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Presolar oxide grains have been previously divided into several groups (Group 1 to 4) based on their isotopic compositions, which can be tied to several stellar sources. Much of available data was acquired on large grains, which may not be fully representative of the presolar grain population present in meteorites. We present here new O isotopic data for 74 small presolar oxide grains (∼200 nm in diameter on average) from Orgueil and Al-Mg isotopic systematics for 25 of the grains. Based on data-model comparisons, we show that (i) Group 1 and Group 2 grains more likely originated in low-mass first-ascent (red giant branch; RGB) and/or second-ascent (asymptotic giant branch; AGB) red giant stars and (ii) Group 1 grains with (26Al/27Al)0 ⪆ 5×10−3 and Group 2 grains with (26Al/27Al)0 ⪅ 1×10−2 all likely experienced extra circulation processes in their parent low-mass stars but under different conditions, resulting in proton-capture reactions occurring at enhanced temperatures. We do not find any large 25Mg excess in Group 1 oxide grains with large 17O enrichments, which provides evidence that 25Mg is not abundantly produced in low-mass stars. We also find that our samples contain a larger proportion of Group 4 grains than so far suggested in the literature for larger presolar oxide grains (≥ 400 nm). We also discuss our observations in the light of stellar dust production mechanisms.

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.

In the modern ocean, U reduction and incorporation into anoxic sediments imparts a large isotopic fractionation of approximately +0.6‰ that shifts the seawater δ238U value (238U/235U, expressed as δ238U per mil deviation relative to CRM-112a) relative to continental runoff. Given the long residence time of U in the modern oceans (∼400 kyr), the isotopic composition of carbonates (taken as a proxy for seawater) reflects the global balance between anoxic and other sinks. The U isotopic composition of open-marine carbonates has thus emerged as a proxy for reconstructing past changes in the redox state of the global ocean. A tenet of this approach is that the δ 238U values of seawater and anoxic sediments should always be fractionated by the same amount. In order to test this hypothesis, we have measured the U concentrations and isotopic compositions of carbonates spanning ages from 3250 Ma to present. A first-order expectation for the Archean and possibly Proterozoic is that near-quantitative U removal to extensive anoxic sediments should have shifted the uranium isotopic composition of seawater and carbonates towards lower values. Instead, the measurements reveal that many Archean and Proterozoic carbonates have unfractionated δ238U values similar to those of continents and riverine runoff. These results are inconsistent with the view that the U isotopic composition of seawater simply reflects the areal extent of anoxic sediments in the past. We consider two plausible explanations for why the U isotopic composition of Archean and Proterozoic carbonates is not fractionated from the crustal and riverine composition: (1) the residence time of U could have been much shorter in the Precambrian oceans when anoxic settings were much more extensive, and (2) the process of incorporation of U into anoxic sediments in the Precambrian imparted a smaller U isotopic fractionation than in the modern because of differences in the efficiency or mechanism of uranium removal. This study highlights the challenges inherent to applying knowledge of the modern marine U isotopic cycle to periods of Earth’s history when ocean-floor anoxia was much more extended, anoxic basins were ferruginous, and atmospheric oxygen content was significantly lower than present.

Rare-earth elements (REEs) are known for their similar behaviors, which make their purification through chromatographic techniques particularly challenging. The use of α-hydroxyisobutyric acid (α-HIBA) in combination with a cation-exchange resin is perhaps the most widely used chromatographic technique to separate individual REEs from each other. However, only limited REE partition data between α-HIBA and cation resins exist, which makes it challenging to develop and optimize purification techniques using this platform. Here, we report distribution coefficients (K_d) of REEs, as well as Sr, Y, Ba, Th, and U, between α-HIBA at pH = 4.50 and AG50W-X8 cation-exchange resin, obtained by batch equilibration experiments. For all 19 elements, the distribution coefficients decrease with increasing acid concentration. For the REEs, a linear relationship is observed in log–log space between K_d values and α-HIBA molarity. While the K_d values have been calibrated at pH = 4.50, formulas are provided allowing recasting of the K_d values at any pH. To test the accuracy of the data, we compare elution curves simulated using the newly determined distribution coefficients to actual elution curves. The close agreement between simulated and experimental elution curves demonstrates that the distribution coefficients obtained in this study are effective to devise multielement extraction and purification scheme for high-precision elemental and isotopic analyses of REEs for various applications.

The compositions of the first solar system solids were shaped by nonequilibrium condensation and evaporation., Equilibrium condensation of solar gas is often invoked to explain the abundance of refractory elements in planets and meteorites. This is partly motivated, by the observation that the depletions in both the least and most refractory rare earth elements (REEs) in meteoritic group II calcium-aluminum–rich inclusions (CAIs) can be reproduced by thermodynamic models of solar nebula condensation. We measured the isotopic compositions of Ce, Nd, Sm, Eu, Gd, Dy, Er, and Yb in eight CAIs to test this scenario. Contrary to expectation for equilibrium condensation, we find light isotope enrichment for the most refractory REEs and more subdued isotopic variations for the least refractory REEs. This suggests that group II CAIs formed by a two-stage process involving fast evaporation of preexisting materials, followed by near-equilibrium recondensation. The calculated time scales are consistent with heating in events akin to FU Orionis– or EX Lupi–type outbursts of eruptive pre–main-sequence stars.

