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Chromium isotopes in an acidic fluvial system: Implications for modern and ancient Cr isotope records
Chromium is an important redox-active element, with significant Cr isotope fractionations driven by redox transformations in the natural environment and quantified through laboratory experiments. Recent work has demonstrated that non-redox-driven transformations can also produce small variations in Cr isotopes, but the role of these processes in controlling environmental Cr isotope variations remains unclear. The highly acidic but biologically diverse acid rock drainage system in Río Tinto, Spain (and affiliated rivers) provides a unique opportunity to examine how non-redox-related processes can substantially affect the isotopic composition of Cr in a natural system. Our results suggest that under conditions where Cr redox transformations are obviated, Cr cycling is largely controlled by formation of Fe-oxyhydroxides and Fe-hydroxysulfates, Cr adsorption, and Cr speciation, with little apparent Cr isotope fractionation between source materials, waters, and sediments. Moderate Cr isotope shifts, however, may be the result of non-redox processes, including adsorption to organic ligands and potentially biological uptake. These results add to a growing body of evidence for the importance of non-redox transformations in contributing to environmental Cr isotope variations, with implications for the use of chromium isotopes in studies of sedimentary Cr isotope records. In particular, this study is a validation of the potential for sulfide weathering in the Proterozoic to deliver relatively unfractionated Cr isotopes to the ocean, despite rising and sustained high oxygen levels.
Chromium isotope fractionation during reduction of Chromium(VI) by Iron(II/III)-bearing clay minerals
Chromium stable isotope ratios are used to trace the reduction of Cr(VI) to Cr(III) in both ancient and modern systems. However, quantitative interpretation of Cr isotopic signatures has been stymied by the large variability in isotopic fractionation factors for Cr(VI) reduction by different reductants. Here we determine Cr isotope fractionation factors during Cr(VI) reduction by Fe(II/III)-bearing clay minerals, which are abundant in subsurface environments. Several variables were tested: pH, total Fe content of the clay, and the fraction of reduced Fe within the clay (Fe(II)/Fe(total)). The latter controls the standard reduction potential of the clay. Our results demonstrate that neither pH nor total Fe content of the clay have major effects on isotopic fractionation. In contrast, as the effective standard reduction potential of the clay and thus the standard free energy of Cr(VI) reduction become more negative, Cr isotope fractionation factors decrease in magnitude from - 4.9 to -1.3‰ according to a linear free energy relationship. This linear free energy relationship can be predicted from Marcus electron transfer theory and allows first-order predictions of Cr isotope fractionation factors to be made from the standard reduction potential or Fe(II)/Fe(total) of a clay, potentially improving our ability to model Cr isotope signatures in geochemical systems. Chromium is the first isotope system to show such a linear free energy relationship over a diverse range of reductants, including both aqueous and solid-phase reductants, and may provide a model for determining other redox-driven kinetic isotope effects in environmentally important isotope systems.
Chromium isotopes as indicators of hexavalent chromium reduction
This is the final report for a university research project which advanced development of a new technology for identifying chemical reduction of hexavalent chromium contamination in groundwater systems. Reduction renders mobile and toxic hexavalent chromium immobile and less toxic. The new method uses stable isotope ratio measurements, which are made using multicollector ICP-mass spectrometry. The main objectives of this project were completed during the project period and two peer-reviewed articles were published to disseminate the information gained.
Time-of-flight mass measurements of neutron-rich chromium isotopes up to N = 40 and implications for the accreted neutron star crust
Here, we present the mass excesses of 59-64 Cr, obtained from recent time-of-flight nuclear mass measurements at the National Superconducting Cyclotron Laboratory at Michigan State University. The mass of 64Cr is determined for the first time, with an atomic mass excess of -33.48(44) MeV. We find a significantly different two-neutron separation energy S 2n trend for neutron-rich isotopes of chromium, removing the previously observed enhancement in binding at N = 38. Additionally, we extend the S 2n trend for chromium to N = 40, revealing behavior consistent with the previously identified island of inversion in this region. We compare our results to state-of-the-art shell-model calculations performed with a modified Lenzi-Nowacki-Poves-Sieja interaction in the fp shell, including the g 9/2 and d 5/2 orbits for the neutron valence space. We employ our result for the mass of 64 Cr in accreted neutron star crust network calculations and find a reduction in the strength and depth of electron-capture heating from the A = 64 isobaric chain, resulting in a cooler than expected accreted neutron star crust. This reduced heating is found to be due to the >1-MeV reduction in binding for 64 Cr with respect to values from commonly used global mass models.
