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Despite their unusual chemical composition, it is often proposed that the enstatite chondrites represent a significant component of Earth’s building materials, based on their terrestrial similarity for numerous isotope systems. In order to investigate a possible genetic relationship between the Fe isotope composition of enstatite chondrites and the Earth, we have analyzed 22 samples from different subgroups of the enstatite meteorites, including EH and EL chondrites, aubrites (main group and Shallowater) and the Happy Canyon impact melt. We have also analyzed the Fe isotopic compositions of separated (magnetic and non-magnetic) phases from both enstatite chondrites and achondrites. On average, EH3–5 chondrites (δ56Fe = 0.003 ± 0.042‰; 2 standard deviation; n = 9; including previous literature data) as well as EL3 chondrites (δ56Fe = 0.030 ± 0.038‰; 2 SD; n = 2) have identical and homogeneous Fe isotopic compositions, indistinguishable from those of the carbonaceous chondrites and average terrestrial peridotite. In contrast, EL6 chondrites display a larger range of isotopic compositions (−0.180‰ Enstatite achondrites (aubrites) also exhibit a relatively large range of Fe isotope compositions: all main group aubrites are enriched in the light Fe isotopes (δ56Fe = −0.170 ± 0.189‰; 2 SD; n = 6), while Shallowater is, isotopically, relatively heavy (δ56Fe = 0.045 ± 0.101‰; 2 SD; n = 4; number of chips). We take this variation to suggest that the main group aubrite parent body formed a discreet heavy Fe isotope-enriched core, whilst the Shallowater meteorite is most likely from a different parent body where core and silicate material remixed. This could be due to intensive impact-induced shearing stress, or the ultimate destruction of the Shallowater parent body. Analysis of separated enstatite meteorite mineral phases show that the magnetic phase (Fe metal) is systematically enriched in the heavier Fe isotopes when compared to non-magnetic phases (Fe hosted in troilite), which agrees with previous experimental observations and theoretical calculations. The difference between magnetic and non-magnetic phases from enstatite achondrites provides an equilibrium metal–sulfide Fe isotopic fractionation factor of Δ56Femetal–troilite = δ56Femetal − δ56Fetroilite of 0.129 ± 0.060‰ (2 SE) at 1060 ± 80 K, which confirms the predictions of previous theoretical calculations.

The Moon is depleted in volatile elements relative to the Earth and Mars. Low abundances of volatile elements, fractionated stable isotope ratios of S, Cl, K and Zn, highμ(238U/204Pb) and long-term Rb/Sr depletion are distinguishing features of the Moon, relative to the Earth. These geochemical characteristics indicate both inheritance of volatile-depleted materials that formed the Moon and planets and subsequent evaporative loss of volatile elements that occurred during lunar formation and differentiation. Models of volatile loss through localized eruptive degassing are not consistent with the available S, Cl, Zn and K isotopes and abundance data for the Moon. The most probable cause of volatile depletion is global-scale evaporation resulting from a giant impact or a magma ocean phase where inefficient volatile loss during magmatic convection led to the present distribution of volatile elements within mantle and crustal reservoirs. Problems exist for models of planetary volatile depletion following giant impact. Most critically, in this model, the volatile loss requires preferential delivery and retention of late-accreted volatiles to the Earth compared with the Moon. Different proportions of late-accreted mass are computed to explain present-day distributions of volatile and moderately volatile elements (e.g. Pb, Zn; 5 to >10%) relative to highly siderophile elements (approx. 0.5%) for the Earth. Models of early magma ocean phases may be more effective in explaining the volatile loss. Basaltic materials (e.g. eucrites and angrites) from highly differentiated airless asteroids are volatile-depleted, like the Moon, whereas the Earth and Mars have proportionally greater volatile contents. Parent-body size and the existence of early atmospheres are therefore likely to represent fundamental controls on planetary volatile retention or loss.

This paper reports the values of reduced partition function ratios (as 1000 ln β ) for Fe, Ni, Cu, and Zn bound to a number of inorganic and organic ligands. We used Density Functional Techniques to update the existing data and calculate ln β for new ligands. This work allows for the mass-dependent isotope fractionation to be predicted for various inorganic (hydrated cation, hydroxide, chloride, sulfate, sulfide, phosphate) and organic (citrate, amino acid) complexes of Fe, Ni, Cu, and Zn. Isotope fractionation among coexisting complexes of these metals was evaluated from the ln β values in a variety of geochemical and biological environments. The results provide a framework for interpretation of isotope fractionation observed in seawater and chemical sediments, in the roots and aerial parts of plants, and among the organs and body fluids of mammals.

The 53Mn-53Cr chronometer applied to bulk carbonaceous chondrites constrains the solar nebula volatile element fractionation, chondrule formation, and stage I planetary accretion timescale to within +0.91 to –1.17 Myr at 4568 Myr ago. The difference between the initial 53Cr/52Cr ratio of ordinary chondrites, defined by Chainpur (LL3.4) chondrules, and carbonaeous chondrites suggests that the former is coming from an isotopically evolved reservoir.

International audience; To examine the iron (Fe) isotopic heterogeneities of CI and ordinary chondrites, we have analyzed several large chips (approximately 1 g) from three CI chondrites and three ordinary chondrites (LL5, L5, and H5). The Fe isotope compositions of five different samples of Orgueil, one from Ivuna and one from Alais (CI chondrites), are highly homogeneous. This new dataset provides a δ56Fe average of 0.02 ± 0.04‰ (2SE, n = 7), which represents the best available value for the Fe isotopic composition of CI chondrites and probably the best estimate of the bulk solar system. We conclude that the homogeneity of CI chondrites reflects the initial Fe isotopic homogeneity of the well-mixed solar nebula. In contrast, larger (up to 0.26‰ in δ56Fe) isotopic variations have been found between separate approximately 1 g pieces of the same ordinary chondrite sample. The Fe isotope heterogeneities in ordinary chondrites appear to be controlled by the abundances of chondritic components, specifically chondrules, whose Fe isotope compositions have been fractionated by evaporation and recondensation during multiple heating events.

International audience; Asteroids impacting the Earth partly volatilize, partly melt (O’Keefe, J.D., Ahrens, T.J. [1977]. Proc. Lunar Sci. Conf. 8, 3357–3374). While metal rapidly segregates out of the melt and sinks into the core, the vaporized material orbits the Earth and eventually rains back onto its surface. The content of the mantle in siderophile elements and their chondritic relative abundances hence is accounted for, not by the impactors themselves, as in the original late-veneer model (Chou, C.L. [1978]. Proc. Lunar Sci. Conf. 9, 219–230; Morgan, J.W. et al. [1981]. Tectonophysics 75, 47–67), but by the vapor resulting from impacts. The impactor’s non-siderophile volatiles, notably hydrogen, are added to the mantle and hydrosphere. The addition of late veneer may have lasted for 130 Ma after isolation of the Solar System and probably longer, i.e., well beyond the giant lunar impact. Constraints from the stable isotopes of oxygen and other elements suggest that, contrary to evidence from highly siderophile elements, ∼4% of CI chondrites accreted to the Earth. The amount of water added in this way during the waning stages of accretion, and now dissolved in the deep mantle or used to oxidize Fe in the mantle and the core, may correspond to 10–25 times the mass of the present-day ocean. The Moon is at least 100 times more depleted than the Earth in volatile elements with the exception of some isolated domains, such as the mantle source of 74220 pyroclastic glasses, which appear to contain significantly higher concentrations of water and other volatiles.