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.

The iron did it What factors controlled the accumulation of atmospheric oxygen gas (O 2 ) early in the history of Earth? Heard et al. used high-precision iron isotopic measurements of Archean-Paleoproterozoic sediments, with ages between 3.8 billion and 2.3 billion years ago, and laboratory data about synthetic pyrites to show that pyrite, or iron sulfide, burial could have resulted in net O 2 export. These reactions therefore may have contributed to early episodes of transient oxygenation before the Great Oxidation Event that began about 2.4 billion years ago. Science , this issue p. 446

Recent analytical developments have made possible the determination of the isotopic composition of tin in igneous rocks. In order to establish a framework to interpret the mass-dependent tin isotopic signatures of planetary materials, seven geologically-relevant silicate glasses (basalt, rhyolite, enstatite and anorthite glasses) were synthesized with moderate amounts of 119Sn (on the order of a weight percent). Redox conditions were controlled during sample synthesis to set the redox ratio (Sn2+/Sntot) from stannous (Sn2+) to stannic (Sn4+) glasses. The mean force constants of tin bonds in these glasses were determined by synchrotron nuclear resonant inelastic X-ray scattering (NRIXS) in order to determine the reduced isotopic partition function ratios (β-factors) of these glasses. Clues on the coordination chemistry and the valence state of tin in these glasses were also derived from synchrotron Mossbauer spectroscopy (SMS). The force constants of tin drastically increases from Sn2+-bearing to Sn4+-bearing glasses and varies significantly with the glass composition at a given redox state. The average coordination number of tin likely controls these variations with glass composition as suggested by SMS results. It is concluded that large isotope fractionation is expected between materials containing Sn2+ and Sn4+ respectively even at magmatic temperatures and that the coordination chemistry of tin in silicates strongly affect its isotope partitioning behavior. Our experimental data are finally used to interpret available Sn isotope data collected in terrestrial rocks. The incompatible behavior of Sn4+ in mantle minerals leads to a enrichment in heavy isotopes in mantle melts and to the depletion in heavy isotopes in solid residues of melting with a magnitude consistent with the isotope fractionation between Sn2+ and Sn4+ predicted by NRIXS data. Finally, we show that during fractional crystallization of basalt and considering the effect of tin coordination number in minerals and melts, the partitioning of Sn4+ into ilmenite leads to an enrichment in light isotopes in the residual melt.

Isotope anomalies among planetary bodies provide key constraints on planetary genetics and the Solar System's dynamical evolution. However, to unlock the full potential of these anomalies for constraining the processing, mixing, and transport of material in the disk it is essential to identify the main components responsible for producing planetary-scale isotope variations, and to investigate how they relate to the isotopic heterogeneity inherited from the Solar System's parental molecular cloud. To address these issues we measured the Ti and Sr isotopic compositions of Ca,Al-rich inclusions (CAIs) from the Allende CV3 chondrite, as well as acid leachates and an insoluble residue from the Murchison CM2 chondrite, and combine these results with literature data for presolar grains, hibonites, chondrules, and bulk meteorites. Our analysis reveals that the mineral-scale nebular isotopic heterogeneity as sampled by leachates and presolar grains is largely decoupled from the planetary-scale isotope anomalies. Combining isotope anomaly data for a large number of elements reveals that the difference between non-carbonaceous (NC) and carbonaceous (CC) meteorites is the product of mixing between NC material and a nebular reservoir (termed IC) whose isotopic composition is similar to that of CAIs, but whose chemical composition is similar to bulk chondrites. In our preferred model, the distinct isotopic compositions of these two nebular reservoirs reflect an inherited heterogeneity of the solar system's parental molecular cloud core, which therefore has never been fully homogenized during collapse. Planetary-scale isotopic anomalies are thus caused by variable mixing of isotopically distinct primordial disk reservoirs, the selective processing of these reservoirs in different nebular environments, and the heterogeneous distribution of the thereby forming nebular products., Accepted for publication in Geochimica et Cosmochimica Acta

