Cr Isotopes Research Articles

Global trends in novel stable isotopes in basalts: Theory and observations

The geochemistry of global mantle melts suggests that both mid-ocean ridge basalts (MORB) and ocean island basalts (OIB) sample lithological and temperature heterogeneities originating in both the upper and lower mantle. Recently, non-traditional stable isotopes have been suggested as a new tool to complement existing tracers of mantle heterogeneity (e.g., major and trace elements, radiogenic isotopes), because mineral- and redox-specific equilibrium stable isotope fractionation effects can link the stable isotope ratios of melts to their source mineralogy and melting degree. Here, we investigate five stable isotope systems (Mg-Ca-Fe-V-Cr) that have shown promise in models or natural samples as tracers of mantle temperature and/or lithological heterogeneity. We use a quantitative model, combining thermodynamically self-consistent mantle melting and equilibrium isotope fractionation models, to explore the behaviour of the isotope ratios of these elements during melting of three mantle lithologies (peridotite, and silica-excess and silica-deficient pyroxenites), responding to changes in mantle mineralogy, oxygen fugacity, temperature and pressure. We find that, given current analytical precision, the stable isotope systems examined here are not predicted to be sensitive to mantle potential temperature variations through equilibrium isotope fractionation processes. By contrast, source lithological heterogeneity is predicted to be detectable in some cases in the stable isotope ratios of erupted basalts, although generally only at proportions of >10% MORB-like pyroxenite in the mantle source, given current analytical precision. Magnesium and Ca stable isotopes show most sensitivity to a garnet-bearing source lithology, and Fe and Cr stable isotopes are potentially sensitive to the presence of MORB-like pyroxenite in the mantle source, although the behaviour of Cr isotopes is comparatively under-constrained and requires further work to be applied with confidence to mantle melts. When comparing the magnitude and direction of predicted equilibrium isotopic fractionation of peridotite and pyroxenite melts to natural MORB and OIB data, we find that aspects of the natural data (including the mean Mg-Ca-Fe-V isotopic composition of MORB, the range of Mg-Ca isotopic compositions seen in MORB data, the mean Mg-Ca-Cr isotopic composition of OIB, and the range of Mg-V-Cr isotopic compositions in OIB data) can be matched by equilibrium isotope fractionation during partial melting of peridotite and pyroxenite sources – with pyroxenite required even for some MORB data. However, even when considering analytical uncertainty on natural sample measurements, the range in stable isotope compositions seen across the global MORB and OIB datasets suggests that kinetic isotope fractionation, or processes modifying the isotopic composition of recycled crustal material such that it is distinct from MORB, may be required to explain all the natural data. We conclude that the five stable isotope systems considered here have potential to be powerful complementary tracers to other geochemical tracers of the source lithology of erupted basalts. However, continued improvements in analytical precision in conjunction with experimental and theoretical predictions of isotopic fractionation between mantle minerals and melts are required before these novel stable isotopes can be unambiguously used to understand source heterogeneity in erupted basalts.

Reaching into the N = 40 Island of Inversion with Nucleon Removal Reactions

One ambitious goal of nuclear physics is a predictive model of all nuclei, including the ones at the fringes of the nuclear chart which may remain out of experimental reach. Certain regions of the chart are providing formidable testing grounds for nuclear models in this quest as they display rapid structural evolution from one nucleus to another or phenomena such as shape coexistence. Observables measured for such nuclei can confirm or refute our understanding of the driving forces of the evolution of nuclear structure away from stability where textbook nuclear physics has been proven to not apply anymore. This paper briefly reviews the emerging picture for the very neutron-rich Fe, Cr, and Ti isotopes within the so-called N=40 island of inversion as obtained with nucleon knockout reactions. These have provided some of the most detailed nuclear spectroscopy in very neutron-rich nuclei produced at rare-isotope facilities. The results indicate that our current understanding, as encoded in large-scale shell-model calculations, appears correct with exciting predictions for the N=40 island of inversion left to be proven in the experiment. A bright future emerges with predictions of continued shell evolution and shape coexistence out to neutron number N=50, below 78Ni on the chart of nuclei.

