Constraints on the composition of the Earth's core from ab initio calculations

Knowledge of the composition of the Earth's core is important for understanding its melting point and therefore the temperature at the inner-core boundary and the temperature profile of the core and mantle. In addition, the partitioning of light elements between solid and liquid, as the outer core freezes at the inner-core boundary, is believed to drive compositional convection, which in turn generates the Earth's magnetic field. It is generally accepted that the liquid outer core and the solid inner core consist mainly of iron. The outer core, however, is also thought to contain a significant fraction of light elements, because its density--as deduced from seismological data and other measurements--is 6-10 per cent less than that estimated for pure liquid iron. Similar evidence indicates a smaller but still appreciable fraction of light elements in the inner core. The leading candidates for the light elements present in the core are sulphur, oxygen and silicon. Here we obtain a constraint on core composition derived from ab initio calculation of the chemical potentials of light elements dissolved in solid and liquid iron. We present results for the case of sulphur, which provide strong evidence against the proposal that the outer core is close to being a binary iron-sulphur mixture.     

Silicon in the Earth's core

Small isotopic differences between the silicate minerals in planets may have developed as a result of processes associated with core formation, or from evaporative losses during accretion as the planets were built up. Basalts from the Earth and the Moon do indeed appear to have iron isotopic compositions that are slightly heavy relative to those from Mars, Vesta and primitive undifferentiated meteorites (chondrites). Explanations for these differences have included evaporation during the 'giant impact' that created the Moon (when a Mars-sized body collided with the young Earth). However, lithium and magnesium, lighter elements with comparable volatility, reveal no such differences, rendering evaporation unlikely as an explanation. Here we show that the silicon isotopic compositions of basaltic rocks from the Earth and the Moon are also distinctly heavy. A likely cause is that silicon is one of the light elements in the Earth's core. We show that both the direction and magnitude of the silicon isotopic effect are in accord with current theory based on the stiffness of bonding in metal and silicate. The similar isotopic composition of the bulk silicate Earth and the Moon is consistent with the recent proposal that there was large-scale isotopic equilibration during the giant impact. We conclude that Si was already incorporated as a light element in the Earth's core before the Moon formed.     

Outer-core compositional stratification from observed core wave speed profiles

Light elements must be present in the nearly pure iron core of the Earth to match the remotely observed properties of the outer and inner cores. Crystallization of the inner core excludes light elements from the solid, concentrating them in liquid near the inner-core boundary that potentially rises and collects at the top of the core, and this may have a seismically observable signal. Here we present array-based observations of seismic waves sensitive to this part of the core whose wave speeds require there to be radial compositional variation in the topmost 300?km of the outer core. The velocity profile significantly departs from that of compression of a homogeneous liquid. Total light-element enrichment is up to five weight per cent at the top of the core if modelled in the Fe-O-S system. The stratification suggests the existence of a subadiabatic temperature gradient at the top of the outer core.     

Seismological evidence for mosaic structure of the surface of the Earth's inner core

The transition from the Earth's solid inner core to liquid outer core is the location where the inner core grows and from which compositional convection in the outer core originates. Most seismological models of the Earth describe the inner-core boundary as sharp and simple, although experimental data requiring the presence of a thin transition layer at the bottom of the outer core have been reported. The density jump at the inner-core boundary--an important parameter determining gravitational energy release and constraining the compositional difference between the inner and outer core-is also not well known. Estimates of this density jump obtained using free-oscillation eigenfrequencies give low values of 0.25-1.0 g cm(-3), whereas a method using the amplitude ratio of core-reflected phases yielded values of 0.6-1.8 g cm(-3) (refs 14, 15, 16-17). Here we analyse properties of waves precritically reflected from the Earth's inner core (PKiKP phases) that show significant variability in amplitude, consistent high-frequency content and stable travel times with respect to a standard Earth model. We infer that the data are best explained by a mosaic structure of the inner core's surface. Such a mosaic may be composed of patches in which the transition from solid inner to liquid outer core includes a thin partially liquid layer interspersed with patches containing a sharp transition.     

