Microscopic oxygen isotopic homogeneity/heterogeneity in the matrix of the Vigarano CV3 chondrite

Two-dimensional ¹⁸O/¹⁶O isotopic analysis of the Vigarano matrix was conducted by secondary ion-imaging using a novel two-dimensional ion-imager. Quantitative oxygen-isotope images (isotopographs) of the Vigarano matrix show that ¹⁶O-rich micrograins are scattered within ¹⁶O-poor matrix. This heterogeneous O-isotopic distribution indicates that matrix is composed of different O-isotopic components that formed in different locations and/or at different times. However, the O-isotopic composition of groundmass in the matrix is the same as the bulk isotopic composition of the matrix within ±5‰ uncertainty. The spatial resolution and isotopic precision of our technique should allow submicron-size objects (>0.2 μm) with extreme O-isotopic anomalous characteristics (δ¹⁸O_SMOW ∼250‰) to be detectable in isotopographs. Because the mean grain size of the matrix is ∼0.2 μm, the inability to detect such O-isotopic anomalous objects indicates that isotopically anomalous micrograins (e.g., presolar grains) are extremely rare in the Vigarano matrix and that most objects in the matrix were formed in the solar nebula or in the parent body.     

Identification of isotopically primitive interplanetary dust particles: A NanoSIMS isotopic imaging study

We have carried out a comprehensive survey of the isotopic compositions (H, B, C, N, O, and S) of a suite of interplanetary dust particles (IDPs), including both cluster and individual particles. Isotopic imaging with the NanoSIMS shows the presence of numerous discrete hotspots that are strongly enriched in ¹⁵N, up to ∼1300‰. A number of the IDPs also contain larger regions with more modest enrichments in ¹⁵N, leading to average bulk N isotopic compositions that are ¹⁵N-enriched in these IDPs. Although C isotopic compositions are normal in most of the IDPs, two ¹⁵N-rich hotspots have correlated ¹³C anomalies. CN⁻/C⁻ ratios suggest that most of the ¹⁵N-rich hotspots are associated with relatively N-poor carbonaceous matter, although specific carriers have not been determined. H isotopic distributions are similar to those of N: D anomalies are present both as distinct D-rich hotspots and as larger regions with more modest enrichments. Nevertheless, H and N isotopic anomalies are not directly correlated, consistent with results from previous studies. Oxygen isotopic imaging shows the presence of abundant presolar silicate grains in some of the IDPs. The O isotopic compositions of the grains are similar to those of presolar oxide and silicate grains from primitive meteorites. Most of the silicate grains in the IDPs have isotopic ratios consistent with meteoritic Group 1 oxide grains, indicating origins in oxygen-rich red giant and asymptotic giant branch stars, but several presolar silicates exhibit the ¹⁷O and ¹⁸O enrichments of Group 4 oxide grains, whose origin is less well understood. Based on their N isotopic compositions, the IDPs studied here can be divided into two groups. One group is characterized as being “isotopically primitive” and consists of those IDPs that have anomalous bulk N isotopic compositions. These particles typically also contain numerous ¹⁵N-rich hotspots, occasional C isotopic anomalies, and abundant presolar silicate grains. In contrast, the other “isotopically normal” IDPs have normal bulk N isotopic compositions and, although some contain ¹⁵N-rich hotspots, none exhibit C isotopic anomalies and none contain presolar silicate or oxide grains. Thus, isotopically interesting IDPs can be identified and selected on the basis of their bulk N isotopic compositions for further study. However, this distinction does not appear to extend to H isotopic compositions. Although both H and N anomalies are frequently attributed to the survival of molecular cloud material in IDPs and, thus, should be more common in IDPs with anomalous bulk N compositions, D anomalies are as common in normal IDPs as they are in those characterized as isotopically primitive, based on their N isotopes.     

