Cr Isotopic Compositions Research Articles

Chromium cycle in Red Soil Critical Zone constrained by chromium isotopes

Chromium (Cr) isotopic system has been used to trace Cr pollution in the modern surface environment and redox change in the paleoenvironment. However, the transformation mechanism of Cr in soil and the accompanied Cr isotopic fractionation have not been clarified clearly. Here we measured Cr isotopic compositions (δ53Cr) of two paddy field profiles from the Red Soil Critical Zone Observatory in South China. The δ53Cr values of the young paddy fields, which have been cultivated for about 20 years, range from −0.34 ‰ to −0.22 ‰. The old paddy fields have been cultivated for >100 years and have more positive Cr isotopic compositions than the young paddy fields, from −0.20 ‰ to −0.06 ‰. The results of three-step leaching experiments show that iron and manganese oxides are enriched in heavy Cr isotopes, while organic matters have much lower Cr isotopic compositions, likely resulting from back reduction of Cr(VI). Our results suggest that Cr isotopic fractionation during the oxidation of Cr(III) is not the only reason for the depletion of heavy isotopes during oxidative weathering, and the partial back-reduction of generated Cr(VI) by organic matter plays an important role in Cr isotopic fractionation during weathering. Comparison between the old and young paddy fields further indicates that cultivation can significantly affect the Cr cycle in red soils. Paddy fields could be a potential sink for the Cr(VI) contaminant, and soils with a long history of cultivation would be more susceptible.

Oxidative weathering on the continent and seawater upwelling along the passive continental margin promoted widespread phosphorite formation at the Neoproterozoic-Cambrian boundary in South China

The latest Proterozoic to early Cambrian is characterized by major global phosphogenic events and the diversification of complex multicellular life. However, the feedback mechanism of atmospheric oxidation and upwelling processes to form voluminous phosphorite deposits is unclear. South China is a key example of the sedimentary spectrum related to the Neoproterozoic to Early Cambrian bloom of oxygenic photosynthesis, with alginite deposits (sapropelite; “stone coal”), barite, polymetallic black shales and phosphorites along the passive continental paleo-margin of the Yangtze craton. Here, we present a comprehensive geochemical analysis of drill core samples from the Zhijin phosphorite deposit, including Cr isotope, Fe speciation, and bulk elemental composition of dolostone, phosphorite and black shale from the Ediacaran to Early Cambrian sequence. The positively fractionated δ53Cr values of 0.11 to 1.81 ‰ of leachates from Ediacaran dolostone and Terreneuvian phosphorite indicate intensive oxidative terrestrial weathering. The phosphorite samples exhibit REE distribution patterns similar to modern seawater and strongly negative Ce anomalies (0.47–0.61), suggesting an oxic, open ocean environment. In contrast, the absence of Ce anomaly, high FeHR/FeT, and Fepy/FeHR ratios, enhanced redox-sensitive element concentrations, high Mo/TOC and TS/TOC, and high molar Corg:P ratios suggest euxinic to anoxic conditions for the overlying black shale sedimentation in a restricted sedimentary marine environment. Bulk-rock shale samples retain the positively fractionated Cr isotope pattern. The dramatic change from oxic to anoxic conditions aligns with the fossil record, which shows a proliferation of small shelly fossils in the phosphorite and their extinction in the overlying black shales, likely by hydrogen sulfide poisoning. We infer that nutrient-rich, oxidized upwelling seawater transported phosphorus and other nutrients to the photic zone, from where organic matter settled down to the seafloor and formed thick phosphorite beds at the oxic-anoxic boundary at and below the seafloor. Our study highlights that atmospheric and seawater oxygenation accelerated the Early Cambrian bio-diversification, and the subsequent restricted basin situation is responsible for the extinction at the Neoproterozoic-Cambrian boundary.

Tracing the Oxidizing State and Element‐Mobilizing Fluids in Continental Subduction Zones: Insights From the Granitic Melt‐Eclogite Interface

AbstractFluids in subduction zones significantly influence element mobility, isotope fractionation, and mass transfer. However, unraveling the source, composition, and redox state of fluids in continental subduction zones poses a significant challenge. This study focuses on a granitic melt‐eclogite contact interface, along with adjacent granite and eclogite from the Sulu ultrahigh‐pressure metamorphic belt in East China. The interface exhibits complex mineral assemblages, enriched rare earth elements (REEs), and high field strength elements (HFSEs). Zircon grains from the interface show an age of ∼217 ± 9 Ma, slightly later than peak metamorphism, along with the presence of coesite inclusions. These findings suggest that the interfacial fluid likely formed from the mixing of granitic anatectic melt and aqueous fluid from the eclogite during the initial exhumation of the Sulu terrane. The interaction resulted in the eclogite acquiring substantial REEs and HFSEs, suggesting the interfacial fluid's effective element‐transporting capability and potential supercritical fluid properties. Zircon Ce anomaly and Fe3+/Fe2+ oxybarometer data indicate a highly oxidizing interfacial fluid, analogous to arc magmas in oxygen fugacity. This led to the preferential loss of isotopically heavier Cr from the eclogite during fluid‐eclogite interaction, evidenced by heavier Cr isotopic compositions in the interface (δ53Cr = −0.04 to −0.05‰) compared to adjacent eclogite (δ53Cr as low as −0.11‰). In summary, our results highlight the presence of strong oxidizing and element‐mobilizing fluids in continental subduction zones, offering insights into supercritical fluid recognition and the genesis of oxidizing arc magmas in subduction zones.