Melting of the Earth's inner core

The Earth's magnetic field is generated by a dynamo in the liquid iron core, which convects in response to cooling of the overlying rocky mantle. The core freezes from the innermost surface outward, growing the solid inner core and releasing light elements that drive compositional convection. Mantle convection extracts heat from the core at a rate that has enormous lateral variations. Here we use geodynamo simulations to show that these variations are transferred to the inner-core boundary and can be large enough to cause heat to flow into the inner core. If this were to occur in the Earth, it would cause localized melting. Melting releases heavy liquid that could form the variable-composition layer suggested by an anomaly in seismic velocity in the 150 kilometres immediately above the inner-core boundary. This provides a very simple explanation of the existence of this layer, which otherwise requires additional assumptions such as locking of the inner core to the mantle, translation from its geopotential centre or convection with temperature equal to the solidus but with composition varying from the outer to the inner core. The predominantly narrow downwellings associated with freezing and broad upwellings associated with melting mean that the area of melting could be quite large despite the average dominance of freezing necessary to keep the dynamo going. Localized melting and freezing also provides a strong mechanism for creating seismic anomalies in the inner core itself, much stronger than the effects of variations in heat flow so far considered.     

Thermal and electrical conductivity of iron at Earth's core conditions

The Earth acts as a gigantic heat engine driven by the decay of radiogenic isotopes and slow cooling, which gives rise to plate tectonics, volcanoes and mountain building. Another key product is the geomagnetic field, generated in the liquid iron core by a dynamo running on heat released by cooling and freezing (as the solid inner core grows), and on chemical convection (due to light elements expelled from the liquid on freezing). The power supplied to the geodynamo, measured by the heat flux across the core-mantle boundary (CMB), places constraints on Earth's evolution. Estimates of CMB heat flux depend on properties of iron mixtures under the extreme pressure and temperature conditions in the core, most critically on the thermal and electrical conductivities. These quantities remain poorly known because of inherent experimental and theoretical difficulties. Here we use density functional theory to compute these conductivities in liquid iron mixtures at core conditions from first principles--unlike previous estimates, which relied on extrapolations. The mixtures of iron, oxygen, sulphur and silicon are taken from earlier work and fit the seismologically determined core density and inner-core boundary density jump. We find both conductivities to be two to three times higher than estimates in current use. The changes are so large that core thermal histories and power requirements need to be reassessed. New estimates indicate that the adiabatic heat flux is 15 to 16 terawatts at the CMB, higher than present estimates of CMB heat flux based on mantle convection; the top of the core must be thermally stratified and any convection in the upper core must be driven by chemical convection against the adverse thermal buoyancy or lateral variations in CMB heat flow. Power for the geodynamo is greatly restricted, and future models of mantle evolution will need to incorporate a high CMB heat flux and explain the recent formation of the inner core.     

Accretion of the Earth and segregation of its core

The Earth took 30-40 million years to accrete from smaller 'planetesimals'. Many of these planetesimals had metallic iron cores and during growth of the Earth this metal re-equilibrated with the Earth's silicate mantle, extracting siderophile ('iron-loving') elements into the Earth's iron-rich core. The current composition of the mantle indicates that much of the re-equilibration took place in a deep (> 400 km) molten silicate layer, or 'magma ocean', and that conditions became more oxidizing with time as the Earth grew. The high-pressure nature of the core-forming process led to the Earth's core being richer in low-atomic-number elements, notably silicon and possibly oxygen, than the cores of the smaller planetesimal building blocks.     

Volatile accretion history of the Earth

It has long been thought that the Earth had a protracted and complex history of volatile accretion and loss. Albarède paints a different picture, proposing that the Earth first formed as a dry planet which, like the Moon, was devoid of volatile constituents. He suggests that the Earth's complement of volatile elements was only established later, by the addition of a small veneer of volatile-rich material at ～100 Myr (here and elsewhere, ages are relative to the origin of the Solar System). Here we argue that the Earth's mass balance of moderately volatile elements is inconsistent with Albarède's hypothesis but is well explained by the standard model of accretion from partially volatile-depleted material, accompanied by core formation.     