Chromium isotopic anomalies in the Allende meteorite
Abundances of the chromium isotopes in terrestrial and bulk meteorite samples are identical to 0.01 percent. However, Ca-Al-rich inclusions from the Allende meteorite show endemic isotopic anomalies in chromium which require at least three nucleosynthetic components. Large anomalies at Cr-54 in a special class of inclusions are correlated with large anomalies at Ca-48 and Ti-50 and provide strong support for a component reflecting neutron-rich nucleosynthesis at nuclear statistical equilibrium. This correlation suggests that materials from very near the core of an exploding massive star may be injected into the interstellar medium.
Chromium Isotope Fractionation During Reduction of Cr(VI) Under Saturated Flow Conditions
Chromium isotopes are potentially useful indicators of Cr(VI) reduction reactions in groundwater flow systems; however, the influence of transport on Cr isotope fractionation has not been fully examined. Laboratory batch and column experiments were conducted to evaluate isotopic fractionation of Cr during Cr(VI) reduction under both static and controlled flow conditions. Organic carbon was used to reduce Cr(VI) in simulated groundwater containing 20 mg L{sup -1} Cr(VI) in both batch and column experiments. Isotope measurements were performed on dissolved Cr on samples from the batch experiments, and on effluent and profile samples from the column experiment. Analysis of the residual solid-phase materials by scanning electron microscopy (SEM) and by X-ray absorption near edge structure (XANES) spectroscopy confirmed association of Cr(III) with organic carbon in the column solids. Decreases in dissolved Cr(VI) concentrations were coupled with increases in {delta}{sup 53}Cr, indicating that Cr isotope enrichment occurred during reduction of Cr(VI). The {delta}{sup 53}Cr data from the column experiment was fit by linear regression yielding a fractionation factor ({alpha}) of 0.9979, whereas the batch experiments exhibited Rayleigh-type isotope fractionation ({alpha} = 0.9965). The linear characteristic of the column {delta}{sup 53}Cr data may reflect the contribution of transport on Cr isotope fractionation.
Nickel and chromium isotopes in Allende inclusions
High-precision nickel and chromium isotopic measurements were carried out on nine Allende inclusions. It is found that Ni-62, Ni-64, excesses are present in at least three of the samples. The results suggest that the most likely mechanism for the anomalies is a neutron-rich statistical equilibrium process. An indication of elevated Ni-60 is found in almost every inclusion measured. This effect is thought to be related to the decay of now extinct Fe-60. An upper limit of 1.6 X 10 to the -6th is calculated for the Fe-60/Fe-56 ratio at the time these Allende inclusions crystallized.
Neodymium, strontium and chromium isotopic studies of the LEW86010 and Angra dos Reis meteorites and the chronology of the angrite parent body
Neodymium, stontium, and chromium isotopic studies of the LEW86010 angrite established its absolute age and the formation interval between its crystallization and condensation of Allende CAIs from the solar nebula. Pyroxene and phosphate were found to contain approximately 8% of its Sm and Nd inventory. A conventional Sm-147-Nd-143 isochron yielded an age of 4.53 +/- 0.04 Ga (2 sigma and Epsilon(sub Nd sup 143)) = 0.45 +/- 1.1. An Sm-146-Nd-142 isochron gives initial Sm-146/Sm-144 = 0.0076 +/- 0.0009 and Epsilon (sub Nd sup 142) = -2.5 +/- 0.4. The Rb-Sr analyses give initial Sr-87/Sr-86 Iota(sub Sr sup 87) = 0.698972 +/- 8 and 0.698970 +/- 18 for LEW and ADOR, respectively, relative to Sr-87/Sr-86 = 0.71025 for NBS987. The difference, Delta Iota(sub Sr Sup 87), between Iota (sub sr sup 87) for the angrites and literature values for Allende CAIs, corresponds to approximately Ma of growth in a solar nebula with a CI chondrite value of Rb-87/Sr-86 = 0.91, or approximately 5 Ma in a nebula with solar photospheric Rb-87/Sr-86 = 1.51. Excess Cr-53 from extinct Mn-53(t(sub 1/2) = 3.7 Ma)in LEW86010 corresponds to initial Mn-53/Mn-55 = 4.4 +/- 1.0 x 10(exp -5) for the inclusions as previously reported by the Paris group (Birck and Allegre, 1988). The Sm-146/Sm-144 value found for LEW86010 corresponds to solar system initial (Sm-146/Sm-144) = 0.0080 +/- 0.0009 for crystallization 8 Ma after Allende, the difference between Pb-Pb ages of angrites and Allende, or 0.0086 +/- 0.0009 for crystallation 18 Ma after Allende, using the Mn-Cr formation interval. The isotopic data are discussed in the context of a model in which an undifferentiated 'chondritic' parent body formed from the solar nebula approximately Ma after Allende CAIs and subsequently underwent differentiation accompanied by loss of volatiles. Parent bodies with Rb/Sr similar to that of CI, CM, or CO chondrites could satisfy the Cr and Sr isotopic systematics. If the angrite parent body had Rb/Sr similar to that of CV meteorites, it would have to form slightly later, approximately 2.6 Ma after the CAIs, to satisfy the Sr and CR isotopic systematics.
