Thermodynamics of Element Volatility and its Application to Planetary Processes

Despite its importance in geological sciences, our understanding of interactions between gas and condensed phases (comprising solids and liquids) remains clouded by the fact that, often, only indirect evidence remains for their occurrence. This arises from the tendency for the vapour phase to escape from the condensed phase with which it interacts, owing to its much lower density and thus greater volume. For a gas that is sufficiently tenuous that interactions do not occur between its constituent molecules, this relationship is quantified in the ideal gas law (Clapeyron 1834): $PV=nRT$ (1) where $P$ is the total pressure exerted by the gas, $V$ its volume, $n$ is the number of moles, $R$ the gas constant 8.3145 $Jmol^{-1}K^{-1}$, Horstmann, 1873) and $T$ the absolute temperature. One mole of an ideal gas at 273.15 $K$ and $10^5$ $Pa$ (standard temperature and pressure for gases) has a molar volume of 22,711 $cm^3/mol$, $10^3$ x greater than typical silicate liquids or minerals. As a result, vaporisation processes in nature are often informed by chemical and textural evidence remaining in the condensed phase.Comment: 95 pages 19 figures 5 table

Refined separation of combined Fe-Hf from rock matrices for isotope analyses using AG-MP-1M and Ln-Spec chromatographic extraction resins

A combined procedure for separating Fe and Hf from a single rock digestion is presented. In a two-stage chromatographic extraction process, a purified Fe fraction is first quantitatively separated from the rock matrix using AG-MP-1M resin in HCl. Hafniu

Iron isotopic evidence for convective resurfacing of recycled arc-front mantle beneath back-arc basins

Geophysical observations suggest sub-arc convective flow transports melt-exhausted and metasomatized wedge mantle into deeper mantle regions. Reciprocally, asthenospheric, fertile mantle may supply back-arc ridges distal to the trench by shallow, latera

Retention of water in terrestrial magma oceans and carbon-rich early atmospheres

Massive steam and CO$_2$ atmospheres have been proposed for magma ocean outgassing of Earth and terrestrial planets. Yet formation of such atmospheres depends on volatile exchange with the molten interior, governed by volatile solubilities and redox reactions. We determine the evolution of magma ocean--atmosphere systems for a range of oxygen fugacities, C/H ratios and hydrogen budgets that include redox reactions for hydrogen (H$_2$--H$_2$O), carbon (CO--CO$_2$), methane (CH$_4$), and solubility laws for H$_2$O and CO$_2$. We find that small initial budgets of hydrogen, high C/H ratios, and oxidizing conditions, suppress outgassing of hydrogen until the late stage of magma ocean crystallization. Hence early atmospheres in equilibrium with magma oceans are dominantly carbon-rich, and specifically CO-rich except at the most oxidizing conditions. The high solubility of H$_2$O limits its outgassing to melt fractions below $\sim$30\%, the fraction at which the mantle transitions from vigorous to sluggish convection with melt percolation. Sluggish melt percolation could enable a surface lid to form, trapping water in the interior and thereby maintaining a carbon-rich atmosphere (equilibrium crystallization). Alternatively, efficient crystal settling could maintain a molten surface, promoting a transition to a water-rich atmosphere (fractional crystallization). However, additional processes, including melt trapping and H dissolution in crystallizing minerals, further conspire to limit the extent of H outgassing, even for fractional crystallization. Hence, much of the water delivered to planets during their accretion can be safely harbored in their interiors during the magma ocean stage, particularly at oxidizing conditions.Comment: 35 pages, 16 figures, accepted version in The Planetary Science Journa

VapoRock: Thermodynamics of vaporized silicate melts for modeling volcanic outgassing and magma ocean atmospheres

