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Element Partitioning (Mineral-Melt, Metal-/Sulfide-Silicate) in Planetary Sciences  

Brandon Mahan

Element partitioning—at its most basic—is the distribution of an element of interest between two constituent phases as a function of some process. Major constituent elements generally affect the thermodynamic environment (chemical equilibrium) and therefore trace element partitioning is often considered, as trace elements are present in minute quantities and their equilibrium exchange reactions do not impart significant changes to the larger system. Trace elements are responsive to thermodynamic conditions, and thus they act as passive tracers of chemical reactions without appreciably influencing the bulk reactions themselves. In planetary sciences, the phase pairs typically considered are mineral-melt, metal-silicate, and sulfide-silicate, owing largely to the ubiquity of their coexistence in planetary materials across scales and context, from the micrometer-sized components of meteorites up to the size of planets (thousands of kilometers). It is common to speak of trace elements in terms of their tendency toward forming metallic, sulfidic, or oxide phases, and the terms “siderophile,” “chalcophile,” and “lithophile” (respectively) are used to define these tendencies under what is known as the Goldschmidt Classification scheme. The metric of an element’s tendency to concentrate into one phase relative to another is expressed as the ratio of its concentration (as a weight or molar fraction) in one phase over another, where convention dictates the reference frame as solid over liquid, and metal or sulfide over silicate; this mathematical term is the element’s partition coefficient, or distribution coefficient, between the two respective phases, D M Phase B Phase A (where M is the element of interest, most often reported as molar fraction), or simply D M . In general, trace elements obey Henry’s Law, where the element’s activity and concentration are linearly proportional. Practically speaking, this means that the element is sufficiently dilute in the system such that its atoms interact negligibly with one another compared to their interactions with major element phases, and thus the trace element’s partition coefficient in most settings is not appreciably affected by its concentration. The radius and charge of an element’s ionized species (its ionic radius and valence state)—in relation to either the major element ion for which it is substituting or the lattice site vacancy or interstitial space it is filling—generally determine the likelihood of trace element substitution or vacancy/interstitial fill (along with the net charge of the lattice space). The key energy consideration that underlies an element’s partitioning is the Gibbs free energy of reaction between the phases involved. Gibbs free energy is the change in internal energy associated with a chemical reaction (at a given temperature and pressure) that can be used to do work, and is denoted as Δ G rxn . Reactions with negative Δ G rxn values are spontaneous, and the magnitude of this negative value for a given phase, for example, a metal oxide, denotes the relative affinity of the metal toward forming oxides. That is to say, an element with a highly negative Δ G rxn for its oxide species at relevant pressure-temperature conditions will tend to be found in oxide and silicate minerals, that is, it will be lithophile (and vice versa for siderophile elements). Trace element partitioning systematics in mineral-melt and metal-/sulfide-silicate systems have boundless applications in planetary science. A growing collective understanding of the partition coefficients of elements has been built on decades of physical chemistry, deterministic theory, petrology, experimental petrology, and natural observations. Leveraging this immense intellectual, technical, and methodological foundation, modern trace element partitioning research is particularly aimed at constraining the evolution of plate tectonics on Earth (conditions and timing of onset), understanding the formation history of planetary materials such as chondrite meteorites and their constituents (e.g., chondrules), and de-convolving the multiply operating processes at play during the accretion and differentiation of Earth and other terrestrial planets.

Article

Formation, Composition, and Evolution of the Earth’s Core  

Francis Nimmo

The Earth’s core formed by multiple collisions with differentiated protoplanets. The Hf-W (hafnium-tungsten) isotopic system reveals that these collisions took place over a timescale of tens of megayears (Myr), in agreement with accretion simulations. The degree to which the iron and silicates re-equilibrated during each collision is uncertain and affects the apparent core age derived from tungsten isotopic measurements. Seismological data reveal that the core contains light elements in addition to Fe-Ni, and the outer core is more enriched in such elements than the inner core. Because O is excluded efficiently from solid iron, O is almost certainly an important constituent of the outer core. The identity of other elements is less certain, despite intensive measurements of their effects on seismic velocities, densities, and partitioning behavior at appropriate pressures and temperatures. Si and O are very likely present, with perhaps some S; C and H are less likely. Si and Mg may have exsolved over time, potentially helping to drive the geodynamo and producing a low-density layer at the top of the core. Radioactive elements (U, Th, K) are unlikely to be present in important concentrations. The cooling of the core is controlled by the mantle’s ability to extract heat. The geodynamo has existed for at least 3.5 gigayears (Gyr), placing a lower bound on the heat flow out of the core. Because the thermal conductivity of the core is uncertain by a factor of ~3, the lower bound on this heat flow is similarly uncertain. Once the inner core started to crystallize, additional sources of energy were available to power the geodynamo. Inner core crystallization likely started in the time range 0.5 to 2.0 Gyr Before Present (BP); paleomagnetic arguments have been advanced for inner core growth starting at several different epochs within this time range.