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Tellurium stable isotope compositions and abundances (δ128/126Te relative to SRM 3156) are reported for 43 ordinary, enstatite, and Rumuruti chondrites, which together with results from a companion study on carbonaceous chondrites are used to assess the origin of volatile element fractionations in chondrites. Whereas Te isotope variations among carbonaceous chondrites predominantly reflect mixing between isotopically light chondrules/chondrule precursors and CI-like matrix, Te isotope variations among non-carbonaceous chondrites mainly result from Te redistribution during parent body thermal metamorphism. The enstatite chondrites in particular display increasingly heavy Te isotopic compositions and decreasing Te concentrations with increasing degree of metamorphism, indicating migration of isotopically light Te from the strongly metamorphosed inner parts towards the cooler outer regions of the parent bodies. By contrast, ordinary and Rumuruti chondrites display less systematic Te isotope variations, implying more localized redistribution of Te during parent body thermal metamorphism. We also report Te stable isotope data for 19 terrestrial mantle-derived rocks. Peridotites with Al2O3 contents close to those inferred for the bulk silicate Earth (BSE) exhibit uniform δ128/126Te values, which we interpret to represent the Te isotopic composition of the BSE. This composition overlaps with the Te isotope composition of some volatile-rich carbonaceous chondrites (most notably CM chondrites), but also with that of enstatite chondrites. Comparison of the Te results to Se isotopes and Se/Te ratios shows that due to uncertainties in the composition of the BSE and the isotopic composition of bulk chondrite parent bodies, neither Te isotopes alone nor the combined Se-Te elemental and isotopic systematics can distinguish between a carbonaceous and enstatite chondrite-like late veneer, which is the presumed source of Se and Te in the BSE. Together, the results of this study illustrate that the relative abundances and mass-dependent isotope compositions of volatile elements like Se and Te are modified by physical and chemical processes occurring after planetary accretion, which severely complicates their use as genetic tracers. A corollary of this is that contrary to prior proposals the Se-Te systematics are not contradicting an inner solar system origin of the late veneer, as it has been inferred using nucleosynthetic isotope anomalies of other elements.

Primitive achondrites derive from the residual mantle of incompletely differentiated planetesimals, from which partial silicate and metallic melts were extracted. As such, primitive achondrites are uniquely useful to examine the early stages of planetesimal melting and differentiation. To better understand this early melting and melt segregation as well as the nature of the melts involved, we obtained mass-dependent Ru isotopic compositions of 17 primitive achondrites, including winonaites, acapulcoite-lodranites, ureilites, brachinites, and two ungrouped samples. Most primitive achondrites with subchondritic Ru concentrations are characterized by heavy Ru isotopic compositions relative to chondrites, likely reflecting the extraction of isotopically light partial metallic melts. While the segregation of early-formed partial Fe-Ni-S melts likely had no effect on the Ru isotope compositions, the subsequent extraction of S-free partial metallic melts at higher temperatures provides a viable mechanism for producing the observed Ru isotopic fractionation and fractionated highly siderophile element ratios among primitive achondrites. Together, these observations indicate that differentiation of primitive achondrite parent bodies involved the segregation of distinct partial metallic melts over a range of temperatures, and that these melts ultimately formed a partial core with fractionated and light Ru isotopic composition. This contrasts with the unfractionated Ru isotope signatures previously estimated for bulk iron meteorite cores, which therefore indicates quantitative metal segregation during core formation in the iron meteorite parent bodies. The less efficient metal segregation in primitive achondrite parent bodies most likely reflects lower initial amounts of heat-producing 26Al due to later accretion or impact disruption of the parent bodies during differentiation.

Moderately volatile elements (MVEs) are variably depleted in planetary bodies, reflecting the imprints of nebular and planetary processes. Among MVEs, Na, K, and Rb are excellent tracers for unrave...

