Microbial mass-dependent fractionation of chromium isotopes

Mass-dependent fractionation of Cr isotopes occurs during dissimilatory Cr(VI) reduction by Shewanella oneidensis strain MR-1. Cells suspended in a simple buffer solution, with various concentrations of lactate or formate added as electron donor, reduced 5 or 10 μM Cr(VI) to Cr(III) over days to weeks. In all nine batch experiments, ⁵³Cr/⁵²Cr ratios of the unreacted Cr(VI) increased as reduction proceeded. In eight experiments covering a range of added donor concentrations up to 100 μM, isotopic fractionation factors were nearly invariant, ranging from 1.0040 to 1.0045, with a mean value somewhat larger than that previously reported for abiotic Cr(VI) reduction (1.0034). One experiment containing much greater donor concentration (10 mM lactate) reduced Cr(VI) much faster and exhibited a lesser fractionation factor (1.0018). These results indicate that ⁵³Cr/⁵²Cr measurements should be effective as indicators of Cr(VI) reduction, either bacterial or abiotic. However, variability in the fractionation factor is poorly constrained and should be studied for a variety of microbial and abiotic reduction pathways.     

High‐Precision Measurement of Stable Cr Isotopes in Geological Reference Materials by a Double‐Spike TIMS Method

Chromium (Cr) isotopes have been widely used in various fields of Earth and planetary sciences. However, high‐precision measurements of Cr stable isotope ratios are still challenged by difficulties in purifying Cr and organic matter interference from resin using double‐spike thermal ionisation mass spectrometry. In this study, an improved and easily operated two‐column chemical separation procedure using AG50W‐X12 (200–400 mesh) resin is introduced. This resin has a higher cross‐linking density than AG50W‐X8, and this higher density generates better separation efficiency and higher saturation. Organic matter from the resin is a common cause of inhibition of the emission of Cr during analysis by TIMS. Here, perchloric and nitric acids were utilised to eliminate organic matter interference. The Cr isotope ratios of samples with lower Cr contents could be measured precisely by TIMS. The long‐term intermediate measurement precision of δ^53/52Cr_{NIST SRM 979} for BHVO‐2 is better than ± 0.031‰ (2s) over one year. Replicated digestions and measurements of geological reference materials (OKUM, MUH‐1, JP‐1, BHVO‐1, BHVO‐2, AGV‐2 and GSP‐2) yield δ^53/52Cr_{NIST SRM 979} results ranging from ?0.129‰ to ?0.032‰. The Cr isotope ratios of geological reference materials are consistent with the δ^53/52Cr_{NIST SRM 979} values reported by previous studies, and the measurement uncertainty (± 0.031‰, 2s) is significantly improved.     

Geochemical and isotopic signatures of Archaean to Palaeoproterozoic extraterrestrial impact ejecta/fallout units

Criteria allowing diagnostic identification of asteroid and comet impact fallout units (impactites), including fragmental ejecta, microtektites and microkrystite spherules (impact vapour condensates) comprise: (i) unique mineral fallout phases—shocked quartz grains, coesite and nano-diamonds; (ii) unique intra-microkrystite phases—Ni-chromite, Ni-nanonuggets and Ir-nanonuggets, condensed from vapour enriched in meteoritic components; (iii) geochemical features such as high abundance and unique ratios of the platinum group (PGE) and other siderophile elements (Ni, Co); (iv) meteoritic isotopic ratios including ε_53Cr (⁵³Cr/⁵²Cr), ε_54Cr (⁵⁴Cr/⁵²Cr), ε_182W (¹⁸²W/¹⁸³W) or (¹⁸²W/¹⁸⁴W), ε_Os (¹⁸⁷Os/¹⁸⁸Os), ε_17O (¹⁷O/¹⁶O), ε_18O (¹⁸O/¹⁶O); and (v) cometary seeding of ³He/⁴He and racemic organic molecules (AIB) and possibly fullerenes (C₆₀). Relic nickel chromites and metasomatically derived sulfides may contain PGE nanonuggets. Alteration, burial metamorphism and open-system mobility of uranium in hydrous terrestrial environments renders preservation of meteoritic ε_207Pb (²⁰⁷Pb/²⁰⁴Pb) and ε_206Pb (²⁰⁶Pb/²⁰⁴Pb) values unlikely. Where least affected, PGE patterns of microkrystites and microtektite-bearing impact fallout units (impactites) are the reverse of terrestrial PGE patterns, including low Pd/Pt ratios, which provide some of the more readily identified and analytically practical criteria for identifying a meteoritic component. ε_Cr?–?ε_Cr relations in Barberton Greenstone Belt impact fallout units (3.26?–?3.24 Ga) identify a carbonaceous chondrite composition of the parental asteroids. PGE abundances (Ir, Pt) and ε_Cr isotope values allow mass-balance estimates of parental projectiles in the order of 20?–?30 km diameter. Ir and Pt mass-balance estimates correspond to projectiles ～20 km in diameter or larger in the Pilbara Craton for the JIL (>?2.63 Ga) and DGS4 (2.5?–?2.47 Ga) impact fallout units. The Ni, Co and Cr enriched composition of most Precambrian microkrystite spherules militates for mafic/ultramafic target crust which, coupled with the estimated diameter of the ensuing craters, implies the existence of maria-scale impact basins in oceanic-type crustal regions during the Archaean and Palaeoproterozoic.     

