publications

Nitrogen (N) is the most abundant element in Earth's atmosphere, but is extremely depleted in the silicate Earth. However, it is not clear whether core sequestration or early atmospheric loss was responsible for this depletion. Here we study the effect of core formation on the inventory of nitrogen using laser-heated diamond anvil cells. We find that, due to the simultaneous dissolution of oxygen in the metal, N becomes much less siderophile (iron-loving) at pressures and temperatures up to 104 GPa and 5000 K, a thermodynamic condition relevant to the bottom of the magma ocean in the aftermath of the moon-forming giant impact. Using a core–mantle–atmosphere coevolution model, we show that the impact-induced processes (core formation and/or atmospheric loss) are unlikely to account for the observed N anomaly, which is instead best explained by the accretion of mainly N-poor impactors. The terrestrial volatile pattern requires severe N depletion on precursor bodies, prior to their accretion to the proto-Earth.

Transport properties of silicate melts control magma ocean dynamics on the early terrestrial planets and rocky exoplanets. Here we calculate the viscosity (transport of momentum) of peridotite liquid at potential magma ocean conditions (0–159 GPa, 2,200–6,000 K) using ab initio molecular dynamics simulations. We find that, unlike MgSiO 3 or basaltic melts, the viscosity of the highly depolymerized peridotite liquid (a) increases monotonically with pressure without an anomalous drop and (b) is lower than those of other melts over the entire mantle pressure range. Low viscosity would promote fractional crystallization in a less polymerized magma ocean and thus contribute to mantle heterogeneity from its earliest stage. Given the compositional dependence of magma ocean properties, emphasis on multicomponent bulk silicate Earth‐like composition, instead of simple end‐members, are rendered necessary, in order to better understand high‐energy planetary accretion processes and their aftermaths.

Earth's mantle has a two-layered structure, with the upper and lower mantle domains separated by a seismic discontinuity at about 660 km (refs. 1,2 ). The extent of mass transfer between these mantle domains throughout Earth's history is, however, poorly understood. Continental crust extraction results in Ti-stable isotopic fractionation, producing isotopically light melting residues 3–7 . Mantle recycling of these components can impart Ti isotope variability that is trackable in deep time. We report ultrahigh-precision 49 Ti/ 47 Ti ratios for chondrites, ancient terrestrial mantle-derived lavas ranging from 3.8 to 2.0 billion years ago (Ga) and modern ocean island basalts (OIBs). Our new Ti bulk silicate Earth (BSE) estimate based on chondrites is 0.052 ± 0.006‰ heavier than the modern upper mantle sampled by normal mid-ocean ridge basalts (N-MORBs). The 49 Ti/ 47 Ti ratio of Earth's upper mantle was chondritic before 3.5 Ga and evolved to a N-MORB-like composition between approximately 3.5 and 2.7 Ga, establishing that more continental crust was extracted during this epoch. The +0.052 ± 0.006‰ offset between BSE and N-MORBs requires that <30% of Earth's mantle equilibrated with recycled crustal material, implying limited mass exchange between the upper and lower mantle and, therefore, preservation of a primordial lower-mantle reservoir for most of Earth's geologic history. Modern OIBs record variable 49 Ti/ 47 Ti ratios ranging from chondritic to N-MORBs compositions, indicating continuing disruption of Earth's primordial mantle. Thus, modern-style plate tectonics with high mass transfer between the upper and lower mantle only represents a recent feature of Earth's history.

Seismic recordings made during the InSight mission 1 suggested that Mars's liquid core would need to be approximately 27% lighter than pure liquid iron 2,3 , implying a considerable complement of light elements. Core compositions based on seismic and bulk geophysical constraints, however, require larger quantities of the volatile elements hydrogen, carbon and sulfur than those that were cosmochemically available in the likely building blocks of Mars 4 . Here we show that multiply diffracted P waves along a stratified core–mantle boundary region of Mars in combination with first-principles computations of the thermoelastic properties of liquid iron-rich alloys 3 require the presence of a fully molten silicate layer overlying a smaller, denser liquid core. Inverting differential body wave travel time data with particular sensitivity to the core–mantle boundary region suggests a decreased core radius of 1,675 ± 30 km associated with an increased density of 6.65 ± 0.1 g cm −3 , relative to previous models 2,4–8 , while the thickness and density of the molten silicate layer are 150 ± 15 km and 4.05 ± 0.05 g cm −3 , respectively. The core properties inferred here reconcile bulk geophysical and cosmochemical requirements, consistent with a core containing 85–91 wt% iron–nickel and 9–15 wt% light elements, chiefly sulfur, carbon, oxygen and hydrogen. The chemical characteristics of a molten silicate layer above the core may be revealed by products of Martian magmatism.