Symplectite formation in ultramafic achondrites by impact percolation of a sulfide melt

The ungrouped dunitic achondrite Northwest Africa (NWA) 12217 contains symplectic spinel-pyroxene veins that are mineralogically identical to symplectites in other ultramafic planetary materials. The morphology and amount of chromite present in these features relative to the Cr in their olivine hosts suggest an exogenous origin. Petrological experiments show that a Cr laden sulfide liquid reacts with olivine to produce pyroxene by scavenging Mg and Fe from olivine to crystallize chromite. The liquid infiltrates cracks and grain boundaries within the olivine and produces a vein-like symplectic chromite-pyroxene mineralogy similar to that observed in NWA 12217. This process is likely responsible for forming the symplectites in the related ultramafic achondrites NWA 12319, 12562, and 13954, along with many other achondrites. The nucleosynthetic Cr isotopic composition of chromites appears to be in disequilibrium with that of silicates in NWA 12217, suggesting that the liquids responsible for the symplectite forming reaction are at least partially sourced from a different parent body and result from an impact.

Lithium isotopic records of anthropogenic activity in the Xiaoqing River basin, eastern China

The environmental impact of the discharge of lithium (Li) by anthropogenic activity has been overlooked. By analyzing Li concentrations and isotope compositions (δ7Li) of water and sediment samples, this study evaluates the influence of anthropogenic Li discharge on the Xiaoqing River and Laizhou Bay, which are heavily polluted areas in China. High Li concentrations of the river water (up to 7.8 μmol/L) should be linked to anthropogenic Li discharge. However, no profound δ7Li anomalies were observed, preventing identification of the exact discharge sources. In the river sediments, Li concentrations (19.0–45.0 μg/g) were weakly correlated with Zn, Cu, and Cr concentrations, whereas δ7Li values ranged from 0.6 ‰ to 13.9 ‰ with high values being accompanied by high contents of total organic carbon and heavy Cr isotope compositions (δ53Cr). All these point to significant influence of anthropogenic activity on the Li budget of river sediments. A simple mass balance calculation indicates that smelters, Li-bearing therapeutic drugs, and secondary Li-ion batteries are the main anthropogenic Li sources. In contrast to river sediments, marine sediments in the Laizhou Bay were broadly homogeneous at both spatial and temporal scales, indicating no significant influence of anthropogenic Li discharge. Overall, our data indicate that Li isotope systematics in river sediments, especially sediments near intense anthropogenic activity, are effective at tracing potential Li pollution and can help obtain accurate results for environmental inspection.

Impactor identification with spallogenic Cr isotopes: The Wabar impact craters (Saudi Arabia)

AbstractPrecise measurements of Cr isotopic composition of terrestrial impactites have successfully provided evidence for the presence of extraterrestrial material and have, in some cases, allowed the identification of the type of impactor responsible for the formation of the impact structure. The high Cr abundance in most meteorite groups aids in detecting extraterrestrial contamination while their distinct isotopic compositions can help with the identification of the nature of the projectile. However, this common approach of detection and identification of extraterrestrial contamination using mass‐independent 53Cr and 54Cr variations fails when the impactor type is an iron meteorite because of their low Cr abundances (which are in a similar range to terrestrial rocks). The present study demonstrates the viability of a spallogenic Cr contribution in iron meteorites (resulting from their long cosmic ray exposure times), which compensates for their low Cr abundances and facilitates the identification of iron‐meteoritic contamination in terrestrial impactites. Thus, it broadens the scope of impactors (and impactites) that can be investigated using mass‐independent Cr isotopes from solely chondrites and primitive achondrites to include iron meteorites. The Wabar impact craters are an optimal candidate for this study, characterized by low weathering, diverse impactites, partial meteorite survival, substantial impactor material contamination, and a felsic target lithology with low background Cr concentration. The Cr isotopic composition of the Wabar background sand, which represents the target lithology, is indistinguishable from the terrestrial Cr isotopic composition range, whereas the Wabar iron meteorites show coupled spallogenic excesses in ε53Cr and ε54Cr. The Cr isotopic compositions of Wabar impactites show resolved deviations from the terrestrial Cr isotopic composition, thereby indicating the presence of Wabar meteoritic contamination. Moreover, the study demonstrates that even an impactor with a non‐carbonaceous chondritic origin, such as a IIIAB iron meteorite, can have a carbonaceous chondrite‐like signature in ε54Cr anomalies due to spallogenic Cr contamination. The study advocates for a comprehensive investigation combining platinum group elements and Cr (and/or Ni, Ru) isotopes to accurately characterize impactor types.

