Hexagonal Si-Ge Class of Semiconducting Alloys Prepared by Using Pressure and Temperature.

Multi-anvil and laser-heated diamond anvil methods have been used to subject Ge and Si mixtures to pressures and temperatures of between 12 and 17 GPa and 1500-1800 K, respectively. Synchrotron angle dispersive X-ray diffraction, precession electron diffraction and chemical analysis using electron microscopy, reveal recovery at ambient pressure of hexagonal Ge-Si solid solutions (P63 /mmc). Taken together, the multi-anvil and diamond anvil results reveal that hexagonal solid solutions can be prepared for all Ge-Si compositions. This hexagonal class of solid solutions constitutes a significant expansion of the bulk Ge-Si solid solution family, and is of interest for optoelectronic applications.

Evidence for complex iron oxides in the deep mantle from FeNi(Cu) inclusions in superdeep diamond.

The recent discovery in high-pressure experiments of compounds stable to 24-26 GPa with Fe4O5, Fe5O6, Fe7O9, and Fe9O11 stoichiometry has raised questions about their existence within the Earth's mantle. Incorporating both ferric and ferrous iron in their structures, these oxides if present within the Earth could also provide insight into diamond-forming processes at depth in the planet. Here we report the discovery of metallic particles, dominantly of FeNi (Fe0.71Ni0.24Cu0.05), in close spatial relation with nearly pure magnetite grains from a so-called superdeep diamond from the Earth's mantle. The microstructural relation of magnetite within a ferropericlase (Mg0.60Fe0.40)O matrix suggests exsolution of the former. Taking into account the bulk chemistry reconstructed from the FeNi(Cu) alloy, we propose that it formed by decomposition of a complex metal M oxide (M4O5) with a stoichiometry of (Fe3+2.15Fe2+1.59Ni2+0.17Cu+0.04)Σ=3.95O5 We further suggest a possible link between this phase and variably oxidized ferropericlase that is commonly trapped in superdeep diamond. The observation of FeNi(Cu) metal in relation to magnetite exsolved from ferropericlase is interpreted as arising from a multistage process that starts from diamond encapsulation of ferropericlase followed by decompression and cooling under oxidized conditions, leading to the formation of complex oxides such as Fe4O5 that subsequently decompose at shallower P-T conditions.

Reduced methane-bearing fluids as a source for diamond.

Diamond formation in the Earth has been extensively discussed in recent years on the basis of geochemical analysis of natural materials, high-pressure experimental studies, or theoretical aspects. Here, we demonstrate experimentally for the first time, the spontaneous crystallization of diamond from CH4-rich fluids at pressure, temperature and redox conditions approximating those of the deeper parts of the cratonic lithospheric mantle (5-7 GPa) without using diamond seed crystals or carbides. In these experiments the fluid phase is nearly pure methane, even though the oxygen fugacity was significantly above metal saturation. We propose several previously unidentified mechanisms that may promote diamond formation under such conditions and which may also have implications for the origin of sublithospheric diamonds. These include the hydroxylation of silicate minerals like olivine and pyroxene, H2 incorporation into these phases and the "etching" of graphite by H2 and CH4 and reprecipitation as diamond. This study also serves as a demonstration of our new high-pressure experimental technique for obtaining reduced fluids, which is not only relevant for diamond synthesis, but also for investigating the metasomatic origins of diamond in the upper mantle, which has further implications for the deep carbon cycle.

Deep magma ocean formation set the oxidation state of Earth's mantle.

The composition of Earth's atmosphere depends on the redox state of the mantle, which became more oxidizing at some stage after Earth's core started to form. Through high-pressure experiments, we found that Fe2+ in a deep magma ocean would disproportionate to Fe3+ plus metallic iron at high pressures. The separation of this metallic iron to the core raised the oxidation state of the upper mantle, changing the chemistry of degassing volatiles that formed the atmosphere to more oxidized species. Additionally, the resulting gradient in redox state of the magma ocean allowed dissolved CO2 from the atmosphere to precipitate as diamond at depth. This explains Earth's carbon-rich interior and suggests that redox evolution during accretion was an important variable in determining the composition of the terrestrial atmosphere.

Quantitative description of 1H SQ and DQ coherences for the hydroxyl disorder within hydrous ringwoodite.