The Earth's missing lead may not be in the core

Relative to the CI chondrite class of meteorites (widely thought to be the 'building blocks' of the terrestrial planets), the Earth is depleted in volatile elements. For most elements this depletion is thought to be a solar nebular signature, as chondrites show depletions qualitatively similar to that of the Earth. On the other hand, as lead is a volatile element, some Pb may also have been lost after accretion. The unique (206)Pb/(204)Pb and (207)Pb/(204)Pb ratios of the Earth's mantle suggest that some lead was lost about 50 to 130 Myr after Solar System formation. This has commonly been explained by lead lost via the segregation of a sulphide melt to the Earth's core, which assumes that lead has an affinity towards sulphide. Some models, however, have reconciled the Earth's lead deficit with volatilization. Whichever model is preferred, the broad coincidence of U-Pb model ages with the age of the Moon suggests that lead loss may be related to the Moon-forming impact. Here we report partitioning experiments in metal-sulphide-silicate systems. We show that lead is neither siderophile nor chalcophile enough to explain the high U/Pb ratio of the Earth's mantle as being a result of lead pumping to the core. The Earth may have accreted from initially volatile-depleted material, some lead may have been lost to degassing following the Moon-forming giant impact, or a hidden reservoir exists in the deep mantle with lead isotope compositions complementary to upper-mantle values; it is unlikely though that the missing lead resides in the core.     

Mars' core and magnetism.

The detection of strongly magnetized ancient crust on Mars is one of the most surprising outcomes of recent Mars exploration, and provides important insight about the history and nature of the martian core. The iron-rich core probably formed during the hot accretion of Mars approximately 4.5 billion years ago and subsequently cooled at a rate dictated by the overlying mantle. A core dynamo operated much like Earth's current dynamo, but was probably limited in duration to several hundred million years. The early demise of the dynamo could have arisen through a change in the cooling rate of the mantle, or even a switch in convective style that led to mantle heating. Presently, Mars probably has a liquid, conductive outer core and might have a solid inner core like Earth.     

Core formation in planetesimals triggered by permeable flow

The tungsten isotope composition of meteorites indicates that core formation in planetesimals occurred within a few million years of Solar System formation. But core formation requires a mechanism for segregating metal, and the 'wetting' properties of molten iron alloy in an olivine-rich matrix is thought to preclude segregation by permeable flow unless the silicate itself is partially molten. Excess liquid metal over a percolation threshold, however, can potentially create permeability in a solid matrix, thereby permitting segregation. Here we report the percolation threshold for molten iron-sulphur compounds of approximately 5 vol.% in solid olivine, based on electrical conductivity measurements made in situ at high pressure and temperature. We conclude that heating within planetesimals by decay of short-lived radionuclides can increase temperature sufficiently above the iron-sulphur melting point (approximately 1,000 degrees C) to trigger segregation of iron alloy by permeable flow within the short timeframe indicated by tungsten isotopes. We infer that planetesimals with radii greater than about 30 km and larger planetary embryos are expected to have formed cores very early, and these objects would have contained much of the mass in the terrestrial region of the protoplanetary nebula. The Earth and other terrestrial planets are likely therefore to have formed by accretion of previously differentiated planetesimals, and Earth's core may accordingly be viewed as a blended composite of pre-formed cores.     

Spin crossover and iron-rich silicate melt in the Earth's deep mantle

A melt has greater volume than a silicate solid of the same composition. But this difference diminishes at high pressure, and the possibility that a melt sufficiently enriched in the heavy element iron might then become more dense than solids at the pressures in the interior of the Earth (and other terrestrial bodies) has long been a source of considerable speculation. The occurrence of such dense silicate melts in the Earth's lowermost mantle would carry important consequences for its physical and chemical evolution and could provide a unifying model for explaining a variety of observed features in the core-mantle boundary region. Recent theoretical calculations combined with estimates of iron partitioning between (Mg,Fe)SiO(3) perovskite and melt at shallower mantle conditions suggest that melt is more dense than solids at pressures in the Earth's deepest mantle, consistent with analysis of shockwave experiments. Here we extend measurements of iron partitioning over the entire mantle pressure range, and find a precipitous change at pressures greater than ～76?GPa, resulting in strong iron enrichment in melts. Additional X-ray emission spectroscopy measurements on (Mg(0.95)Fe(0.05))SiO(3) glass indicate a spin collapse around 70?GPa, suggesting that the observed change in iron partitioning could be explained by a spin crossover of iron (from high-spin to low-spin) in silicate melt. These results imply that (Mg,Fe)SiO(3) liquid becomes more dense than coexisting solid at ～1,800?km depth in the lower mantle. Soon after the Earth's formation, the heat dissipated by accretion and internal differentiation could have produced a dense melt layer up to ～1,000?km in thickness underneath the solid mantle. We also infer that (Mg,Fe)SiO(3) perovskite is on the liquidus at deep mantle conditions, and predict that fractional crystallization of dense magma would have evolved towards an iron-rich and silicon-poor composition, consistent with seismic inferences of structures in the core-mantle boundary region.     