Titanium and chromium isotopic compositions of calcium-aluminum-rich inclusions: Implications for the sources of isotopic anomalies and the formation of distinct isotopic reservoirs in the early Solar System
As the earliest-dated solids in our Solar System, calcium-aluminum-rich inclusions (CAIs) provide a record of their formation environment near the young Sun and hold clues to the formation of planetary-scale isotopic reservoirs in the solar protoplanetary disk. Although CAIs from several CV, CK, CM, CO, and ordinary chondrites have been analyzed previously for their Ti isotopic compositions, CAIs from just three CV chondrites have been analyzed for their Cr isotopic compositions, and only a handful of CAIs have been measured for both their Ti and Cr isotopic compositions. We report mass-independent Ti and Cr isotopic anomalies in several CAIs from CV and CK chondrites; this is the first report of the Cr isotopic composition of a CAI from a CK chondrite. With this data, we aim to better constrain the compositional range of CAIs in ε 50 Ti versus ε 54 Cr space, thereby facilitating the isotopic characterization of the material inherited by the solar protoplanetary disk and the role of CAIs in the formation of distinct planetary-scale isotopic reservoirs in our early Solar System. The narrow range in isotopic anomalies in CAIs when compared to other early-formed refractory inclusions such as platy hibonite crystals (PLACs) and spinel-hibonite inclusions (SHIBs) suggests that CAIs record the mixing of these precursor materials and the averaging of their larger isotopic anomalies. The isotopic composition of CAIs is therefore likely the result of a combination of factors, including mixing of material inherited from their formation region, heterogeneous carrier phase distribution, and thermal processing in the disk. The ε 50 Ti and ε 54 Cr isotopic compositions of CAIs are not correlated, further demonstrating that these isotopic anomalies have different carrier phases. The Ti and Cr isotopic compositions of CAIs additionally show that CAIs alone cannot be responsible for the compositional difference between the non-carbonaceous chondritic (NC) and carbonaceous chondritic (CC) isotopic reservoirs but nevertheless do play a role in the formation of these large-scale isotopic reservoirs in the early Solar System.
Chromium isotopes in meteorites.
Isotopic composition of Cr in meteorites indicates lack of high energy proton irradiation in early solar system
Newly Evaluated Neutron Reaction Data on Chromium Isotopes
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Reduced transition strengths of low-lying yrast states in chromium isotopes in the vicinity of N = 40
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Chromium Isotopic Evidence for Mixing of NC and CC Reservoirs in Polymict Ureilites: Implications for Dynamical Models of the Early Solar System
Nucleosynthetic isotope anomalies show that the first few million years of solar system history were characterized by two distinct cosmochemical reservoirs, CC (carbonaceous chondrites and related differentiated meteorites) and NC (the terrestrial planets and all other groups of chondrites and differentiated meteorites), widely interpreted to correspond to the outer and inner solar system, respectively. At some point, however, bulk CC and NC materials became mixed, and several dynamical models offer explanations for how and when this occurred. We use xenoliths of CC materials in polymict ureilite (NC) breccias to test the applicability of such models. Polymict ureilites represent regolith on ureilitic asteroids but contain carbonaceous chondrite-like xenoliths. We present the first 54 Cr isotope data for such clasts, which, combined with oxygen and hydrogen isotopes, show that they are unique CC materials that became mixed with NC materials in these breccias. It has been suggested that such xenoliths were implanted into ureilites by outer solar system bodies migrating into the inner solar system during the gaseous disk phase ~3–5 Myr after CAI, as in the "Grand Tack" model. However, combined textural, petrologic, and spectroscopic observations suggest that they were added to ureilitic regolith at ~50–60 Myr after CAI, along with ordinary, enstatite, and Rumuruti-type chondrites, as a result of the breakup of multiple parent bodies in the asteroid belt at this time. This is consistent with models for an early instability of the giant planets. The C-type asteroids from which the xenoliths were derived were already present in inner solar system orbits.