Using a leaching protocol designed for the study of U isotopes in recent carbonates, we measured the U isotope composition, both ^(238)U/^(235)U and ^(234)U/^(238)U, of modern and ancient corals (n = 6), a limestone and a dolostone, as well as 43 shallow-water carbonate sediments from the ODP Leg 166 Site 1009 drill core, on the slope of the Bahamas platform. Although bulk corals record the seawater δ^(238)U value within ±0.02‰, differences of up to 0.30‰ in the δ^(238)U of individual leachates suggest a control of the coral structure and a more positive ^(238)U/^(235)U ratio in the centers of calcification. The drill core δ^(238)U data shows that the ^(238)U/^(235)U ratio of shallow-water carbonates is controlled mainly by (1) variations in sea-level through the mixing of different amounts of platform-derived sediments (with δ^(238)U ∼0.50–0.60‰ heavier than seawater) and pelagic sediments (with seawater-like δ^(238)U values), (2) authigenic U enrichment via pore-watercirculation and U reduction both on the platform and down to ∼5 m below the surface (mbsf) after deposition of the sediment, and, to a lesser extent, by (3) early diagenetic processes (i.e., carbonate dissolution and/or recrystallization) during sediment burial. The global effect of these processes leaves the δ^(238)U values of shallow-water carbonates offset relative to that of seawater by Δ_(Carbonates-SW) = +0.24 ± 0.06‰ (95% CI, including all samples). This shift can be used in seawater paleoredox reconstructions based on carbonates deposited on shallow-water platform, shelf and slope environments (i.e., most of the carbonate sedimentary record prior to the Mesozoic) to account for the average effect of carbonate diagenesis. Assuming that the ^(238)U/^(235)U ratio of carbonate platform sediments directly records the seawater ^(238)U/^(235)U ratio would underestimate the extent of ocean-seafloor anoxia by at least a factor 10. The rapid fluctuations in δ^(238)U values due to sea-level changes (i) is a factor that should be considered before interpreting δ^(238)U variations as reflecting changes in oceanic paleoredox conditions and (ii) reinforces the need for statistically meaningful data sets. The δ(^(234)U) data suggest that the (^(234)U/^(238)U) ratio of the seawater has remained within ∼20‰ of the modern seawater value during the last 1–1.4 Myr. Furthermore, we find that small-scale (1–15‰) variations in seawater δ(^(234)U) mirror sea-level changes during the penultimate glacial-interglacial period (∼140 to ∼200 ka), thus confirming the record of lower δ(^(234)U)_(SW) during periods of low sea-level stand and expanding it to at least the last two glacial-interglacial events (i.e., ∼0.23 Ma). Such fluctuations in δ(^(234)U)_(initial) values should be taken into account when screening carbonate sediments U-Th ages on the basis of the initial (^(234)U/^(238)U) ratios of the samples.

The early evolution of planetesimals and planets can be constrained using variations in the abundance of neodymium-142 ((142)Nd), which arise from the initial distribution of (142)Nd within the protoplanetary disk and the radioactive decay of the short-lived samarium-146 isotope ((146)Sm). The apparent offset in (142)Nd abundance found previously between chondritic meteorites and Earth has been interpreted either as a possible consequence of nucleosynthetic variations within the protoplanetary disk or as a function of the differentiation of Earth very early in its history. Here we report high-precision Sm and Nd stable and radiogenic isotopic compositions of four calcium-aluminium-rich refractory inclusions (CAIs) from three CV-type carbonaceous chondrites, and of three whole-rock samples of unequilibrated enstatite chondrites. The CAIs, which are the first solids formed by condensation from the nebular gas, provide the best constraints for the isotopic evolution of the early Solar System. Using the mineral isochron method for individual CAIs, we find that CAIs without isotopic anomalies in Nd compared to the terrestrial composition share a (146)Sm/(144)Sm-(142)Nd/(144)Nd isotopic evolution with Earth. The average (142)Nd/(144)Nd composition for pristine enstatite chondrites that we calculate coincides with that of the accessible silicate layers of Earth. This relationship between CAIs, enstatite chondrites and Earth can only be a result of Earth having inherited the same initial abundance of (142)Nd and chondritic proportions of Sm and Nd. Consequently, (142)Nd isotopic heterogeneities found in other CAIs and among chondrite groups may arise from extrasolar grains that were present in the disk and incorporated in different proportions into these planetary objects. Our finding supports a chondritic Sm/Nd ratio for the bulk silicate Earth and, as a consequence, chondritic abundances for other refractory elements. It also removes the need for a hidden reservoir or for collisional erosion scenarios to explain the (142)Nd/(144)Nd composition of Earth.

Radiometric dating indicates that Mars accreted in the first ~4 Myr of solar system formation, which coincides with the formation and possible migration of Jupiter. While nebular gas from the protoplanetary disk was still present, Jupiter may have migrated inwards and tacked at 1.5 AU in a 3:2 resonance with Saturn. This migration excited planetary building blocks in the inner solar system, resulting in extensive mixing and planetesimal removal. Here we evaluate the plausible nature of Mars' building blocks, focusing in particular on how its growth was influenced by the formation and migration of Jupiter. We use a combination of dynamical simulations and an isotopic mixing model that traces the accretion of elements with different affinities for metal. Dynamical simulations show that Jupiter's migration causes the late stages of Earth's and Mars' accretion to be dominated by EC-type (enstatite chondrite) material due to the loss of OC (ordinary chondrite) planetesimals. Our analysis of available isotopic data for SNC meteorites shows that Mars consists of approximately 68%$^{+0}_{-39}$ EC + 32%$^{+35}_{-0}$ OC by mass (2{\sigma}). The large uncertainties indicate that isotopic analyses of martian samples are for the most part too imprecise to definitely test model predictions; in particular it remains uncertain whether or not Mars accreted predominantly EC material in the latter stages of its formation history. Dynamical simulations also provide no definitive constraint on Mars' accretion history due to the great variety of dynamical pathways that the martian embryo exhibits. The present work calls for new measurements of isotopic anomalies in SNC meteorites targeting siderophile elements (most notably Ni, Mo and Ru) to constrain Mars' accretion history and its formation location., Comment: Accepted for publication in GRL

