Rates of protoplanetary accretion and differentiation set nitrogen budget of rocky planets.

The effect of protoplanetary differentiation on the fate of life-essential volatiles like nitrogen and carbon and its subsequent effect on the dynamics of planetary growth is unknown. Because the dissolution of nitrogen in magma oceans depends on its partial pressure and oxygen fugacity, it is an ideal proxy to track volatile re-distribution in protoplanets as a function of their sizes and growth zones. Using high pressure-temperature experiments in graphite-undersaturated conditions, here we show that the siderophile (iron-loving) character of nitrogen is an order of magnitude higher than previous estimates across a wide range of oxygen fugacity. The experimental data combined with metal-silicate-atmosphere fractionation models suggest that asteroid-sized protoplanets, and planetary embryos that grew from them, were nitrogen-depleted. However, protoplanets that grew to planetary embryo-size before undergoing differentiation had nitrogen-rich cores and nitrogen-poor silicate reservoirs. Bulk silicate reservoirs of large Earth-like planets attained nitrogen from the cores of latter type of planetary embryos. Therefore, to satisfy the volatile budgets of Earth-like planets during the main stage of their growth, the timescales of planetary embryo accretion had to be shorter than their differentiation timescales, i.e., Moon- to Mars-sized planetary embryos grew rapidly within ~1-2 Myrs of the Solar System's formation.

Mineralogy, Structure, and Habitability of Carbon-Enriched Rocky Exoplanets: A Laboratory Approach.

Carbon-enriched rocky exoplanets have been proposed to occur around dwarf stars as well as binary stars, white dwarfs, and pulsars. However, the mineralogical make up of such planets is poorly constrained. We performed high-pressure high-temperature laboratory experiments (P = 1-2 GPa, T = 1523-1823 K) on chemical mixtures representative of C-enriched rocky exoplanets based on calculations of protoplanetary disk compositions. These P-T conditions correspond to the deep interiors of Pluto- to Mars-sized planets and the upper mantles of larger planets. Our results show that these exoplanets, when fully differentiated, comprise a metallic core, a silicate mantle, and a graphite layer on top of the silicate mantle. Graphite is the dominant carbon-bearing phase at the conditions of our experiments with no traces of silicon carbide or carbonates. The silicate mineralogy comprises olivine, orthopyroxene, clinopyroxene, and spinel, which is similar to the mineralogy of the mantles of carbon-poor planets such as the Earth and largely unaffected by the amount of carbon. Metals are either two immiscible iron-rich alloys (S-rich and S-poor) or a single iron-rich alloy in the Fe-C-S system with immiscibility depending on the S/Fe ratio and core pressure. We show that, for our C-enriched compositions, the minimum carbon abundance needed for C-saturation is 0.05-0.7 wt% (molar C/O ∼0.002-0.03). Fully differentiated rocky exoplanets with C/O ratios more than that needed for C-saturation would contain graphite as an additional layer on top of the silicate mantle. For a thick enough graphite layer, diamonds would form at the bottom of this layer due to high pressures. We model the interior structure of Kepler-37b and show that a mere 10 wt% graphite layer would decrease its derived mass by 7%, which suggests that future space missions that determine both radius and mass of rocky exoplanets with insignificant gaseous envelopes could provide quantitative limits on their carbon content. Future observations of rocky exoplanets with graphite-rich surfaces would show low albedos due to the low reflectance of graphite. The absence of life-bearing elements other than carbon on the surface likely makes them uninhabitable.

Delivery of carbon, nitrogen, and sulfur to the silicate Earth by a giant impact.

Earth's status as the only life-sustaining planet is a result of the timing and delivery mechanism of carbon (C), nitrogen (N), sulfur (S), and hydrogen (H). On the basis of their isotopic signatures, terrestrial volatiles are thought to have derived from carbonaceous chondrites, while the isotopic compositions of nonvolatile major and trace elements suggest that enstatite chondrite-like materials are the primary building blocks of Earth. However, the C/N ratio of the bulk silicate Earth (BSE) is superchondritic, which rules out volatile delivery by a chondritic late veneer. In addition, if delivered during the main phase of Earth's accretion, then, owing to the greater siderophile (metal loving) nature of C relative to N, core formation should have left behind a subchondritic C/N ratio in the BSE. Here, we present high pressure-temperature experiments to constrain the fate of mixed C-N-S volatiles during core-mantle segregation in the planetary embryo magma oceans and show that C becomes much less siderophile in N-bearing and S-rich alloys, while the siderophile character of N remains largely unaffected in the presence of S. Using the new data and inverse Monte Carlo simulations, we show that the impact of a Mars-sized planet, having minimal contributions from carbonaceous chondrite-like material and coinciding with the Moon-forming event, can be the source of major volatiles in the BSE.

The fate of nitrogen during core-mantle separation on Earth.

Nitrogen, the most dominant constituent of Earth's atmosphere, is critical for the habitability and existence of life on our planet. However, its distribution between Earth's major reservoirs, which must be largely influenced by the accretion and differentiation processes during its formative years, is poorly known. Sequestration into the metallic core, along with volatility related loss pre- and post-accretion, could be a critical process that can explain the depletion of nitrogen in the Bulk Silicate Earth (BSE) relative to the primitive chondrites. However, the relative effect of different thermodynamic parameters on the alloy-silicate partitioning behavior of nitrogen is still poorly known. Here we present equilibrium partitioning data of N between alloy and silicate melt ( D N alloy / silicate ) from 67 new high pressure (P = 1-6 GPa)-temperature (T = 1500-2200 °C) experiments under graphite saturated conditions at a wide range of oxygen fugacity (logfO2 ~ΔIW - 4.2 to - 0.8), mafic to ultramafic silicate melt compositions (NBO/T = 0.4 to 2.2), and varying chemical composition of the alloy melts (S and Si contents of 0-32.1 wt.% and 0-3.1 wt.%, respectively). Under relatively oxidizing conditions (~ΔIW - 2.2 to - 0.8) nitrogen acts as a siderophile element ( D N alloy / silicate between 1.1 and 52), where D N alloy / silicate decreases with decrease in fO2 and increase in T, and increases with increase in P and NBO/T. Under these conditions D N alloy / silicate remains largely unaffected between S-free conditions and up to ~17 wt.% S content in the alloy melt, and then drops off at > ~20 wt.% S content in the alloy melt. Under increasingly reduced conditions (< ~ ΔIW - 2.2), N becomes increasingly lithophile ( D N alloy / silicate between 0.003 and 0.5) with D N alloy / silicate decreasing with decrease in fO2 and increase in T. At these conditions fO2, along with Si content of the alloy under the most reduced conditions (< ~ΔIW - 3.0), is the controlling parameter with T playing a secondary role, while, P, NBO/T, and S content of the alloy have minimal effects. A multiple linear least-squares regression parametrization for D N alloy / silicate based on the results of this study and previous studies suggests, in agreement with the experimental data, that fO2 (represented by Si content of the alloy melt and FeO content of the silicate melt), followed by T, has the strongest control on D N alloy / silicate . Based on our modeling, to match the present-day BSE N content, impactors that brought N must have been moderately to highly oxidized. If N bearing impactors were reduced, and/or there was significant disequilibrium core formation, then the BSE would be too N-rich and another mechanism for N loss, such as atmospheric loss, would be required.