Neon and argon in the Allende meteorite

Trapped and cosmogenic Ne and Ar were measured in Ca,Al-rich aggregates and chondrules, mafic chondrules, and bulk and matrix samples from the Allende C3V chondritic meteorite to investigate the possible occurrence of anomalous isotopic compositions of noble gases that would correlate with oxygen or magnesium isotopic anomalies previously found in this meteorite.Large enrichments of both ²²Ne and ³⁶Ar were observed in low-temperature release fractions from several Ca,Al-rich inclusions, but the enrichments are consistent with galactic cosmic-ray production of ²²Ne by spallation from sodium and ³⁶Ar by neutron capture on chlorine. Trapped neon in matrix samples is comprised of two distinctive compositions, with (²⁰Ne/²²Ne)_t equal to 8.7 ± 0.1 and 10.4 ± 1.0, that appear to correlate with the two gas-rich trace phases chromite/carbon and ‘Q’ described by Lewis et al. (1975). Several Ca,Al-rich aggregates which have high contents of the volatile elements Na, Cl, K, and Rb also contain trapped neon. However, no neon-E has been identified in any of the samples studied, including samples of several inclusions known to contain isotopically anomalous oxygen and magnesium.     

Solar and cosmogenic argon in dated lunar impact spherules

We have studied lunar impact spherules from the Apollo 12 and Apollo 14 landing sites, examining the isotopic composition of argon released by stepwise heating. Elsewhere, we reported the formation ages of these spherules, determined by the ⁴⁰Ar/³⁹Ar isochron method. Here, we discuss solar and cosmogenic argon from the same spherules, separating these two components by correlating their partial releases with the releases of calcium-derived ³⁷Ar on a “cosmochron” diagram. We use the abundances of cosmogenic argon to derive a cosmic ray exposure age for each spherule, and demonstrate that single scoops of lunar soil contain spherules which have experienced very different histories of exposure and burial. The solar argon is seen to be separated into isotopically lighter and heavier fractions, which presumably were implanted to different depths in the spherules. The abundance of the isotopically heavy solar argon is too great to explain as a minor constituent of the solar particle flux, such as the suprathermal tail of the solar wind. The fact that the spherules have been individually dated allows us to look for possible variations in the solar wind as a function of time, over the history of the Solar System. However, the isotopic composition and fluence of solar argon preserved in the lunar spherules appear to be independent of formation age. We believe that most of the spherules are saturated with solar argon, having reached a condition in which implantation by the solar wind is offset by losses from solar-wind sputtering and diffusion.     

Do lunar and meteoritic archives record temporal variations in the composition of solar wind noble gases and nitrogen? A reassessment in the light of Genesis data

Since about half a century samples from the lunar and asteroidal regoliths been used to derive information about elemental and isotopic composition and other properties of the present and past solar wind, predominantly for the noble gases and nitrogen. Secular changes of several important compositional parameters in the solar wind were proposed, as was a likely secular decrease of the solar wind flux. In 2004 NASA’s Genesis mission returned samples which had been exposed to the solar wind for almost 2.5 years. Their analyses resulted in an unprecendented accuracy for the isotopic and elemental composition of several elements in the solar wind, including noble gases, O and N. The Genesis data therefore also allow to re-evaluate the lunar and meteorite data, which is done here. In particular, claims for long-term changes of solar wind composition are reviewed.Outermost grain layers from relatively recently irradiated lunar regolith samples conserve the true isotopic ratios of implanted solar wind species. This conclusion had been made before Genesis based on the agreement of He and Ne isotopic data measured in the aluminum foils exposed to the solar wind on the Moon during the Apollo missions with data obtained in the first gas release fractions of stepwise in-vacuo etch experiments. Genesis data allowed to strengthen this conclusion and to extend it to all five noble gases. Minor variations in the isotopic compositions of implanted solar noble gases between relatively recently irradiated samples (<100 Ma) and samples irradiated billions of years ago are very likely the result of isotopic fractionation processes that happened after trapping of the gases rather than indicative of true secular changes in the solar wind composition. This is particularly important for the ³He/⁴He ratio, whose constancy over billions of years indicates that hardly any ³He produced as transient product of the pp-chains has been mixed from the solar interior into its outer convective zone. The He isotopic composition measured in the present-day solar wind therefore is identical to the (D + ³He)/⁴He ratio at the start of the suns’s main sequence phase and hence can be used to determine the protosolar D/H ratio.Genesis settled the long-standing controversy on the isotopic composition of nitrogen in lunar regolith samples. The ¹⁵N/¹⁴N ratio in the solar wind as measured by Genesis is lower than in any lunar sample. This proves that nitrogen in regolith samples is dominated by non-solar sources. A postulated secular increase of ¹⁵N/¹⁴N by some 30% over the past few Ga is not tenable any longer. Genesis also provided accurate data on the isotopic composition of oxygen in the solar wind, invaluable for cosmochemisty. These data superseded but essentially confirmed one value – and disproved a second one – derived from lunar regolith samples shortly prior to Genesis.Genesis also confirmed prior conclusions that lunar regolith samples essentially conserve the true elemental ratios of the heavy noble gases in the solar wind (Ar/Kr, Kr/Xe). Several secular changes of elemental abundances of noble gases in the solar wind had been proposed based on lunar and meteoritic data. I argue here that lunar data – in concert with Genesis – provide convincing evidence only for a long-term decrease of the Kr/Xe ratio by almost a factor of two over the past several Ga. It appears that the enhancement of abundances of elements with a low first ionisation potential in the solar wind (FIP effect) changed with time.Finally, Genesis allows a somewhat improved comparison of the present-day flux of solar wind Kr and Xe with the total amount of heavy solar wind noble gases in the lunar regolith. It remains unclear whether the past solar wind flux has been several times higher on average than it is today.     