International audience; The Earth-Moon system likely formed as a result of a collision between two large planetary objects. Debate about their relative masses, the impact energy involved, and the extent of isotopic homogenization continues. We present the results of a high-precision oxygen isotope study of an extensive suite of lunar and terrestrial samples. We demonstrate that lunar rocks and terrestrial basalts show a 3 to 4 ppm (parts per million), statistically resolvable, difference in D 17 O. Taking aubrite meteorites as a candidate impactor material, we show that the giant impact scenario involved nearly complete mixing between the target and impactor. Alternatively, the degree of similarity between the D 17 O values of the impactor and the proto-Earth must have been significantly closer than that between Earth and aubrites. If the Earth-Moon system evolved from an initially highly vaporized and isotopically homogenized state, as indicated by recent dynamical models, then the terrestrial basalt-lunar oxygen isotope difference detected by our study may be a reflection of post-giant impact additions to Earth. On the basis of this assumption, our data indicate that post-giant impact additions to Earth could have contributed between 5 and 30% of Earth's water, depending on global water estimates. Consequently, our data indicate that the bulk of Earth's water was accreted before the giant impact and not later, as often proposed.

Titanium isotopic compositions (mass-dependent fractionation and isotopic anomalies) were measured in 46 calcium-, aluminum-rich inclusions (CAIs) from the Allende CV chondrite. After internal normalization to ^(49)Ti/^(47)Ti, we found that e^(50)Ti values are somewhat variable among CAIs, and that e^(46)Ti is highly correlated with e^(50)Ti, with a best-fit slope of 0.162 ± 0.030 (95% confidence interval). The linear correlation between e^(46)Ti and e^(50)Ti extends the same correlation seen among bulk solar objects (slope 0.184 ± 0.007). This observation provides constraints on dynamic mixing of the solar disk and has implications for the nucleosynthetic origin of titanium isotopes, specifically on the possible contributions from various types of supernovae to the solar system. Titanium isotopic mass fractionation, expressed as δ′^(49)Ti, was measured by both sample-standard bracketing and double-spiking. Most CAIs are isotopically unfractionated, within a 95% confidence interval of normal, but a few are significantly fractionated and the range δ′^(49)Ti is from ∼−4 to ∼+4. Rare earth element patterns were measured in 37 of the CAIs. All CAIs with significant titanium mass fractionation effects have group II and related REE patterns, implying kinetically controlled volatility fractionation during the formation of these CAIs.

The history of the growth of continental crust is uncertain, and several different models that involve a gradual, decelerating, or stepwise process have been proposed1–4. Even more uncertain is the timing and the secular trend of the emergence of most landmasses above the sea (subaerial landmasses), with estimates ranging from about one billion to three billion years ago5–7. The area of emerged crust influences global climate feedbacks and the supply of nutrients to the oceans 8 , and therefore connects Earth’s crustal evolution to surface environmental conditions9–11. Here we use the triple-oxygen-isotope composition of shales from all continents, spanning 3.7 billion years, to provide constraints on the emergence of continents over time. Our measurements show a stepwise total decrease of 0.08 per mille in the average triple-oxygen-isotope value of shales across the Archaean–Proterozoic boundary. We suggest that our data are best explained by a shift in the nature of water–rock interactions, from near-coastal in the Archaean era to predominantly continental in the Proterozoic, accompanied by a decrease in average surface temperatures. We propose that this shift may have coincided with the onset of a modern hydrological cycle owing to the rapid emergence of continental crust with near-modern average elevation and aerial extent roughly 2.5 billion years ago. The use of triple-oxygen-isotope data from continental shales spanning the past 3.7 billion years suggests that continental crust with near-modern average elevation and extent emerged about 2.5 billion years ago.

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., Terrestrial basalts have a unique iron isotopic signature taken as fingerprints of core formation. Here, high pressure studies show that force constants of iron bonds increase with pressure similarly for silicate and metals suggesting interplanetary isotopic variability is not due to core formation.

Titanium isotopes are potential tracers of processes of evaporation/condensation in the solar nebula and magmatic differentiation in planetary bodies. To gain new insights into the processes that control Ti isotopic variations in planetary materials, 25 komatiites, 15 chondrites, 11 HED-clan meteorites, 5 angrites, 6 aubrites, a martian shergottite, and a KREEP-rich impact melt breccia have been analyzed for their mass-dependent Ti isotopic compositions, presented using the δ49Ti notation (deviation in permil of the 49Ti/47Ti ratio relative to the OL-Ti standard). No significant variation in δ49Ti is found among ordinary, enstatite, and carbonaceous chondrites, and the average chondritic δ49Ti value of +0.004 ± 0.010‰ is in excellent agreement with the published estimate for the bulk silicate Earth, the Moon, Mars, and the HED and angrite parent-bodies. The average δ49Ti value of komatiites of −0.001 ± 0.019‰ is also identical to that of the bulk silicate Earth and chondrites. OL-Ti has a Ti isotopic composition that is indistinguishable from chondrites and is therefore a suitable material for reporting δ49Ti values. Previously published isotope data on another highly refractory element, Ca, show measurable variations among chondrites. The decoupling between Ca and Ti isotope systematics most likely occurred during condensation in the solar nebula. Aubrites exhibit significant variations in δ49Ti, from −0.07 to +0.24‰. This is likely due to the uniquely reducing conditions under which the aubrite parent-body differentiated, allowing chalcophile Ti3+ and lithophile Ti4+ to co-exist. Consequently, the observed negative correlation between δ49Ti values and MgO concentrations among aubrites is interpreted to be the result of isotope fractionation driven by the different oxidation states of Ti in this environment, such that isotopically heavy Ti4+ was concentrated in the residual liquid during magmatic differentiation. Finally, KREEPy impact melt breccia SaU 169 exhibits a heavy δ49Ti value of +0.330 ± 0.034‰ which is interpreted to result from Ti isotopic fractionation during ilmenite precipitation in the late stages of lunar magma ocean crystallization. A Rayleigh distillation calculation predicts that a δ49Ti value of +0.330‰ is achieved after removal of 94% of Ti in ilmenite.