The isotopic compositions of alkali metal elements are powerful tracers of various geological processes. Coupled K and Rb isotopic studies can potentially yield new clues on the mechanisms responsible for the depletions in moderately volatile elements in planetary objects, global surface geochemical cycles, and mechanistic aspects of water–rock interactions. Rubidium isotopic studies have however been hampered by difficulties in purifying Rb from rocks, notably due to its similar chemical behavior to K. Here we characterize the properties of three different types of resins (AMP-PAN resin; AG50W-X8 and AG50W-X12 cation-exchange resins; Sr resin) for Rb and K purification. We show that AMP-PAN resin and Sr resin can readily separate Rb from K and other matrix elements. However, AMP-PAN resin has a high Rb blank (∼80 ng) and is cumbersome to use, which limits its applicability. For cation resins, we test the effects of column length, acid molarity, temperature, pressure drop (flow rate), and resin cross-linkage on the Rb separation using a Fluoropolymer Pneumatic Liquid Chromatography (FPLC) unit built in our laboratory. Increasing column length or resin cross-linkage has a positive effect on the separation, while increasing acid molarity, temperature, or pressure drop (flow rate) has negative impacts. Gravity-driven cation-exchange resin columns fail to cleanly separate Rb from K, but an AG50W-X12 resin column of 150 cm length and 0.16 cm inner diameter installed on a FPLC unit can cleanly separate Rb from K. We separated Rb from synthetic and natural rock samples using three different purification schemes designed based on the three types of resins, and measured the Rb isotopic compositions of the Rb separates by MC-ICPMS. The three methods yielded consistent results, demonstrating the efficacy of our Rb separation and the accuracy of our Rb isotopic analyses. The Rb isotopic compositions of several geostandards were analyzed (BCR-2, BHVO-2, BE-N, AGV-2, GS-N, G-3, and G-A), which can be used in future studies for ground-truthing methodologies used for studying natural samples. Among the three methods, the Sr resin method is the most straightforward for purifying Rb and K simultaneously, and measuring their isotopic compositions in natural samples.

Description, Potassium and rubidium isotopes reveal the cause for the depletion of moderately volatile elements in planetary building blocks., 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.

International audience; To improve the understanding of large-scale planetary processes, i.e. differentiation and core formation, of Earth and other planetary bodies, we performed experiments at 1 GPa in a range of 2 temperatures to investigate mass-dependent isotope fractionation of ruthenium (Ru) between metal, silicate, and sulfide melts. Metal silicate fractionation is Ru/ 99 Rusilicate-102 Ru/ 99 Rumetal = 0.02 ± 0.02 ‰ (95% confidence interval) at °C and therefore negligible for Earth's core formation. However, there is resolvable Ru isotope fractionation between liquid metal and liquid sulfide: The 102 Ru/ 99 Ru ratio of liquid sulfide is 0.11 ± 0.03 ‰ lighter than that of liquid metal at 1400 °C in sulfur (S)-bearing experiments. The unexpected lighter Ru isotope composition of the sulfide can be best explained with different Ru-S bonding environments. Our results show furthermore, that addition of tin (Sn) instead of S to experimental charges affects Ru isotope fractionation significantly. The 102 Ru/ 99 Ru ratios in the Sn-bearing phase are 0.18 ‰ ± 0.01 ‰ heavier than metal; hence, the presence of Sn not only changes the magnitude of the Ru isotope fractionation but also its direction. The observed Ru isotope fractionations are too small to preserve a resolvable isotope fractionation signature during core formation or the Hadean matte scenario at very high temperatures.

Nucleosynthetic Fe isotopic anomalies in meteorites may be used to reconstruct the early dynamical evolution of the solar system and to identify the origin and nature of the material that built planets. Using high-precision iron isotopic data of 23 iron meteorites from nine major chemical groups we show that all iron meteorites show the same fundamental dichotomy between non-carbonaceous (NC) and a carbonaceous (CC) meteorites previously observed for other elements. The Fe isotopic anomalies are predominantly produced by variation in 54Fe, where all CC iron meteorites are characterized by an excess in 54Fe relative to NC iron meteorites. This excess in 54Fe is accompanied by an excess in 58Ni observed in the same CC meteorite groups. Together, these overabundances of 54Fe and 58Ni are produced by nuclear statistical equilibrium either in type Ia supernovae or in the Si/S shell of core-collapse supernovae. The new Fe isotopic data reveal that Earth's mantle plots on or close to correlations defined by Fe, Mo, and Ru isotopic anomalies in iron meteorites, indicating that throughout Earth's accretion, the isotopic composition of its building blocks did not drastically change. While Earth's mantle has a similar Fe isotopic composition to CI chondrites, the latter are clearly distinct from Earth's mantle for other elements (e.g., Cr and Ni) whose delivery to Earth coincided with Fe. The fact that CI chondrites exhibit large Cr and Ni isotopic anomalies relative to Earth's mantle, therefore, demonstrates that CI chondrites are unlikely to have contributed significant Fe to Earth., Comment: 1 Table, 9 Figures

