Abstract Planetary formation involves highly energetic collisions, the consequences of which set the stage for the ensuing planetary evolution. During accretion, Earth's mantle was largely molten, a so‐called magma ocean, and its oxidation state was determined by equilibration with metal‐rich cores of infalling planetesimals through redox buffering reactions. We test two proposed mechanisms (metal layer and metal droplets) for equilibration in a magma ocean and the resulting oxidation state (Fe3+/ΣFe). Using scaling laws on convective mixing, we find that the metal layer could promote oxidation of a magma ocean, but this layer is too short‐lived to reproduce present‐day mantle Fe3+/ΣFe (2%–6%). Metal droplets produced by the fragmentation of impactor cores can also promote oxidation of a magma ocean. We use Monte Carlo sampling on two possible accretion scenarios to determine the likely range of oxidation states by metal droplets. We find that equilibration between silicate and metal droplets tends toward higher mantle Fe3+/ΣFe than presently observed. To achieve present‐day mantle Fe3+/ΣFe and maintain the degree of equilibration suggested by Hf‐W and U‐Pb systematics (30%–70%), the last (Moon‐forming) giant impact likely did not melt the entire mantle, therefore leaving the mantle stratified in terms of oxidation state after main accretion completes. Furthermore, late accretion impacts during the Hadean (4.5–4.0 Ga) could generate reduced domains in the shallow upper mantle, potentially sustaining surface environments conducive for prebiotic chemistry.
more »
« less
Ferric iron stabilization at deep magma ocean conditions
Fe2O3produced in a deep magma ocean in equilibrium with core-destined alloy sets the early redox budget and atmospheric composition of terrestrial planets. Previous experiments (≤28 gigapascals) and first-principles calculations indicate that a deep terrestrial magma ocean produces appreciable Fe3+but predict Fe3+/ΣFe ratios that conflict by an order of magnitude. We present Fe3+/ΣFe of glasses quenched from melts equilibrated with Fe alloy at 38 to 71 gigapascals, 3600 to 4400 kelvin, analyzed by synchrotron Mössbauer spectroscopy. These indicate Fe3+/ΣFe of 0.056 to 0.112 in a terrestrial magma ocean with mean alloy-silicate equilibration pressures of 28 to 53 gigapascals, producing sufficient Fe2O3to account for the modern bulk silicate Earth redox budget and surficial conditions near or more oxidizing than the iron-wüstite buffer, which would stabilize a primitive CO- and H2O-rich atmosphere.
more »
« less
- PAR ID:
- 10555676
- Publisher / Repository:
- Science
- Date Published:
- Journal Name:
- Science Advances
- Volume:
- 10
- Issue:
- 42
- ISSN:
- 2375-2548
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract Alkaline iron (Fe) batteries are attractive due to the high abundance, low cost, and multiple valent states of Fe but show limited columbic efficiency and storage capacity when forming electrochemically inert Fe3O4on discharging and parasitic H2on charging. Herein, sodium silicate is found to promote Fe(OH)2/FeOOH against Fe(OH)2/Fe3O4conversions. Electrochemical experiments,operandoX‐ray characterization, and atomistic simulations reveal that improved Fe(OH)2/FeOOH conversion originates from (i) strong interaction between sodium silicate and iron oxide and (ii) silicate‐induced strengthening of hydrogen‐bond networks in electrolytes that inhibits water transport. Furthermore, the silicate additive suppresses hydrogen evolution by impairing energetics of water dissociation and hydroxyl de‐sorption on iron surfaces. This new silicate‐assisted redox chemistry mitigates H2and Fe3O4formation, improving storage capacity (199 mAh g−1in half‐cells) and coulombic efficiency (94 % after 400 full‐cell cycles), paving a path to realizing green battery systems built from earth‐abundant materials.more » « less
-
Abstract 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 with gas-species properties from multiple thermochemistry tables. 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 to (Na, Ca, and Al) or more realistic than (K, Si, Mg, Fe, and Ti) those of the closed-source MAGMA code (with maximum deviations by factors of 10–300 for K and 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 pseudospecies, which only roughly approximates the nonideal compositional interactions typical of many-component natural silicate melts. Finally, we explore how relative abundances of SiO and SiO2provide a spectroscopically measurable proxy for oxygen fugacity in devolatilized exoplanetary atmospheres, potentially constrainingfO2in outgassed exoplanetary mantles.more » « less
-
Abstract The viscosity of iron alloy liquids is the key for the core dynamo and core‐mantle differentiation of terrestrial bodies. Here we measured the viscosity of Fe‐Ni‐C liquids up to 7 GPa using the floating sphere viscometry method and up to 330 GPa using first‐principles calculations. We found a viscosity increase at ∼3–5 GPa, coincident with a structural transition in the liquids. After the transition, the viscosity reaches ∼14–27 mPa·s, a factor of 2–4 higher than that of Fe and Fe‐S liquids. Our computational results from 5 to 330 GPa also indicate a high viscosity of the Fe‐Ni‐C liquids. For a carbon‐rich core in large terrestrial body, the level of turbulence in the outer core would be lessened approaching the inner core boundary. It is also anticipated that Fe‐Ni‐C liquids would percolate in Earth's deep silicate mantle at a much slower speed than Fe and Fe‐S liquids.more » « less
-
Abstract Iron ion batteries using Fe2+as a charge carrier have yet to be widely explored, and they lack high‐performing Fe2+hosting cathode materials to couple with the iron metal anode. Here, it is demonstrated that VOPO4∙2H2O can reversibly host Fe2+with a high specific capacity of 100 mAh g−1and stable cycling performance, where 68% of the initial capacity is retained over 800 cycles. In sharp contrast, VOPO4∙2H2O's capacity of hosting Zn2+fades precipitously over tens of cycles. VOPO4∙2H2O stores Fe2+with a unique mechanism, where upon contacting the electrolyte by the VOPO4∙2H2O electrode, Fe2+ions from the electrolyte get oxidized to Fe3+ions that are inserted and trapped in the VOPO4∙2H2O structure in an electroless redox reaction. The trapped Fe3+ions, thus, bolt the layered structure of VOPO4∙2H2O, which prevents it from dissolution into the electrolyte during (de)insertion of Fe2+. The findings offer a new strategy to use a redox‐active ion charge carrier to stabilize the layered electrode materials.more » « less
An official website of the United States government