Proton-containing point defects in solid materials are important for a variety of properties ranging from ionic transport over thermal conductivity up to compressibility. Ultrafast magic-angle spinning techniques nowadays offer high-resolution solid-state NMR spectra, even for 1H, and thus open up possibilities to study the underlying defect chemistry. Nevertheless, disorder within such defects again leads to heavy spectral overlap of 1H resonances, which prevents quantitative analysis of defect concentrations, if several defect types are present. Here, we present a strategy to overcome this limitation by simulating the 1H lineshape as well as 1H-1H double-quantum buildup curves, which we then validate against the experimental data in a joint cost function. To mimic the local structural disorder, we use molecular dynamics simulations at the DFT level. It turned out to be advantageous for the joint refinement to put the computational effort into the structural optimisation to derive accurate proton positions and to use empirical correlations for the relation between isotropic and anisotropic 1H chemical shifts and structural elements. The expressiveness of this approach is demonstrated on ringwoodite's (γ-Mg2SiO4) OH defect chemistry containing four different defect types in octahedral and tetrahedral voids with both pure Mg and mixed Si and Mg cation environments. Still, we determine the ratio for each defect type with an accuracy of about 5% as a result of the minimization of the joint cost function. We expect that our approach is generally applicable for local proton disorder and might prove to be a valuable alternative to the established AIRSS and Monte Carlo methods, respectively.

Hidden Oceans? Unraveling the Structure of Hydrous Defects in the Earth's Deep Interior.

High-pressure silicates making up the main proportion of the earth's interior can incorporate a significant amount of water in the form of OH defects. Generally, they are charge balanced by removing low-valent cations such as Mg2+. By combining high-resolution multidimensional single- and double-quantum 1H solid-state NMR spectroscopy with density functional theory calculations, we show that, for ringwoodite (γ-Mg2SiO4), additionally, Si4+ vacancies are formed, even at a water content as low as 0.1 wt %. They are charge balanced by either four protons or one Mg2+ and two protons. Surprisingly, also a significant proportion of coupled Mg and Si vacancies are present. Furthermore, all defect types feature a pronounced orientational disorder of the OH groups, which results in a significant range of OH···O bond distributions. As such, we are able to present unique insight into the defect chemistry of ringwoodite's spinel structure, which not only accounts for a potentially large fraction of the earth's entire water budget, but will also control transport properties in the mantle. We expect that our results will even impact other hydrous spinel-type materials, helping to understand properties such as ion conduction and heterogeneous catalysis.

Highly siderophile elements were stripped from Earth's mantle by iron sulfide segregation.

Highly siderophile elements (HSEs) are strongly depleted in the bulk silicate Earth (BSE) but are present in near-chondritic relative abundances. The conventional explanation is that the HSEs were stripped from the mantle by the segregation of metal during core formation but were added back in near-chondritic proportions by late accretion, after core formation had ceased. Here we show that metal-silicate equilibration and segregation during Earth's core formation actually increased HSE mantle concentrations because HSE partition coefficients are relatively low at the high pressures of core formation within Earth. The pervasive exsolution and segregation of iron sulfide liquid from silicate liquid (the "Hadean matte") stripped magma oceans of HSEs during cooling and crystallization, before late accretion, and resulted in slightly suprachondritic palladium/iridium and ruthenium/iridium ratios.

The oxidation state of the mantle and the extraction of carbon from Earth's interior.

Determining the oxygen fugacity of Earth's silicate mantle is of prime importance because it affects the speciation and mobility of volatile elements in the interior and has controlled the character of degassing species from the Earth since the planet's formation. Oxygen fugacities recorded by garnet-bearing peridotite xenoliths from Archaean lithosphere are of particular interest, because they provide constraints on the nature of volatile-bearing metasomatic fluids and melts active in the oldest mantle samples, including those in which diamonds are found. Here we report the results of experiments to test garnet oxythermobarometry equilibria under high-pressure conditions relevant to the deepest mantle xenoliths. We present a formulation for the most successful equilibrium and use it to determine an accurate picture of the oxygen fugacity through cratonic lithosphere. The oxygen fugacity of the deepest rocks is found to be at least one order of magnitude more oxidized than previously estimated. At depths where diamonds can form, the oxygen fugacity is not compatible with the stability of either carbonate- or methane-rich liquid but is instead compatible with a metasomatic liquid poor in carbonate and dominated by either water or silicate melt. The equilibrium also indicates that the relative oxygen fugacity of garnet-bearing rocks will increase with decreasing depth during adiabatic decompression. This implies that carbon in the asthenospheric mantle will be hosted as graphite or diamond but will be oxidized to produce carbonate melt through the reduction of Fe(3+) in silicate minerals during upwelling. The depth of carbonate melt formation will depend on the ratio of Fe(3+) to total iron in the bulk rock. This 'redox melting' relationship has important implications for the onset of geophysically detectable incipient melting and for the extraction of carbon dioxide from the mantle through decompressive melting.