Thulium is a heavy rare earth element (REE) whose geochemical behavior is intermediate between Er and Yb, and that is not expected to be decoupled from these elements during accretion of planetary bodies and geological processes. However, irregularities in REE volatilities at higher temperature could have decoupled the REEs relative to one another during the early stages of condensation of the solar nebula. Indeed, positive Tm anomalies are found in some refractory inclusions from carbonaceous chondrites, and it is possible that large scale nebular reservoirs displaying positive or negative Tm anomalies were formed during the early history of the solar system. We analyzed a series of meteorites and terrestrial rocks in order to evaluate the existence of Tm anomalies in planetary materials. Relative to CIs (Ivuna-type carbonaceous chondrites), carbonaceous chondrites display unresolved or positive Tm anomalies, while most of the noncarbonaceous chondrites show slightly negative Tm anomalies. Quantification of these anomalies in terrestrial samples is complicated when samples display fractionated heavy REE patterns. Taking this effect into account, we show that the Earth, Mars, Vesta, the aubrite and ureilite parent bodies display small negative anomalies (Tm/Tm* approximate to 0.975), very similar to those found in ordinary and enstatite chondrites. We suggest that a slight negative Tm anomaly relative to CI is a widespread feature of the materials from the inner solar system. This finding suggests that CI chondrites may not be appropriate for normalizing REE abundances of most planetary materials as they may be enriched in a high-temperature refractory component with non-solar composition. The presence of Tm anomalies at a bulk planetary scale is, to this day, the strongest piece of evidence that refractory lithophile elements are not present in constant CI proportions in planetary bodies. (C) 2015 Elsevier Ltd. All rights reserved.

The ^(238)U/^(235)U isotopic composition of uranium in seawater can provide important insights into the modern U budget of the oceans. Using the double spike technique and a new data reduction method, we analyzed an array of seawater samples and 41 geostandards covering a broad range of geological settings relevant to low and high temperature geochemistry. Analyses of 18 seawater samples from geographically diverse sites from the Atlantic and Pacific oceans, Mediterranean Sea, Gulf of Mexico, Persian Gulf, and English Channel, together with literature data (n = 17), yield a δ^(238)U value for modern seawater of −0.392 ± 0.005‰ relative to CRM-112a. Measurements of the uranium isotopic compositions of river water, lake water, evaporites, modern coral, shales, and various igneous rocks (n = 64), together with compilations of literature data (n = 380), allow us to estimate the uranium isotopic compositions of the various reservoirs involved in the modern oceanic uranium budget, as well as the fractionation factors associated with U incorporation into those reservoirs. Because the incorporation of U into anoxic/euxinic sediments is accompanied by large isotopic fractionation (Δ_(Anoxic/Euxinic-SW) = +0.6‰), the size of the anoxic/euxinic sink strongly influences the δ^(238)U value of seawater. Keeping all other fluxes constant, the flux of uranium in the anoxic/euxinic sink is constrained to be 7.0 ± 3.1 Mmol/yr (or 14 ± 3% of the total flux out of the ocean). This translates into an areal extent of anoxia into the modern ocean of 0.21 ± 0.09% of the total seafloor. This agrees with independent estimates and rules out a recent uranium budget estimate by Henderson and Anderson (2003). Using the mass fractions and isotopic compositions of various rock types in Earth’s crust, we further calculate an average δ^(238)U isotopic composition for the continental crust of −0.29 ± 0.03‰ corresponding to a ^(238)U/^(235)U isotopic ratio of 137.797 ± 0.005. We discuss the implications of the variability of the ^(238)U/^(235)U ratio on Pb–Pb and U–Pb ages and provide analytical formulas to calculate age corrections as a function of the age and isotopic composition of the sample. The crustal ratio may be used in calculation of Pb–Pb and U–Pb ages of continental crust rocks and minerals when the U isotopic composition is unknown.

International audience; First-principles calculations based on the density functional theory (DFT) with or without the addition of a Hubbard U correction, are performed on goethite in order to determine the iron and oxygen reduced partition function ratios (β-factors). The calculated iron phonon density of states (pDOS), force constant and β-factor are compared with reevaluated experimental β-factors obtained from Nuclear Resonant Inelastic X-ray Scattering (NRIXS) measurements. The reappraisal of old experimental data is motivated by the erroneous previous interpretation of the low- and high-energy ends of the NRIXS spectrum of goethite and jarosite samples (Dauphas et al. 2012). Here the NRIXS data are analyzed using the SciPhon software that corrects for non-constant baseline. New NRIXS measurements also demonstrate the reproducibility of the results. Unlike for hematite and pyrite, a significant discrepancy remains between DFT, NRIXS and the existing Mössbauer-derived data. Calculations suggest a slight overestimation of the NRIXS signal possibly related to the baseline definition. The intrinsic features of the samples studied by NRIXS and Mössbauer spectroscopy may also contribute to the discrepancy (e.g. internal structural and/or chemical defects, microstructure, surface contribution). As for oxygen, DFT results indicate that goethite and hematite have similar β-factors, which suggests almost no fractionation between the two minerals at equilibrium.