δ53Cr values of catchment runoff exhibit seasonality regardless of bedrock Cr concentrations: Role of periodically changing chromium export fluxes

AbstractOne pre‐requisite for the construction of a global chromium isotope mass balance is detailed understanding of Cr isotope systematics in the critical zone where redox‐processes can modify the isotope signature of geogenic Cr input into the hydrosphere. A Cr isotope inventory of bedrock, soil, and runoff was performed in a Central European headwater catchment underlain by amphibolite, situated in the vicinity of two previously studied catchments underlain by different bedrock types (serpentinite and leucogranite). Fresh bedrock in the amphibolite catchment NAZ contained ~300 mg/kg Cr, serpentinite at PLB contained ~800 mg/kg Cr, and leucogranite at LYS contained ~2 mg/kg Cr. Monthly hydrochemical monitoring at all three sites revealed higher Cr(VI) export fluxes in winter than in summer. NAZ was characterized by a distinct seasonality in the δ53Cr values, with minima during winter/spring snowmelts (−0.35‰) and maxima during dry summers (0.40‰). Similar seasonality in δ53Cr values had been reported from PLB and LYS. Bedrock at all three sites had similar Cr isotope composition close to −0.10‰, a value indistinguishable from the δ53Cr value of bulk silicate Earth (BSE). Positive mean δ53Cr value of NAZ runoff indicated Cr‐isotope fractionations during weathering of geogenic Cr(III), combined with adsorption of the resulting Cr(VI) on soil particles during pedogenesis. However, the mass‐weighted mean δ53Cr of NAZ runoff was lower (−0.08‰), indistinguishable from the Cr isotope signature of bedrock. The same pattern of lower mass‐weighted mean δ53Cr values of runoff, compared to arithmetic mean δ53Cr values of runoff, were observed also at PLB and LYS. We suggest that elevated Cr runoff fluxes in winter remove some of the residual isotopically light Cr that accumulated in the soil during summer. Seasonality in runoff δ53Cr values appears to be a relatively widespread phenomenon, de‐coupled from Cr availability for chemical weathering.

Chromium Stable Isotope Panorama of Chondrites and Implications for Earth Early Accretion

Abstract We investigated the stable isotope fractionation of chromium (Cr) for a panorama of chondrites, including EH and EL enstatite chondrites and their chondrules and different phases (by acid leaching). We observed that chondrites have heterogeneous δ 53Cr values (per mil deviation of the 53Cr/52Cr from the NIST SRM 979 standard), which we suggest reflect different physical conditions in the different chondrite accretion regions. Chondrules from a primitive EH3 chondrite (SAH 97096) possess isotopically heavier Cr relative to their host bulk chondrite, which may be caused by Cr evaporation in a reduced chondrule-forming region of the protoplanetary disk. Enstatite chondrites show a range of bulk δ 53Cr values that likely result from variable mixing of isotopically different sulfide-silicate-metal phases. The bulk silicate Earth (δ 53Cr = –0.12 ± 0.02‰, 2SE) has a lighter Cr stable isotope composition compared to the average δ 53Cr value of enstatite chondrites (–0.05 ± 0.02‰, 2SE, when two samples out of 19 are excluded). If the bulk Earth originally had a Cr isotopic composition that was similar to the average enstatite chondrites, this Cr isotope difference may be caused by evaporation under equilibrium conditions from magma oceans on Earth or its planetesimal building blocks, as previously suggested to explain the magnesium and silicon isotope differences between Earth and enstatite chondrites. Alternatively, chemical differences between Earth and enstatite chondrite can result from thermal processes in the solar nebula and the enstatite chondrite-Earth, which would also have changed the Cr isotopic composition of Earth and enstatite chondrite parent body precursors.

Cr Isotopes and the Engineered Attenuation of Cr(VI)-Rich Runoff.

The leaching of lateritic soils can result in drainage waters with high concentrations of Cr(VI). Such Cr(VI)-rich waters have developed in streams that drain lateritic soils in Central Sulawesi Island, Indonesia. Chromium in this lateritic drainage system is removed by reduction of Cr(VI) to Cr(III) through two faucets delivering an FeSO4 solution to the drainage waters. Cr stable isotope compositions from both water and sediment samples along the drainage path were used to evaluate the efficacy of this remediation strategy. Overall, dissolved [Cr(VI)] decreased moving downstream, but there was an increase in [Cr(VI)] after the first faucet that was effectively removed at the second faucet. This intermittent increase in [Cr(VI)] was the likely result of oxidative remobilization of sediment Cr(III) through reaction with Mn oxides. Cr isotope distributions reflect near quantitative reduction associated with the FeSO4 faucets but also reveal that Cr isotope fractionation is imparted due to Cr redox cycling, downstream. During this redox cycling, fractionation appeared to accompany oxidation, with the product Cr(VI) becoming enriched in 53Cr relative to the reactant Cr(III) with an apparent fractionation factor of 0.7 ± 0.3‰. This study suggests that while FeSO4 effectively removes Cr(VI) from the drainage, the presence of Mn oxides can confound attenuation and improvements to Cr(VI) remediation should consider means of preventing the back reaction of Cr(III) with Mn oxides.