Mn-Cr systematics of the early Solar System revisited

We have reinvestigated the Mn-Cr systematics in a number of primitive meteorites, differentiated planetesimals and terrestrial planets in order to address the chronology of the early stages of protoplanetary disk evolution and planetary formation. Our analytical procedure is based on the assumption of terrestrial abundances for ⁵⁰Cr and ⁵²Cr only; recognizing that a data reduction scheme based on Earth-like ⁵⁴Cr/⁵²Cr abundances in all meteorites is not tenable. Here we show that initial ε_⁵³Cr compositions of ⁵⁴Cr-rich and ⁵⁴Cr-poor acid leach fractions in the primitive carbonaceous chondrite Orgueil differ by 0.9ε, reflecting primordial mineral-scale heterogeneity. However, asteroidal processing effectively homogenized any ε_⁵³Cr variations on the planetesimal scale, providing a uniform present-day solar ε_⁵³Cr=0.20±0.10. Thus, our ⁵³Mn-⁵³Cr data argue against the previously suggested ⁵³Mn heliocentric gradient. Instead, we suggest that inner Solar System objects possessed an initially homogeneous ⁵³Mn/⁵⁵Mn composition, which determined by two independent means is estimated at (6.28 ± 0.66) × 10⁻⁶. Our revised Mn-Cr age for Ste. Marguerite (SM) metamorphism of 4562.9 ± 1.0 Ma is identical to the Pb-Pb age of SM phosphates. Using this age, we confirm that mantle differentiation of the eucrite parent body occurred 4564.9 ± 1.1 Ma ago, and revise the time interval between this event and CAI formation to 2.2 ± 1.1 Ma. We also constrain metamorphism in carbonaceous chondrites of type 2 and 3 to have occurred between 1 and 6 Ma after CAI formation. The ⁵³Mn-⁵³Cr correlation among chondrites, planetesimals and terrestrial planets (the eucrite parent body, Mars and Earth) provides evidence for Mn/Cr fractionation within the protoplanetary disk recorded by all precursor materials of the terrestrial planets and primitive asteroids. This fractionation appears to have occurred within 2 Ma of CAI formation.     

Delta Chromium-53/52 isotopic composition of native and contaminated groundwater,Mojave Desert,USA

Chromium(VI) concentrations in groundwater sampled from three contaminant plumes in aquifers in the Mojave Desert near Hinkley, Topock and El Mirage, California, USA, were as high as 2600, 5800 and 330 μg/L, respectively. δ^53/52Cr compositions from more than 50 samples collected within these plumes ranged from near 0‰ to almost 4‰ near the plume margins. Assuming only reductive fractionation of Cr(VI) to Cr(III) within the plume, apparent fractionation factors for δ^53/52Cr isotopes ranged from ε_app = 0.3 to 0.4 within the Hinkley and Topock plumes, respectively, and only the El Mirage plume had a fractionation factor similar to the laboratory derived value of ε = 3.5. One possible explanation for the difference between field and laboratory fractionation factors at the Hinkley and Topock sites is localized reductive fractionation of Cr(VI) to Cr(III), with subsequent advective mixing of native and contaminated water near the plume margin. Chromium(VI) concentrations and δ^53/52Cr isotopic compositions did not uniquely define the source of Cr near the plume margin, or the extent of reductive fractionation within the plume. However, Cr(VI) and δ^53/52Cr data contribute to understanding of the interaction between reductive and mixing processes that occur within and near the margins of Cr contamination plumes. Reductive fractionation of Cr(VI) predominates in plumes having higher ε_app, these plumes may be suitable for monitored natural attenuation. In contrast, advective mixing predominates in plumes having lower ε_app, the highly dispersed margins of these plumes may be difficult to define and manage.     