International audience; The heavy iron isotopic composition of Earth's crust relative to chondrites has been explained by vaporization during the Moon-forming impact, equilibrium partitioning between metal and silicate at core–mantle-boundary conditions, or partial melting and magma differentiation. The latter view is supported by the observed difference in the iron isotopic compositions of MORBS and peridotites. However, the precise controls on iron isotope variations in igneous rocks remain unknown. Here, we show that equilibrium iron isotope fractionation is mainly controlled by redox (Fe3+/Fetot ratio) and structural (e.g. , polymerization) conditions in magmas. We measured, for the first time, the mean force constants of iron bonds in silicate glasses by synchrotron Nuclear Resonant Inelastic X-ray Scattering (NRIXS, also known as Nuclear Resonance Vibrational Spectroscopy – NRVS, or Nuclear Inelastic Scattering – NIS). The same samples were studied by conventional Mössbauer and X-ray Absorption Near Edge Structure (XANES) spectroscopy. The NRIXS results reveal a +0.2 to +0.4‰+0.4‰ equilibrium fractionation on 56Fe/54Fe ratio between Fe2+ and Fe3+ end-members in basalt, andesite, and dacite glasses at magmatic temperatures. These first measurements can already explain ∼1/3∼1/3 of the iron isotopic shift measured in MORBs relative to their source. Further work will be required to investigate how pressure, temperature, and structural differences between melts and glasses affect equilibrium fractionation factors. In addition, large fractionation is also found between rhyolitic glass and commonly occurring oxide and silicate minerals. This fractionation reflects mainly changes in the coordination environment of Fe2+ in rhyolites relative to less silicic magmas and mantle minerals, as also seen by XANES. We provide a new calibration of XANES features vs. Fe3+/Fetot ratio determinations by Mössbauer to estimate Fe3+/Fetot ratio in situ in glasses of basaltic, andesitic, dacitic, and rhyolitic compositions. Modeling of magma differentiation using rhyolite-MELTS shows that iron structural changes in silicic magmas can explain the heavy iron isotopic compositions of granitoids and rhyolites. This study demonstrates that iron stable isotopes can help reveal planetary redox conditions and igneous processes. Other heterovalent elements such as Ti, V, Eu, Cr, Ce, or U may show similar isotopic variations in bulk rocks and individual minerals, which could be used to establish past and present redox condition in the mantles of Earth and other planets.

International audience; The Paleoproterozoic Era was a time of remarkable importance in the redox evolution of Earth's atmosphere and oceans. Here, we present a multi-proxy study of Mo, U and Fe isotopes together with Fe speciation of black shales and siltstones from the upper Zaonega Formation of the Onega Basin in Karelia. We attempt to better understand oceanic redox conditions during the 2.05 Ga Shunga Event as the next step following the Great Oxidation Event (GOE) and the Lomagundi carbon isotope excursion Event. A cautious examination of the Fe speciation data shows that the studied section was deposited under dominantly euxinic conditions (anoxic and sulfidic) and that the lower part of the section experienced metamorphism through which pyrite was altered to pyrrhotite. During this episode, the system was closed with respect to Fe but not sulfur. The Mo and U isotopic compositions (corrected for detrital input) were not affected by the metamorphism and loss of S and are fairly uniform throughout the entire section. The Fe isotope compositions are exceptionally heavy in the lower part of the section (up to δ56FeIRMM-14 = 0.83‰) and become lighter towards the upper intervals, which also show significant [Mo] and [U] enrichments. We suggest that this pattern reflects changes in the position of the deposition site relative to the redox structure of the water column. The upper part was deposited within a locally euxinic portion of the basin where H2S availability was highest, removal of Mo and U was more efficient and precipitated pyrite captured relatively non-fractionated dissolved Fe. In other words, quantitative uptake of Fe was favored. In contrast, the lower interval was deposited on the lower margin of a euxinic wedge where H2S availability was lower, and removal of Mo and U was less efficient. Pyrite precipitation in this part of the water column reflected a more fractionated dissolved Fe reservoir due to more protracted, non-quantitative Fe uptake because of less efficient pyrite formation under lower sulfide conditions and greater access to the large oceanic pool of Fe. The U isotopic signal was corrected for detrital contribution giving compositions similar to the riverine input and suggesting that co-precipitation into carbonates was the main process of U removal at this time. We estimate the Mo isotope composition of the contemporaneous ocean to be δ98MoSW = 0.85 ± 0.21‰. This is the lowest value yet reported for the Proterozoic ocean, suggesting that the oceanic Mo cycle was dominated by euxinic and anoxic sinks with negligible Mo removal into oxic environments. Recent studies have proposed a sharp increase in ocean-atmosphere oxygen levels during the Lomagundi Event followed by a dramatic crash. Our results from black shales of the 2.05 Ga Shunga Event are consistent with a post-Lomagundi decrease in biospheric oxygen levels.