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; The δ66Zn (permil deviation of the 66Zn/64Zn ratio from a terrestrial standard) values for a suite of 20 non-Antarctic HED (howardite - eucrite - diogenite) meteorites and one mesosiderite, and for 8 Antarctic eucrites and diogenites, were measured in order to determine the role of volatization in the formation of their presumed parent body, the asteroid 4-Vesta. The 20 non-Antarctic HEDs had δ66Zn values that ranged from -2.0 ‰ to +1.67 ‰, with a mean value of -0.01 ± 0.39 ‰ (2se); this range likely represents a small-scale heterogeneity due to brecciation induced by multiple impacts. The non-Antarctic eucrites (δ66Zn = +0.00 ± 0.58 ‰ (2se), n=12) were isotopically the same as the diogenites (δ66Zn = -0.31 ± 0.80 ‰ (2se), n=4), and the howardites (δ66Zn = +0.26 ± 0.37 ‰ (2se), n=4). On average, non-Antarctic eucrite falls were isotopically heavier (+0.50 ‰) than non-Antarctic finds (-1.00 ‰). The Antarctic finds studied were all unbrecciated samples, and they were significantly heavier than the non-Antarctic samples with a δ66Zn range of +1.63 to +6.22‰ for 4 eucrites (mean, +4.32‰) and +0.94 to +1.60‰ for 3 diogenites (mean +1.23‰), excluding one anomalous sample, while their Zn concentration is significantly lower than the brecciated samples. These data suggest that the unbrecciated eucrites probably represent the eucritic crust shortly after differentiation and cooling of the parent asteroid, at which time volatization of lighter zinc isotopes led to an isotopically heavy crust. Early impact events caused the ejection of these unbrecciated meteorites, which were subsequently spared from brecciation caused by multiple additional impacts on the much larger Vesta. The range of δ66Zn values and Zn concentration for the brecciated HEDs in this study supports a major contribution to the Vestan surface by chondritic impactors (-1.30 < δ66Zn < +0.76 ‰ for ordinary and carbonaceous chondrites). The anomalous eucrite PCA 82502 (δ66Zn= -7.75 ‰) is significantly isotopically lighter than the other HEDs and is the natural sample with the lightest Zn isotopic composition reported in the solar system to date. This meteorite most likely originated from a distinct parent body.

International audience; In order to check the heterogeneity of the CI chondrites and determine the average composition of this group of meteorites, we analyzed a series of six large chips (weighing between 0.6 and 1.2 g) of Orgueil prepared from five different stones. In addition, one sample from each of Ivuna and Alais was analyzed. Although the sizes of the chips used in this study were "large", our results show evidence for minor chemical heterogeneity in Orgueil, particularly for alkali elements and U. After removal of one outlier sample, the spread of the results is considerably reduced. For most of the 46 elements analyzed in this study, the average composition calculated for Orgueil is in very good agreement with previous CI estimates. This average, obtained with a "large" mass of samples, is analytically homogeneous and is suitable for normalization purposes. Finally, the Cu and Zn isotopic ratios are homogeneously distributed within the CI parent body with a spread of less than 100 ppm per atomic mass unit (amu).

We have measured the bi directional reflectance phase function on selected meteorite samples (1 howardite 1 eucrite 1 diogenite Orgeuil (CI). Tagish Lake (CC) Allende (CV) Lunar meteorite (MAC 88105) Forest Vale (H4)) covering part of the geochemical and petrologic diversity expected for asteroid surfaces. Samples were measured as powders for which we achieved reflectance measurements from phase angles down to 3 degrees and up to 150 degrees at five different wavelengths covering the VIS NIR spectral region. The data were fitted by the photometric model of Hapke (Hapke B. [1993]. Theory of reflectance and emittance spectroscopy. Cambridge University Press Cambridge). The physical sense of the retrieved Hapke's parameters seems unclear but they permit to interpolate the data to any observation geometry. Strong opposition effects were observed for all samples. The absolute intensity of this effect appears moderately variable among our sample suite and is not correlated with the average sample reflectance. We interpret this observation as Shadow Hiding Opposition Effect (SHOE). In the case of samples presenting intense absorption bands (the Fe crystal field band at 1 mu m of HED and the ordinary chondrite) we observe significant dependence of band depth to phase angle up to 70 degrees even for moderate variation of phase angle. In addition a general trend of spectral reddening with phase angle is observed. This reddening linear with phase angle is present in all meteorites studied. This behavior is not predicted by classical radiative theories. We propose that small scale roughness (of the order of or below the wavelength) may induce such a behavior. (C) 2011 Elsevier Inc. All rights reserved.

The Howardite-Eucrite-Diogenite (HED) suite is a family of differentiated meteorites that provide a unique opportunity to study the differentiation of small bodies. The likely parent-body of this meteorite group, (4) Vesta is presently under study by the Dawn mission, scrutinizing its surface in the visible and NIR infrared range. Here, we discuss how well the magmatic trends observed in HED might be retrieved from NIR spectroscopy, by studying laboratory spectra of 10 HED meteorites together with spectra from the RELAB database. We show that although an exsolution process did occur for most eucrites (i.e. decomposition of a primary calcic pyroxene into a high-Ca and low-Ca pyroxene), it does not affect the "bulk pyroxene" trend retrieved from the location of the pyroxene crystal field bands (Band I with a maximum of absorption around at about 1 mu m and Band II around 2 mu m). Absolute values of the chemical composition appears however to deviate from the expected chemical composition. We show that mechanical mixture (i.e. impact gardening) will produce a linear mixing in the pyroxenes band position diagram (Band I position vs Band II position). This diagram also reveals that howardite are not pure mixtures of an average eucrite and average diogenite. Because asteroid surfaces are expected to show topography, we also study the effect of observation geometry on the NIR spectra of an eucrite and a diogenite by measuring the bi-directional reflectance spectra from 0.4 to 4.6 mu m. Results show that these meteorites tend to act as forward scatterers, leading to a decrease of integrated band area (relative to the continuum) at high phase angles. The position of the two strong crystal field bands shows only small variability with observation geometry. Retrieval of the magmatic trends from the Band I vs Band II diagram should not be affected by observation geometry effects. Finally we performed NIR reflectance measurement on olivine diogenites. The presence of olivine can be suggested by using the Band Area Ratio vs Band I diagram, but this phase might affect the retrieval of pyroxene composition from the position of Band I and Band II. (C) 2011 Elsevier Inc. All rights reserved.

Palladium isotopes were fractionated by the solvent extraction technique with a crown ether. After purification by ion-exchange chemistry, the isotopic ratios of 105Pd/106Pd, 108Pd/106Pd, and 110Pd/106Pd were determined by multiple-collector inductively coupled plasma mass spectrometry. Isotope fractionations between the two phases were found to be larger than 0.1‰. The isotope fractionation of the odd atomic mass isotope (105Pd) showed a deviation from that estimated from the even atomic mass isotopes (106Pd, 108Pd, and 110Pd). The mass-independent isotope fractionation found was attributable to the nuclear field shift effect. The quantum chemical calculations for the different Pd species supported the validity of the isotope fractionation factors obtained.