Contributors to chromium isotope variation of meteorites

We report the results of a comprehensive, high precision survey of the Cr isotopic compositions of primitive chondrites, along with some differentiated meteorites. To ensure complete dissolution of our samples, they were first fused with lithium borate-tetraborate at 1050-1000 °C. Relative to the NIST Cr standard SRM 3112a, carbonaceous chondrites exhibit excesses in ⁵⁴Cr/⁵²Cr from 0.4 to 1.6ε (1ε = 1 part in 10,000), and ordinary chondrites display a common ⁵⁴Cr/⁵²Cr deficit of ∼0.4ε. Analyses of acid-digestion residues of chondrites show that carbonaceous and ordinary chondrites share a common ⁵⁴Cr-enriched carrier, which is characterized by a large excess in ⁵⁴Cr/⁵²Cr (up to 200ε) associated with a very small deficit in ⁵³Cr/⁵²Cr (<2ε). We did not find ⁵⁴Cr anomalies in either bulk enstatite chondrites or in leachates of their acid-digestion residues. This either requires that the enstatite chondrite parent bodies did not incorporate the ⁵⁴Cr anomaly carrier phase during their accretion, or the phase was destroyed by parent body metamorphism. Chromium in the terrestrial rocks and lunar samples analyzed here show no deviation from the NIST SRM 3112a Cr standard. The eucrite and Martian meteorites studied exhibit small deficits in ⁵⁴Cr/⁵²Cr. The ⁵⁴Cr/⁵²Cr variations among different meteorite classes suggest that there was a spatial and/or temporal heterogeneity in the distribution of a ⁵⁴Cr-rich component in the inner Solar System.We confirm the correlated excesses in ⁵⁴Cr/⁵²Cr and ⁵³Cr/⁵²Cr for bulk carbonaceous chondrites, but the new data yield a steeper slope (∼6.6) than that reported in Shukolyukov and Lugmair (2006). The correlated excesses may affect the use of the Mn-Cr chronometer in carbonaceous chondrites. We could not confirm the bulk carbonaceous chondrite Mn-Cr isochron reported by Shukolyukov and Lugmair (2006) and Moynier et al. (2007), mostly because we find much smaller total variations in ε⁵³Cr (∼0.2). All bulk chondrites have small ε⁵³Cr excesses (up to 0.3) relative to the Earth, most likely reflecting the sub-chondritic Mn/Cr ratio of the Earth. The ε⁵³Cr variations in chondrites do seem to grossly correlate with Mn/Cr and yield an initial Solar System ⁵³Mn/⁵⁵Mn value of 5.4(±2.4) × 10⁻⁶, corresponding to an absolute age of 4566.4 (±2.2) Ma.Nuclear interactions with cosmic rays result in coupled excesses in ε⁵⁴Cr and ε⁵³Cr with a ∼4:1 ratio in phases with high Fe/Cr. These are most dramatically demonstrated in the iron meteorite Carbo, showing excesses in ε⁵⁴Cr of up to 140ε. These new results show that the Mn-Cr chronometer should be used with caution in samples/minerals with high Fe/Cr and long cosmic ray exposure ages.     

Ab-initio structure, energy and stable Cr isotopes equilibrium fractionation of some geochemically relevant H-O-Cr-Cl complexes

Twelve Cr(III) molecules and six Cr(VI) molecules of geochemical interest in the system Cr-H-O-Cl were investigated by ab initio Density Functional Theory in the aim of determining stationary state geometries, electronic energies and vibrational properties. The vibrational analysis conducted on the ⁵⁰Cr, ⁵²Cr, ⁵³Cr and ⁵⁴Cr isotopomers indicates important separative effects which result in mass spectrometric measurable fractionation factors in a wide thermal range. The effect of the central cation on the computed vibrational modes is interpreted in terms of Redlich’s product rule with the introduction of an isotopic ergodicity factor related to the effect of bulk molecular masses and momenta of inertia about the principal rotational axes. After the initial gas phase optimization, some relevant molecules were subjected to the effects of reaction field through Onsager’s Model, Tomasi’s continuum Model and Conductor-like Screening Model procedures. Structures and vibrational properties prove in all cases not to be severely affected by solvation, although the effect of the reaction field is to reduce somewhat the isotopic fractionation in Cr(III)-Cr(VI) aqueous redox equilibria, with respect to the gaseous state. Some of the computed separative effects are applicable to geochemical investigations.     