Tarda and Tagish Lake: Samples from the same outer Solar System asteroid and implications for D- and P-type asteroids

We report a comprehensive study of the ungrouped type 2 carbonaceous chondrite, Tarda, which fell in Morocco in 2020. This meteorite exhibits substantial similarities to Tagish Lake, Wisconsin Range 91600, and Meteorite Hills 00432, which are generally considered to have originated from a D-type asteroid(s). We constrain the compositions and petrologies of the materials present in a potential sample of a D-type asteroid by reporting the petrography, bulk chemical compositions, bulk H, C, N, Cr, and Ti isotopic compositions, reflectance spectra, and in situ chemical compositions of metals, sulfides, carbonates, and FeO-poor and FeO-rich chondrule silicates of Tarda. We also present new data for Tagish Lake. We then compare Tarda with the other Tagish Lake-like meteorites.Tarda and Tagish Lake appear to be from the same parent body, as demonstrated by their similar petrologies (modal abundances, chondrule sizes), mineral compositions, bulk chemical and isotopic compositions, and reflectance spectra. While the two other Tagish Lake-like meteorites, Wisconsin Range 91600 and Meteorite Hills 00432, show some affinities to Tagish Lake and Tarda, they also share similar characteristics to the Mighei-like carbonaceous (CM) chondrites, warranting further study. Similarities in reflectance spectra suggest that P-type asteroids 65 Cybele and 76 Freia are potential parent bodies of Tarda and the Tagish Lake-like meteorites, or at least have similar surface materials. Since upcoming spacecraft missions will spectrally survey D-type, P-type, and C-type Trojan asteroids (NASA's Lucy) and spectrally study and return samples from Mars' moon Phobos (JAXA's Martian Moons eXploration mission), which is spectrally similar to D-type asteroids, these meteorites are of substantial scientific interest. Furthermore, since Tarda closely spectrally matches P-type asteroids (but compositionally matches the D-type asteroid like Tagish Lake meteorite), P-type and D-type asteroids may represent fragments of the same or similar parent bodies.

Stable Chromium Isotope Fractionation During the Alteration of Abyssal Peridotite: Implications for Marine Chromium Isotope Mass Balance

AbstractThe stable chromium isotope system has been widely used as a redox proxy to reconstruct the oxygenation history of ocean atmosphere systems. However, the Cr isotope mass balance in modern oceans (i.e., inputs and outputs) remains poorly constrained. To investigate the influence of seawater‐peridotite reaction on the global marine Cr isotope mass balance, we report high‐precision Cr isotope data (δ53Cr) on a series of fresh and altered abyssal peridotites from the Gakkel Ridge and the Southwest Indian Ridge (SWIR). The least altered peridotites give a δ53Cr value of −0.08 ± 0.06‰ (2SD, n = 4) for the oceanic mantle which is consistent with the established δ53Cr of the Bulk Silicate Earth. Compared to fresh peridotites, a subset of altered peridotites exhibit a loss of isotopically light Cr with relatively positive δ53Cr values (up to 0.04‰). These altered peridotites are characterized by significant Cr loss and likely have been subject to serpentinization. By contrast, seafloor weathering has limited influence on the Cr concentrations and isotopic compositions of the altered peridotites. Monte Carlo (MC) simulations of marine alteration suggest a net Cr flux into seawater from altered abyssal peridotites of ∼3.5 × 108 mol/yr, which is on the same order of magnitude as the riverine input flux of 108–109 mol/yr. Furthermore, the MC results suggest that the peridotite‐sourced net Cr flux has a negative δ53Cr signature (−0.33 ± 0.21‰, 2SD). Thus, seawater‐peridotite interactions must be considered when evaluating the modern oceanic Cr isotope mass balance.