Irradiation records in regolith materials. I: isotopic compositions of solar-wind neon and argon in single lunar mineral grains

We have applied a stepwise pyrolytic extraction technique to eleven individual lunar regolith grains to investigate the compositions of light noble gases embedded in grain surfaces by solar wind irradiation, with emphasis on the rather poorly known isotopic composition of solar-wind argon. Results are intriguing: average ²⁰Ne/²²Ne ratios observed in early pyrolytic releases from ilmenite grains separated from lunar soils 71501, 79035 and 10084 agree very well with both direct measures of the solar wind neon composition in the Apollo foils and with values obtained in first releases from acid-etched ilmenites by the Zürich laboratory, whereas these same pyrolytic and acid-etch fractions carry argon isotopic signatures that significantly disagree—average ³⁶Ar/³⁸Ar ratios near 5.8 for thermal extraction compared to 5.4–5.5 for chemical etching at Zürich. Consideration of the isotopic and elemental data from these grains in the context of first-order diffusive modeling calculations points to gas release at low temperatures, without significant isotopic or elemental fractionation, from isolated grain-surface reservoirs of solar wind composition. The physical nature of these reservoirs is presently unknown. In this interpretation the preferred solar wind ²⁰Ne/²²Ne and ²¹Ne/²²Ne ratios deduced from this study are respectively 13.81 ± 0.08 and 0.0333 ± 0.0003, both within error of the Zürich acid-etch values, and ³⁶Ar/³⁸Ar = 5.77 ± 0.08. It may be possible to reconcile the discrepancy between the acid-etch and pyrolytic estimates for the solar wind ³⁶Ar/³⁸Ar ratio in the context of arguments originally advanced by Benkert et al. (1993) to account for their He and Ne isotopic compositions. At the other, high-temperature end of the release profile from one of these grains there are clear isotopic indications of the presence of a Ne constituent with ²⁰Ne/²²Ne close to the 11.2 ratio found at Zürich and attributed by these workers to a deeply-sited component implanted by solar energetic particles.     