International audience; Magmatic differentiation produces positive correlations between δ49Ti and SiO2. The equilibrium Ti isotope fractionation factors of Ti-bearing minerals are essential for understanding the mechanisms driving this isotopic fractionation. We present ab initio-derived mean force constants of Ti-bearing minerals (barium orthotitanate, potassium titanium oxide, fresnoite, diopside, geikielite, karrooite, titanite, pseudobrookite, anatase, and titanium oxide) based on density functional theory (DFT) to calculate equilibrium isotopic fractionation factors. We find that the main driver for Ti isotopic fractionation is its coordination, with four-, five-, and sixfold-coordinated Ti characterized by mean force constants of 547, 462, and 310 N/m, respectively. The coordination number of Ti in silicate melts is thought to be lower than in minerals, driving magmas toward higher δ49Ti values by fractional crystallization. The mineral-melt fractionation factors allow modeling of the observed Ti isotope trends in tholeiitic and calc-alkaline rocks. Our model results indicate that to first order, the steeper δ49Ti trend observed in tholeiitic versus calc-alkaline magmas is most likely due to enhanced removal of Ti into sequestered minerals at low SiO2 concentration in tholeiitic series compared to calc-alkaline series. The δ49Ti–SiO2 differentiation trends, however, depend on Ti coordination in the melt and the strengths of Ti bonds in diverse Fe- and Ti-oxides, which are still uncertain. Our results show that Ti isotopes can be used to reconstruct the crystallization history and identify the magmatic series parentage of magmas that otherwise lack context, but further work is needed to identify the drivers behind Ti isotopic fractionation in igneous rocks.

Compared to the composition of CI chondrites and the Sun, all other carbonaceous chondrites are variably depleted in volatile elements. However, the origin of these depletions, and how they are related to volatile loss during high-temperature processes within the solar nebula, are unclear. To better understand the processes that caused volatile element fractionations among carbonaceous chondrites, we obtained mass-dependent Te isotopic compositions and Te concentrations for a comprehensive set of samples from the major carbonaceous chondrite groups. The chondrites exhibit well-resolved inter-group Te isotope variations towards lighter isotopic compositions for increasingly volatile-depleted samples. The Te isotopic compositions and concentrations are also correlated with the mass fraction of matrix and with nucleosynthetic e 54 Cr anomalies. Combined, these correlations indicate mixing between volatile-rich, isotopically heavy, and 54Cr-rich CI-like matrix with volatile-poor, isotopically light, and 54Cr-poorer chondrules or chondrule precursors. The Te-Cr isotopic correlation suggests that all carbonaceous chondrites contain CI-like matrix, and that chondrules and this CI-like matrix formed from isotopically distinct material originating from different regions of the disk. The only samples plotting off the Te-Cr correlation are CR chondrites, indicating that CR chondrules formed from different precursor material than chondrules from other carbonaceous chondrites, either because they formed at greater heliocentric distance and/or at a later time. Plots of volatile element abundances versus matrix mass fraction reveal that chondrules/chondrule precursors display CI-chondritic ratios for volatile elements with 50% condensation temperatures below ∼750 K, with an overall abundance of ∼0.13 × CI. Mixing between these two components, therefore, naturally results in CI-like ratios for these elements in all carbonaceous chondrites, in spite of different degrees of volatile depletion. A corollary of this observation is that the CI-like ratios of volatile elements in the bulk silicate Earth may result from the accretion of volatile-depleted materials and do not require accretion of CI chondrites themselves.

Understanding the circumstances of the undeclared 2017 nuclear release of ruthenium that led to widespread detections of the radioisotope 106Ru in the Eurasian region, and whether it derives from a civilian or military source, is of major importance for society and future improvements in nuclear safety. Until now, the released nuclear material has merely been studied by analyzing short-lived radioisotopes. Here, we report precise measurements of the stable isotopic composition of ruthenium captured in air filters before, during, and after the nuclear release, and find that the ruthenium collected during the period of the 2017 nuclear release has a non-natural isotopic composition. By comparing our results with ruthenium isotopic compositions of spent nuclear fuels, we show that the release is consistent with the isotopic fingerprints of a civilian Russian water-water energetic reactor (VVER) fuel at the end of its lifetime, and is not related to the production of plutonium for nuclear weapons., A cloud of enhanced ruthenium concentrations has been observed over Europe in 2017, but no country has acknowledged responsibility for this nuclear release. Here, the authors show that the stable isotopic composition of ruthenium emitted from nuclear fuel reprocessing during the 2017 event is consistent with the isotopic signature of civilian Russian nuclear reactor fuel.