Lead isotopes were fractionated by the liquid-liquid extraction technique between an aqueous phase and a crown ether. After purification by ion-exchange chemistry, the 207Pb/206Pb and 208Pb/206Pb isotopic ratios were measured by multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). Isotope fractionations > 0.05‰ have been found. The conventional equilibrium mass-dependent isotope effect estimated by an ab initio calculation was smaller than the Pb isotope fractionation experimentally obtained. Conventional mass-dependent isotope fractionation is not a valuable explanation for our results. The nuclear field shift effect, which results from the isotopic change in the nuclear size and shape, was also estimated by an ab initio method combined with a finite nucleus model. The nuclear field shift effect calculated was in agreement with our experimental results. Therefore, this study reports the first nuclear field shift effect of Pb in an equilibrium ligand exchange reaction.

International audience; The Isua Supracrustal Belt, Greenland, of Early Archean age (3.81-3.70 Ga) represents the oldest crustal segment on Earth. Its complex lithology comprises an ophiolite-like unit and volcanic rocks reminiscent of boninites, which tie Isua supracrustals to an island arc environment. We here present zinc (Zn) isotope compositions measured on serpentinites and other rocks from the Isua supracrustal sequence and on serpentinites from modern ophiolites, midocean ridges, and the Mariana forearc. In stark contrast to modern midocean ridge and ophiolite serpentinites, Zn in Isua and Mariana serpentinites is markedly depleted in heavy isotopes with respect to the igneous average. Based on recent results of Zn isotope fractionation between coexisting species in solution, the Isua serpentinites were permeated by carbonate- rich, high- pH hydrothermal solutions at medium temperature (100-300 degrees C). Zinc isotopes therefore stand out as a pH meter for fossil hydrothermal solutions. The geochemical features of the Isua fluids resemble the interstitial fluids sampled in the mud volcano serpentinites of the Mariana forearc. The reduced character and the high pH inferred for these fluids make Archean serpentine mud volcanoes a particularly favorable setting for the early stabilization of amino acids.

International audience; No (60)Ni or (61)Ni anomalies have been detected in troilite inclusions from Muonionalusta, a 4565.3 +/- 0.1 Ma old IVA iron meteorite, to the level of the analytical precision of 10 ppm. Because Muonionalusta troilite is very old, has a high Fe/Ni ratio, and is free of (61)Ni anomalies, it is the ideal material in which to search for potential excesses of (60)Ni produced by the decay of (60)Fe (t(1/2) = 2.62 Ma). The (60)Ni/(58)Ni and Fe/Ni ratios (up to 1680) measured here imply an upper limit for the initial (60)Fe/(56)Fe for the Muonionalusta troilite of 3 x 10(-9). Assuming that (60)Fe was homogeneously distributed across the nebula, this result suggests that the solar system initial (60)Fe/(56)Fe ratio was less than 5 x 10(-9), which is lower than previously measured by at least a factor of 50

Lunar magmatic rocks are shown to be enriched in the heavy isotopes of zinc and to have lower zinc concentrations than terrestrial or Martian igneous rocks; these variations represent the large-scale evaporation of zinc, most probably in the aftermath of the Moon-forming giant impact event. The heavily favoured theory for the origin of the Earth–Moon system is a giant impact between the proto-Earth and a Mars-sized body. Such a cataclysmic event would have left its mark on the isotopic composition of the Moon, because light isotopes evaporate more readily than heavier ones. Zinc in particular is a powerful indicator of the volatile histories of planets — it undergoes strong isotopic fractionation in planetary rocks, but is hardly fractionated following volcanic activity on Earth. This study compares high-precision zinc isotopic data for lunar basalts, Martian meteorites and terrestrial igneous rocks, and finds that lunar magmatic rocks are enriched in the heavy isotopes of zinc and have lower zinc concentrations than terrestrial or Martian samples. The authors conclude that these variations are the result of large-scale evaporation of zinc in the aftermath of the Moon-forming giant-impact event. Volatile elements have a fundamental role in the evolution of planets. But how budgets of volatiles were set in planets, and the nature and extent of volatile-depletion of planetary bodies during the earliest stages of Solar System formation remain poorly understood1,2. The Moon is considered to be volatile-depleted and so it has been predicted that volatile loss should have fractionated stable isotopes of moderately volatile elements3. One such element, zinc, exhibits strong isotopic fractionation during volatilization in planetary rocks4,5, but is hardly fractionated during terrestrial igneous processes6, making it a powerful tracer of the volatile histories of planets. Here we present high-precision zinc isotopic and abundance data which show that lunar magmatic rocks are enriched in the heavy isotopes of zinc and have lower zinc concentrations than terrestrial or Martian igneous rocks. Conversely, Earth and Mars have broadly chondritic zinc isotopic compositions. We show that these variations represent large-scale evaporation of zinc, most probably in the aftermath of the Moon-forming event, rather than small-scale evaporation processes during volcanism. Our results therefore represent evidence for volatile depletion of the Moon through evaporation, and are consistent with a giant impact origin for the Earth and Moon.

International audience; Knowledge of the copper cycle in the plant-soil-water system is needed in order to better constrain proper plant micronutrient nutrition, control pollution, and determine sustainable soil management practices. Here, we report the Cu isotopic compositions of different components (seeds, germinated seeds, leaves, and stems) of the dicot, lentil (Lens culinaris), and of two monocots, Virginia wild rye (Elymus virginicus) and hairy-leaved sedge (Carex hirsutella). According to our data, the isotopic compositions of these plants are systematically enriched in the lighter isotope of Cu ((63)Cu) in comparison to the soil in which they grow. Furthermore, different components within the plants themselves are isotopically fractionated. The shoots (stems, leaves and seeds) are systematically lighter than the germinated seeds of the plants and the Cu isotopic compositions of individual leaves correlate with their heights on the plant. These results are similar to what has been observed for Zn isotopes, which are assumed to be transported through plants by means of diffusion and kinetic fractionation across cell membranes. Because of this similarity, we suggest that the same transport mechanisms are also responsible for the observed isotopic fractionation of Cu. As a side-note, the Cu isotopic variations measured in plants are similar in magnitude to the differences previously measured in various soils, and therefore should not be neglected while interpreting the isotopic composition of soils

The distribution of chemical elements in primitive meteorites (chondrites), as building blocks of terrestrial planets, provides insight into the formation and early differentiation of Earth. The processes that resulted in the depletion of some elements [such as chromium (Cr)] in the bulk silicate Earth relative to chondrites, however, remain debated between leading candidate causes: volatility versus core partitioning. We show through high-precision measurements of Cr stable isotopes in a range of meteorites, which deviate by up to ~0.4 per mil from those of the bulk silicate Earth, that Cr depletion resulted from its partitioning into Earth’s core, with a preferential enrichment in light isotopes. Ab initio calculations suggest that the isotopic signature was established at mid-mantle magma ocean depth as Earth accreted planetary embryos and progressively became more oxidized.