High-precision osmium isotopes in enstatite and Rumuruti chondrites

Isotopic heterogeneity within the solar nebula has been a long-standing issue. Studies on primitive chondrites and chondrite components for Ba, Sm, Nd, Mo, Ru, Hf, Ti, and Os yielded conflicting results, with some studies suggesting large-scale heterogeneity. Low-grade enstatite and Rumuruti chondrites represent the most extreme ends of the chondrite meteorites in terms of oxidation state, and might thus also present extremes if there is significant isotopic heterogeneity across the region of chondrite formation. Osmium is an ideal tracer because of its multiple isotopes generated by a combination of p-, r-, and s-process and, as a refractory element; it records the earliest stages of condensation.Some grade 3-4 enstatite and Rumuruti chondrites show similar deficits of s-process components as revealed by high-precision Os isotope studies in some low-grade carbonaceous and ordinary chondrites. Enstatite chondrites of grades 5-6 have Os isotopic composition identical within error to terrestrial and solar composition. This supports the view of digestion-resistant presolar grains, most likely SiC, as the major carrier of these anomalies. Destruction of presolar grains during parent body processing, which all high-grade enstatite chondrites, but also some low-grade chondrites seemingly underwent, makes the isotopically anomalous Os accessible for analysis. The magnitude of the anomalies is consistent with the presence of a few ppm of presolar SiC with a highly unusual isotopic composition, produced in a different stellar environment like asymptotic giant branch stars (AGB) and injected into the solar nebula. The presence of similar Os isotopic anomalies throughout all major chondrite groups implies that carriers of Os isotopic anomalies were homogeneously distributed in the solar nebula, at least across the formation region of chondrites.     

53Mn-53Cr evolution of the early solar system

The model of Cr isotopic evolution presented here, relies on the relative volatility properties of the two elements: Mn-Cr in planetary formation processes. The Mn/Cr ratio of the respective parent bodies correlate in most cases with the K/U ratio. With the exception of Allende inclusions, the ⁵³Mn/⁵⁵Mn and ⁵³Cr/⁵²Cr isotopic ratios were homogeneous in the solar nebula. The Cr isotopic evolution of the bulk solar system corresponds to the C1 carbonaceous chondrites. In this figure the Earth is isolated within a few million years of the C1 formation, from the solar nebula before complete decay of ⁵³Mn. It has a Cr isotopic composition which is depleted in ⁵³Cr with respect to the solar system as a whole. The parent bodies of the different meteorite classes display various behaviour with no case of Mn enrichment relative to Cr when compared to C1. The ⁵³Mn-⁵³Cr isotopic system is a precise tool for the exploration of the early solar sytem history, bringing constraints both on time and processes in this phase of the evolution where the face of the planetary system was changing rapidly. The chronology deduced from Mn-Cr systematics, is generally in good agreement with other chronometers.     

Mineralogical and isotopic evidence for phenocryst-matrix disequilibrium in the Garner Mountain andesite

Petrographic, trace element and isotopic evidence demonstrates that magma mixing preceded the eruption of the Garner Mountain andesite. The flow contains reversely zoned plagioclase phenocrysts and amphibole pseudomorphs composed of plagioclase, clinopyroxene, orthopyroxene and opaque oxides. Partially resorbed quartz grains are also present. In contrast to the isotopically uniform matrix, plagioclase phenocrysts have ⁸⁷Sr/⁸⁶Sr ratios that correlate negatively with matrix Sr and positively with matrix Rb abundances. These observations demonstrate increasing isotopic disequilibrium between the plagioclase and matrix in the more evolved varieties of the flow.Plagioclase phenocrysts and matrix are assumed to record fractionation-assimilation events in different parts of the magma chamber. Early formed plagioclase phenocrysts crystallized under AFC conditions close to the roof of the chamber and were subsequently entrained in a liquid mixture composed of evolved interstitial liquid held in the partly crystallized roof zone and newly injected parental magma.     