LATE ARCHEAN SHELF-TO-BASIN IRON SHUTTLE CONTRIBUTES TO THE FORMATION OF THE WORLD-CLASS DATAIGOU BANDED IRON FORMATION

Abstract Banded iron formations (BIFs) are among the few chemical sedimentary archives that capture the biogeo-chemical evolution of Fe cycling and the redox evolution of the early Earth. Although biologically recycled continental Fe has been previously proposed to be a significant source of Fe in BIFs deposited from a stratified ocean at the onset of the Great Oxidation Event (GOE; ~2.5–2.2 Ga), constraining Fe sources and pathways in Archean BIFs remains challenging. Here we present major and trace element and Fe-Nd-Cr isotope data for the largest BIF (i.e., Dataigou) in China to test whether a benthic Fe shuttle was operative during deposition of pre-GOE BIFs. The absence of true, shale-normalized Ce anomalies, coupled with unfractionated Cr and positive Fe isotope compositions, suggests that BIF deposition occurred in an anoxic water column under reducing atmospheric conditions, whereas positive Eu anomalies indicate a significant input from a high-temperature hydrothermal source. Based on a significant correlation between initial Nd and Fe isotope data, we suggest that two Fe sources were periodically mixed and resulted in deposition of the Dataigou BIF. Here, we suggest the following sources: (1) hydrothermal fluids from sea-floor systems (low εNd(t) and high δ56Fe), derived from the interaction of fluids with underlying, older continental crust, and (2) a benthic Fe flux (high εNd(t) and low δ56Fe), generated by microbial Fe(III) reduction in coastal sediments during weathering of a nearby depleted landmass. Results presented here confirm, for the first time, that a microbially driven Fe shuttle was operational and supplied Fe on a basin-wide scale in the absence of atmospheric oxygen.

A common isotopic reservoir for amoeboid olivine aggregates (AOAs) and calcium-aluminum-rich inclusions (CAIs) revealed by Ti and Cr isotopic compositions

Amoeboid olivine aggregates (AOAs) are the most abundant type of refractory inclusions found in most carbonaceous chondrite groups. AOAs are thought to be genetically related to calcium-aluminum-rich inclusions (CAIs) and potential chondrule precursor components, although the precise physical and temporal details of AOA formation and their relationship to other chondritic components remain unclear. In this study, we measured the chromium and titanium isotopic compositions of eight AOAs from four different CV chondrites with the goal of evaluating potential genetic links between AOAs, CAIs, and chondrules. These are the first Cr and Ti isotopic data reported beyond a single AOA previously measured for Cr and a different single AOA previously measured for Ti. The results presented here show that the ε54Cr and ε50Ti isotopic compositions of AOAs are indistinguishable from those of CAIs, suggesting that AOAs and CAIs formed from a common region of the disk. We also demonstrate, based on the comparison of the Cr and Ti isotopic composition of AOAs to previously measured chondrules, that mixing between AOAs and an NC compositional endmember alone cannot fully explain the range of measured chondrule compositions. Although AOAs may have been important chondrule precursor components along with AOA olivine, CAIs, fragments of earlier generation chondrules, and fine-grained matrix material, this observation requires another currently unknown component to be involved in chondrule formation.

Role of redox conditions and thermal metamorphism in the preservation of Cr isotopic anomalies in components of non-carbonaceous chondrites

Mass-independent isotopic anomalies in meteorites are probes to the dynamics and evolution of the protoplanetary disc and the reservoirs from which planetary bodies accreted. Variable Cr nucleosynthetic compositions between meteorite groups are observed but the cause is not well understood. Investigations on presolar carriers in unequilibrated chondrites are thus required to establish these relationships. For that purpose, we analysed the Cr isotope compositions of leachates (stepwise dissolution solutions) of one ordinary chondrite and two enstatite chondrites of EL and EH subgroups previously measured for Nd and Sm isotopes. The leachates of the ordinary chondrite display large variations of their Cr isotope compositions, whereas the leachates of the enstatite chondrites show very limited variations of their nucleosynthetic compositions, confirming other studies. The Cr isotope compositions of leachates of unequilibrated chondrites are significantly modified by thermal processing and aqueous alteration under various conditions. The leachates of the enstatite chondrites are relatively homogeneous for Cr isotope composition, suggesting that presolar carriers of Cr are not stable under very reduced conditions and are likely oxidised phases. After careful examination of the role of parent body processing, we conclude that there is one predominant presolar carrier enriched in 54Cr that produced most of the nucleosynthetic variations observed in leachates. This carrier is likely depleted in the carbonaceous reservoir relative to the non-carbonaceous reservoir. The drastically different isotope compositions of Cr and heavy refractory lithophile elements such as Nd of leachates of chondrites reflect relative preservation biases of their respective presolar carriers, namely a still poorly characterised presolar oxide and silicon carbide (SiC), respectively.