Cadmium isotopes in Bahamas platform carbonates: A base for reconstruction of past surface water bioproductivity and their link with chromium isotopes

The distribution of cadmium (Cd) within the oceans strongly suggests that it is used as a nutrient by marine phytoplankton. Biologically induced removal of Cd from modern surface waters is accompanied by an isotopic fractionation leaving surface-waters enriched in isotopically heavy Cd. This first study focusses on tying the Cd isotopic record preserved in modern shallow platform carbonates of the Great Bahama Bank (GBB) to conditions in the upper water column, and provides a base for future studies aiming at reconstructing past bioproductivity levels in ancient ocean/basin surface waters. In addition, we compare δ114Cd values with previously published chromium (Cr) isotope values and link signals of bioproductivity with redox conditions in the surface waters. The GBB core samples yield [Cd] (21–188 μg/kg), which increases with depth alongside changes in carbonate mineralogy related to sediment supply and diagenesis. The δ114Cd values of these carbonates are mainly positively fractionated with an average of 0.11‰ ± 0.17 (2σ; n = 17) relative to the NIST 3108 reference standard. Unlike previously observed for Cr isotopes, there is no control of δ114Cd values by relative abundances of the carbonate polymorphs aragonite and calcite in the studied profile. Likewise, δ114Cd values are not correlated to major and trace element (e.g. Ca, Mg, Mn and Sr) contents. We postulate that the burial and diagenetic processes of carbonate cannot modify the Cd isotope signals. Using the experimental fractionation factor for Cd into calcite (−0.45‰), calculated seawater δ114Cd of +0.56 ± 0.17‰ is in agreement with values for modern North Atlantic Surface Seawater. This study's results suggest that δ114Cd values in carbonates are a reliable tool for reconstruction of bioproductivity levels in past surface seawaters, and open new possibilities in combination with Cr isotopes to link these with past ocean redox.

Chromium stable isotope geochemistry in the Mobile Bay Estuary

The chromium (Cr) isotope system is an important redox proxy for understanding Earth's oxygenation history. However, quantitative application of this proxy is hindered by a lack of clear understanding of the global Cr isotope mass balance. Estuarine environments potentially play important roles in influencing the global oceanic Cr mass balance because riverine Cr derived from continental weathering must first travel through estuaries before entering the open ocean. We collected water, suspended particulate matter, and sediment samples across a salinity gradient in the Mobile Bay Estuary located in the Northern Gulf of Mexico, with a purpose of evaluating whether Cr behaves conservatively in estuarine environments. A simple conservative mixing model between the fresh Mobile River water and Gulf of Mexico seawater alone was insufficient to explain the Cr concentration and isotope data, suggesting that Cr behaves non-conservatively in this estuary system. A model incorporating conservative mixing, partial Cr(VI) reduction and partial scavenging of the produced Cr(III) is developed to reproduce the observed data. Our data and modeling exercise suggest that up to 60% of Cr(VI) is reduced to Cr(III) in the Mobile Bay Estuary with a Cr isotope fractionation factor of −1.2‰, and 40% of the produced Cr(III) is removed from solution. Although these parameters may not be the sole solution to the system of equations involved, they are consistent with previous estimates. Future redox-specific Cr isotope data in estuarine environments are needed to place finer constraints on these parameters in estuaries, which is critical for estimating global marine Cr isotope mass balance using riverine Cr concentration and isotope data.

The coordination of Cr2+ in silicate glasses and implications for mineral-melt fractionation of Cr isotopes

The Cr2+-O and Cr3+-O bond lengths in CaO-MgO-Al2O3-SiO2 glasses containing ~0.3 wt% Cr with Cr2+/ΣCr = ~ 1 or 0 (where ΣCr = Cr2+ + Cr3+) were determined by extended X-ray absorption fine structure (EXAFS) spectroscopy to be 2.034(5) and 1.967(7) Å, respectively. The Cr2+-O bond length is consistent with square planar coordination and the Cr3+-O bond length with octahedral coordination. These bond lengths were used to calculate force constants of 1206(9) Nm−1 for Cr2+-O and 2001(21) Nm−1 for Cr3+-O in silicate melts. The value for Cr3+-O is similar to previous estimates but that for Cr2+-O is almost 20% lower. The force constants were used to calculate the difference in Cr isotopic composition (Δ53Cr) between both olivine and melt and spinel and melt for MORB with equal amounts of Cr2+ and Cr3+ at 1150 °C. The resulting values, Δ53Crol-mlt = −0.050(4) and Δ53Crspl-mlt = 0.087(4), are larger by ~0.03 than those obtained using Cr-O bond lengths estimated from ionic radii. For Δ53Crspl-mlt this difference is equivalent to a change in temperature of over 300 °C at constant Cr2+/ΣCr. The fractionation of Cr isotopes in ocean island basalts should be larger for fractional crystallisation in the crust than partial melting in the mantle due to the strong negative effect of pressure on Cr2+/ΣCr. The new bond length data for Cr2+-O provide an additional constraint for modelling and interpreting Cr isotope fractionation during igneous petrogenesis.