International audience; The iron isotopic compositions of 93 well-characterized basalts from geochemically and geologically diverse mid-ocean ridge segments, oceanic islands and back arc basins were measured. Forty-three MORBs have homogeneous Fe isotopic composition, with δ56Fe ranging from +0.07‰ to +0.14‰ and an average of +0.105 ± 0.006‰ (2SD/√n, n = 43, MSWD = 1.9). Three back arc basin basalts have similar δ56Fe to MORBs. By contrast, OIBs are slightly heterogeneous with δ56Fe ranging from +0.05‰ to +0.14‰ in samples from Koolau and Loihi, Hawaii, and from +0.09‰ to +0.18‰ in samples from the Society Islands and Cook-Austral chain, French Polynesia. Overall, oceanic basalts are isotopically heavier than mantle peridotite and pyroxenite xenoliths, reflecting Fe isotope fractionation during partial melting of the mantle. Iron isotopic variations in OIBs mainly reflect Fe isotope fractionation during fractional crystallization of olivine and pyroxene, enhanced by source heterogeneity in Koolau samples.

Meteorites contain relict decay products of short-lived radionuclides that were present in the protoplanetary disk when asteroids and planets formed. Several studies reported a high abundance of 60Fe (t1/2=2.62+/-0.04 Myr) in chondrites (60Fe/56Fe~6*10-7), suggesting that planetary materials incorporated fresh products of stellar nucleosynthesis ejected by one or several massive stars that exploded in the vicinity of the newborn Sun. We measured 58Fe/54Fe and 60Ni/58Ni isotope ratios in whole rocks and constituents of differentiated achondrites (ureilites, aubrites, HEDs, and angrites), unequilibrated ordinary chondrites Semarkona (LL3.0) and NWA 5717 (ungrouped petrologic type 3.05), metal-rich carbonaceous chondrite Gujba (CBa), and several other meteorites (CV, EL H, LL chondrites; IIIAB, IVA, IVB iron meteorites). We derive from these measurements a much lower initial 60Fe/56Fe ratio of (11.5+/-2.6)*10-9 and conclude that 60Fe was homogeneously distributed among planetary bodies. This low ratio is consistent with derivation of 60Fe from galactic background (60Fe/56Fe=2.8*10-7 in the interstellar medium from gamma-ray observations) and can be reconciled with high 26Al/27Al=5*10-5 in chondrites if solar material was contaminated through winds by outer layers of one or several massive stars (e.g., a Wolf-Rayet star) rich in 26Al and poor in 60Fe. We present the first chronological application of the 60Fe-60Ni decay system to establish the time of core formation on Vesta at 3.7 (+2.5/-1.7) Myr after condensation of calcium-aluminum-rich inclusions (CAIs)., 32 pages, 7 figures, 3 tables

We measured the reduced partition function ratios for iron isotopes in goethite FeO(OH), potassium-jarosite KFe3(SO4)2(OH)6, and hydronium-jarosite (H3O)Fe3(SO4)2(OH)6, by Nuclear Resonant Inelastic X-Ray Scattering (NRIXS, also known as Nuclear Resonance Vibrational Spectroscopy -NRVS- or Nuclear Inelastic Scattering -NIS) at the Advanced Photon Source. These measurements were made on synthetic minerals enriched in 57Fe. A new method (i.e., the general moment approach) is presented to calculate {\beta}-factors from the moments of the NRIXS spectrum S(E). The first term in the moment expansion controls iron isotopic fractionation at high temperature and corresponds to the mean force constant of the iron bonds, a quantity that is readily measured and often reported in NRIXS studies., Comment: 38 pages, 2 tables, 8 figures. In press at Geochimica et Cosmochimica Acta. Appendix C contains new derivations relating the moments of the iron PDOS to the moments of the excitation probability function measured in Nuclear Resonant Inelastic X-ray Scattering

International audience; We present new high precision iron isotope data (δ56Fe vs. IRMM-014 in per mil) for four groups of achondrites: one lunar meteorite, 11 martian meteorites, 32 howardite-eucrite-diogenite meteorites (HEDs), and eight angrites. Angrite meteorites are the only planetary materials, other than Earth/Moon system, significantly enriched in the heavy isotopes of Fe compared to chondrites (by an average of +0.12‰ in δ56Fe). While the reason for such fractionation is not completely understood, it might be related to isotopic fractionation by volatilization during accretion or more likely magmatic differentiation in the angrite parent-body. We also report precise data on martian and HED meteorites, yielding an average δ56Fe of 0.00 ± 0.01‰. Stannern-trend eucrites are isotopically heavier by +0.05‰ in δ56Fe than other eucrites. We show that this difference can be ascribed to the enrichment of heavy iron isotopes in ilmenite during igneous differentiation. Preferential dissolution of isotopically heavy ilmenite during remelting of eucritic crust could have generated the heavy iron isotope composition of Stannern-trend eucrites. This supports the view that Stannern-trend eucrites are derived from main-group eucrite source magma by assimilation of previously formed asteroidal crust. These new results show that iron isotopes are not only fractionated in terrestrial and lunar basalts, but also in two other differentiated planetary crusts. We suggest that igneous processes might be responsible for the iron isotope variations documented in planetary crusts.