Chromium isotope variations in garnet-facies mantle rocks and their minerals: Implications for Cr isotope behavior in high-temperature processes

Previous work on Cr isotope composition of the lithospheric mantle focused on shallow spinel-facies peridotites and invoked the effects of partial melting and metasomatism. However, little is known on the Cr isotope composition and behavior in the deeper and more voluminous garnet-facies mantle, notably during generation and passage of magmas and fluids. Here, we present Cr isotope data for 26 garnet and ten spinel whole-rock peridotite xenoliths (mainly harzburgites) from the Udachnaya kimberlite on the Siberian craton and minerals from five of them, as well as for minerals of 14 eclogites and four garnet clinopyroxenites from the Dabie orogen in eastern China. Garnet (Gt) and clinopyroxene (Cpx) are major Cr hosts in the mantle. Our ionic modeling suggests the following order of 53Cr/52Cr values in coexisting minerals: garnet ≈ spinel > Cpx > olivine. Cr isotopes are equally partitioned between garnet and Cpx in four peridotites, while garnet is enriched in heavy Cr in one peridotite and all the eclogites (Δ53CrGt-Cpx 0.01‰ to 0.27‰, av. 0.10‰), but depleted in heavy Cr in the pyroxenites (Δ53CrGt-Cpx −0.03‰ to −0.16‰, av. −0.10‰). The Δ53CrGt-Cpx variations are attributed to effects of chemical composition, equilibration temperature and oxygen fugacity on equilibrium Cr isotope fractionation. Further, the anomalous Δ53CrGt-Cpx values in the Dabie pyroxenites and one peridotite may indicate disequilibrium inter-mineral isotope fractionation via kinetic diffusion during phase transitions as a result of pressure-temperature (P-T) changes and metasomatism.The whole-rock δ53Cr range in the garnet peridotites (−0.27 to 0.13‰; average −0.08 ± 0.18‰, 2 SD, n = 25, excluding an outlier with −0.86‰) overlaps bulk silicate Earth estimates whereas the spinel peridotites tend to have higher δ53Cr (−0.12 to 0.16‰; av. 0.02 ± 0.20‰, 2 SD, n = 10). While these rocks are residues of high degrees (30–40%) of melt extraction, their range contrasts with limited equilibrium Cr isotope fractionation we calculated for melting residues of both spinel and garnet peridotites (Δ53Crresidue-source < 0.03‰). The δ53Cr values in the spinel peridotites show correlations with modal abundances of Cpx, garnet and spinel, as well as major and trace element composition. We posit that the Cr isotope variations in these peridotites are somehow linked to solid–melt and inter-mineral diffusive exchanges during P-T changes, deformation and ingress of metasomatic media previously documented in the Udachnaya peridotites. The average δ53Cr value (−0.09 ± 0.16‰, 2 SD, n = 31) for garnet peridotites (excluding U9) in this and previous studies is similar to those previously obtained for (mainly off-craton) spinel peridotites and komatiites, and appears to be representative of the Cr isotope composition for bulk mantle. Numerical modeling for mantle magmas derived at different depths and by different melting degrees of garnet and spinel peridotites and eclogites yields a narrow δ53Cr range, possibly affected by oxygen fugacity.

Chromium isotopic compositions of a reef in the South China Sea: Biological effects and influence from early diagenetic Mn-oxides reduction

Global climate fluctuations have been inextricably linked with changes in the marine environment and ecosystems' evolution during the Cenozoic. The chromium isotopic compositions (δ53Cr) of marine carbonates have been used to study changes in ocean redox conditions. However, whether δ53Cr of carbonates faithfully reflect the information of ambient seawater at the time of deposition remains controversial. Here, we report major and trace element concentrations, as well as the Cr isotopic compositions for samples from a Neogene–Quaternary biogenic reef (Core NK-1) in the South China Sea. The samples exhibit highly variable Cr concentrations and δ53Cr values. The Cr concentrations range from 0.76 μg/g to 8.58 μg/g with an average of 3.96 μg/g, and the δ53Cr values vary from −0.54‰ to 0.68‰ with an average of 0.06‰, which are generally lower than the reported Cr isotopic compositions for global seawater. The fluctuation of δ53Cr values is unlikely to be controlled by changes in the redox conditions of seawater. Biogenic processes may have affected some samples with relatively low Cr concentrations and δ53Cr values. Other samples may have been affected by post-depositional addition of Cr from pore water. Early diagenetic reduction of ferromanganese oxides is likely another significant control factor for the variation of δ53Cr values. The results suggest that the factors influencing the Cr isotopic compositions of biogenic carbonate reefs are complex, and the variation of Cr isotopic compositions should not be directly linked to the redox state of the ocean. After evaluating the potential influences of multiple factors, the inferred Cr isotopic compositions of syn-depositional fluids of the carbonates from Core NK-1 are similar, which may suggest a relatively stable redox environment in the South China Sea during the Neogene to Quaternary period.