Geochemical and isotopic constraints on the dynamics of the Earth: a Special Issue dedicated to Jan Dirk Kramers and his legacy to geochemistry

Chromium exists in two oxidation states Cr2+ and Cr3+ during high-temperature magmatic processes and changes in Cr redox are often associated with stable isotopic fractionation. Thus, the stable chromium isotope compositions of mantle-derived magmas bear the potential to trace the oxidation states of their mantle sources as well as any post melting changes in Cr redox (e.g. during magmatic differentiation), in a manner similar to magmatic stable Fe isotopic fractionation. However, these stable isotope fractionation effects are less understood for Cr relative to Fe. Komatiites and tholeiitic basalts represent a wide range of mantle-derived partial melts with variable fractional crystallization of phases with different affinity for Cr2+ and Cr3+. Thus, they offer potential archives to better understand high-temperature Cr isotope fractionation processes and mantle redox.Here, we report major and trace elements as well as coupled stable Cr and Fe isotope compositions of two well-characterized Archean komatiite-tholeiite suites from the Barberton Greenstone Belt, South Africa and Eswatini, and Belingwe Greenstone Belt, Zimbabwe. The sample suites range in MgO concentrations from 3.85 to 34.33 wt%, which allows investigation of the impact of large degrees of magmatic differentiation in a komatiite-basalt system. Whole-rock δ53/52CrSRM979 and δ56/54FeIRMM014 values range from −0.390 ± 0.016 to −0.061 ± 0.016‰ and −0.014 ± 0.018 to +0.192 ± 0.018‰, respectively. The komatiites have a very narrow range in their Cr isotopic composition with an average δ53/52CrSRM979 value of −0.122 ± 0.050‰ (2SD; n = 21), which supports previous estimates of the bulk silicate Earth δ53/52CrSRM979 value. However, high-Mg tholeiites and basaltic andesites exhibit significantly lighter δ53/52CrSRM979 and heavier δ56/54FeIRMM014 values than komatiites. These variations can be linked to crystallization and accumulation of mineral phases observed from fractionation trends of the two Archean komatiite-tholeiite suites. In detail, during crystallization and accumulation of olivine the Cr isotope compositions of komatiites stay invariant, whereas at the onset of Cr-bearing spinel and pyroxene crystallization the Cr isotope signatures of komatiitic basalts, high-Mg tholeiites and basaltic andesites become progressively lighter, which is attributed to the preferential incorporation of isotopically heavier Cr3+ in these mineral phases. The gradual increase of δ56/54FeIRMM014 with increasing magmatic differentiation, does not allow identifying the crystallization of particular mineral phases using Fe isotopes alone. Ultimately, this study demonstrates the power of combining stable Cr and Fe isotopic analyses to examine the effects of fractional crystallization on modifying melt source values and thus to ensure accurate mantle redox estimations.

Deformation effect on nuclear density profile and radius enhancement in light- and medium-mass neutron-rich nuclei

Abstract The mass number dependence of nuclear radii is closely related to the properties of nuclear matter. It is known that most nuclei exhibit some deformation. We discuss how the nuclear density profile is modified by nuclear deformation to elucidate the enhancement mechanism of nuclear radii through a systematic investigation of neutron-rich Ne, Mg, Si, S, Ar, Ti, Cr, and Fe isotopes. Skyrme–Hartree–Fock calculations are performed in a 3D Cartesian grid to describe the nuclear deformation in a non-empirical way. The role of nuclear deformation in nuclear density profiles is explored in comparison to calculations with a spherical limit. We find correlations between nuclear deformation and the internal nuclear density. The evolution of nuclear radii appears to follow the core swelling mechanism recently proposed in spherical nuclei [W. Horiuchi and T. Inakura, Phys. Rev. C 101, 061301(R) (2020)], and the radius is further enhanced by nuclear deformation. This study demands further theoretical and experimental investigations for the internal density.