Elevated abundances of highly siderophile elements in Earth's mantle are thought to reflect the late accretion of primitive material after the cessation of core formation, but the origin of this material, and whether or not it can be linked to specific types of meteorites remain debated. Here, mass-dependent Ru isotopic data for chondrites and terrestrial peridotites are reported to evaluate the chemical nature and type of the late-accreted material. After correction for nucleosynthetic Ru isotope anomalies, enstatite, ordinary and carbonaceous chondrites all have indistinguishable mass-dependent Ru isotopic compositions. Thus, neither distinct formation conditions in the solar nebula nor parent body processes resulted in significant mass-dependent Ru isotope fractionation. All five terrestrial peridotites analyzed have mass-dependent Ru isotopic compositions that are indistinguishable from each other and from the composition of chondrites. The chondritic mass-dependent Ru isotopic composition of Earth's mantle is difficult to reconcile with prior suggestions that the late accretionary assemblage was a mixture of chondrites with a chemically evolved metal component. Although this mixture can reproduce the suprachondritic Ru/Ir inferred for Earth's mantle, it consistently predicts a heavy Ru isotopic composition of Earth's mantle with respect to chondrites. This is because metal components with elevated Ru/Ir are also enriched in heavy Ru isotopes, resulting from isotope fractionation during core crystallization. Thus, if late accretion involved impacts of differentiated protoplanetary bodies, then the projectile cores must have been either homogenized upon impact, or added to Earth's mantle completely, because otherwise Earth's mantle would have inherited a non-chondritic mass-dependent Ru isotopic composition from the unrepresentative sampling of core material.

Mass-dependent Ru isotope variations (δ102/99Ru) and Ru concentrations were determined for 35 magmatic iron meteorites from the five major chemical groups (IIAB, IID, IIIAB, IVA, IVB). In addition, four equilibrated ordinary chondrites were analyzed. The IIAB, IIIAB and IVB iron meteorites display increasingly heavier Ru isotopic compositions with decreasing Ru content. Modeling demonstrates that the trends for these three iron groups can be reproduced by the incremental extraction of isotopically lighter Ru into solids, which leads to progressively heavier δ102/99Ru in the remaining melt. The modeling further shows that the Ru isotopic variations of the IIAB and IIIAB irons are consistent with derivation from parental melts with an ordinary chondrite-like δ102/99Ru, whereas the IVB irons more likely derive from a melt with heavier δ102/99Ru. This heavy Ru isotopic composition of the IVB parental melt probably results from high-temperature processing of the IVB precursor material. The Ru isotope systematics of the IID and IVA irons are more complex and show no correlation between δ102/99Ru and Ru content. Although most samples exhibit heavy Ru isotopic compositions, especially the late-crystallized irons of these groups deviate from the expected fractional crystallization trends. This deviation most likely results from mixing and re-equilibration of early-crystallized solids and late-stage liquids, followed by further fractional crystallization. The mixing might be related to the migration of liquids through a complex network of dendrites or to the overturn of a cumulate inner core, and bears testimony to the complex solidification history of at least some protoplanetary cores.

Nanoscale amorphous silicates are a major component in primitive carbonaceous chondrite matrices and anhydrous interplanetary dust particles. Owing to their metastability and sensitive response to reactions with water, this material is of particular interest in understanding nebular and parent body processes in the early solar system. Here we investigated the amorphous silicate matrix (ASM) in the ungrouped carbonaceous chondrite Acfer 094 regarding its texture, chemical composition, and Fe oxidation state. We applied transmission electron microscopy techniques on six, focused ion beam technique-prepared, electron-transparent lamellae of Acfer 094 to determine the textures of this material. Furthermore, we used energy-dispersive X-ray analysis and electron energy loss spectroscopy to quantify the Fe content and the Fe oxidation state of the ASM. Textural investigations reveal differences in sulfide content, porosity, and distribution of the ASM among the samples, as well as evidence for rare recrystallization of phyllosilicate fibers. The chemical composition reveals mobilization of Fe. Furthermore, the determined Fe3+/ΣFe ratios of the ASM in the six samples display a homogeneously high oxidation state (0.66–0.73). This high and homogeneous Fe oxidation state in the ASM of Acfer 094 disagrees with its formation as a primary phase in a reduced solar gas and must have been induced in a later stage process. Most likely, this process was aqueous alteration on the Acfer 094 parent body, which led to hydration and oxidation of the ASM, which is supported by textural and chemical evidence of aqueous alteration.