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.     

Effective Correction of Mass Bias for Rhenium Measurements by MC-ICP-MS

The geochemistry of Re-Os and the recent use of Re as a non-traditional stable isotope both need accurate and precise quantification of ¹⁸⁷Re/¹⁸⁵Re ratios. This paper reports rhenium isotopic data obtained from the analysis of a standard solution and geological samples by MC-ICP-MS. We show that measured isotopic ratios are modified by matrix effects that cannot be accounted for by the standard solution bracketing technique. The bias resulting from measurements on a spiked (¹⁸⁵Re-enriched) sample is shown to alter the apparent Re concentration by several percent. When spiking samples and calibrators with tungsten, simultaneous measurement of tungsten and rhenium isotopes compensates for the matrix-induced modification of mass bias. Rhenium and tungsten are shown to have different fractionation factors. This may be due to the fact that the two elements fractionate in a different but systematic way, or that the reference isotopic ratios used for elemental Re and W are incoherent with one another. The consistency of fractionation through time can be used to obtain an empirical relationship between W and Re measured ratios from a standard solution to obtain a sample's fractionation-corrected ¹⁸⁷Re/¹⁸⁵Re spiked ratio on samples containing pg g⁻¹ levels of Re, even if some matrix capable of affecting mass bias remains in the final solution.     

Isotopic fractionation and reaction kinetics between Cr(III) and Cr(VI) in aqueous media

The redox-sensitive stable isotope geochemistry of chromium bears the potential to monitor the attenuation of chromate pollution and to investigate changes in environmental conditions in the present and the past. The use of stable Cr isotope data as a geo-environmental tracer, however, necessitates an understanding of the reaction kinetics and Cr fractionation behaviour during redox transition and isotope exchange. Here, we report stable chromium isotope fractionation data for Cr(VI) reduction, Cr(III) oxidation and isotopic exchange between soluble Cr(III) and Cr(VI) in aqueous media. The reduction of Cr(VI) to Cr(III) with H₂O₂ under strongly acidic conditions shows a near-equilibrium isotope fractionation of Δ^53/52Cr_{(Cr(III)-Cr(VI))} of −3.54 ± 0.35‰. At pH neutrality, however, the reduction experiments show a kinetic isotope fractionation Δ^53/52Cr_{(Cr(III)-Cr(VI))} of −5‰ for the extent of reduction of up to 85% of the chromium. The oxidation of Cr(III) to Cr(VI) in alkaline media, using H₂O₂ as the oxidant, cannot be explained by a single, unidirectional reaction. Our experiments indicate that the involvement of the unstable intermediates Cr(IV) and Cr(V) and their disproportionation during redox reactions between Cr(III) and Cr(VI) influence the overall fractionation factor, depending on the prevailing pH conditions and the reaction rates. No detectable isotope exchange between soluble Cr(VI) and Cr(III) species at pH values of 5.5 and 7 was revealed over a timescale of days to weeks. This means that, at least within such a time frame, the isotopic composition of Cr(VI) in a natural system will not be influenced by equilibration with any Cr(III) and thus reveal the true extent of reduction, given that the Cr isotope composition of the source Cr(VI) and the fractionation factor for the prevailing conditions are known.     

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.     

地球早期演化的Hf-W同位素制约

~(182)Hf-~(182)W作为短周期放射性衰变体系,可有效约束地球早期演化吸积增生和内部分异过程。本文通过系统总结、归纳太阳系形成初期地球核幔分异过程中Hf-W同位素变化规律、月球与地球硅酸盐的W同位素组成,提出利用~(182)Hf-~(182)W体系测定地球核幔分异时间不确定性的主要原因是地球核幔分异的持续性及开放性,大碰撞时间的~(182)Hf-~(182)W同位素限定主要受控于硅酸盐地球和硅酸盐月球的Hf/W比值,讨论了地幔W同位素不均一性的形成机制,与现代地幔不同的~(182)W/~(184)W组成可能代表了后增生作用之前整体硅酸盐地球的W同位素组成,也可能是~(182)Hf未完全灭绝时形成的区域性Hf/W比值差异经~(182)Hf衰变形成的结果。这些结论为探索类地行星形成与演化提供了重要制约。     