Ocean redox changes from the latest Permian to Early Triassic recorded by chromium isotopes

Multiple observations have shown that widespread oceanic anoxia may have played an important role in the end-Permian mass extinction and delayed biotic recovery in the Early Triassic. However, it has not been reached a consensus on the temporal and spatial changes in oceanic redox conditions at that time. Chromium (Cr) isotopes have been widely used to trace redox processes in surface environments. Here, we present the Cr isotope compositions (δ53Cr) of the Upper Permian–Lower Triassic carbonate ramp from the Xiakou section in South China (eastern Paleotethys). We observed largely fractionated δ53Cr values (1.15‰ to 2.16‰) in the latest Permian, which are higher than most values among Phanerozoic sedimentary carbonates. Such high values may result from Cr reduction facilitated by the development of a reducing environment during the latest Permian. The high Cr isotope ratios were followed by an abrupt negative excursion of δ53Cr values (from average 1.78‰ to average −0.13‰) across the extinction horizon, which may be attributed to a rapid expansion of oceanic anoxia in the eastern Paleotethys. Persistent negative δ53Cr values covering the Early Triassic indicate that the ocean may not have recovered from anoxia for an extended period. Our Cr isotope results support a stepwise deterioration of oceanic redox environments, which has been previously proposed as a possible cause of the most severe biotic catastrophe in the Phanerozoic.

Constraining Shallow Seawater Oxygenation for the Yangtze Platform During the Early Cambrian

AbstractWhile atmospheric oxygenation occurred largely in two major steps, the oxygenation of Earth's oceans is assumed to be more complicated, shifting repeatedly between oxic and anoxic conditions. The exact timeline and causal drivers of these changes, which seemingly culminated in the well‐ventilated oceans we see today are not well understood. This study presents Cr isotope and rare earth element + yttrium (REE + Y) data combined with V/Cr ratios for the calcareous Yanjiahe and shaley Shuijingtuo Formations from the shelf of the Yangtze Block, South China, to improve our understanding of marine redox conditions during the early Cambrian. We measured authigenic δ53Cr values of up to 1.38‰ for the carbonates of the Yanjiahe Formation as well as Ce anomalies as low as 0.57 suggesting deposition under oxic conditions. The Shuijingtuo Formation is characterized by authigenic δ53Cr values as high as 1.27‰ at its base, but shows a strong increase in detrital content upwards, masking authigenic Cr isotope values and dissolved marine REE + Y profiles. The upper Shuijingtuo Formation is characterized by V/Cr ratios as high as 27, which indicate anoxic conditions. Hence, our data support a prevalence of oxic seawater conditions in the shallow seawater of the Yangtze Block during the Ediacaran‐Cambrian transition, which shifted repeatedly to anoxic during the early Cambrian likely as a result of sea level rise and a redox‐stratified ocean.

Tracing serpentinite dehydration in a subduction channel: Chromium element and isotope evidence from subducted oceanic crust

Serpentinite is one of the most important sources of volatiles and fluid-mobile elements in subduction zones. Attempts have been made to discriminate serpentinite-derived fluid from other sources (e.g., sediments, altered oceanic crusts) using a variety of geochemical tools, but such differentiation has proven to be changeling because fluids from different lithologies are dynamically mixed in the subduction channel. Serpentinites are essentially distinguished by high Cr contents and variable degrees of 53Cr excess. Given high Cr mobility in Cl-rich metamorphic fluids based on experimental determination, Cr elemental and isotope compositions could be potential markers for fluid-mediated mass transfer from serpentinites. Here, we test this hypothesis by analyzing Cr concentrations and isotope compositions of meta-basalts, as well as country mica schists, marbles and serpentinites from the southwestern Tianshan Orogen. The meta-basalts have highly variable Cr concentrations (30.0–625 ppm) and resolvable δ53Cr variations (−0.25‰ to −0.05‰), while mica schists and marbles have similar isotope compositions and low Cr contents (δ53Cr of −0.15‰ to −0.14‰ with Cr contents of 89.5–110 ppm for mica schists, δ53Cr of −0.21‰ to −0.17‰ with Cr contents of 4.1–8.73 ppm for marbles, respectively). Most of the investigated meta-basalts were carbonated. The positive correlations of loss on ignition (LOI), CO2, Sb and Sb/Ce with Cr contents, as well as with δ53Cr for these carbonated meta-basalts indicate that the metamorphic fluids are at least partially sourced from serpentinites and sedimentary carbonates. High pressure serpentinites display similar δ53Cr variations from −0.19‰ to −0.02‰, but high Cr contents ranging from 934 to 4920 ppm. Chromium isotope variations of these serpentinites could not be generated by serpentinization, due to opposite trends of Cr isotopes and serpentinization indexes compared with previous observations. Instead, dehydration of serpentinites during subduction/exhumation accounts for Cr isotope variations, generating fluids with high Cr concentrations and relatively lighter isotope compositions. According to a Rayleigh dehydration model, the estimated Cr isotope fractionation factor (αfluid-residue) between fluids and residual serpentinites is approximately 0.99995 –0.99975, implying that Cr species in the subducted serpentine derived fluid is probably as complexes of Cr3+-Cl−H2O(OH–). The mixing model reveals that investigated carbonated meta-basalts were sourced from initial evolved oceanic basalts metamorphosed by fluids from serpentinite dehydrations, with contributions from sedimentary carbonates. This work emphasizes that coupled Cr element and isotope systems present the potential ability to discriminate the complex fluid sources in subduction zones, particularly serpentinites.