International audience; Enstatite meteorites include the undifferentiated enstatite chondrites and the differentiated enstatite achondrites (aubrites). They are the most reduced group of all meteorites. The oxygen isotope compositions of both enstatite chondrites and aubrites plot along the terrestrial mass fractionation line, which suggests some genetic links between these meteorites and the Earth as well. For this study, we measured the Zn isotopic composition of 25 samples from the following groups: aubrites (main group and Shallowater), EL chondrites, EH chondrites and Happy Canyon (impact-melt breccia). We also analyzed the Zn isotopic composition and elemental abundance in separated phases (metal, silicates, and sulfides) of the EH4, EL3, and EL6 chondrites. The different groups of meteorites are isotopically distinct and give the following values (parts per thousand): aubrite main group (-7.08 < delta Zn-66

International audience; High-precision stable Sr isotopic variations (88Sr/86Sr) are reported in a variety of terrestrial samples, martian and lunar meteorites, HED, undifferentiated primitive meteorites, chondrules and refractory inclusions. Almost all the whole-rock samples are isotopically indistinguishable at a 50 parts per million (ppm) level. The exceptions are CV and CO chondrites which are isotopically light and for which we believe that their isotopic composition is controlled by the proportion of refractory material. Five separated chondrules and one refractory inclusion from Allende are isotopically light, with δ88/86Sr fractionations up to −1.73‰, whereas the matrix is enriched in the heavy isotopes (δ88/86Sr = + 0.66‰). The depletion in heavy isotopes observed in chondrules and refractory inclusions could be attributed to the condensation of a material already depleted in Sr, however, in that case more than 60% of the original material would be unaccounted. We propose instead that isotopic fractionation by electromagnetic sorting of ionized heavy Sr from neutral Sr in the early solar system for the origin of the fractionation observed in refractory inclusions and redistribution of Sr by aqueous alteration for the origin of the fractionation observed in chondrules and matrix. We conclude that CV and CO chondrites are not the primary building blocks for Earth and Mars. Research Highlights ► The Sr of most planetary materials is isotopically indistinguishable at a 50 ppm level. ► Exceptions are CV and CO chondrites which are isotopically light. ► Their isotopic composition is controlled by the proportion of refractory material. ► Chondrules and refractory inclusion from Allende are isotopically light. ► The Sr isotopic composition of CAIs can be explained by electromagnetic separation in the early solar system. ► The Sr isotopic composition of chondrules and matrix can be explained by aqueous alteration.

International audience; The IVA iron meteorites are magmatic cumulates from the core of a small asteroid, which broke apart similar to 400 Ma ago. As the depletion of this planetary body in volatile elements is expected to be reflected in high U/Pb ratios of its minerals, we embarked on analyzing the isotope composition of Pb in the cm-sized troilite inclusions of Muonionalusta and Gibeon, both iron meteorites belonging to the IVA family. The bulk of the data for nine troilite subsamples of Muonionalusta scatter with an apparent age of 4.57 Ga, which is shown to reflect the presence of both primordial and common terrestrial Pb components, in addition to radiogenic Pb. The most radiogenic subsample, however, has fractions with Pb-206/Pb-204 ratios as high as over 1000 and gives a statistically significant (207)pb*/Pb-206* age of 4565.3 +/- 0.1 Ma (MSWD = 0.08), consistent with the Hf-182-W-182 metal-silicate segregation age of 2.4 +/- 2.0 Ma. These data make the age of Muonionalusta the oldest documented yet for all differentiated bodies in the Solar System and constitute the first high-precision Pb-Pb age determined for crystallization of a phase contained within an iron meteorite group, hence advancing our understanding of early Solar System chronology. Using literature values for the cooling rate, and assuming a closure temperature for Pb of 300 degrees C, it is further estimated that the IVA parent body accreted within 1 Ma of CAI formation and had cooled to the Pb closure temperature within an additional 1-2 Ma. The overlap between the high-precision Pb-Pb and Hf-W ages points to a small, or rapidly fragmented, planetary body. The isotopic composition of Pb in Gibeon troilite yields a significantly younger age of 4544 +/- 7 Ma (MSWD = 1.5), consistent with evidence from the Pd-107-Ag-107 chronometer, but we believe this age has been reset by melting upon shock. One puzzling observation is that the apparent Th-232/U-238 of Muonionalusta troilite is particularly low (similar to 0.32), requiring a mechanism capable of efficiently fractionating Th from U, presumably the reduction of U to its trivalent form or the crystallization of phosphate. Average Pb concentrations of the order of 5-10 ppb and high U-238/Pb-204 ratios of > 1000 require U concentrations in troilite in the sub-ppb to one ppb range. This may indicate that troilite inclusions in IVA meteorites do not represent metal-sulfide unmixing, but rather correspond to late-stage S-rich liquid residues from extreme crystallization of the interstitial melts.

International audience; This work reports on the chemical isotope fractionation of Zn(II) by a solvent extraction method with the crown ether dicyclohexano-18-crown-6. The (m)Zn/(64)Zn ratios (m = 66, 67, and 68) were analyzed by multiple-collector inductively coupled plasma mass spectrometry. The relative deviations of the (66)Zn/(64)Zn ratios relative to the unprocessed material (delta(66)Zn) was determined to be -0.51 to -0.32 in the acidity region 1.0-6.0 mol dm(-3) (M) HCl. The acidity dependence or delta(m)Zn was explained by the isotope exchange reactions between Zn(II) species (Zn(2+), ZnCl(+), ZnCl(2), ZnCl(3)(-), and ZnCl(4)(2-)) and the mole fractions of them. The magnitude of delta(m)Zn due to the related Zn(II) species estimated by quantum chemical calculations was in agreement with delta(m)Zn experimentally obtained. Contribution of nuclear field shift to the isotope fractionation was estimated to be less than 10% of delta(m)Zn by quantum chemical calculations.

International audience; Tektites are terrestrial natural glasses of up to a few centimeters in size that were produced during hypervelocity impacts on the Earth's surface. It is well established that the chemical and isotopic composition of tektites is generally identical to that of the upper terrestrial continental crust. Tektites typically have very low water content, which has generally been explained by volatilization at high temperature; however, the exact mechanism is still debated. Because volatilization can fractionate isotopes, comparing the isotopic composition of volatile elements in tektites with those of their source rocks may help to understand the physical conditions during tektite formation. Interestingly, volatile chalcophile elements (e.g., Cd and Zn) seem to be the only elements for which isotopic fractionation is known so far in tektites. Here, we extend this study to Cu, another volatile chalcophile element. We have measured the Cu isotopic composition for 20 tektite samples from the four known different strewn fields. All of the tektites (except the Muong Nong-types) are enriched in the heavy isotopes of Cu (1.98 < delta(61)Cu < 6.99) in comparison to the terrestrial crust (delta(65)Cu approximate to 0) with no clear distinction between the different groups. The Muong Nong-type tektites and a Libyan Desert Glass sample are not fractionated, (delta(65)Cu approximate to 0) in comparison to the terrestrial crust. To refine the Cu isotopic composition of the terrestrial crust, we also present data for three geological reference materials (delta(65)Cu approximate to 0). An increase of delta(65)Cu with decreasing Cu abundance probably reflects that the isotopic fractionation occurred by evaporation during heating. A simple Rayleigh distillation cannot explain the Cu isotopic data and we suggest that the isotopic fractionation is governed by a diffusion-limited regime. Copper is isotopically more fractionated than the more volatile element Zn (delta(66/64)Zn up to 2.49 parts per thousand). This difference of behavior between Cu and Zn is predicted in a diffusion-limited regime, where the magnitude of the isotopic fractionation is regulated by the competition between the evaporative flux and the diffusive flux at the diffusion boundary layer. Due to the difference of ionic charge in silicates (Zn(2+) vs. Cu(+)), Cu has a diffusion coefficient that is larger than that of Zn by at least two orders of magnitude. Therefore, the larger isotopic fractionation in Cu than in Zn in tektites is due to the significant difference in their respective chemical diffusivity. (C) 2009 Elsevier Ltd. All rights reserved.