High-pressure synthetic (Na(0.97)Mg(0.03))(Mg(0.43)Fe(0.17)Si(0.40))Si(2)O(6), with six-coordinated silicon, isostructural with P2/n omphacite.

The title compound, (sodium magnesium) [magnesium iron(III) silicon] disilicate, (Na(0.97)Mg(0.03))(Mg(0.43)Fe(0.17) (3+)Si(0.40))Si(2)O(6), is isotypic with ordered P2/n omphacite. Its structure is characterized by single chains of corner-sharing SiO(4) tetra-hedra, extending along the c axis, which are crosslinked by bands of edge-sharing octa-hedra (site symmetry 2), statistically occupied by (Mg(2+) + Fe(3+) + Si(4+)). Between the bands built up of the octahedra are two non-equivalent highly distorted six-coordinated sites (site symmetry 2), statistically occupied by (Na + Mg). In contrast to omphacites, the great differences in size and charge between Mg(2+) and Si(4+) result in complete, rather than partial, ordering of Mg and Si into two distinct octa-hedral sites, whereas Fe(3+) is disordered between the two sites. The octa-hedron filled by (Mg + Fe) is larger and markedly more distorted than that occupied by (Si + Fe). The average (Mg + Fe)-O and ((VI)Si + Fe)-O bond lengths are 2.075 and 1.850 Å, respectively.

Iron partitioning and density changes of pyrolite in Earth's lower mantle.

Phase transitions and the chemical composition of minerals in Earth's interior influence geophysical interpretations of its deep structure and dynamics. A pressure-induced spin transition in olivine has been suggested to influence iron partitioning and depletion, resulting in a distinct layered structure in Earth's lower mantle. For a more realistic mantle composition (pyrolite), we observed a considerable change in the iron-magnesium partition coefficient at about 40 gigapascals that is explained by a spin transition at much lower pressures. However, only a small depletion of iron is observed in the major high-pressure phase (magnesium silicate perovskite), which may be explained by preferential retention of the iron ion Fe3+. Changes in mineral proportions or density are not associated with the change in partition coefficient. The observed density profile agrees well with seismological models, which suggests that pyrolite is a good model composition for the upper to middle parts of the lower mantle.

Elastic shear anisotropy of ferropericlase in Earth's lower mantle.

Seismic shear anisotropy in the lowermost mantle most likely results from elastic shear anisotropy and lattice preferred orientation of its constituent minerals, including perovskite, post-perovskite, and ferropericlase. Measurements of the elastic shear anisotropy of single-crystal (Mg0.9Fe0.1)O up to 69 gigapascals (GPa) show that it increased considerably across the pressure-induced spin transition of iron between 40 and 60 GPa. Increasing iron content further enhances the anisotropy. This leads to at least 50% stronger elastic shear anisotropy of (Mg,Fe)O in the lowermost mantle compared to MgO, which is typically used in geodynamic modeling. Our results imply that ferropericlase is the dominant cause of seismic shear anisotropy in the lower mantle.

Splitting of the 520-kilometer seismic discontinuity and chemical heterogeneity in the mantle.

Seismic studies indicate that beneath some regions the 520-kilometer seismic discontinuity in Earth's mantle splits into two separate discontinuities (at approximately 500 kilometers and approximately 560 kilometers). The discontinuity near 500 kilometers is most likely caused by the (Mg,Fe)2SiO4 beta-to-gamma phase transformation. We show that the formation of CaSiO3 perovskite from garnet can cause the deeper discontinuity, and by determining the temperature dependence for this reaction we demonstrate that regional variations in splitting of the discontinuity arise from variability in the calcium concentration of the mantle rather than from temperature changes. This discontinuity therefore is sensitive to large-scale chemical heterogeneity. Its occurrence and variability yield regional information on the fertility of the mantle or the proportion of recycled oceanic crust.

17O and 29Si NMR parameters of MgSiO3 phases from high-resolution solid-state NMR spectroscopy and first-principles calculations.

The 29Si and 17O NMR parameters of six polymorphs of MgSiO3 were determined through a combination of high-resolution solid-state NMR and first-principles gauge including projector augmented wave (GIPAW) formalism calculations using periodic boundary conditions. MgSiO3 is an important component of the Earth's mantle that undergoes structural changes as a function of pressure and temperature. For the lower pressure polymorphs (ortho-, clino-, and protoenstatite), all oxygen species in the 17O high-resolution triple-quantum magic angle spinning (MAS) NMR spectra were resolved and assigned. These assignments differ from those tentatively suggested in previous work on the basis of empirical experimental correlations. The higher pressure polymorphs of MgSiO3 (majorite, akimotoite, and perovskite) are stabilized at pressures corresponding to the Earth's transition zone and lower mantle, with perovskite being the major constituent at depths >660 km. We present the first 17O NMR data for these materials and confirm previous 29Si work in the literature. The use of high-resolution multiple-quantum MAS (MQMAS) and satellite-transition MAS (STMAS) experiments allows us to resolve distinct oxygen species, and full assignments are suggested. The six polymorphs exhibit a wide variety of structure types, providing an ideal opportunity to consider the variation of NMR parameters (both shielding and quadrupolar) with local structure, including changes in coordination number, local geometry (bond distances and angles), and bonding. For example, we find that, although there is a general correlation of increasing 17O chemical shift with increasing Si-O bond length, the shift observed also depends upon the exact coordination environment.