Tracing the origin and core formation of the enstatite achondrite parent bodies using Cr isotopes

Enstatite achondrites (including aubrites) are the only differentiated meteorites that have similar isotope compositions to the Earth-Moon system for most of the elements. However, the origin and differentiation of enstatite achondrites and their parent bodies remain poorly understood. Here, we report high-precision mass-independent and mass-dependent Cr isotope data for 10 enstatite achondrites, including eight aubrites, Itqiy and one enstatite-rich clast in Almahatta Sitta, to further constrain the origin and evolution of their parent bodies. The ε54Cr (per 10,000 deviation of the mass bias corrected 54Cr/52Cr ratio from a terrestrial standard) systematics define three groups: main-group aubrites with ε54Cr = 0.06 ± 0.12 (2SD, N = 7) that is similar to the enstatite chondrites and the Earth-Moon system, Shallowater aubrite with ε54Cr = −0.12 ± 0.04 and Itqiy-type meteorites with ε54Cr = −0.26 ± 0.03 (2SD, N = 2). This shows that there were at least three enstatite achondrite parent bodies in the Solar System. This is confirmed by their distinguished mass-dependent Cr isotope compositions (δ53Cr values): 0.24 ± 0.03‰, 0.10 ± 0.03‰ and −0.03 ± 0.03‰ for main-group, Shallowater and Itqiy parent bodies, respectively. Aubrites are isotopically heavier than chondrites (δ53Cr = −0.12 ± 0.04‰), which likely results from the formation of an isotopically light sulfur-rich core. We also obtained the abundance of the radiogenic 53Cr (produced by the radioactive decay of 53Mn, T1/2 = 3.7 million years). The radiogenic ε53Cr excesses correlate with the 55Mn/52Cr ratios for aubrites (except Shallowater and Bustee) and also the Cr stable isotope compositions (δ53Cr values). We show that these correlations represent mixing lines that also hold chronological significance since they are controlled by the crystallization of sulfides and silicates, which mostly reflect the main-group aubrite parent body differentiation at 4562.5 ± 1.1 Ma (i.e., 4.8 ± 1.1 Ma after Solar System formation). Furthermore, the intercept of these lines with the ordinate axis which represent the initial ε53Cr value of main-group aubrites (0.50 ± 0.16, 2σ) is much higher than the average ε53Cr value of enstatite chondrites (0.15 ± 0.10, 2SD), suggesting an early sulfur-rich core formation that effectively increased the Mn/Cr ratio of the silicate fraction of the main-group aubrite parent body.

The chromium isotope fractionation factor in seawater

The chromium (Cr) stable isotope system is an increasingly used redox proxy for studying the oxygenation history of Earth's ocean-atmosphere system, but understanding of Cr isotope fractionation in modern seawater is still nascent. A linear relationship has been found between the isotope composition and the logarithmic concentration of total dissolved Cr in the global ocean. Such relationship was used to extract an ‘effective’ Cr isotope fractionation factor of ca. 0.7‰ associated with the removal of Cr from seawater. However, there is a statistically significant proportion of data that deviate from the global linear array, and the proportion of data plotting below the array is higher than that plotting above the array. Such scattering and skewing patterns are present even after excluding data that may have been caused by freshwater influences and potential inconsistency in methods used to purify Cr from seawater. A simple numerical exercise was conducted to demonstrate that the observed data scattering and skewing could be explained by parallel removal pathways with ‘intrinsic’ Cr isotope fractionation factors ranging from −0.8‰ to −1.6‰ combined with the presence of variable amount of dissolved Cr(III) in seawater. These results based on global seawater Cr isotope data are consistent with previous conclusions based on individual oceanographic sites.

Stable W and Mo isotopic evidence for increasing redox-potentials from the Paleoarchean towards the Paleoproterozoic deep ocean