Recent high precision 142 Nd isotope measurements showed that global silicate differentiation may have occurred as early as 30–75 Myr after the Solar System formation [Bennett V, et al. (2007) Science 318:1907–1910]. This time scale is almost contemporaneous with Earth’s core formation at ∼30 Myr [Yin Q, et al. (2002) Nature 418:949–952]. The 182 Hf- 182 W system provides a powerful complement to the 142 Nd results for early silicate differentiation, because both core formation and silicate differentiation fractionate Hf from W. Here we show that eleven terrestrial samples from diverse tectonic settings, including five early Archean samples from Isua, Greenland, of which three have been previously shown with 142 Nd anomalies, all have a homogeneous W isotopic composition, which is ∼2 ε -unit more radiogenic than the chondritic value. By using a 3-stage model calculation that describes the isotopic evolution in chondritic reservoir and core segregation, as well as silicate differentiation, we show that the W isotopic composition of terrestrial samples provides the most stringent time constraint for early core formation (27.5–38 Myr) followed by early terrestrial silicate differentiation (38–75 Myr) that is consistent with the terrestrial 142 Nd anomalies.

High-precision Ni isotopic variations are reported for the metal phase of equilibrated and unequilibrated ordinary chondrites, carbonaceous chondrites, iron meteorites, mesosiderites, and pallasites. We also report new Zn and Cu isotopic data for some of these samples and combine them with literature Fe, Cu, and Zn isotope data to constrain the fractionation history of metals during nebular (vapor/solid) and planetary (metal/sulfide/silicate) phase changes. The observed variations of the Ni-62/Ni-58, Ni-61/Ni-58, and Ni-60/Ni-58 ratios vary linearly with mass difference and define isotope fractionation lines in common with terrestrial samples. This implies that Ni was derived from a single homogeneous reservoir. While no Ni-60 anomaly is detected within the analytical uncertainties, Ni isotopic fractionation up to 0.45 parts per thousand per mass-difference unit is observed. The isotope compositions of Ni and Zn in chondrites are positively correlated. We suggest that, in ordinary chondrites, exchange between solid phases, in particular metal and silicates, and vapor followed by mineral sorting during accretion are the main processes controlling these isotopic variations. The positive correlation between Ni and Zn isotope compositions contrasts with a negative correlation between Ni (and Zn) and Cu isotope compositions, which, when taken together, do not favor a simple kinetic interpretation. The observed transition element similarities between different groups of chondrites and iron meteorites are consistent with the genetic relationships inferred from oxygen isotopes (IIIA/pallasites and IVA/L chondrites). Copper is an exception, which we suggest may be related to separate processing of sulfides either in the vapor or during core formation. (C) 2007 Elsevier Ltd. All rights reserved.

We have analyzed the Pb isotopic compositions of whole-rocks and various components (CAIs, chondrules, and/or mineral separates) of two carbonaceous chondrites, Allende (CV3) and Murchison (CM2), and nine ordinary chondrites, Sainte Marguerite (H4), Nadiabondi and Forest City (H5), Kernouve (H6), Bjurbole (L/LL4), Elenovka and Ausson (L5), Tuxtuac (LL5), and Saint-Severin (LL6) by MC-ICP-MS. Three CAI fractions from Allende define an isochron with an age of 4568.1 ± 9.4 Ma (MSWD = 0.08) and plot on the same isochron as fragments of the Efremovka inclusion E60 analyzed by Amelin et al. [Amelin, Y., Krot, A. N., Hutcheon, I. D., and Ulyanov, A. A. (2002a). Lead isotopic ages of chondrules and calcium–aluminum-rich inclusions. Science 297 , 1679–1683]. When these two groups of samples are combined, the isochron yields an age of 4568.5 ± 0.5 (MSWD = 0.90), which is our best estimate of the age of the Solar System. Chondrules and pyroxene–olivine fractions from the ordinary chondrites yield ages that reflect the blocking of Pb isotope equilibration with the nebular gas. The combination of these ages with the corresponding metamorphic phosphate ages provides constraints on the thermal history of the different chondrite parent bodies. Among the H chondrites, Sainte Marguerite cooled to below ∼1100 K within a few My at 4565 Ma and to ∼800 K at 4563 Ma. Nadiabondi appears to have experienced a slightly more protracted cooling history with the corresponding interval lasting from 4559 to 4556 Ma. The data from Forest City and Kernouve show evidence of late-stage perturbation with resulting U/Pb fractionation. Likewise, Pb isotopes in Tuxtuac (LL5) record a cooling history lasting from ∼4555 to 4544 Ma, which may indicate that the cooling history for the LL parent body was more prolonged than for the H parent body. We suggest a thermal evolution model for the growth of the planetary bodies based on the release of radiogenic heat from 26 Al and 60 Fe. This model incorporates the accretion rate, which determines the time at which the radiogenic heat becomes efficiently trapped, and the terminal size of the parent body, which controls its overall thermal inertia. The parent bodies of carbonaceous chondrites, which show little indication of metamorphic transformation, collect cooler nebular material at a relatively late stage. Small asteroids of ∼10–50 km radius accreting within 1–3 My could be the parent bodies of H and LL chondrites. The parent body of the L chondrites is likely to be a larger asteroid ( r > 100 km) or possibly the product of collisions of smaller planetary bodies.

We determined by ICP-MS the concentrations and isotopic ratios of Fe, Cu, and Zn in the Ti-rich lunar basalt 74275, in the lunar orange glass 74220, and in up to 10 lunar soils, namely, 14163, 15231, 64501, 66041, 68841, 69941, 70011, 72501, 75081, and 76501. Two analyses of zinc in lunar basalt 74275 give δ 66 Zn = 0.17‰ and 0.75‰, values within the range of those measured in terrestrial basalts; copper in lunar basalt 74275 has δ 65 Cu ∼ +1.4‰, which is isotopically heavier than values observed in terrestrial basalts. In the orange glass, we measured δ 56 Fe = −0.24‰, δ 65 Cu = −0.42‰, and δ 66 Zn ∼ −3.6‰. These values of δ are more negative than those obtained for 74275 and for typical lunar basalts, but for Cu, comparable to those observed in terrestrial sulfides and meteorites. In lunar soils we found 0.11‰ ⩽ δ 56 Fe ⩽ 0.51‰, 2.6‰ ⩽ δ 65 Cu ⩽ 4.5‰, and 2.2‰ ⩽ δ 66 Zn ⩽ 6.4‰. Insofar as we can generalize from a small sample set, S, Fe, Cu, Zn, and Cd show similar trends in isotopic fractionation on the Moon. Lunar basalts have nearly terrestrial isotopic ratios. Relative to the lunar basalt 74275, the pyroclastic glass 74220 is enriched in the lighter isotopes of Fe, Cu, and Zn, and the soils are enriched in the heavier isotopes of Fe, Cu, and Zn. The patterns in the basalts are likely inherited from the source material; the light-isotope enrichments seen in the orange glass originated during lava fountaining or, less probably, during partial condensation of vapor; and the heavy-isotope enrichments in the lunar soils were likely created by a combination of processes that included micrometeorite vaporization and sputtering. In the orange glass, the light-isotope enrichments (relative to lunar basalts) of Zn are larger than those of Cu. If these enrichments reflect accurately the isotopic composition of the gas, they suggest that Cu is more volatile than Zn in the liquid from which the gas derived. A simple model built on the known flux of micrometeorites to the lunar surface and a published estimate that micrometeorites generate 10 times their own mass of vapor, predicts heavy-isotope enrichments comparable to those observed in soils but only if the regolith gardening rate is set at about one twentieth of the generally accepted value of 1 cm/My. This discrepancy may reflect the difference in the time constants for micrometeorite milling and decimeter-scale gardening, or the importance of sputtering.