Seismic measurements made on Mars indicate that the liquid iron‐nickel core is rich in light elements; however, the effects of these light components on the elasticity of Mars' core remain poorly constrained. Here, we calculate elastic properties of various liquid Fe‐X (X = Ni, S, C, O and H) mixtures using ab initio molecular dynamics simulations. We find that, at martian core conditions, the addition of S and O most effectively decreases the density of liquid iron, followed by C and H, while Ni has a minimal effect. As for compressional sound velocity (Vp), C increases Vp of liquid Fe throughout Mars' core, while both S and O reduce Vp, the intensity of which diminishes with increasing pressure. Assuming a martian core made of a binary mixture, the seismically‐inferred density would require the presence of at least 30 wt% S.

Sodium chloride is expected to be found on many of the surfaces of icy moons like Europa and Ganymede. However, spectral identification remains elusive as the known NaCl-bearing phases cannot match current observations, which require higher number of water of hydration. Working at relevant conditions for icy worlds, we report the characterization of three “hyperhydrated” sodium chloride (SC) hydrates, and refined two crystal structures [2NaCl·17H 2 O (SC8.5); NaCl·13H 2 O (SC13)]. We found that the dissociation of Na + and Cl − ions within these crystal lattices allows for the high incorporation of water molecules and thus explain their hyperhydration. This finding suggests that a great diversity of hyperhydrated crystalline phases of common salts might be found at similar conditions. Thermodynamic constraints indicate that SC8.5 is stable at room pressure below 235 K, and it could be the most abundant NaCl hydrate on icy moon surfaces like Europa, Titan, Ganymede, Callisto, Enceladus, or Ceres. The finding of these hyperhydrated structures represents a major update to the H 2 O–NaCl phase diagram. These hyperhydrated structures provide an explanation for the mismatch between the remote observations of the surface of Europa and Ganymede and previously available data on NaCl solids. It also underlines the urgent need for mineralogical exploration and spectral data on hyperhydrates at relevant conditions to help future icy world exploration by space missions.

Structure and properties of terrestrial magma oceans control the co-evolution of the core, mantle and atmosphere of the early Earth, but are poorly understood because discrepancies remain between experiments and theoretical calculations. Here we combine acoustic velocity measurements and ab initio simulations on pyrolite glass/melt with a silicate Earth-like composition. In the complex system, we find a gradual increase of sound velocity with increasing pressure. Through ab initio simulations, this is explicable by the transition from four- to six-fold coordinated Si occurring over the entire mantle regime. These results are at odds with recent X-ray diffraction measurements, which show an abrupt change in Si-O coordination at 35 GPa. It is however consistent with recent high-pressure data, where Ni partitioning between molten metal and silicate exhibits a similar gradual change with pressure. Unlike amorphous silica, smooth structural evolution in a multicomponent system implies progressive changes in magma ocean properties with depth, such as density, element partitioning and transport properties, which, when incorporated into magma ocean models, may improve our understanding of early history of the Earth and other rocky planets.

Nitrogen (N) is a major ingredient of the atmosphere, but a trace component in the silicate Earth. Its initial inventory in these reservoirs during Earth's early differentiation requires knowledge of N speciation in magmas, for example, whether it outgasses as N 2 or is sequestered in silicate melts as N 3− , which remains largely unconstrained over the entire mantle regime. Here we examine N species in anhydrous and hydrous pyrolitic melts at varying P‐T‐redox conditions by ab‐initio calculations, and find N‐N bonding under oxidizing conditions from ambient to lower mantle pressures. Under reducing conditions, N interacts with the silicate network or forms N‐H bonds, depending on the availability of hydrogen. Redox control of N speciation is demonstrated valid over a P‐T space encompassing probable magma ocean depths. Finally, if the Earth accreted from increasingly oxidized materials toward the end of its accretion, an N‐enriched secondary atmosphere might be produced and persist until later impacts.

The phenomenon of host-guest hydrogen bonding in clathrate hydrate crystal structures and its effect on physical and chemical properties have become subjects of extensive research. Hydrogen bonding has been studied for cubic (sI and sII) and hexagonal (sH) binary clathrates, while it has not been addressed for clathrate structures that exist at elevated pressures. Here, four acetone hydrate clathrates have been grown at high-pressure and low-temperature conditions. In situ single-crystal X-ray diffraction revealed that the synthesized phases possess already known trigonal (sTr), orthorhombic (sO), and tetragonal (sT) crystal structures as well as a previously unknown orthorhombic structure, so-called sO-II. Only sO and sII have previously been reported for acetone clathrates. Structural analysis suggests that acetone oxygens are hydrogen-bonded to the closest water oxygens of the host frameworks. Our discoveries show that clathrate hydrates hosting polar molecules are not as exotic as previously thought and could be stabilized at high-pressure conditions through hydrogen bonding.