Doped ceria pellets with a nominal dopant concentration of 1, 2, 5, and 10 mol-% Sb were produced via a mixed-oxide route from CeO2-δ and Sb2O3. From literature, it is known that an oxidation of the Sb2O3 compound to α-Sb2O4 takes place above 1123 K or, respectively, an oxidation to Sb6O13 takes place in the range between 973 and 1173 K, so that Sb3+ as well as Sb5+ could be present in a sample according to heat pretreatment. Samples were sintered at 1123 K and 1473 K. Oxygen partial pressure-dependent measurements of the electron conductivity were executed using a Hebb-Wagner type polarization technique with an ion blocking microcontact completed by total conductivities from impedance spectroscopy in air. 121Sb-Mossbauer spectroscopy of the 10 mol-% doped samples show the presence of Sb5+ for low as well as high sintering temperatures. The high electronic conductivities after high temperature treatment can only be explained by pentavalent Sb which acts as a donor substituting Ce4+. A switch from acceptor to donor type conducting behavior as a function of high temperature treatment becomes especially obvious in the 1 mol-% doped sample, while for the nominally 10 mol-% doped sample for both sintering temperatures, a comparable oxygen partial pressure dependence of the electron conductivity was found. Impedance spectroscopy and Hebb-Wagner measurements show a good accordance of bulk conductivity and electron conductivity for the donor doped samples, whereas the ionic conductivity is comparably small.

We developed a new technique for precise measurements of ruthenium (Ru) stable isotope compositions by multiple-collector inductively coupled plasma mass spectrometry (MC-ICPMS). Instrumental mass bias and potential isotope fractionation induced during the chemical purification of Ru were corrected using a 98Ru–101Ru double spike added prior to sample digestion. The separation and purification of Ru from natural samples is achieved by cation exchange chromatography followed by distillation of Ru as volatile oxides. A series of analytical tests demonstrates that this method results in very pure Ru cuts and accurate and reproducible Ru isotope measurements. The Ru isotope results are expressed relative to an Alfa Aesar™ Ru standard solution as the permil deviations of the 102Ru/99Ru ratio (δ102/99Ru). The external reproducibility (2 s.d.) of the entire analytical procedure (including sample digestion, chemical purification and isotope measurement) that has been determined using several doped terrestrial rock standards is 0.05‰ for δ102/99Ru. We obtained Ru stable isotope data for three different Ru standard solutions and five chromitite samples from two different localities in the Shetland Ophiolite Complex and from the Bushveld complex. All three standard solutions are isotopically distinct with δ102/99Ru values up to ca. 0.9‰. The different chromitite samples also show different Ru stable isotope compositions with δ102/99Ru values between ca. 0.2‰ and ca. 0.7‰. These natural Ru stable isotope variations can be readily resolved using the 98Ru–101Ru double spike method presented here. Overall, these data show that Ru stable isotopes hold promise as a tracer of a wide range of geochemical and cosmochemical processes.

The Mo and Ru isotopic compositions of meteorites and the bulk silicate Earth (BSE) hold important clues about the provenance of Earth's building material. Prior studies have argued that non-carbonaceous (NC) and carbonaceous (CC) meteorite groups together define a Mo-Ru ‘cosmic’ correlation, and that the BSE plots on the extension of this correlation. These observations were taken as evidence that the final 10–15% of Earth's accreted material derived from a homogeneous inner disk reservoir with an enstatite chondrite-like isotopic composition. Here, using new Mo and Ru isotopic data for previously uninvestigated meteorite groups, we show that the Mo-Ru correlation only exists for NC meteorites, and that both the BSE and CC meteorites fall off this Mo-Ru correlation. These observations indicate that the final stages of Earth's accretion were heterogeneous and consisted of a mixture of NC and CC materials. The Mo-Ru isotope systematics are best accounted for by either an NC heritage of the late veneer combined with a CC heritage of the Moon-forming giant impactor, or by mixed NC-CC compositions for both components. The involvement of CC bodies in the late-stage accretionary assemblage of Earth is consistent with chemical models for core-mantle differentiation, which argue for the addition of more oxidized and volatile-rich material toward the end of Earth's formation. As such, this study resolves the inconsistencies between homogeneous accretion models based on prior interpretations of the Mo-Ru systematics of meteorites and the chemical evidence for heterogeneous accretion of Earth.