International audience; Komatiites from Alexo, Canada, are well preserved and represent high-degree partial mantle melts (∼50%). They are thus well suited for investigating the Mg and Fe isotopic compositions of the Archean mantle and the conditions of magmatic differentiation in komatiitic lavas. High precision Mg and Fe isotopic analyses of 22 samples taken along a 15-m depth profile in a komatiite flow are reported. The δ25Mg and δ26Mg values of the bulk flow are −0.138 ± 0.021‰ and −0.275 ± 0.042‰, respectively. These values are indistinguishable from those measured in mantle peridotites and chondrites, and represent the best estimate of the composition of the silicate Earth from analysis of volcanic rocks. Excluding the samples affected by secondary Fe mobilization, the δ56Fe and δ57Fe values of the bulk flow are +0.044 ± 0.030‰, and +0.059 ± 0.044‰, respectively. These values are consistent with a near-chondritic Fe isotopic composition of the silicate Earth and minor fractionation during komatiite magma genesis. In order to explain the early crystallization of pigeonite relative to augite in slowly cooled spinifex lavas, it was suggested that magmas trapped in the crystal mush during spinifex growth differentiated by Soret effect, which should be associated with large and coupled variations in the isotopic compositions of Mg and Fe. The lack of variations in Mg and Fe isotopic ratios either rules out the Soret effect in the komatiite flow or the effect is effaced as the solidification front migrates downward through the flow crust. Olivine separated from a cumulate sample has light δ56Fe and slightly heavy δ26Mg values relative to the bulk flow, which modeling shows can be explained by kinetic isotope fractionation associated with Fe-Mg inter-diffusion in olivine. Such variations can be used to identify diffusive processes involved in the formation of zoned minerals.

High-precision Fe isotopic data for 104 samples, including modern and ancient (≥ 3.7 Ga) subduction-related magmas and mantle peridotites, are presented. These data demonstrate that mid-ocean ridge and oceanic-island basalts (MORBs and OIBs) have on average small, but distinctly (~+ 0.06‰) higher ^(56)Fe/^(54)Fe ratios than both modern and Eoarchean boninites and many island arc basalts (IABs) that are interpreted to form by large degrees of flux melting of depleted mantle sources. Additionally boninites and many IABs have iron isotopic compositions similar to chondrites, fertile mantle peridotites, Eoarchean mantle peridotites, and basalts from Mars and Vesta. The observed variations are best explained by the bulk silicate Earth having a near-chondritic iron isotopic composition, with ~ + 0.3‰ equilibrium isotope fractionation between Fe^(3+) and Fe^(2+) and preferential extraction of isotopically heavier, incompatible Fe^(3+) during mantle melting to form oceanic crust (as represented by MORBs and OIBs). A quantitative model that relates the iron isotopic composition of basaltic magmas to the degree of partial melting, Fe^(3+)/Fe^(2+) ratio, and buffering capacity of the mantle is presented. The concept that redox conditions may influence iron isotopic fractionation during melting provides a new approach for understanding the redox conditions of magma genesis on early Earth and Mars. Experimental and theoretical work is required to establish iron isotopic fractionation as an oxybarometer of mantle melting.

We present osmium isotopic results obtained by sequential leaching of the Murchison meteorite, which reveal the existence of very large internal anomalies of nucleosynthetic origin. The Os isotopic anomalies are correlated, and can be explained by the variable contributions of components derived from the s, r and p-processes of nucleosynthesis. Much of the s-process rich osmium is released by relatively mild leaching, suggesting the existence of an easily leachable s-process rich presolar phase, or alternatively, of a chemically resistant r-process rich phase. The s-process composition of Os released by mild leaching diverges slightly from that released by aggressive digestion techniques, perhaps suggesting that the presolar phases attacked by these differing procedures condensed in different stellar environments. The correlation between 190Os and 188Os can be used to constrain the s-process 190Os/188Os ratio to be 1.275 pm 0.043. Such a ratio can be reproduced in a nuclear reaction network for a MACS value for 190Os of ~200 pm 22 mbarn at 30 keV. We also present evidence for extensive internal variation of 184Os abundances in the Murchison meteorite. This suggests that p process rich presolar grains (e.g., supernova condensates) may be present in meteorites in sufficient quantities to influence the Os isotopic compositions of the leachates., Comment: 40 pages, 9 figures, 2 tables. Accepted for publication in Earth and Planetary Science Letters

Among extinct radioactivities present in meteorites, 60Fe (t1/2 = 1.49 Myr) plays a key role as a high-resolution chronometer, a heat source in planetesimals, and a fingerprint of the astrophysical setting of solar system formation. A critical issue with 60Fe is that it could have been heterogeneously distributed in the protoplanetary disk, calling into question the efficiency of mixing in the solar nebula or the timing of 60Fe injection relative to planetesimal formation. If this were the case, one would expect meteorites that did not incorporate 60Fe (either because of late injection or incomplete mixing) to show 60Ni deficits (from lack of 60Fe decay) and collateral effects on other neutron-rich isotopes of Fe and Ni (coproduced with 60Fe in core-collapse supernovae and AGB-stars). Here, we show that measured iron meteorites and chondrites have Fe and Ni isotopic compositions identical to Earth. This demonstrates that 60Fe must have been injected into the protosolar nebula and mixed to less than 10 % heterogeneity before formation of planetary bodies., 15 pages, 5 figures, ApJ in press