Determination of Rare Earth Element Isotopic Compositions Using Sample-Standard Bracketing and Double-Spike Approaches.

Rare earth elements (REEs) have been found to have numerous uses to trace geological and cosmochemical processes through analyses of elemental patterns, radioactive decay, nucleosynthetic anomalies, and cosmogenic effects. Stable isotopic fractionation is one aspect of REE geochemistry that has been seldom studied, with most publications focusing on the development of analytical methodologies for individual REEs, and most applications concerning terrestrial igneous rocks. In this study, we present a method to systematically analyze stable isotopic fractionations of 8 REEs, including Ce, Nd, Sm, Eu, Gd, Dy, Er, and Yb, using sample-standard bracketing (SSB) and double-spike (DS) approaches. All REEs are separated and purified using a fluoropolymer pneumatic liquid chromatography (FPLC) system. We introduce procedures for identifying and correcting some isobaric interferences in double-spike data reduction. Several geostandards, including igneous rocks and sediments, are analyzed using SSB and DS methods. The results indicate that REE isotopic fractionation in igneous processes is limited, except for Eu. Other REEs can still be isotopically fractionated by low-temperature processes and kinetic effects at a high temperature.

Imprint of chondrule formation on the K and Rb isotopic compositions of carbonaceous meteorites.

Chondrites display isotopic variations for moderately volatile elements, the origin of which is uncertain and could have involved evaporation/condensation processes in the protoplanetary disk, incomplete mixing of the products of stellar nucleosynthesis, or aqueous alteration on parent bodies. Here, we report high-precision K and Rb isotopic data of carbonaceous chondrites, providing new insights into the cause of these isotopic variations. We find that the K and Rb isotopic compositions of carbonaceous chondrites correlate with their abundance depletions, the fractions of matrix material, and previously measured Te and Zn isotopic compositions. These correlations are best explained by the variable contribution of chondrules that experienced incomplete condensation from a supersaturated medium. From the data, we calculate an average chondrule cooling rate of ~560 ± 180 K/hour, which agrees with values constrained from chondrule textures and could be produced in shocks induced by nebular gravitational instability or motion of large planetesimals through the nebula.

Iron isotopic fractionation between silicate mantle and metallic core at high pressure.

The +0.1‰ elevated 56Fe/54Fe ratio of terrestrial basalts relative to chondrites was proposed to be a fingerprint of core-mantle segregation. However, the extent of iron isotopic fractionation between molten metal and silicate under high pressure-temperature conditions is poorly known. Here we show that iron forms chemical bonds of similar strengths in basaltic glasses and iron-rich alloys, even at high pressure. From the measured mean force constants of iron bonds, we calculate an equilibrium iron isotope fractionation between silicate and iron under core formation conditions in Earth of ∼0-0.02‰, which is small relative to the +0.1‰ shift of terrestrial basalts. This result is unaffected by small amounts of nickel and candidate core-forming light elements, as the isotopic shifts associated with such alloying are small. This study suggests that the variability in iron isotopic composition in planetary objects cannot be due to core formation.