Early Archean Spherule Beds: Chromium Isotopes Confirm Origin Through Multiple Impacts of Projectiles of Carbonaceous Chondrite Type
Three Early Archean spherule beds from Barberton, South Africa, have anomalous Cr isotope compositions in addition to large Ir anomalies, confirming the presence of meteoritic material with a composition similar to that in carbonaceous chondrites. The extra-terrestrial components in beds S2, S3, and S4 are estimated to be approx. l%, 50% - 60%, and 15% - 30%, respectively. These beds are probably the distal, and possibly global, ejecta from major large-body impacts. These impacts were probably much larger than the Cretaceous-Tertiary event, and all occurred over an interval of approx. 20 m.y., implying an impactor flux at 3.2 Ga that was more than an order of magnitude greater than the present flux.
Manganese-Chromium Isotope Systematics of Ivuna, Kainsaz and Other Carbonaceous Chondrites
We have shown earlier that the bulk samples of carbonaceous chondrites [CC] reveal excesses in both Cr-53 (Cr-53*) and Cr-54 (Cr-54*) as compared to the terrestrial standard value. The Cr-53/52 ratios in bulk samples of Orgueil (CI), Murray (CM), Allende (CV), and the Bencubbin/CH-like meteorite Hammadah Al Hambra 237 (HH237) are correlated with the respective Mn/Cr ratios. In contrast to CC, HH237 is characterized by a deficit of Cr-53 (-0.15 +/- 0.10(epsilon)) at a low Mn/Cr ratio of 0.07. The HH237 data point, however, falls on the CC line. Here we report new Mn-53 - Cr-53 results for the CC Kainsaz (CO) and Ivuna (CI).
Early Archean Spherule Beds: Chromium Isotopes Confirm Origin through Multiple Impacts of Projectiles of Carbonaceous Chondrite Type: Comment and Reply
This is a exchange in the form of a comment and a reply in regards to an earlier article. The authors of the original article, consider it likely that virtually all of the projectile will condense with the silicate fraction, resulting in very little platinum group element fractionation in the final ejecta deposit. Further, we find no evidence in the commentator's, (i.e., Glikson), comment to support vapor fractionation. We note that the Pd/Ir ratios of published data on 2.56 Ga Hamersley Basin spherules are all greater than in chondrites, contrary to the assertion by Glikson. This is consistent with relatively high Pd concentrations (and Pd/Ir ratios) in crustal rocks.
A Case for Nebula Scale Mixing Between Non-Carbonaceous and Carbonaceous Chondrite Reservoirs: Testing the Grand Tack Model with Chromium Isotopic Composition of Almahata Sitta Stone 91A
There is an increasing number of Cr-O-Ti isotope studies that show solar system materials are divided into two main populations, one carbonaceous chondrite (CC)-like and the other is non-carbonaceous (NC)-like, with minimal mixing attributed to a gap opened in the protoplanetary disk due to Jupiter's formation. The Grand Tack model suggests there should be large-scale mixing between S- and C-type asteroids, an idea supported by our recent work on chondrule (Delta)17O-ε54Cr isotope systematics. The Almahata Sitta (AhS) meteorite provides a unique opportunity to test the Grand Tack model. The meteorite fell to Earth in October 2008 and has been linked to the asteroid 2008 TC3 which was discovered just prior to the fall of the AhS stones. The AhS meteorite is composed of up to 700 individual pieces with approx.140 of those pieces having some geochemical and/or petrologic studies. Almahata Sitta is an anomalous polymict ureilite with other meteorite components, including enstatite, ordinary, and carbonaceous chondrites with an approximate abundance of 70% ureilites and 30% chondrites. This observation has lead to the suggestion that TC3 2008 was a loosely aggregated rubble pile-like asteroid with the non-ureilite sample clasts within the rubble-pile. Due to the loosely-aggregated nature of AhS, the object disintegrated during atmospheric entry resulting in the weakly held clasts falling predominantly as individual stones in the AhS collection area. However, recent work has identified one sample of AhS, sample 91A, which may represent two different lithologies coexisting within a single stone. The predominate lithology type in 91A appears to be that of a C2 chondrite based on mineralogy but also contains olivine, pyroxene, and albite that have ureilite-like compositions. Previous Cr isotope investigations into AhS stones are sparse and what data is available show nearly uniform isotopic composition similar to that of typical ureilites with negative ε54Cr values.