Fe-Mg interdiffusion in (Mg,Fe)SiO3 Perovskite and lower mantle reequilibration.

Fe-Mg interdiffusion coefficients for (Mg,Fe)SiO3 perovskite have been measured at pressures of 22 to 26 gigapascals and temperatures between 1973 and 2273 kelvin. Perovskite Fe-Mg interdiffusion is as slow as Si self-diffusion and is orders of magnitude slower than Fe-Mg diffusion in other mantle minerals. Length scales over which chemical heterogeneities can homogenize, throughout the depth range of the lower mantle, are limited to a few meters even on time scales equivalent to the age of Earth. Heterogeneities can therefore only equilibrate chemically when they are stretched and thinned by intense deformation.

Pressure sensitivity of olivine slip systems and seismic anisotropy of Earth's upper mantle.

The mineral olivine dominates the composition of the Earth's upper mantle and hence controls its mechanical behaviour and seismic anisotropy. Experiments at high temperature and moderate pressure, and extensive data on naturally deformed mantle rocks, have led to the conclusion that olivine at upper-mantle conditions deforms essentially by dislocation creep with dominant [100] slip. The resulting crystal preferred orientation has been used extensively to explain the strong seismic anisotropy observed down to 250 km depth. The rapid decrease of anisotropy below this depth has been interpreted as marking the transition from dislocation to diffusion creep in the upper mantle. But new high-pressure experiments suggest that dislocation creep also dominates in the lower part of the upper mantle, but with a different slip direction. Here we show that this high-pressure dislocation creep produces crystal preferred orientations resulting in extremely low seismic anisotropy, consistent with seismological observations below 250 km depth. These results raise new questions about the mechanical state of the lower part of the upper mantle and its coupling with layers both above and below.

Partitioning of oxygen during core formation on the Earth and Mars.

Core formation on the Earth and Mars involved the physical separation of metal and silicate, most probably in deep magma oceans. Although core-formation models explain many aspects of mantle geochemistry, they have not accounted for the large differences observed between the compositions of the mantles of the Earth (approximately 8 wt% FeO) and Mars (approximately 18 wt% FeO) or the smaller mass fraction of the martian core. Here we explain these differences as a consequence of the solubility of oxygen in liquid iron-alloy increasing with increasing temperature. We assume that the Earth and Mars both accreted from oxidized chondritic material. In a terrestrial magma ocean, 1,200-2,000 km deep, high temperatures resulted in the extraction of FeO from the silicate magma ocean owing to high solubility of oxygen in the metal. Lower temperatures of a martian magma ocean resulted in little or no extraction of FeO from the mantle, which thus remains FeO-rich. The FeO extracted from the Earth's magma ocean may have contributed to chemical heterogeneities in the lowermost mantle, a FeO-rich D" layer and the light element budget of the core.

Experimental evidence for the existence of iron-rich metal in the Earth's lower mantle.

The oxidation state recorded by rocks from the Earth's upper mantle can be calculated from measurements of the distribution of Fe3+ and Fe2+ between the constituent minerals. The capacity for minerals to incorporate Fe3+ may also be a significant factor controlling the oxidation state of the mantle, and high-pressure experimental measurements of this property might provide important insights into the redox state of the more inaccessible deeper mantle. Here we show experimentally that the Fe3+ content of aluminous silicate perovskite, the dominant lower-mantle mineral, is independent of oxygen fugacity. High levels of Fe3+ are present in perovskite even when it is in chemical equilibrium with metallic iron. Silicate perovskite in the lower mantle will, therefore, have an Fe3+/total Fe ratio of at least 0.6, resulting in a whole-rock ratio of over ten times that of the upper mantle. Consequently, the lower mantle must either be enriched in Fe3+ or Fe3+ must form by the disproportionation of Fe2+ to produce Fe3+ plus iron metal. We argue that the lower mantle contains approximately 1 wt% of a metallic iron-rich alloy. The mantle's oxidation state and siderophile element budget have probably been influenced by the presence of this alloy.