Genetic relationships of solar system bodies based on their nucleosynthetic Ti isotope compositions and sub-structures of the solar protoplanetary disk

Nucleosynthetic isotope variations are powerful tools to investigate genetic relationships between meteorite groups and planets. They are instrumental to assess the early evolution of the solar system, including mixing and reservoir formation in the protoplanetary disk, as well as planet formation. To address these questions, we report high-precision nucleosynthetic Ti isotope compositions of a wide range of bulk meteorites, partially complemented with new Cr isotope data. New Ti isotope data confirm the first order dichotomy observed between carbonaceous chondrites (CC), representing outer solar system compositions, and non-carbonaceous (NC) meteorites from the inner solar system. The data in combination with nucleosynthetic isotope data of other elements (e.g., Cr, Ca) indicate that isotopically heterogeneous reservoirs were also present as sub-reservoirs in the inner disk (NC reservoir), generating two or more clusters i.e., (i) the Vesta-like howardites-eucrites-diogenites (HEDs), mesosiderites, angrites, acapulcoites, lodranites, and brachinites and (ii) the Earth-Mars-like ordinary chondrites (OC), aubrites, enstatite chondrites (EC), winonaites, IAB silicates, rumuruti chondrites (R), Martian and terrestrial samples. These reservoirs likely represent disk substructures such as secondary gaps and ring-structures, created by spiral arms, which were emitted from the growing Jupiter and/or Saturn. The distinct isotopic compositions of these reservoirs may reflect thermal processing of material within the disk in combination with temporal isotopic variations either due to isotopically variable infalling material from a heterogeneous molecular cloud and/or thermal processing during the infall that induced such heterogeneities. Such effects were likely reinforced by thermal processing of the material within the disk itself and by physical size- and density sorting of dust caused by the giant planets, creating gaps and pressure bumps in the disk.Genetic relationships of meteorite groups and their implications on parent body formation are evaluated. New high precision Ti isotope data are consistent with that (i) CH and CB meteorites derive from a common parent body, which most likely accreted material from the same isotopic reservoir as the parent body of CR chondrites, (ii) silicates of IAB irons and winonaites originate from the same parent body, and (iii) mesosiderites and HED meteorites have a common origin on Vesta. The indistinguishable Ti and Cr isotope compositions of HEDs/mesosiderites to acapulcoites are not attributed to a common parent body, because of petrologic and chemical differences in addition to their distinct O isotope compositions. Their parent bodies likely accreted in the same disk region, which showed a higher level of O isotope heterogeneity compared to that of Ti, Cr and other refractory nucleosynthetic tracers. The similarity in Ti isotope compositions of Martian meteorites and OCs indicates that OC-like material belongs to the main building blocks of Mars.

Chromium isotope system of intraplate basaltic lavas: Implication for recycling materials into mantle

To explore the mantle source properties and the magmatic evolution process for intraplate basaltic lavas, as well as to investigate the potential of Cr isotopes to trace recycled crustal materials, we present Cr isotope compositions for 72 well-characterized samples of Cenozoic intraplate basaltic lavas from eastern China. These basalts display a resolvable δ53Cr range of −0.24‰ to −0.03‰ (n = 72), comparable to MORB and OIB. With respect to the evolved lavas, their δ53Cr scatter can be interpreted as a result of fractional crystallization of predominant olivine (or/and clinopyroxene) with 1% to 3% spinel from heterogeneous magma sources under different oxygen fugacity conditions. Combined with Sr-Nd-Zn-Fe isotope data, the least evolved basalts with MgO of ∼10% display a large δ53Cr range, indicating the presence of different magma component end-members, including one low-Si and two high-Si components. Two high-Si enriched components have δ53Cr values lower than those of primitive N-MORB and OIB magmas, consistent with their derivations most likely from relatively enriched mantle pyroxenites. Notably, the low-Si nephelinitic component could not be a simple end-member as proposed before. Correlations of δ53Cr with εNd(t)-87Sr/86Sr(i)-Fe/Mn-Ti/Ti*-Hf/Hf*-δ66Zn-δ56Fe [Ti/Ti* = TiN/(NdN-0.055 × SmN0.333 × GdN0.722), Hf/Hf* = HfN/(SmN × NdN)0.5. N represents the primitive mantle-normalized values] for nephelinites from both the North China Block and the South China Block suggest mixing between partial melts of carbonated peridotite and pyroxenite sources. The carbonated peridotite derived melt is characterized by depleted SrNd isotopes, low Fe/Mn, Ti/Ti* and Hf/Hf* ratios, and heavier than BSE's Cr-Fe-Zn isotope compositions. The highly oxidized environment induced by carbonatization effectively reduces Cr isotope fractionation between melts and residues during partial melting of the carbonated peridotite, resulting in the heavy Cr isotope feature of melts being inherited from the carbonated mantle source, consistent with the heavy Cr isotope compositions of carbonated mantle xenoliths obtained previously. Thus, this work highlights that Cr isotopes might act as a potential tracer for subducted sedimentary carbonates.