Noble gas composition of the solar wind as collected by the Genesis mission

We present the elemental and isotopic composition of noble gases in the bulk solar wind collected by the NASA Genesis sample return mission. He, Ne, and Ar were analyzed in diamond-like carbon on a silicon substrate (DOS) and ^84,86Kr and ^129,132Xe in silicon targets by UV laser ablation noble gas mass spectrometry. Solar wind noble gases are quantitatively retained in DOS and with exception of He also in Si as shown by a stepwise heating experiment on a flown DOS target and analyses on other bulk solar wind collector materials. Solar wind data presented here are absolutely calibrated and the error of the standard gas composition is included in stated uncertainties. The isotopic composition of the light noble gases in the bulk solar wind is as follows: ³He/⁴He: (4.64 ± 0.09) × 10⁻⁴, ²⁰Ne/²²Ne: 13.78 ± 0.03, ²¹Ne/²²Ne: 0.0329 ± 0.0001, ³⁶Ar/³⁸Ar 5.47 ± 0.01. The elemental composition is: ⁴He/²⁰Ne: 656 ± 5, and ²⁰Ne/³⁶Ar 42.1 ± 0.3. Genesis provided the first Kr and Xe data on the contemporary bulk solar wind. The preliminary isotope and elemental composition is: ⁸⁶Kr/⁸⁴Kr: 0.302 ± 0.003, ¹²⁹Xe/¹³²Xe: 1.05 ± 0.02, ³⁶Ar/⁸⁴Kr 2390 ± 150, and ⁸⁴Kr/¹³²Xe 9.5 ± 1.0. The ³He/⁴He and the ⁴He/²⁰Ne ratios in the Genesis DOS target are the highest solar wind values measured in exposed natural and artificial targets. The isotopic composition of the other noble gases and the Kr/Xe ratio obtained in this work agree with data from lunar samples containing “young” (∼100 Ma) solar wind, indicating that solar wind composition has not changed within at least the last 100 Ma. Genesis could provide in many cases more precise data on solar wind composition than any previous experiment. Because of the controlled exposure conditions, Genesis data are also less prone to unrecognized systematic errors than, e.g., lunar sample analyses. The solar wind is the most authentic sample of the solar composition of noble gases, however, the derivation of solar noble gas abundances and isotopic composition using solar wind data requires a better understanding of fractionation processes acting upon solar wind formation.     

Mercury abundances and isotopic compositions in the Murchison (CM) and Allende (CV) carbonaceous chondrites

The abundance and isotopic composition of Hg was determined in bulk samples of both the Murchison (CM) and Allende (CV) carbonaceous chondrites using single- and multi-collector inductively coupled plasma mass spectrometry (ICP-MS). The bulk abundances of Hg are 294 ± 15 ng/g in Murchison and 30.0 ± 1.5 ng/g in Allende. These values are within the range of previous measurements of bulk Hg abundances by neutron activation analysis (NAA). Prior studies suggested that both meteorites contain isotopically anomalous Hg, with δ^196/202Hg values for the anomalous, thermal-release components from bulk samples ranging from −260 ‰ to +440 ‰ in Murchison and from −620 ‰ to +540 ‰ in Allende Jovanovic and Reed 1976a, Jovanovic and Reed 1976b, Kumar and Goel 1992. Our multi-collector ICP-MS measurements suggest that the relative abundances of all seven stable Hg isotopes in both meteorites are identical to terrestrial values within 0.2 to 0.5 ‰.On-line thermal-release experiments were performed by coupling a programmable oven with the single-collector ICP-MS. Powdered aliquots of each meteorite were linearly heated from room temperature to 900°C over twenty-five minutes under an Ar atmosphere to measure the isotopic composition of Hg released from the meteorites as a function of temperature. In separate experiments, the release profiles of S and Se were determined simultaneously with Hg to constrain the Hg distribution within the meteorites and to evaluate the possibility of Se interferences in previous NAA studies. The Hg-release patterns differ between Allende and Murchison. The Hg-release profile for Allende contains two distinct peaks, at 225° and 343°C, whereas the profile for Murchison has only one peak, at 344°C. No isotopically anomalous Hg was detected in the thermal-release experiments at a precision level of 5 to 30 ‰, depending on the isotope ratio. In both meteorites the Hg peak at ∼340°C correlates with a peak in the S-release profile. This correlation suggests that Hg is associated with S-bearing phases and, thus, that HgS is a major Hg-bearing phase in both meteorites. The Hg peak at 225°C for Allende is similar to release patterns of physically adsorbed Hg on silicate and metal grains. Prior studies suggested that the isotopic anomalies reported from NAA resulted from interference between ²⁰³Hg and ⁷⁵Se. However, the amount of Se released from both meteorites, relative to Hg, is insufficient to produce all of the observed anomalies.     