Comparative Re-Os systematics of chondrites: Implications regarding early solar system processes

A suite of 47 carbonaceous, enstatite, and ordinary chondrites are examined for Re-Os isotopic systematics. There are significant differences in the ¹⁸⁷Re/¹⁸⁸Os and ¹⁸⁷Os/¹⁸⁸Os ratios of carbonaceous chondrites compared with ordinary and enstatite chondrites. The average ¹⁸⁷Re/¹⁸⁸Os for carbonaceous chondrites is 0.392 ± 0.015 (excluding the CK chondrite, Karoonda), compared with 0.422 ± 0.025 and 0.421 ± 0.013 for ordinary and enstatite chondrites (1σ standard deviations). These ratios, recast into elemental Re/Os ratios, are as follows: 0.0814 ± 0.0031, 0.0876 ± 0.0052 and 0.0874 ± 0.0027, respectively. Correspondingly, the ¹⁸⁷Os/¹⁸⁸Os ratios of carbonaceous chondrites average 0.1262 ± 0.0006 (excluding Karoonda), and ordinary and enstatite chondrites average 0.1283 ± 0.0017 and 0.1281 ± 0.0004, respectively (1σ standard deviations). The new results indicate that the Re/Os ratios of meteorites within each group are, in general, quite uniform. The minimal overlap between the isotopic compositions of ordinary and enstatite chondrites vs. carbonaceous chondrites indicates long-term differences in Re/Os for these materials, most likely reflecting chemical fractionation early in solar system history.A majority of the chondrites do not plot within analytical uncertainties of a 4.56-Ga reference isochron. Most of the deviations from the isochron are consistent with minor, relatively recent redistribution of Re and/or Os on a scale of millimeters to centimeters. Some instances of the redistribution may be attributed to terrestrial weathering; others are most likely the result of aqueous alteration or shock events on the parent body within the past 2 Ga.The ¹⁸⁷Os/¹⁸⁸Os ratio of Earth’s primitive upper mantle has been estimated to be 0.1296 ± 8. If this composition was set via addition of a late veneer of planetesimals after core formation, the composition suggests the veneer was dominated by materials that had Re/Os ratios most similar to ordinary and enstatite chondrites.     

The influence of cosmic-ray production on extinct nuclide systems

Variations in the atomic abundances of ⁵³Cr, ⁹²Zr, ⁹⁸Ru, ⁹⁹Ru, and ¹⁸²W in meteorites and lunar samples relative to terrestrial values may imply the early decay of radioactive ⁵³Mn, ⁹²Nb, ⁹⁸Tc, ⁹⁹Tc and ¹⁸²Hf, respectively. From this one can deduce nucleosynthetic sites and early solar system timescales. Because these effects are very small, production and consumption of the respective isotopes by cosmic-ray interactions is a concern. It has recently been demonstrated that ¹⁸²W production by neutron capture reactions on ¹⁸¹Ta is crucial for most lunar samples (Leya et al., 2000a). In this study the neutron fluence of each sample was estimated from its nominal cosmic-ray exposure age as deduced from noble gas data. This approach overestimates the true cosmogenic isotopic shift for samples that might have been irradiated very close to the regolith surface. Here we therefore combine our model calculations with the neutron dose proxies ¹⁵⁷Gd/¹⁵⁸Gd and ¹⁴⁹Sm/¹⁵⁰Sm. This allows us to accurately correct the measured W isotopic data for cosmic-ray induced shifts without the explicit knowledge of the exposure age or the shielding depth of the sample simply by measuring ¹⁵⁷Gd/¹⁵⁸Gd and/or ¹⁴⁹Sm/¹⁵⁰Sm in an aliquot. In addition we present new model results for the GCR-induced effects on ⁵³Mn-⁵³Cr, ⁹²Nb-⁹²Zr and ⁹⁸Tc-⁹⁹Tc-⁹⁸Ru-⁹⁹Ru. For each of these systems, except Tc-Ru, a proper cosmic-ray dose proxy is given, permitting the accurate correction of measured isotopic ratios for cosmogenic contributions.     