The Earth's 'missing' niobium may be in the core

As the Earth's metallic core segregated from the silicate mantle, some of the moderately siderophile ('iron-loving') elements such as vanadium and chromium are thought to have entered the metal phase, thus causing the observed depletions of these elements in the silicate part of the Earth. In contrast, refractory 'lithophile' elements such as calcium, scandium and the rare-earth elements are known to be present in the same proportions in the silicate portion of the Earth as in the chondritic meteorites-thought to represent primitive planetary material. Hence these lithophile elements apparently did not enter the core. Niobium has always been considered to be lithophile and refractory yet it has been observed to be depleted relative to other elements of the same type in the crust and upper mantle. This observation has been used to infer the existence of hidden niobium-rich reservoirs in the Earth's deep mantle. Here we show, however, that niobium and vanadium partition in virtually identical fashion between liquid metal and liquid silicate at high pressure. Thus, if a significant fraction of the Earth's vanadium entered the core (as is thought), then so has a similar fraction of its niobium, and no hidden reservoir need be sought in the Earth's deep mantle.     

Inner-core shear-wave anisotropy and texture from an observation of PKJKP waves

Since the discovery of the Earth's core a century ago, and the subsequent discovery of a solid inner core (postulated to have formed by the freezing of iron) seismologists have striven to understand this most remote part of the deep Earth. The most direct evidence for a solid inner core would be the observation of shear-mode body waves that traverse it, but these phases are extremely difficult to observe. Two reported observations in short-period data have proved controversial. Arguably more successful have been studies of longer-period data, but such averaging limits the usefulness of the observations to reported sightings. We present two observations of an inner-core shear-wave phase at higher frequencies in stacked data from the Japanese High-Sensitivity Array, Hi-Net. From an analysis of timing, amplitude and waveform of the 'PKJKP' phase we derive constraints on inner-core compressional-wave velocity and shear attenuation at about 0.3 Hz which differ from standard isotropic core models. We can explain waveform features and can partially reconcile the otherwise large differences between core wavespeed and attenuation models that our observations apparently suggest if we invoke shear-wave anisotropy in the inner core. A simple model of an inner core composed of hexagonal close-packed iron with its c axis aligned perpendicular to the rotation axis yields anisotropy that is compatible with both the shear-wave anisotropy that we observe and the well-established 3 per cent compressional-wave anisotropy.     

Atmospheric carbon dioxide concentrations before 2.2 billion years ago

The composition of the Earth's early atmosphere is a subject of continuing debate. In particular, it has been suggested that elevated concentrations of atmospheric carbon dioxide would have been necessary to maintain normal surface temperatures in the face of lower solar luminosity in early Earth history. Fossil weathering profiles, known as palaeosols, have provided semi-quantitative constraints on atmospheric oxygen partial pressure (pO2) before 2.2 Gyr ago. Here we use the same well studied palaeosols to constrain atmospheric pCO2 between 2.75 and 2.2 Gyr ago. The observation that iron lost from the tops of these profiles was reprecipitated lower down as iron silicate minerals, rather than as iron carbonate, indicates that atmospheric pCO2 must have been less than 10(-1.4) atm--about 100 times today's level of 360 p.p.m., and at least five times lower than that required in one-dimensional climate models to compensate for lower solar luminosity at 2.75 Gyr. Our results suggest that either the Earth's early climate was much more sensitive to increases in pCO2 than has been thought, or that one or more greenhouse gases other than CO2 contributed significantly to the atmosphere's radiative balance during the late Archaean and early Proterozoic eons.     