Biogeochemical cycling of chromium and chromium isotopes in the sub-tropical North Atlantic Ocean

Chromium (Cr) is a redox-sensitive element and because Cr isotopes are fractionated by redox and/or biological processes, the Cr isotopic composition of ancient marine sediments may be used to infer changes in past seawater oxygenation or biological productivity. While there appears to be a ‘global correlation’ between the dissolved Cr concentration and Cr isotopic composition of seawater, there is ongoing debate about the relative importance of external sources and internal cycling on shaping the distribution of dissolved Cr that needs to be resolved to validate the efficacy of using Cr isotopes as a paleo proxy. Here, we present full water column depth profiles of total dissolved Cr (Cr(VI)+Cr(III)) and dissolved Cr isotopes (δ53Cr), together with ancillary data, for three stations along a transect (GEOTRACES GApr08) across the sub-tropical North Atlantic. Concentrations of dissolved Cr ranged between 1.84 and 2.63 nmol kg-1, and δ53Cr values varied from 1.06 to 1.42‰. Although atmospheric dust, hydrothermal vents and seabed sediments have the potential to modify the distribution of Cr in the oceans, based on our observations, there is no clear evidence for substantial input of Cr from these sources in our study region although benthic inputs of Cr may be locally important in the vicinity of hydrothermal vents. Subsurface waters (below the surface mixed layer to 700 m water depth) were very slightly depleted in Cr (by up to ~0.4 nmol kg-1), and very slightly enriched in heavy Cr isotopes (by up to ~0.14‰), relative to deeper waters and the lowest Cr concentrations and highest δ53Cr values coincided with lowest concentrations of colloidal (0.02 to 0.2 μm size fraction) Fe. We found no direct evidence for biological uptake of dissolved Cr in the oligotrophic euphotic zone or removal of Cr in modestly oxygen depleted waters (O2 concentrations ~130 μmol kg-1). Rather, we suggest removal of Cr (probably in the form of Cr(III)) in subsurface waters is associated with the formation of colloid aggregates of Fe-(oxyhydr)oxides. This process is likely enhanced by the high lithogenic particle load in this region, and represents a previously unrecognized export flux of Cr. Regeneration of Cr in deeper waters leads to subtly increased levels of Cr alongside decreased δ53Cr values at individual sites, but this trend is more obvious at the global scale, with δ53Cr values decreasing with increasing radiocarbon age of deep waters, from 1.16 ± 0.10‰ (1SD, n=11) in deep Atlantic waters to 0.77 ± 0.10‰ (1SD, n=25) in deep Pacific waters. Removal of relatively isotopically light Cr from subsurface waters onto particulate material and regeneration of this Cr back into the dissolved phase in deep waters partly accounts for the systematic relationship between δ53Cr and Cr concentrations in seawater discussed by other studies.

The formation and aqueous alteration of CM2 chondrites and their relationship to CO3 chondrites: A fresh isotopic (O, Cd, Cr, Si, Te, Ti, and Zn) perspective from the Winchcombe CM2 fall

AbstractAs part of an integrated consortium study, we have undertaken O, Cd, Cr, Si, Te, Ti, and Zn whole rock isotopic measurements of the Winchcombe CM2 meteorite. δ66Zn values determined for two Winchcombe aliquots are +0.29 ± 0.05‰ (2SD) and +0.45 ± 0.05‰ (2SD). The difference between these analyses likely reflects sample heterogeneity. Zn isotope compositions for Winchcombe show excellent agreement with published CM2 data. δ114Cd for a single Winchcombe aliquot is +0.29 ± 0.04‰ (2SD), which is close to a previous result for Murchison. δ130Te values for three aliquots gave indistinguishable results, with a mean value of +0.62 ± 0.01‰ (2SD) and are essentially identical to published values for CM2s. ε53Cr and ε54Cr for Winchcombe are 0.319 ± 0.029 (2SE) and 0.775 ± 0.067 (2SE), respectively. Based on its Cr isotopic composition, Winchcombe plots close to other CM2 chondrites. ε50Ti and ε46Ti values for Winchcombe are 3.21 ± 0.09 (2SE) and 0.46 ± 0.08 (2SE), respectively, and are in line with recently published data for CM2s. The δ30Si composition of Winchcombe is −0.50 ± 0.06‰ (2SD, n = 11) and is essentially indistinguishable from measurements obtained on other CM2 chondrites. In conformity with petrographic observations, oxygen isotope analyses of both bulk and micromilled fractions from Winchcombe clearly demonstrate that its parent body experienced extensive aqueous alteration. The style of alteration exhibited by Winchcombe is consistent with relatively closed system processes. Analysis of different fractions within Winchcombe broadly support the view that, while different lithologies within an individual CM2 meteorite can be highly variable, each meteorite is characterized by a predominant alteration type. Mixing of different lithologies within a regolith environment to form cataclastic matrix is supported by oxygen isotope analysis of micromilled fractions from Winchcombe. Previously unpublished bulk oxygen isotope data for 12 CM2 chondrites, when combined with published data, define a well‐constrained regression line with a slope of 0.77. Winchcombe analyses define a more limited linear trend at the isotopically heavy, more aqueously altered, end of the slope 0.77 CM2 array. The CM2 slope 0.77 array intersects the oxygen isotope field of CO3 falls, indicating that the unaltered precursor material to the CMs was essentially identical in oxygen isotope composition to the CO3 falls. Our data are consistent with earlier suggestions that the main differences between the CO3s and CM2s reflect differing amounts of water ice that co‐accreted into their respective parent bodies, being high in the case of CM2s and low in the case of CO3s. The small difference in Si isotope compositions between the CM and CO meteorites can be explained by different proportions of matrix versus refractory silicates. CMs and COs may also be indistinguishable with respect to Ti and Cr isotopes; however, further analysis is required to test this possibility. The close relationship between CO3 and CM2 chondrites revealed by our data supports the emerging view that the snow line within protoplanetary disks marks an important zone of planetesimal accretion.