Extreme Cr-rich nano-oxides in the CI chondrite Orgueil - Implication for a late supernova injection into the solar system

Systematic variations in ⁵⁴Cr/⁵²Cr ratios between meteorite classes ( [Trinquier et al., 2007] and [Qin et al., 2010a]) point to large scale spatial and/or temporal isotopic heterogeneity in the solar protoplanetary disk. Two explanations for these variations have been proposed, with important implications for the formation of the Solar System: heterogeneous seeding of the disk with dust from a supernova, or energetic-particle irradiation of dust in the disk. The key to differentiating between them is identification of the carrier(s) of the ⁵⁴Cr anomalies. Here we report the results of our recent NanoSIMS imaging search for the ⁵⁴Cr-rich carrier in the acid-resistant residue of the CI chondrite Orgueil. A total of 10 regions with extreme ⁵⁴Cr-excesses (δ⁵⁴Cr values up to 1500‰) were found. Comparison between SEM, Auger and NanoSIMS analyses showed that these ⁵⁴Cr-rich regions are associated with one or more sub-micron (typically less than 200 nm) Cr oxide grains, most likely spinels. Because the size of the NanoSIMS primary O⁻ ion beam is larger than the typical grain size on the sample mount, the measured anomalies are lower limits, and we estimate that the actual ⁵⁴Cr enrichments in three grains are at least 11 times Solar and in one of these may be as high as 50 times Solar. Such compositions strongly favor a Type II supernova origin. The variability in bulk ⁵⁴Cr/⁵²Cr between meteorite classes argues for a heterogeneous distribution of the ⁵⁴Cr carrier in the solar protoplanetary disk following a late supernova injection event. Such a scenario is also supported by the O-isotopic distribution and variable abundances in different planetary materials of other presolar oxide and silicate grains from supernovae.     

Calcium Isotopic Fractionation and Compositions of Geochemical Reference Materials

High‐precision calcium isotopic compositions of a set of geological reference materials from the IAG (OU‐6), ANRT (UB‐N), MPI‐DING, USGS and GSJ, relative to NIST SRM 915a, are reported here. Measurements were performed by thermal ionisation mass spectrometry (Triton instrument) using a ⁴²Ca–⁴³Ca double spike. δ^44/40Ca values of selected reference materials, mainly felsic rocks, are reported for the first time. Felsic rock values of δ^44/40Ca ranged from 0.13‰ to 1.17‰, probably implying Ca isotopic fractionation could occur during magma evolution. δ^44/40Ca values of ultramafic rocks, ranging from 0.74‰ to 1.51‰, were positively correlated with MgO and negatively with CaO contents, possibly owing to Ca isotopic fractionation during partial melting. δ^44/40Ca of intermediate‐mafic rocks were around 0.78‰ and displayed limited variation, suggesting Ca isotopic fractionation is insignificant during magma evolution processes. As expected, δ^44/40Ca of sedimentary and metamorphic rocks varied widely due to complex geological processes.     

Sequential Chemical Separation of Cr and Ti from a Single Digest for High‐Precision Isotope Measurements of Planetary Materials

Combined determination of Cr and Ti isotopes of planetary materials offers a means with which to investigate their genetic relationship and the evolution of the protoplanetary disk. Here, we report the new sequential chemical separation procedure for combined Cr and Ti isotope ratio measurements. It comprises three steps: (a) Fe removal using AG1‐X8 anion exchange resin, (b) Ti separation using TODGA resin and (c) Cr separation using AG50W‐X8 cation exchange resin (with one additional step of Ti purification using AG1‐X8 anion exchange resin for samples having high Cr/Ti and Ca/Ti ratios). We applied the proposed procedure to terrestrial and meteorite samples with various compositions. Typical recovery rates of 90–100% were achieved with total procedural Cr and Ti blanks of 3–5 and 2–3 ng, respectively. We measured the Cr and Ti isotope compositions of the separated samples using thermal ionisation mass spectrometry and multiple collector‐inductively coupled plasma‐mass spectrometry, respectively. Our Cr and Ti isotope data were found to be consistent with those of previous studies of individual Cr and Ti isotopic compositions of the meteorites. These results demonstrate the capability of our separation method when applied to combined high‐precision Cr and Ti isotope analyses for single digests of planetary materials.     