An Fe isotope study of ordinary chondrites

The Fe isotope composition of ordinary chondrites and their constituent chondrules, metal and sulphide grains have been systematically investigated. Bulk chondrites fall within a restricted isotopic range of <0.2‰ δ⁵⁶Fe, and chondrules define a larger range of >1‰ (−0.84‰ to 0.21‰ relative to the IRMM-14 Fe standard). Fe isotope compositions do not vary systematically with the very large differences in total Fe concentration, or oxidation state, of the H, L, and LL chondrite classes. Similarly, the Fe isotope compositions of chondrules do not appear to be determined by the H, L or LL classification of their host chondrite. This may support an origin of the three ordinary chondrite groups from variable accretion of identical Fe-bearing precursors.A close relationship between isotopic composition and redistribution of Fe during metamorphism on ordinary chondrite parent bodies was identified; the largest variations in chondrule compositions were found in chondrites of the lowest petrologic types. The clear link between element redistribution and isotopic composition has implications for many other non-traditional isotope systems (e.g. Mg, Si, Ca, Cr). Isotopic compositions of chondrules may also be determined by their melting history; porphyritic chondrules exhibit a wide range in isotope compositions whereas barred olivine and radial pyroxene chondrules are generally isotopically heavier than the ordinary chondrite mean. Very large chondrules preserve the greatest heterogeneity of Fe isotopes.The mean Fe isotope composition of bulk ordinary chondrites was found to be −0.06‰ (±0.12‰ 2 SD); this is isotopically lighter than the terrestrial mean composition and all other published non-chondritic meteorite suites e.g. lunar and Martian samples, eucrites, pallasites, and irons. Ordinary chondrites, though the most common meteorites found on Earth today, were not the sole building blocks of the terrestrial planets.     

Kinetics of C, N, and Xe release during the quasi-isothermal pyrolysis and subsequent oxidation of nanodiamond from the Orgueil CI meteorite

Analysis of the C, N, and Xe release kinetics of intermediate-sized nanodiamond fraction from the Orgueil CI meteorite during isothermal pyrolysis conducted for the first time and subsequent oxidation indicates that (a) the rate of C, N, and Xe release at pyrolysis at a constant temperature decreases with time; (b) the relative amount of released Xe, which mostly has a normal isotopic composition (Xe-P3) at various pyrolysis time up to 800°C, is controlled, first of all, by the heating temperature, whereas the amount of N is controlled by both the temperature and heating time; and (c) prolonged pyrolysis notably modifies the distribution of nitrogen of normal (δ¹⁵N = 0) and anomalous (δ¹⁵N= ?350‰) isotopic composition in diamond grains. The identified features of the C and N release kinetics are explained by differences in the binding energy of chemically adsorbed O with C atoms and the accommodation of the main amounts of N in extended defects of the crystal structure of nanodiamond. The major factors of the decrease in the Xe-P3 release rate during the isothermal pyrolysis of nanodiamond are either the differences between the Xe desorption parameters of the traps in graphite-like phases containing Xe-P3 or the differences between the radiation-induced defectiveness of grains of the population containing implanted Xe-P3. Our results led us to conclude that (1) meteoritic nanodiamond contains relatively low amounts of a phases carrying the P3 component of noble gases, regardless of the nature of this component, and (2) the population of nanodiamond grains containing most of isotopically anomalous nitrogen was produced at a high rate to preserve this nitrogen, first of all, at extended defects in the diamond crystal structure.     

Light element geochemistry of the Apollo 12 site

Analytical techniques of improved sensitivity have revealed details of the concentrations and isotopic compositions of light elements for a comprehensive suite of samples from the Apollo 12 regolith. These samples show a wide spread in maturity, although maximum contents observed for solar wind elements are less than observed at other sites, possibly reflecting relative recency of craters at the Apollo 12 site. Isotopic composition of nitrogen is consistent with the idea that ¹⁵N/¹⁴N in the solar wind has increased with time, at least a major part of this increase having occurred in the past 3.1 Gyr. Sulfur isotope systematics support a model in which sulfur is both added to the regolith, by meteoritic influx and lost, by an isotopically selective process. Most soils from this site are heavily contaminated with terrestrial carbon.     

