Crystal-chemical and biological controls of trace and minor element incorporation into magnetite nanocrystals

Magnetite nanoparticles possess numerous fundamental, biomedical and industrial applications, many of which depend on tuning the magnetic properties. This is often achieved by the incorporation of trace and minor elements into the magnetite lattice. Such incorporation was shown to depend strongly on the magnetite formation pathway (i.e., abiotic vs biological), but the mechanisms controlling element partitioning between magnetite and its surrounding precipitation solution remain to be elucidated. Here, we used a combination of theoretical modelling (lattice and crystal field theories) and experimental evidence (high-resolution inductively coupled plasma mass spectrometry and X-ray absorption spectroscopy) to demonstrate that element incorporation into abiotic magnetite nanoparticles is controlled principally by cation size and valence. Elements from the first series of transition metals (Cr to Zn) constituted exceptions to this finding as their incorporation appeared to be also controlled by the energy levels of their unfilled 3d orbitals, in line with crystal field mechanisms. We then show that element incorporation into biological magnetite nanoparticles produced by magnetotactic bacteria (MTB) cannot be explained by crystal-chemical parameters alone, which points to the biological control exerted by the bacteria over the element transfer between MTB growth medium and the intracellular environment. This screening effect generates biological magnetite with a purer chemical composition than the abiotic materials formed in a solution of similar composition. Our work establishes a theoretical framework for understanding the crystal-chemical and biological controls of trace and minor cation incorporation into magnetite, thereby providing predictive methods to tailor the composition of magnetite nanoparticles for improved control over magnetic properties.

Melting conditions and mantle source composition from probabilistic joint inversion of major and rare earth element concentrations

The chemical composition of erupted basalts provides a record of the thermo-chemical state of their source region and the melting conditions that lead to their formation. Here we present the first probabilistic inversion framework capable of inverting both trace and major element data of mafic volcanic rocks to constrain mantle potential temperature, depth of melting, and major and trace element source composition. The inversion strategy is based on the combination of i) a two-phase multi-component reactive transport model, ii) a thermodynamic solver for the evolution of major elements and mineral/liquid phases, (iii) a disequilibrium model of trace element partitioning and iv) an adaptive Markov chain Monte Carlo algorithm. The mechanical and chemical evolution of melt and solid residue are therefore modelled in an internally- and thermodynamically-consistent manner. We illustrate the inversion approach and its sensitivity to relevant model parameters with a series of numerical experiments with increasing level of complexity. We show the benefits and limitations of using major and trace element compositions separately before demonstrating the advantages of a joint inversion. We show that such joint inversion has great sensitivity to mantle temperature, pressure range of melting and composition of the source, even when realistic uncertainties are assigned to both data and predictions. We further test the reliability of the approach on a real dataset from a well-characterised region: the Rio Grande Rift in western North America. We obtain estimates of mantle potential temperature ($\sim$ 1340 $^o$C), lithospheric thickness ($\sim$ 60 km) and source composition that are in excellent agreement with numerous independent geochemical and geophysical estimates. In particular, this study suggests that the basalts in this region originated from a moderately hot upwelling and include the contribution from a slightly depleted source that experienced a small degree of melt or fluid metasomatism. This component is likely associated with partial melting of the lower portions of the lithosphere. The flexibility of both the melting model and inversion scheme developed here makes the approach widely applicable to assessing the thermo-chemical structure and evolution of the lithosphere-asthenosphere system and paves the way for truly joint geochemical-geophysical inversions.

Trace-Element Geochemistry of Sulfides in Upper Mantle Lherzolite Xenoliths from East Antarctica

Sulfides in upper mantle lherzolite xenoliths from Cretaceous alkaline-ultramafic rocks in the Jetty Peninsula (East Antarctica) were studied for their major and trace-element compositions using SEM and LA-ICP-MS applied in situ. Modal abundance of sulfides is the lowest in Cpx-poor lherzolites ≤ Spl-Grt lherzolites << Cpx-rich lherzolites. Most sulfides are either interstitial (i-type) or inclusions in rock-forming minerals (e-type) with minor sulfide phases mostly present in metasomatic veinlets and carbonate-silicate interstitial patches (m-type). The main sulfide assemblage is pentlandite + chalcopyrite ± pyrrhotite; minor sulfides are polydymite, millerite, violarite, siegenite, and monosulfide solution (mss). Sulfide assemblages in the xenolith matrix are a product of the subsolidus re-equilibration of primary mss at temperatures below ≤300 °C. Platinum group elements (PGE) abundances suggest that most e-type sulfides are the residues of melting processes and that the i-type sulfides are crystallization products of sulfide-bearing fluids/liquids. The m-type sulfides might have resulted from low-temperature metasomatism by percolating sulfide-carbonate-silicate fluids/melts. The PGE in sulfide record processes are related to partial melting in mantle and intramantle melt migration. Most other trace elements initially partitioned into interstitial sulfide liquid and later metasomatically re-enriched residual sulfides overprinting their primary signatures. The extent of element partitioning into sulfide liquids depends on P, T, fO2, and host peridotite composition.