The origin and history of ordinary chondrites: A study by iron isotope measurements of metal grains from ordinary chondrites

Chondrules and chondrites provide unique insights into early solar system origin and history, and iron plays a critical role in defining the properties of these objects. In order to understand the processes that formed chondrules and chondrites, and introduced isotopic fractionation of iron isotopes, we measured stable iron isotope ratios ⁵⁶Fe/⁵⁴Fe and ⁵⁷Fe/⁵⁴Fe in metal grains separated from 18 ordinary chondrites, of classes H, L and LL, ranging from petrographic types 3-6 using multi-collector inductively coupled plasma mass spectrometry. The δ⁵⁶Fe values range from −0.06 ± 0.01 to +0.30 ± 0.04‰ and δ⁵⁷Fe values are −0.09 ± 0.02 to +0.55 ± 0.05‰ (relative to IRMM-014 iron isotope standard). Where comparisons are possible, these data are in good agreement with published data. We found no systematic difference between falls and finds, suggesting that terrestrial weathering effects are not important in controlling the isotopic fractionations in our samples. We did find a trend in the ⁵⁶Fe/⁵⁴Fe and ⁵⁷Fe/⁵⁴Fe isotopic ratios along the series H, L and LL, with LL being isotopically heavier than H chondrites by ∼0.3‰ suggesting that redox processes are fractionating the isotopes. The ⁵⁶Fe/⁵⁴Fe and ⁵⁷Fe/⁵⁴Fe ratios also increase with increasing petrologic type, which again could reflect redox changes during metamorphism and also a temperature dependant fractionation as meteorites cooled. Metal separated from chondrites is isotopically heavier by ∼0.31‰ in δ⁵⁶Fe than chondrules from the same class, while bulk and matrix samples plot between chondrules and metal. Thus, as with so many chondrite properties, the bulk values appear to reflect the proportion of chondrules (more precisely the proportion of certain types of chondrule) to metal, whereas chondrule properties are largely determined by the redox conditions during chondrule formation. The chondrite assemblages we now observe were, therefore, formed as a closed system.     

Iron isotope fractionation during microbially stimulated Fe(II) oxidation and Fe(III) precipitation

Interpretation of the origins of iron-bearing minerals preserved in modern and ancient rocks based on measured iron isotope ratios depends on our ability to distinguish between biological and non-biological iron isotope fractionation processes. In this study, we compared ⁵⁶Fe/⁵⁴Fe ratios of coexisting aqueous iron (Fe(II)_aq, Fe(III)_aq) and iron oxyhydroxide precipitates (Fe(III)_ppt) resulting from the oxidation of ferrous iron under experimental conditions at low pH (<3). Experiments were carried out using both pure cultures of Acidothiobacillus ferrooxidans and sterile controls to assess possible biological overprinting of non-biological fractionation, and both SO₄²⁻ and Cl⁻ salts as Fe(II) sources to determine possible ionic/speciation effects that may be associated with oxidation/precipitation reactions. In addition, a series of ferric iron precipitation experiments were performed at pH ranging from 1.9 to 3.5 to determine if different precipitation rates cause differences in the isotopic composition of the iron oxyhydroxides. During microbially stimulated Fe(II) oxidation in both the sulfate and chloride systems, ⁵⁶Fe/⁵⁴Fe ratios of residual Fe(II)_aq sampled in a time series evolved along an apparent Rayleigh trend characterized by a fractionation factor α_{Fe(III)aq-Fe(II)aq} ∼ 1.0022. This fractionation factor was significantly less than that measured in our sterile control experiments (∼1.0034) and that predicted for isotopic equilibrium between Fe(II)_aq and Fe(III)_aq (∼1.0029), and thus might be interpreted to reflect a biological isotope effect. However, in our biological experiments the measured difference in ⁵⁶Fe/⁵⁴Fe ratios between Fe(III)_aq, isolated as a solid by the addition of NaOH to the final solution at each time point under N₂-atmosphere, and Fe(II)_aq was in most cases and on average close to 2.9‰ (α_{Fe(III)aq-Fe(II)aq} ∼ 1.0029), consistent with isotopic equilibrium between Fe(II)_aq and Fe(III)_aq. The ferric iron precipitation experiments revealed that ⁵⁶Fe/⁵⁴Fe ratios of Fe(III)_aq were generally equal to or greater than those of Fe(III)_ppt, and isotopic fractionation between these phases decreased with increasing precipitation rate and decreasing grain size. Considered together, the data confirm that the iron isotope variations observed in our microbial experiments are primarily controlled by non-biological equilibrium and kinetic factors, a result that aids our ability to interpret present-day iron cycling processes but further complicates our ability to use iron isotopes alone to identify biological processing in the rock record.