Mo and W in the bulk silicate Earth and their partitioning behavior between molten metal and silicate can be used to constrain the thermochemical conditions during Earth's core-mantle differentiation. In order to improve our understanding of core-forming conditions, we performed a series of superliquidus metal-silicate partitioning experiments on Mo and W at 40–93 GPa and 3000–4700 K in laser-heated diamond anvil cells. Under the extended P-T conditions directly relevant to terrestrial core formation in a deep magma ocean, we find that pressure and temperature have profound yet opposing effects on their partitioning, and a significant amount of O dissolved in the metal. Based on an activity model for liquid Fe-rich metal, it is observed that O enhances the solubility of both Mo and W in the metal, whereas S makes W significantly less siderophile than Mo. Combining our new data with those of the literature, we modeled the effects of pressure, temperature and metal composition on partitioning, and applied them to a multi-stage accretion model. While our model with homogeneous S accretion successfully explains the abundance of Mo, it underestimates that of W and therefore overestimates Mo/W ratio in Earth's mantle, regardless of the oxidation conditions prevailing during core formation. On the other hand, mantle observables (Mo and W abundances, Mo/W ratio) can be reproduced simultaneously if S is supplied to the Earth towards the end of accretion. This corroborates previous work at lower pressures, and agrees with heterogeneous accretion models where the late volatile-rich delivery was envisaged to explain various isotopic signatures of terrestrial bodies. Nonetheless, this conclusion does not discriminate between reducing and oxidizing conditions.

Silicate Earth is widely considered identical to chondrites in its refractory lithophile element ratios. However, its subchondritic Nb/Ta signature deviates from the chondritic paradigm. To resolve this Nb deficit, its sequestration in Earth's core under very reducing core-forming conditions has been proposed based on low-pressure data. Here, we show that under conditions relevant to core formation Nb is siderophile at high pressures under all redox conditions, corroborating Nb inventory in Earth's core. Further core formation modeling shows that Earth's core could have formed under moderately reducing or oxidizing conditions, whereas highly reducing conditions mismatch the geochemical observables; although Earth may have sampled a variety of reservoirs, it is problematic to accrete primarily from materials as reduced as enstatite chondrites.

Abstract Silicon and oxygen are potential light elements in Earth's core because their stronger affinity to metal observed with increasing temperature posits that significant amounts of both can be incorporated into the core. It was proposed that an Fe–Si–O liquid alloy could expel SiO2 at the core-mantle boundary during secular cooling, leaving the core with either silicon or oxygen, not both. This was recently challenged in a study showing no exsolution but immiscibility in the Fe–Si–O system. Here we investigate the liquidus field of Fe–Si and Fe–O binaries and Fe–Si–O ternaries at core-mantle boundary pressures and temperatures using ab initio molecular dynamics. We find that the liquids remain well mixed with ternary properties identical to mixing of binary properties. Two-phase simulations of solid SiO2 and liquid Fe show dissolution at temperatures above 4100 K, suggesting that SiO2 crystallization as well as liquid immiscibility in Fe–Si–O is unlikely to occur in Earth's core.

© 2018 Walter de Gruyter GmbH, Berlin/Boston. Earth's core is essentially composed of a light-element bearing iron-nickel alloy (Birch 1964). The nickel content in the core has negligible effects on physical properties such as density and compressibility (e.g., Lin et al. 2003; Kantor et al. 2007; Martorell et al. 2013; Badro et al. 2014). This deters any attempt to determine or even estimate the nickel content of the core using seismological models, as in the case of light elements. It was recently proposed that the presence of nickel should fractionate iron isotopes in small planetary cores (Elardo and Shahar 2017), but the effect for a large (hot) planet such as the Earth would not be measurable; this observation, however, opens up the possibility that Ni can have an effect on element partitioning between the metallic alloy and the silicate melt during core formation. In this case, the siderophile trace-element composition of the mantle would, in turn, constrain the Fe/Ni ratio in the core. Here, we investigated the effect of nickel concentration in the metallic alloy on the partitioning of other elements at conditions directly relevant to core formation, using the laser-heated diamond-anvil cell. We found no measurable effect of nickel concentration on the partitioning of Ni, Cr, and V; the Fe-Ni alloy is chemically ideal over a broad range of Ni concentrations (3.5 to 48.7 wt%). The ideality of the Fe-Ni solution across a wide range of nickel concentration shows that Fe and Ni are not only twins from the standpoint for material properties, but also from that of chemical properties in those high P-T conditions.