Two oxygen isotopic components with extra-selenial origins observed among lunar metallic grains - In search for the solar wind component

Oxygen isotopic analyses were performed in the surface layers of lunar metallic grains from lunar regolith samples 71501 and 79035, presumably exposed at the Moon surface at different times. We were able to reproduce the two extreme O components previously found [Hashizume K. and Chaussidon M. (2005) A non-terrestrial ¹⁶O-rich isotopic composition for the protosolar nebula. Nature434, 619-622; Ireland T. R., Holden P., Norman M. D. and Clarke J. (2006) Isotopic enhancements of ¹⁷O and ¹⁸O from solar wind particles in the lunar regolith. Nature440, 776-778], with a range observed of −12 ± 5 < Δ¹⁷O < +33 ± 3‰ (1σ). The relatively minor ¹⁶O-rich component corresponding to an end-member Δ¹⁷O value lower than −20‰ is likely the solar component. This comes from the fact that its concentration roughly agrees with the maximum solar wind abundance expected among the grains from the two samples. At variance the ¹⁶O-poor component is 5-10 times more abundant and thus likely non-solar. The δ¹⁸O range found for the ¹⁶O-poor component may reflect various processes such as isotope exchange reaction during oxidation of metallic iron and/or isotope fractionation by evaporation/condensation at the surface of the Moon or during implantation at depth in the lunar metallic grains. The present study suggests that planetary solid materials in bulk are systematically depleted in ¹⁶O relative to the solar isotopic composition, suggesting the existence of non-mass-dependent isotopic fractionations associated to the formation of solids in the accretion disk.     

On the origins of GEMS grains

From their birth as condensates in the outflows of oxygen-rich evolved stars, processing in interstellar space, and incorporation into disks around new stars, amorphous silicates predominate in most astrophysical environments. Amorphous silicates were a major building block of our Solar System and are prominent in infrared spectra of comets. Anhydrous interplanetary dust particles (IDPs) thought to derive from comets contain abundant amorphous silicates known as GEMS (glass with embedded metal and sulfides) grains. GEMS grains have been proposed to be isotopically and chemically homogenized interstellar amorphous silicate dust. We evaluated this hypothesis through coordinated chemical and isotopic analyses of GEMS grains in a suite of IDPs to constrain their origins. GEMS grains show order of magnitude variations in Mg, Fe, Ca, and S abundances. GEMS grains do not match the average element abundances inferred for ISM dust containing on average, too little Mg, Fe, and Ca, and too much S. GEMS grains have complementary compositions to the crystalline components in IDPs suggesting that they formed from the same reservoir. We did not observe any unequivocal microstructural or chemical evidence that GEMS grains experienced prolonged exposure to radiation.We identified four GEMS grains having O isotopic compositions that point to origins in red giant branch or asymptotic giant branch stars and supernovae. Based on their O isotopic compositions, we estimate that 1-6% of GEMS grains are surviving circumstellar grains. The remaining 94-99% of GEMS grains have O isotopic compositions that are indistinguishable from terrestrial materials and carbonaceous chondrites. These isotopically solar GEMS grains either formed in the Solar System or were completely homogenized in the interstellar medium (ISM). However, the chemical compositions of GEMS grains are extremely heterogeneous and seem to rule out this possibility. Based on their solar isotopic compositions and their non-solar elemental compositions we propose that most GEMS grains formed in the nebula as late-stage non-equilibrium condensates.     