Light stable Cr isotope compositions of mid-ocean ridge basalts: Implications for mantle source composition

Stable isotopes of chromium (Cr) and iron (Fe), both multivalent elements in silicate melts, are valuable proxies of redox conditions in magmatic systems. Partial melting and fractional crystallization have been identified as the dominant fractionation processes for Cr and Fe isotopes in high-temperature reservoirs that can lead to small but detectable isotope variations in igneous rocks. More recently, however, the source mineralogy has been suggested to play an important role, which can ultimately affect the magnitude of Cr and Fe isotopic fractionation during partial melting and thus the Cr and Fe isotopic composition of the originating melt.With the aim to investigate the role of magmatic processes and the source Cr and Fe isotope signatures on the isotope composition of these transition metals in normal mid-ocean ridge basalts (N-MORB), we analyzed 21 well-characterized MORB glasses from the southern East-Pacific Rise, Pacific-Antarctic Ridge and Mid-Atlantic Ridge. The Cr isotope compositions of N-MORB show a narrow range from −0.278 to −0.186 ‰ in δ53/52Cr (i.e., difference of a sample’s 53Cr/52Cr ratio relative to the international reference material NIST SRM979), with an average value of −0.237 ± 0.050 ‰ (2SD; n = 19). As such, the average N-MORB δ53/52Cr value is significantly lower than that of Bulk Silicate Earth of −0.12 ± 0.06 ‰ and the Cr isotope compositions reported for most ocean island basalts ranging from ∼ −0.23 to 0.00 ‰. Iron isotopic compositions of these MORB range from +0.032 to +0.137 ‰ in δ56/54Fe (i.e., difference of a sample’s 56Fe/54Fe ratio relative to the international reference material IRMM014) and are within the range of previously published MORB data. The lack of correlations between N-MORB Cr isotope signatures and indices of magmatic differentiation suggests a negligible control of this process on Cr stable isotopes. Partial melting modeling using pMELTS provides evidence that the significant offset towards lower δ53/52Cr values of N-MORB cannot be produced by decompression partial melting of a lherzolithic source such as the depleted upper mantle alone. Instead, we suggest that the lower δ53/52Cr values of MORB could be linked to intrinsic small-scale 53Cr-depleted pyroxene-rich domains in the upper mantle that influence the melt’s Cr isotopic budget during partial melting.

Chromium isotopes identify the extraterrestrial component in impactites from Dhala impact structure, India

AbstractThe Dhala structure in north‐central India is a confirmed complex impact structure of Paleoproterozoic age. The presence of an extraterrestrial component in impactites from the Dhala structure was recognized by geochemical analyses of highly siderophile elements and Os isotopic compositions; however, the impactor type has remained unidentified. This study uses Cr isotope systematics to identify the type of projectile involved in the formation of the Dhala structure. Unlike the composition of siderophile elements (e.g., Ni, Cr, Co, and platinum group elements) and their inter‐element ratios that may get compromised due to the extreme energy generated during an impact, Cr isotopes retain the distinct composition of the impactor. The distinct ε54Cr value of −0.31 ± 0.09 for a Dhala impact melt breccia sample (D6‐57) indicates inheritance from an impactor originating within the non‐carbonaceous reservoir, that is, the inner Solar System. Based on the Ni/Cr ratio, Os abundance, and Cr isotopic composition of the samples, the impactor is constrained to be of ureilite type. Binary mixing calculations also indicate contamination of the target rock by 0.1–0.3 wt% of material from a ureilite‐like impactor. Together with the previously identified impactors that formed El'gygytgyn, Zhamanshin, and Lonar impact structures, the Cr isotopic compositions of the Dhala impactites argue for a much more diverse source of the objects that collided with the Earth over its geological history than has been supposed previously.

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 these additional data, we aim to better constrain the compositional range of CAIs in ε50Ti versus ε54Cr 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 ε50Ti and ε54Cr 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.