Spin transition of iron in magnesiowüstite in the Earth's lower mantle

Iron is the most abundant transition-metal element in the mantle and therefore plays an important role in the geochemistry and geodynamics of the Earth's interior. Pressure-induced electronic spin transitions of iron occur in magnesiowüstite, silicate perovskite and post-perovskite. Here we have studied the spin states of iron in magnesiowüstite and the isolated effects of the electronic transitions on the elasticity of magnesiowüstite with in situ X-ray emission spectroscopy and X-ray diffraction to pressures of the lowermost mantle. An observed high-spin to low-spin transition of iron in magnesiowüstite results in an abnormal compressional behaviour between the high-spin and the low-spin states. The high-pressure, low-spin state exhibits a much higher bulk modulus and bulk sound velocity than the low-pressure, high-spin state; the bulk modulus jumps by approximately 35 percent and bulk sound velocity increases by approximately 15 percent across the transition in (Mg0.83,Fe0.17)O. Although no significant density change is observed across the electronic transition, the jump in the sound velocities and the bulk modulus across the transition provides an additional explanation for the seismic wave heterogeneity in the lowermost mantle. The transition also affects current interpretations of the geophysical and geochemical models using extrapolated or calculated thermal equation-of-state data without considering the effects of the electronic transition.     

Mixing, volatile loss and compositional change during impact-driven accretion of the Earth

The degree to which efficient mixing of new material or losses of earlier accreted material to space characterize the growth of Earth-like planets is poorly constrained and probably changed with time. These processes can be studied by parallel modelling of data from different radiogenic isotope systems. The tungsten isotope composition of the silicate Earth yields a model timescale for accretion that is faster than current estimates based on terrestrial lead and xenon isotope data and strontium, tungsten and lead data for lunar samples. A probable explanation for this is that impacting core material did not always mix efficiently with the silicate portions of the Earth before being added to the Earth's core. Furthermore, tungsten and strontium isotope compositions of lunar samples provide evidence that the Moon-forming impacting protoplanet Theia was probably more like Mars, with a volatile-rich, oxidized mantle. Impact-driven erosion was probably a significant contributor to the variations in moderately volatile element abundance and oxidation found among the terrestrial planets.     

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 that potassium is a substantial radioactive heat source in planetary cores

The hypothesis that (40)K may be a significant radioactive heat source in the Earth's core was proposed on theoretical grounds over three decades ago, but experiments have provided only ambiguous and contradictory evidence for the solubility of potassium in iron-rich alloys. The existence of such radioactive heat in the core would have important implications for our understanding of the thermal evolution of the Earth and global processes such as the generation of the geomagnetic field, the core-mantle boundary heat flux and the time of formation of the inner core. Here we provide experimental evidence to show that the ambiguous results obtained from earlier experiments are probably due to previously unrecognized experimental and analytical difficulties. The high-pressure, high-temperature data presented here show conclusively that potassium enters iron sulphide melts in a strongly temperature-dependent fashion and that (40)K can serve as a substantial heat source in the cores of the Earth and Mars.     

Chemical interaction of Fe and Al(2)O3 as a source of heterogeneity at the Earth's core-mantle boundary

Seismological studies have revealed that a complex texture or heterogeneity exists in the Earth's inner core and at the boundary between core and mantle. These studies highlight the importance of understanding the properties of iron when modelling the composition and dynamics of the core and the interaction of the core with the lowermost mantle. One of the main problems in inferring the composition of the lowermost mantle is our lack of knowledge of the high-pressure and high-temperature chemical reactions that occur between iron and the complex Mg-Fe-Si-Al-oxides which are thought to form the bulk of the Earth's lower mantle. A number of studies have demonstrated that iron can react with MgSiO3-perovskite at high pressures and high temperatures, and it was proposed that the chemical nature of this process involves the reduction of silicon by the more electropositive iron. Here we present a study of the interaction between iron and corundum (Al(2)O3) in electrically- and laser-heated diamond anvil cells at 2,000-2,200 K and pressures up to 70 GPa, simulating conditions in the Earth's deep interior. We found that at pressures above 60 GPa and temperatures of 2,200 K, iron and corundum react to form iron oxide and an iron-aluminium alloy. Our results demonstrate that iron is able to reduce aluminium out of oxides at core-mantle boundary conditions, which could provide an additional source of light elements in the Earth's core and produce significant heterogeneity at the core-mantle boundary.