International audience; Even in the absence of nucleosynthesis, mass-independent isotope effect due to nuclear field can lead to a number of isotope anomalies found in refractory inclusions of chondrites. Isotope anomalies observed for Ba, Ca, Sr, Ti, and Cr in FUN inclusions may simply be explained by the nuclear field effects of these elements. A whole class of isotopic heterogeneities may therefore reflect evaporation/condensation processes in the solar nebula rather than nucleosynthetic effects. We speculate that the current estimates of the r-process component of the normal solar material may be affected by non-mass dependent fractionation effects.

We measured the 153Eu/151Eu ratio by MC-ICP-MS for a terrestrial basalt, two terrestrial soils, and four meteorites (whole rocks and/ or chondrules of Bjurbo¨ le, Forest City, Murchison, and Allende) and found no isotopic variations. By contrast, two CAI separates from two different pieces of Allende show a 153Eu deficit of up to one per mil. Such a shortage in the heavy isotopes, which had also been identified in Allende CAIs for Sr [Patchett, P.J. 1980b. Sr isotopic fractionation in Allende chondrules: a reflection of solar nebular processes. Earth Planet. Sci. Lett. 50, 181–188], cannot reflect evaporative fractionation. The lack of Sm isotope fractionation in the same samples further makes fractionation by purely kinetic processes an unlikely cause of the anomalous Eu isotopic composition. An alternative interpretation is condensation from a vapor already significantly depleted in Eu, but in such a scenario the fate of the missing material is unclear. We therefore prefer yet another interpretation, based on the low ionization potential of Eu (and Sr), in which electromagnetic separation of the ionized gas preferentially depletes the nebular gas in heavy isotopes.

Dauphas et al.'s model for the nucleosynthetic origin of Mo and Ru anomalies in meteorites leaves the case of Murchison (CM2) unexplained. We explore the possibility that such a discrepancy is due to mass-independent effects controlled by nuclear field shift with, in particular, "staggering" between odd and even masses. We first demonstrate the existence of such mass-independent fractionation of Mo and Ru isotopes by chemical exchange of Mo and Ru between DC18C6 crown ether and aqueous solutions. Our results fit the nuclear field shift theory of Bigeleisen. We then review the correlation between the mean-square charge radius (which controls the nuclear field shift) and the isotopic anomalies found in an Allende CAI and in Murchison. Although Mo and Ru in the Allende CAI show a clear indication of nucleosynthetic components, the mass-independent anomalies observed in Murchison show a strong correlation with the nuclear charge distribution. We therefore argue that some isotopic anomalies observed in meteorites may be due to nuclear field shift rather than nucleosynthetic processes. Such effects are temperature dependent and may represent either genuine nebular processes or analytical artifacts. This new interpretation may help assess the existence of anomalies due to the extinct isotopes 97Tc and 98Tc.

I would like to thank the Volcanology, Geochemistry, and Petrology section for awarding me this prize and all the people who were involved in my nomination and wrote the letters. When Catherine McCammon phoned me to let me know that I was awarded the Kuno Award, I was very surprised at first, and then I felt very honored and lucky. I have been very lucky to have Francis Albarede and Janne Blichert-Toft as Ph.D. advisors. Without their mentoring, I would not be standing here today. Completing my Ph.D. in this dynamic laboratory was an incredible experience, and I was very fortunate to meet many people who became mentors, collaborators, and friends, among whom I will cite Arnaud Agranier, Pierre Beck, and Toshi Fujii.

International audience; The presence or absence of variations in the mass-independent abundances of Si isotopes in bulk meteorites provides important clues concerning the evolution of the early solar system. No Si isotopic anomalies have been found within the level of analytical precision of 15 ppm in 29Si/28Si across a wide range of inner solar system materials, including terrestrial basalts, chondrites, and achondrites. A possible exception is the angrites, which may exhibit small excesses of 29Si. However, the general absence of anomalies suggests that primitive meteorites and differentiated planetesimals formed in a reservoir that was isotopically homogenous with respect to Si. Furthermore, the lack of resolvable anomalies in the calcium-aluminum-rich inclusion measured here suggests that any nucleosynthetic anomalies in Si isotopes were erased through mixing in the solar nebula prior to the formation of refractory solids. The homogeneity exhibited by Si isotopes may have implications for the distribution of Mg isotopes in the solar nebula. Based on supernova nucleosynthetic yield calculations, the expected magnitude of heavy-isotope overabundance is larger for Si than for Mg, suggesting that any potential Mg heterogeneity, if present, exists below the 15 ppm level.

Zinc (Zn) is required for the function of more than 300 enzymes involved in many metabolic pathways, and is a vital micronutrient for living organisms. To investigate if Zn isotopes could be used to better understand metal homeostasis, as well as a biomarker for diseases, we assessed the distribution of natural Zn isotopes in various mouse tissues. We found that, with respect to Zn isotopes, most mouse organs are isotopically distinct and that the total range of variation within one mouse encompasses the variations observed in the Earth's crust. Therefore, biological activity may have a major impact on the distribution of Zn isotopes in inorganic materials. The most striking aspect of the data is that red blood cells and bones are enriched by ~0.5 per mil in (66)Zn relative to (64)Zn when compared to serum, and up to ~1 per mil when compared to the brain and liver. This fractionation is well explained by the equilibrium distribution of isotopes between different bonding environments of Zn in different organs. Differences in gender and genetic background did not appear to affect the isotopic distribution of Zn. Together, these results suggest the potential use of Zn isotopes as a tracer for dietary Zn, and for detecting disturbances in Zn metabolism due to pathological conditions.

Isotopic anomalies in planetary materials reflect both early solar nebular heterogeneity inherited from presolar stellar sources and processes that generated non-mass-dependent isotopic fractionations. The characterization of isotopic variations in heavy elements among early solar system materials yields important insight into the stellar environment and formation of the solar system, and about initial isotopic ratios relevant to long-term chronological applications. One such heavy element, strontium, is a central element in the geosciences due to wide application of the long-lived 87 Rb– 87 Sr radioactive as a chronometer. We show that the stable isotopes of Sr were heterogeneously distributed at both the mineral scale and the planetary scale in the early solar system, and also that the Sr isotopic heterogeneities correlate with mass-independent oxygen isotope variations, with only CI chondrites plotting outside of this correlation. The correlation implies that most solar system material formed by mixing of at least two isotopically distinct components: a CV-chondrite-like component and an O-chondrite-like component, and possibly a distinct CI-chondrite-like component. The heterogeneous distribution of Sr isotopes may indicate that variations in initial 87 Sr/ 86 Sr of early solar system materials reflect isotopic heterogeneity instead of having chronological significance, as interpreted previously. For example, given the differences in 84 Sr/ 86 Sr between calcium aluminum inclusions and eucrites (e 84 Sr > 2), the difference in age between these materials would be ∼6 Ma shorter than previously interpreted, placing the Sr chronology in agreement with other long- and short-lived isotope systems, such as U–Pb and Mn–Cr.