The scavenging of dissolved trace metals such as chromium (Cr), molybdenum (Mo) and tungsten (W) and their authigenic enrichment in sedimentary archives mainly occur by particle shuttling that cause resolvable isotope fractionation. Because their scavenging is also dependent on the local marine redox potential and the overall marine chemical environment, the stable isotope composition of these elements in Archean sediments is widely used as paleoredox proxy. Tungsten, a new element in this tool box, is dissolved as the oxyanion tungstate (WO42−) at extremely low marine redox potentials and can thus help to reconstruct the earliest changes in the marine redox state.We tested the applicability of stable W isotopes as a new paleoredox proxy of the atmosphere–ocean system. We analyzed the δ186/184W of Precambrian igneous rocks to investigate the detrital background δ186/184W signature. This Precambrian igneous inventory (PII) shows δ186/184W values between −0.007 and +0.097‰, identical to the range of modern igneous crustal rocks, which indicates that the average Earth’s crust δ186/184W remained constant over billions of years. Furthermore, we present δ186/184W values of euxinic sediments from the Black Sea as a modern sedimentary analog, which we then compare with δ186/184W data of Archean and Proterozoic black shales (3.47–2.3 Ga). Modern Black Sea sapropels reveal crustal-like δ186/184W values between +0.050 and +0.071‰ suggesting limited authigenic enrichment of W in euxinic environments. Similarly, post-Great Oxidation Event shales (2.3 Ga) show crustal- or PII-like δ186/184W values indicating the deposition in euxinic or oxic environment. However, the Archean shale sample suites show elevated W concentrations and fractionated δ186/184W values up to +0.246‰, which we attribute to authigenic enrichment of heavy seawater W in a ferruginous setting. Thus, black shales δ186/184W values can help to distinguish between anoxic-ferruginous and euxinic depositional environments.Furthermore, we combine previously published Cr and Mo isotope data with new Cr and W isotope data to quantify the evolution of the marine redox state during the Archean. By combining the Eh-pH stability fields of W and Mo with the δ186/184W and δ98/95Mo values of Precambrian sediments, we suggest a 3-step evolution of the Precambrian ocean. (1) From 3.47 to 3.0 Ga, the Eh of a dominantly ferruginous ocean was between −0.4 V and −0.25 V, enabling the persistence of soluble WO42− but not MoO42− and thus only the authigenic enrichment of isotopically fractionated W. (2) Starting from 3.0 Ga, the Eh of some shallow-marine environments increased above −0.25 V, as indicated by δ98/95Mo values above the detrital background in shallow-marine sediments, while the Eh of the deep ocean still remained below −0.25 V indicated by the lack of authigenic Mo enrichment and fractionated δ98/95Mo values in deep-sea shales. (3) After 2.7 Ga elevated δ98/95Mo and δ186/184W values in deep-marine sediments suggest that the Eh of the ferruginous open-ocean now also increased above −0.25 V. We therefore suggest that the combination of δ98/95Mo and δ186/184W values of shales is a very promising tool to investigate earliest changes in marine redox conditions during the Archean.

Factors Affecting the Robustness of Data Inversion for Stable Isotope Measurement Using the Double Spike Method: Insights from Chromium Isotope Analysis.

Stable isotope ratios are widely used to solve environmental, geological, medical, and forensic problems. The double spike technique is considered to be one of the most robust and efficient methods to correct for instrumental mass bias and isotopic fractionation that may occur during sample preparation. However, various hidden errors can arise from data processing and have been largely overlooked in previous studies. Several of these hidden errors were investigated in this work using measurement and synthetic data. Double spike inversion of chromium isotope raw data from 1116 natural samples demonstrated that averaging raw isotope ratios before double spike inversion can add significant errors to inverted isotope values, and such errors can be 1.5 times larger than the true analytical precision. Synthetic data were used to investigate the errors on inverted Cr isotope data caused by spike:analyte ratio and Fe-Ti-V interferences, and the following threshold values are recommended to minimize such errors: 54Crspike/52Crsample ratio greater than 0.5, 56Fe/52Cr less than 0.2, 49Ti/52Cr less than 0.04, and 51V/52Cr less than 1. Sample preparation can potentially lead to large errors in inverted Cr isotope data if preparation-induced isotope fractionation deviates from the exponential law used in the double spike inversion, but such errors can be minimized by achieving >70% Cr yield. Our findings provide important insights for the double spike inversion procedure and assessing the reliability of inverted isotope data for not only the chromium isotope system but also other elements commonly analyzed using the double spike technique.

Chromium isotope fractionation during black shale weathering and its environmental implications