Petrogenesis of Sierra Nevada plutons inferred from the Sr, Nd, and O isotopic signatures of mafic igneous complexes in Yosemite Valley, California

Mafic complexes in the central Sierra Nevada batholith record valuable geochemical information regarding the role mafic magmas play in arc magmatism and the generation of continental crust. In the intrusive suite of Yosemite Valley, major and trace element compositions of the hornblende-bearing gabbroic rocks from the Rockslides mafic complex and of the mafic dikes in the North America Wall are compositionally similar to high-alumina basalt. Of these rocks, two samples have higher Ni and Cr abundances as well as higher ε_Nd values than previously recognized for the intrusive suite. Plagioclase crystals in rocks from the North America Wall and the Rockslides have prominent calcic cores and sharply defined sodic rims, a texture commonly associated with mixing of mafic and felsic magmas. In situ analyses of ⁸⁷Sr/⁸⁶Sr in plagioclase show no significant isotopic difference from the cores to the rims of these grains. We propose that the high ⁸⁷Sr/⁸⁶Sr (~0.7067) and low ε_Nd (~?3.4) of bulk rocks, the homogeneity of ⁸⁷Sr/⁸⁶Sr in plagioclase, and the high δ¹⁸O values of bulk rocks (6.6–7.3 ‰) and zircon (Lackey et al. in J Petrol 49:1397–1426, 2008) demonstrate that continental crust was assimilated into the sublithospheric mantle-derived basaltic precursors of the mafic rocks in Yosemite Valley. Contamination (20–40 %) likely occurred in the lower crust as the magma differentiated to high-alumina basalt prior to plagioclase (and zircon) crystallization. As a consequence, the isotopic signatures recorded by whole rocks, plagioclase, and zircon do not represent the composition of the underlying lithospheric mantle. We conclude that the mafic and associated felsic members of the intrusive suite of Yosemite Valley represent 60–80 % new additions to the crust and include significant quantities of recycled ancient crust.     

Calcium isotopes in a proglacial weathering environment: Damma glacier, Switzerland

The biogeochemical cycling and isotopic fractionation of calcium during the initial stages of weathering were investigated in an alpine soil chronosequence (Damma glacier, Switzerland). This site has a homogeneous silicate lithology and minimal biological impacts due to sparse vegetation cover. Calcium isotopic compositions, obtained by TIMS using a ⁴³Ca-⁴⁶Ca double spike, were measured in the main Ca pools. During this very early stage of weathering, the young soils which have formed (δ^44/42Ca=+0.44‰) were indistinguishable to the rocks from which they were derived (δ^44/42Ca=+0.44‰) and stream water (δ^44/42Ca=+0.48‰) was also within error of the average rock. This lack of variation indicates that the dissolution of the bulk silicate rock does not strongly fractionate Ca isotopes. The only Ca pool which was strongly fractionated from bulk rock was vegetation, which exhibited an enrichment of light Ca isotopes. Significant Ca isotope fractionation between bulk rock and the dissolved flux of Ca is likely to only occur where the Ca biogeochemical cycle is dominated by secondary processes such as biological cycling, adsorption and secondary mineral precipitation.     

Calcium Isotopic Fractionation during Ion‐Exchange Column Chemistry and Thermal Ionisation Mass Spectrometry (TIMS) Determination

Significant isotopic fractionation can occur during column chemistry and determination by mass spectrometry. Improper correction may produce uncertainties in the isotopic composition of geological samples. We investigated calcium isotopic fractionation during these two processes and set up a model to check data quality. The δ^44/40Ca_915a value of IAPSO seawater in different Ca cuts (e.g., 0–20, 20–40, 40–60, 60–80 and 80–100%) on column chemistry ranged from ~ 4‰ to 0‰. The more Ca was eluted, the lower the δ^44/40Ca_915a value of the elution was found. The isotopic fractionation of calcium on the column appeared to follow the exponential law. However, TIMS instrumental fractionation during Ca runs did not always follow the exponential law due to mixing effects from sample reservoirs on the filament. Our results show that errors could be caused if the instrumental fractionation deviates from the exponential law, especially when the fractionation degree is large. To improve the measurement uncertainty, a model is proposed to check the behaviour and degree of instrumental fractionation, which will provide a quick and reasonable verdict on the data quality of TIMS runs.