Stepwise dissolution of primitive meteorites exhibits large 54Cr anomalies but no collateral effects on 58Fe and 48Ca, two other neutron-rich nuclides from the iron peak. These results suggest that 54Cr must have been produced in particular zones of the rare Type Ia supernovae or that 48Ca and/or 58Fe were produced together in Type II supernovae and were chemically separated into some mineral phase that favors Cr over Ca and Fe, and it is the dissolution properties of that phase that is driving the isotopic effect in leaching. The recent findings of nanometer-size oxide grains with very large 54Cr excesses favored the latter scenario for the origin of the mono-isotopic Cr isotopic effect. In addition, the absence of isotopic variations in the 58Fe/54Fe ratio at the mineral scale confirms that the short-lived nuclide 60Fe (T 1/2 = 2.62 Myr) was homogeneously distributed to a less than 15% dispersion in the early solar nebula.

Due to the error in production, online supplementary Table S5 of the article by B. Jacobsen et al. EPSL 272, p 353–364 was omitted from itssupplemental files. It contains full details of U–Pb data reduction and related plots. We believe it is useful for the U–Pb practitioners. Table S5 isposted both in excel file as well as pdf file. We also note in the Table 2 of the main text onpage 358, column 5 heading was misprinted as 206Pb/206Pb (raw). It should be 206Pb/204Pb (raw). EPSL and Elsevierdo apologize for the inconvenience this omission to the earlier version mayhavecaused to our readers.Appendix A. Supplementary dataSupplementary data associated with this article can be found, in the online version, at doi:10.1016/j.epsl.2008.12.001.

Significance We present time-anchored elemental abundance data for some of the Solar System’s first solids by tracking Pb−Pb dated chondrule compositions. Volatile element contents generally rise, while redox conditions (based on chondrule Mn/Na ratios) decline beginning ∼1 My after Solar System formation (∼4,567 Ma). These results reflect a continued rise in volatile element contents and their fugacities during chondrule recycling, and early water influx to the inner Solar System followed by its express removal. These observations support the early formation of Mars under oxidizing condition and Earth’s protracted growth under more reducing conditions in an environment increasing in volatile contents with time, while also calling into question the coupling of water and volatile elements during Solar System evolution., Chondrites and their main components, chondrules, are our guides into the evolution of the Solar System. Investigating the history of chondrules, including their volatile element history and the prevailing conditions of their formation, has implications not only for the understanding of chondrule formation and evolution but for that of larger bodies such as the terrestrial planets. Here we have determined the bulk chemical composition—rare earth, refractory, main group, and volatile element contents—of a suite of chondrules previously dated using the Pb−Pb system. The volatile element contents of chondrules increase with time from ∼1 My after Solar System formation, likely the result of mixing with a volatile-enriched component during chondrule recycling. Variations in the Mn/Na ratios signify changes in redox conditions over time, suggestive of decoupled oxygen and volatile element fugacities, and indicating a decrease in oxygen fugacity and a relative increase in the fugacities of in-fluxing volatiles with time. Within the context of terrestrial planet formation via pebble accretion, these observations corroborate the early formation of Mars under relatively oxidizing conditions and the protracted growth of Earth under more reducing conditions, and further suggest that water and volatile elements in the inner Solar System may not have arrived pairwise.

International audience

Modern oceanic crust is constantly produced at oceanic ridges and recycled back into the mantle at subduction zones via plate tectonics. An outstanding question in geology is whether the Earth started in a non-plate tectonic regime, and if it did, when the transition to the modern regime occurred. This is a complicated question to address because Archaean rocks lack modern equivalents to anchor interpretations. Here, we present a silicon isotopic study of 4.0–2.8-Gyr-old tonalite–trondhjemite–granodiorites, as well as Palaeozoic granites and modern adakites. We show that Archaean granitoids have heavier silicon isotopic compositions than granites and adakites, regardless of melting pressure. This is best explained if Archaean granitoids were formed by melting of subducted basaltic crust enriched in sedimentary silica through interaction with seawater. Before the appearance of silica-forming organisms 0.5–0.6 billion years ago, the oceans were close to silicon saturation, which led to extensive precipitation of cherts on the seafloor. This is in contrast to modern oceans, where silica biomineralization maintains dissolved silicon at low concentration. The unique heavy silicon isotope signature of cherts has been transferred to Archaean granitoids during an oceanic subduction process, which was probably responsible for the formation of felsic rocks on Archaean emerged lands. Archaean granitic rocks formed by melting of silica-enriched subducted basaltic crust through interaction with seawater, according to heavy silicon isotopes measured in Archaean samples.

International audience; Zirconium plays a major role in geochemistry as it is the major cation of zircons - the oldest preserved minerals on Earth. While Zr isotopic anomalies in meteorites have been widely studied, mass dependant Zr stable isotope fractionation during geological processing has been untouched. Here, we report Zr stable isotopic data for terrestrial igneous rocks and present a novel method for the determination of Zr stable isotope ratios within natural geological materials using ion exchange, double-spike, multiple-collector inductively coupled mass spectrometry (MC-ICPMS). Zirconium is isolated from the rock matrix via a chromatographic separation protocol using a first pass column with AG1-X8 anion exchange resin, and a second pass column containing Eichrom (R) DGA resin. A Zr-91-Zr-96 double-spike was created from enriched single Zr-91 and Zr-96 isotope spikes. Samples were combined with the Zr double-spike at a 43: 57 spike: sample [Zr] ratio, prior to dissolution and column chemistry. After column chemistry the purified sample solutions were analysed on a Thermo Scientific Neptune Plus MC-ICPMS and the data was reduced using IsoSpike, with the final Zr isotope data being reported as the per mil deviation of the Zr-94/Zr-90 from the IPGP-Zr standard (delta Zr-94/90(IPGP-Zr)). The delta Zr-94/90(IPGP-Zr) of six igneous standard reference materials: two basalts (BHVO-2 and JB-2), one andesite (AGV-2), two granites (GA and GS-N) and a serpentinite (UB-N) as well as one individual zircon grain (Plesovice zircon), are presented using this method. Sample measurements are presented with an analytical uncertainty of +/- similar to 0.05% (2sd) for delta Zr-94/90(IPGP-Zr) and these rocks exhibit isotopic variations of similar to 0.15% for delta Zr-94/90(IPGP-Zr). These results demonstrate that natural variations of Zr isotopes occur within terrestrial igneous rocks, and are resolvable with this method. Finally the variation of delta Zr-94/90(IPGP-Zr) values observed within the magmatic rock reference materials is correlated (R-2 = 0.78; n = 5) with SiO2, suggesting that Zr isotopes could serve as a sensitive tracer of magmatic processes.

Among the elements exhibiting non-mass dependent isotopic variations in meteorites, chromium (Cr) has been central in arguing for an isotopic homogeneity between the Earth and the Moon, thus questioning physical models of Moon formation. However, the Cr isotopic composition of the Moon relies on two samples only, which define an average value that is slightly different from the terrestrial standard. Here, by determining the Cr isotopic composition of 17 lunar, 9 terrestrial and 5 enstatite chondrite samples, we re-assess the isotopic similarity between these different planetary bodies, and provide the first robust estimate for the Moon. In average, terrestrial and enstatite samples show similar e 54 Cr. On the other hand, lunar samples show variables excesses of 53Cr and 54Cr compared to terrestrial and enstatite chondrites samples with correlated e 53 Cr and e 54 Cr (per 10,000 deviation of the 53Cr/52Cr and 54Cr/52Cr ratios normalized to the 50Cr/52Cr ratio from the NIST SRM 3112a Cr standard). Unlike previous suggestions, we show for the first time that cosmic irradiation can affect significantly the Cr isotopic composition of lunar materials. Moreover, we also suggest that rather than spallation reactions, neutron capture effects are the dominant process controlling the Cr isotope composition of lunar igneous rocks. This is supported by the correlation between e 53 Cr and e 54 Cr, and 150Sm/152Sm ratios. After correction of these effects, the average e 54 Cr of the Moon is indistinguishable from the terrestrial and enstatite chondrite materials reinforcing the idea of an Earth–Moon–enstatite chondrite system homogeneity. This is compatible with the most recent scenarios of Moon formation suggesting an efficient physical homogenization after a high-energy impact on a fast spinning Earth, and/or with an impactor originating from the same reservoir in the inner proto-planetary disk as the Earth and enstatite chondrites and having similar composition.