Silicate vapors play a key role in planetary evolution, especially dominating early stages of rocky planet formation through outgassed magma ocean atmospheres. Our open-source thermodynamic modeling software "VapoRock" combines the MELTS liquid model (Ghiorso et al., 1995) with gas-species properties from multiple thermochemistry tables (e.g., Chase et al., 1998). VapoRock calculates the partial pressures of 34 gaseous species in equilibrium with magmatic liquid in the system Si-Mg-Fe-Al-Ca-Na-K-Ti-Cr-O at desired temperatures and oxygen fugacities (fO2, or partial pressure of O2). Comparison with experiments shows that pressures and melt-oxide activities (which vary over many orders of magnitude) are reproduced to within a factor of ~3, consistent with measurement uncertainties. We also benchmark the model against a wide selection of igneous rock compositions including bulk silicate Earth, predicting elemental vapor abundances that are comparable (Na, Ca, & Al) or more realistic (K, Si, Mg, Fe, & Ti) than those of the closed-source MAGMA code (with maximum deviations by factors of 10-300 for K & Si). Vapor abundances depend critically on the activities of liquid components. The MELTS model underpinning VapoRock was calibrated and extensively tested on natural igneous liquids. In contrast, MAGMA's liquid model assumes ideal mixtures of a limited set of chemically simplified pseudo-species, which only roughly approximates the non-ideal compositional interactions typical of many-component natural silicate melts. Finally, we explore how relative abundances of SiO and SiO2 provide a spectroscopically measurable proxy for oxygen fugacity in devolatilized exoplanetary atmospheres, potentially constraining fO2 in outgassed exoplanetary mantles

The effect of a small amount of hydrogen in the atmosphere of ultrahot magma-ocean planets: atmospheric composition and escape

Here we investigate how small amounts of hydrogen (much smaller than the mass of the exoplanet) above a magma ocean on a rocky exoplanet may modify the atmospheric chemistry and atmospheric escape.We use a chemical model of a magma ocean coupled to a gas equilibrium code. An energy-limited model is used to compute atmospheric escape. The composition of the vapor above a magma ocean is drastically modified by hydrogen, even for very modest amounts of H ($\ll 10^{-6}$ planetary mass). Hydrogen consumes much of the O$_2$(g), which, in turn, promotes the evaporation of metals and metal oxides (SiO, Mg, Na, K, Fe) from the magma ocean. Vast amounts of H$_2$O are produced by the same process. At high hydrogen pressures, new hydrogenated species such as SiH$_4$ form in the atmosphere. In all cases, H, H$_2$, and H$_2$O are the dominant nonmetal-bearing volatile species. Sodium is the dominant atmospheric metal-bearing species at T$<$ 2000K and low H content, whereas Fe is dominant at high H content and low temperature, while SiO predominates at T>3000 K. We find that the atmospheric Mg/Fe, Mg/Si, and Na/Si ratios deviate from those in the underlying planet and from the stellar composition. As such, their determination may constrain the planet's mantle composition and H content. As the presence of hydrogen promotes the evaporation of silicate mantles, it is conceivable that some high-density, irradiated exoplanets may have started life as hydrogen-bearing planets and that part of their silicate mantle evaporated (up to a few $10 \%$ of Si, O, and Fe) and was subsequently lost owing to the reducing role of H. Even very small amounts of H can alter the atmospheric composition and promote the evaporation to space of heavy species derived from the molten silicate mantle of rocky planets.Comment: Accepted for publication in A&

Atomic structure and physical properties of peridotite glasses at 1 bar

Earth’s mantle, whose bulk composition is broadly peridotitic, likely experienced periods of extensive melting in its early history that formed magma oceans and led to its differentiation and formation of an atmosphere. However, the physical behaviour of magma oceans is poorly understood, as the high liquidus temperatures and rapid quench rates required to preserve peridotite liquids as glasses have so far limited their investigation. In order to better characterize the atomic structure and estimate the physical properties of such glasses, we examined the Raman spectra of quenched peridotite melts, equilibrated at 1900 °C ± 50 °C at ambient pressure under different oxygen fugacities (fO2), from 1.9 log units below to 6.0 log units above the Iron-Wüstite buffer. Fitting the spectra with Gaussian components assigned to different molecular entities (Q-species) permits extraction of the mean state of polymerisation of the glass. We find that the proportions of Q1 (0.36–0.32), Q2 (0.50–0.43), and Q3 (0.16–0.23) vary with Fe3+/FeTOT (FeTOT = Fe2+ + Fe3+), where increasing Fe3+/FeTOT produces an increase in Q3 at the expense of Q2 at near-constant Q1. To account for the offset between Raman-derived NBO/T (2.06–2.27) with those determined by assuming Fe2+ exists entirely as a network modifier and Fe3+ a network former (2.10–2.44), ∼2/3 of the ferric iron and ∼90% of the ferrous iron in peridotite glasses must behave as network modifiers. We employ a deep neural network model, trained to predict alkali and alkaline-earth aluminosilicate melts properties, to observe how small variations in the atomic structure of peridotite-like melts affect their viscosity. For Fe-free peridotite-like melts, the model yields a viscosity of ∼ −1.75 log Pa s at 2000 °C, similar to experimental determinations for iron-bearing peridotite melts. The model predicts that changes in the peridotite melt atomic structure with Fe3+/FeTOT yield variations in melt viscosity lower than 0.1 log Pa s, barely affecting the Rayleigh number. Therefore, at the high temperatures typical of magma oceans, at least at 1 bar, small changes in melt structure from variations in oxidation state are unlikely to affect magma ocean fluid dynamics