Carbonate clumped isotope thermometry of fault rocks and its possibilities: tectonic implications from calcites within Himalayan Frontal Fold-Thrust Belt

Disentangling the temperature and depth of formation of fault rocks is critical for understanding their rheology, exhumation, and the evolution of fault zones. Estimation of fault rock temperatures mostly relies on conventional geothermometers of metamorphic minerals and element partitioning analysis, which are largely inapplicable in shallow crustal fault rocks. Here, we demonstrate the applicability of the carbonate clumped isotope thermometer in low-grade carbonate-bearing fault rocks from the Himalayan frontal wedge (northwest India). Coalescing carbonate clumped isotope thermometry and calcite e-twin morphology allows us to constrain the temperature and depth of formation of the two main thrusts of the Himalayan frontal wedge, the Nahan thrust (170 ± 10 °C; 6–7 km depth), and the Main Boundary thrust (262 ± 30 °C; 10–11 km depth). The integration of the adopted analytical techniques can promote the application of calcite-based clumped isotope thermometry to the fault zone processes and refinement of shallow crustal fault zone models.

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

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,DMPhaseBPhaseA (where M is the element of interest, most often reported as molar fraction), or simply DM. 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 ΔGrxn. Reactions with negative ΔGrxn 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 ΔGrxn 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.

Immiscible silicate liquids: K and Fe distribution as a test for chemical equilibrium and insight into the kinetics of magma unmixing

Silicate liquid immiscibility leading to formation of mixtures of distinct iron-rich and silica-rich liquids is common in basaltic and andesitic magmas at advanced stages of magma evolution. Experimental modeling of the immiscibility has been hampered by kinetic problems and attainment of chemical equilibrium between immiscible liquids in some experimental studies has been questioned. On the basis of symmetric regular solutions model and regression analysis of experimental data on compositions of immiscible liquid pairs, we show that liquid–liquid distribution of network-modifying elements K and Fe is linked to the distribution of network-forming oxides SiO2, Al2O3 and P2O5 by equation: $$\log K_{{\text{d}}}^{{\text{K/Fe}}} = \, 3.796\Delta X_{{{\text{SiO}}_{2} }}^{{{\text{sf}}}} + \, 4.85\Delta X_{{{\text{Al}}_{2} {\text{O}}_{3} }}^{{{\text{sf}}}} + \, 7.235\Delta X_{{{\text{P}}_{2} {\text{O}}_{5} }}^{{{\text{sf}}}} - \, 0.108,$$ log K d K/Fe = 3.796 Δ X SiO 2 sf + 4.85 Δ X Al 2 O 3 sf + 7.235 Δ X P 2 O 5 sf - 0.108 , where $$K_{{\text{d}}}^{{\text{K/Fe}}}$$ K d K/Fe is a ratio of K and Fe mole fractions in the silica-rich (s) and Fe-rich (f) immiscible liquids: $$K_{d}^{{\text{K/Fe}}} = \, \left( {X_{{\text{K}}}^{s} /X_{{\text{K}}}^{f} } \right)/ \, \left( {X_{{{\text{Fe}}}}^{s} /X_{{{\text{Fe}}}}^{f} } \right)$$ K d K/Fe = X K s / X K f / X Fe s / X Fe f and $$\Delta X_{{\text{i}}}^{sf}$$ Δ X i sf is a difference in mole fractions of a network-forming oxide i between the liquids (s) and (f): $$\Delta X_{i}^{sf} = X_{i}^{s} - X_{i}^{f}$$ Δ X i sf = X i s - X i f . We use the equation for testing chemical equilibrium in experiments not included in the regression analysis and compositions of natural immiscible melts found as glasses in volcanic rocks. Departures from equilibrium that the test revealed in crystal-rich multiphase experimental products and in natural volcanic rocks imply kinetic competition between liquid–liquid and crystal–liquid element partitioning. Immiscible liquid droplets in volcanic rocks appear to evolve along a metastable trend due to rapid crystallization. Immiscible liquids may be closer to chemical equilibrium in large intrusions where cooling rates are lower and crystals may be spatially separated from liquids.