Tin is a volatile as well as chalcophile and siderophile element, and this geochemical behaviour gives rise to a broad range of potential applications for Sn as a stable isotope tracer in geological processes. We present the first high-precision method to analyse the stable isotopic composition of Sn in geological materials using ion-exchange chromatography and double-spike multi-collector inductively-coupled-plasma mass-spectrometry (MC-ICPMS). We apply these methods to analyse the Sn stable isotopic composition of four geological reference materials, including a number of replicate digestions of BHVO-2 and BCR-2 to assess the reproducibility of the technique. Tin was purified prior to analysis using TRU resin to remove matrix and interfering elements. Isotopic ratios were measured using a Thermo-Fischer Neptune Plus MC-ICPMS combined with a 117Sn–122Sn double-spike to correct for any mass dependent fractionation resulting from instrumental mass bias or incomplete yields from chemical purification. Results are expressed in delta notation as δ 122/118Sn, representing the per mil (‰) difference in the 122/118Sn ratio of the sample relative to our in-house standard Sn_IPGP. Based on replicate analyses of the USGS reference materials BHVO-2 and BCR-2, we estimate the external reproducibility to be ca. ± 0.065‰ (2 sd) on the δ 122/118Sn ratio, or ca. ± 0.016‰ per amu. Analyses of these plus two additional USGS reference materials, AGV-2 and GSP-2, show a large range (>0.2‰ on δ 122/118Sn) of Sn stable isotopic compositions that are correlated with igneous differentiation indicators (e.g. SiO2 content), indicating that Sn isotopes are fractionated during igneous processes. These results indicate significant potential for Sn stable isotopes as a tracer of magmatic differentiation and the redox state of the mantle. In addition, Sn stable isotopes may prove useful in tracing diverse geological processes such as volatilisation/condensation and metal–silicate/metal–sulphide differentiation.

Recognizing existing materials that can act as proxies for Earth's building blocks, and understanding the accretionary pathway taken during Earth's growth, persist as outstanding issues in need of resolution. In Mahan, Siebert, Blanchard, Badro, et al. (2018, https://doi.org/10.1029/2018JB015991), we conducted diamond anvil cell (DAC) Cu metal‐silicate partitioning experiments and coupled these results with a large complement of literature data to characterize Cu metal‐silicate partitioning during Earth's core formation and accretion history. The Comment of Jennings, Wade, and Llovet (2019, https://doi.org/ 10.1029/2018JB016930) contends that secondary X‐ray fluorescence, originating from the Cu holders that experiments are routinely welded to (“lift‐out” grids), compromises the novel Cu partitioning data of Mahan, Siebert, Blanchard, Badro, et al. (2018) beyond utility. To dispel these concerns and further validate our data, we have (i) investigated secondary X‐ray fluorescence effects in a Cu‐free experiment and provided a matrix‐matched data correction, and (ii) rewelded a DAC experiment from a Cu grid to a Mo grid for a comparison of compositional analyses and Cu partitioning results. Secondary fluorescence results, in fact much like the simulated results in Jennings, Wade, and Llovet (2019), indicate that this effect is essentially equal in the metal and silicate phases and therefore has no actual impact on Cu metal‐silicate partition coefficients. Moreover, Cu concentrations and partition coefficients determined using the Mo grid are statistically indistinguishable from that determined using the Cu grid. All results decisively illustrate that while secondary X‐ray fluorescence must be considered where absolute concentrations are the final objective, it has had no meaningful impact on the partitioning data and observations of Mahan, Siebert, Blanchard, Badro, et al. (2018).

Stable isotope studies of highly siderophile elements (HSE) have the potential to yield valuable insights into a range of geological processes. In particular, the strong partitioning of these elements into metal over silicates may lead to stable isotope fractionation during metal–silicate segregation, making them sensitive tracers of planetary differentiation processes. We present the first techniques for the precise determination of palladium stable isotopes by MC-ICPMS using a 106Pd–110Pd double-spike to correct for instrumental mass fractionation. Results are expressed as the per mil (‰) difference in the 106Pd/105Pd ratio (δ106Pd) relative to an in-house solution standard (Pd_IPGP) in the absence of a certified Pd isotopic standard. Repeated analyses of the Pd isotopic composition of the chondrite Allende demonstrate the external reproducibility of the technique of ±0.032‰ on δ106Pd. Using these techniques, we have analysed Pd stable isotopes from a range of terrestrial and extraterrestrial samples. We find that chondrites define a mean δ106Pdchondrite = −0.19 ± 0.05‰. Ureilites reveal a weak trend towards heavier δ106Pd with decreasing Pd content, similar to recent findings based on Pt stable isotopes (Creech et al., 2017), although fractionation of Pd isotopes is significantly less than for Pt, possibly related to its weaker metal–silicate partitioning behaviour and the limited field shift effect. Terrestrial mantle samples have a mean δ106Pdmantle = −0.182 ± 0.130‰, which is consistent with a late-veneer of chondritic material after core formation.

The Moon and the Earth's mantle share many chemical and isotopic traits, leading to the prevailing theory that they were formed from similar material. Iron is one element that shows apparent differences between the two bodies, with models for the composition of the Moon having ≈1.5 times more FeO (12–14 wt.%), relative to the Earth's mantle (8 wt.%). This difference is mirrored in their isotope compositions, where lunar mare basalts have δ57Fe (per mille deviation of the 57Fe/54Fe ratio from the IRMM-014 standard) 0.1–0.2‰ higher than peridotitic rocks representative of Earth's mantle, a feature initially attributed to loss of isotopically light Fe following a giant impact. However, whether basaltic rocks are suitable analogues for the Moon's composition is debatable in the light of their distinct source regions that reflect the extensive lithological stratification of the lunar mantle. Here, we evaluate the iron isotope composition of the bulk Moon through the study of igneous cumulate rocks of the lunar highlands Magnesium Suite (Mg Suite). The δ57Fe of Mg Suite rocks spans a limited range, from 0.05‰ to 0.10‰, with an average ( + 0.07 ± 0.02 ‰ ) that overlaps with Earth's mantle ( + 0.05 ± 0.01 ‰ ), similarities that extend to their Mg#s, where both reach 0.9. Numerical modelling of iron isotope fractionation during lunar magma ocean crystallisation shows that the Mg Suite should accurately reflect the composition of the bulk Moon, which is therefore + 0.07 ± 0.02 ‰ , indistinguishable from Earth's mantle but heavier than chondrites ( − 0.01 ± 0.01 ‰ ). Iron thus behaves coherently with other elements that condense at temperatures higher than Li in showing no isotopic difference between the Earth and Moon, suggesting element depletion on the Moon affected only the more volatile elements. Therefore, there is no cosmochemical basis for iron enrichment or depletion in the bulk Moon relative to the Earth's mantle, whose composition is an analogue for that of the Moon.