplied free fluids in the mantle at depths greater than 1000 km. As such, the existence of Fe7(C,N)3 in diamond can be an indicator of water transportation to the deep mantle.
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Core formation has left a lasting geochemical signature on the Earth. In order to constrain the composition of the Earth we must fully understand the processes by which newly formed Earth, and the bodies which accreted to it, differentiated. Percolation of iron-rich melt through solid silicate has been invoked as a mechanism for differentiation and core formation in terrestrial bodies in the early solar system. However, to date the contribution of percolation to core formation cannot be assessed due to the absence of data on Fe-rich melt migration velocities. Here we use a novel experimental design to investigate textural changes in an analogue system, Au melt in polycrystalline h-BN, under the high pressure/temperature (PT) of core formation at 3 GPa, relevant to core formation in the early solar system. Using a combination of high resolution, in-situ X-ray tomography and fast 2-D radiographic imaging, we obtain the first direct data on melt migration velocities at high PT. Melt migration is highly variable and episodic, driven by variations in differential pressure during melt migration and matrix compaction. Smaller scale melt processes, representing migration of melt along pre-existing melt networks, give comparatively fast velocities of 0.6-60 µms-1. Ex-situ experiments are used to compare melt networks in analogue systems to Fe-rich melt in silicates. Two competing processes for melt migration are percolation of melt along grain boundaries, and hydraulic fracturing induced by melt injection. Typically, both processes are noted in experimental and natural systems, although the relative importance of each mechanism is variable. Using a simple model for melt flow through a porous media, migration velocities determined here account for full differentiation of Earth-sized bodies within 101 to 103 Myr, for submicron diameter melt bands, or within a few Myr or micron-sized melt bands. This is consistent with rapid timescales inferred from geochemistry for core formation in planetesimals, implying that percolation may have had an important contribution to core differentiation in the Earth.
Biotite dissolution rates were determined at 25 °C, at pH 2–6, and as a function of mineral composition, grain size, and aqueous organic ligand concentration. Rates were measured using both open- and closed-system reactors in fluids of constant ionic strength. Element release was non-stoichiometric and followed the general trend of Fe, Mg > Al > Si. Biotite surface area normalised dissolution rates (ri) in the acidic range, generated from Si release, are consistent with the empirical rate law:ri=kH,iaH+xiwhere kH,i refers to an apparent rate constant, aH+ designates the activity of protons, and xi stands for a reaction order with respect to protons. Rate constants range from 2.15 × 10−10 to 30.6 × 10−10 (molesbiotite m−2 s−1) with reaction orders ranging from 0.31 to 0.58. At near-neutral pH in the closed-system experiments, the release of Al was stoichiometric compared to Si, but Fe was preferentially retained in the solid phase, possibly as a secondary phase. Biotite dissolution was highly spatially anisotropic with its edges being ∼120 times more reactive than its basal planes. Low organic ligand concentrations slightly enhanced biotite dissolution rates. These measured rates illuminate mineral–fluid–organism chemical interactions, which occur in the natural environment, and how organic exudates enhance nutrient mobilisation for microorganism acquisition.
Abstract Recent studies geared toward understanding the volatile abundances of the lunar interior have focused on the volatile‐bearing accessory mineral apatite. Translating measurements of volatile abundances in lunar apatite into the volatile inventory of the silicate melts from which they crystallized, and ultimately of the mantle source regions of lunar magmas, however, has proved more difficult than initially thought. In this contribution, we report a detailed characterization of mesostasis regions in four Apollo mare basalts (10044, 12064, 15058, and 70035) in order to ascertain the compositions of the melts from which apatite crystallized. The texture, modal mineralogy, and reconstructed bulk composition of these mesostasis regions vary greatly within and between samples. There is no clear relationship between bulk‐rock basaltic composition and that of bulk‐mesostasis regions, indicating that bulk‐rock composition may have little influence on mesostasis compositions. The development of individual melt pockets, combined with the occurrence of silicate liquid immiscibility, exerts greater control on the composition and texture of mesostasis regions. In general, the reconstructed late‐stage lunar melts have roughly andesitic to dacitic compositions with low alkali contents, displaying much higher SiO 2 abundances than the bulk compositions of their host magmatic rocks. Relevant partition coefficients for apatite‐melt volatile partitioning under lunar conditions should, therefore, be derived from experiments conducted using intermediate compositions instead of compositions representing mare basalts.
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