Black shale contains abundant pyrite and organic matter that are susceptible to weathering when exposed to the air. In the process of weathering, acid mine drainage can be produced, and a range of toxic trace elements including Cr can be released and transported into rivers, groundwater and soils, potentially leading to severe environmental pollution. In order to study Cr migration and Cr isotopic fractionation during black shale weathering, we sampled metalliferous black shales and cherts from two weathering profiles at Shadi and Yutangba from the Permian Maokou Formation in Enshi Prefecture. The unweathered samples in Shadi and Yutangba have high Cr contents (1562 μg/g and 643 μg/g, respectively), and highly fractionated Cr isotopic compositions (2.04 ± 0.11‰ and 1.91 ± 0.09‰, respectively, expressed as δ53Cr). The narrow range of authigenic δ53Cr in these unweathered shales suggests that the δ53Cr value of the seawater was relatively stable during the period of deposition.Strongly weathered shales in Shadi and Yutangba both display significant Cr losses compared to the unweathered counterparts. Their average δ53Cr values are 1.75 ± 0.12‰ and 1.85 ± 0.39‰ for Shadi and Yutangba, respectively, which are isotopically lighter than fresh samples. This indicates that heavier Cr isotopes are preferentially leached into fluids, leaving the residues enriched in lighter isotopes during black shale weathering. However, the δ53Cr values of the samples close to the water table are higher than those of the unaltered ones, which can be explained by adsorption or quantitative reduction of Cr(VI) near the water table. The fact that Cr isotopes are fractionated during black shale weathering may complicate the application of δ53Cr in polluted samples to identify the Cr sources in areas with exposed black shales. The δ53Cr of seepage water can be measured and treated as a more realistic source signal.

Chromium isotope heterogeneity on a modern carbonate platform

Chromium isotope (δ53Cr) values of marine sedimentary rocks are increasingly utilised for monitoring changes in redox conditions in the Earth's ancient oceans and atmosphere. Carbonate rocks are of particular interest as they are relatively common in the sedimentary record and have been shown under laboratory conditions to be capable of recording the Cr isotope composition of precipitating fluids. However, little data from appropriate modern analogues is currently available to constrain the variability in δ53Cr values within a carbonate platform and slope system and assess the preservation potential of marine δ53Cr values during burial, lithification and diagenesis. In this paper we investigate the heterogeneity of δ53Cr values on a modern marine carbonate platform in the context of carbonate sediment deposition, mineralogy, and the influence of burial and early lithification. We present new δ53Cr values from carbonate sediments in the upper 200 m of ODP Leg 166 Site 1003 taken from the western margin of the Great Bahama Bank (GBB) and compare these data to modern carbonate sediments accumulating on the GBB platform-top. Shallow-water surface sediments record a range of heavy δ53Cr values from +0.77 to +1.07‰ while drill core samples record a larger range of δ53Cr values from +0.51 to +0.97‰. Down-core variability in δ53Cr values occurs systematically with changes in sediment composition and mineralogy, where more positive δ53Cr values occur in drill core samples that preserve proportionally more banktop-derived carbonate and less well developed diagenetic textures. These values decrease down-core where proportionally more pelagic carbonate exists, and with increasing neomorphism of primary aragonite to low-Mg calcite. The mineralogical dependence of δ53Cr values at Site 1003 appears to be related to variations in relative sea-level across the platform and the degree of lithification and diagenetic recrystallization with depth, rather than in response to changes in the δ53Cr composition of the overlying water column. As the GBB represents a reasonable modern analogue for many Phanerozoic and Precambrian carbonate successions, the preliminary framework presented here may have significant implications for the interpretation of vertical profiles of δ53Cr values in paleo-redox studies. In particular, smaller scale variability in ancient carbonate sections can be more simply explained by local variations in depositional environment and diagenetic regime rather than fluctuations in water column redox conditions.

Hybrid Accretion of Carbonaceous Chondrites by Radial Transport across the Jupiter Barrier

Abstract Understanding the origin of chondritic components and their accretion pathways is critical to unraveling the magnitude of mass transport in the protoplanetary disk, as well as the accretionary history of the terrestrial planet region and, by extension, its prebiotic inventory. Here we trace the heritage of pristine components from the relatively unaltered CV chondrite Leoville through their mass-independent Cr and mass-dependent Zn isotope compositions. Investigating these chondritic fractions in such detail reveals an onion-shell structure of chondrules, which is characterized by 54Cr- and 66Zn-poor cores surrounded by increasingly 54Cr- and 66Zn-rich igneous rims and an outer coating of fine-grained dust. This is interpreted as a progressive addition of 54Cr- and 66Zn-rich, CI-like material to the accretion region of these carbonaceous chondrites. Our findings show that the observed Cr isotopic range in chondrules from more altered CV chondrites is the result of chemical equilibration between the chondrules and matrix during secondary alteration. The 54Cr-poor nature of the cores of Leoville chondrules implies formation in the inner solar system and subsequent massive outward chondrule transport past the Jupiter barrier. At the same time, CI-like dust is transferred inward. We propose that the accreting Earth acquired CI-like dust through this mechanism within the lifetime of the disk. This radial mixing of the chondrules and matrix shows the limited capacity of Jupiter to act as an efficient barrier and maintain the proposed noncarbonaceous and carbonaceous chondrite dichotomy over time. Finally, also considering current astrophysical models, we explore both inner and outer solar system origins for the CV chondrite parent body.