Late delivery of exotic chromium to the crust of Mars by water-rich carbonaceous asteroids.

The terrestrial planets endured a phase of bombardment following their accretion, but the nature of this late accreted material is debated, preventing a full understanding of the origin of inner solar system volatiles. We report the discovery of nucleosynthetic chromium isotope variability (μ54Cr) in Martian meteorites that represent mantle-derived magmas intruded in the Martian crust. The μ54Cr variability, ranging from -33.1 ± 5.4 to +6.8 ± 1.5 parts per million, correlates with magma chemistry such that samples having assimilated crustal material define a positive μ54Cr endmember. This compositional endmember represents the primordial crust modified by impacting outer solar system bodies of carbonaceous composition. Late delivery of this volatile-rich material to Mars provided an exotic water inventory corresponding to a global water layer >300 meters deep, in addition to the primordial water reservoir from mantle outgassing. This carbonaceous material may also have delivered a source of biologically relevant molecules to early Mars

Extensive crustal extraction in Earth’s early history inferred from molybdenum isotopes

Estimates of the volume of the earliest crust based on zircon ages and radiogenic isotopes remain equivocal. Stable isotope systems, such as molybdenum, have the potential to provide further constraints but remain underused due to the lack of complementarity between mantle and crustal reservoirs. Here we present molybdenum isotope data for Archaean komatiites and Phanerozoic komatiites and picrites and demonstrate that their mantle sources all possess subchondritic signatures complementary to the superchondritic continental crust. These results confirm that the present-day degree of mantle depletion was achieved by 3.5 billion years ago and that Earth has been in a steady state with respect to molybdenum recycling. Mass balance modelling shows that this early mantle depletion requires the extraction of a far greater volume of mafic-dominated protocrust than previously thought, more than twice the volume of the continental crust today, implying rapid crustal growth and destruction in the first billion years of Earth’s history

On the iron isotope composition of Mars and volatile depletion in the terrestrial planets

Iron is the most abundant multivalent element in planetary reservoirs, meaning its isotope composition (expressed as δ57Fe) may record signatures of processes that occurred during the formation and subsequent differentiation of the terrestrial planets. Chondritic meteorites, putative constituents of the planets and remnants of undifferentiated inner solar system bodies, have δ57Fe ≈ 0‰; an isotopic signature shared with the Martian Shergottite–Nakhlite–Chassignite (SNC) suite of meteorites. The silicate Earth and Moon, as represented by basaltic rocks, are distinctly heavier, δ57Fe≈+0.1‰. However, some authors have recently argued, on the basis of iron isotope measurements of abyssal peridotites, that the composition of the Earth’s mantle is δ57Fe = +0.04 ± 0.04‰, indistinguishable from the mean Martian value. To provide a more robust estimate for Mars, we present new high-precision iron isotope data on 17 SNC meteorites and 5 mineral separates. We find that the iron isotope compositions of Martian meteorites reflect igneous processes, with nakhlites and evolved shergottites displaying heavier δ57Fe(+0.05 ± 0.03‰), whereas MgO-rich rocks are lighter (δ57Fe≈−0.01 ±0.02‰). These systematics are controlled by the fractionation of olivine and pyroxene, attested to by the lighter isotope composition of pyroxene compared to whole rock nakhlites. Extrapolation of the δ57Fe SNC liquid line of descent to a putative Martian mantle yields a δ57Fe value lighter than its terrestrial counterpart, but indistinguishable from chondrites. Iron isotopes in planetary basalts of the inner solar system correlate positively with Fe/Mn and silicon isotopes. While Mars and IV-Vesta are undepleted in iron and accordingly have chondritic δ57Fe, the Earth experienced volatile depletion at low (1300 K) temperatures, likely at an early stage in the solar nebula, whereas additional post-nebular Fe loss is possible for the Moon and angrites