Chromium Isotopic Composition Research Articles

NWA 11562: A Unique Ureilite with Extreme Mg-rich Constituents

A comprehensive study of an ungrouped achondrite meteorite, North West Africa (NWA) 11562, was conducted, involving petrology, mineralogy, and mass-independent chromium isotopic composition. NWA 11562 comprises 34.9 vol% olivine, 56.1 vol% pyroxenes, 6.7 vol% Fe–Ni metal and oxides, 2.2 vol% carbon, and 0.2 vol% anhydrite. The oxygen isotopic composition (δ 18O = 6.24‰ ± 0.13‰ and Δ17O = −1.81‰ ± 0.03‰; Meteoritical Bulletin Database) and chromium isotopic compositions (ε 54Cr = −0.82 ± 0.10, 2SE) are consistent with NWA 11562 being a ureilite, and petrographic observations show features similar to those of the common ureilite group meteorites. Olivine (core: Fo99.0 ± 0.1; rim: Fo98.9 ± 0.1) and pyroxene (orthopyroxene: Mg# 99.0 ± 0.2; clinopyroxene: Mg# 99.1 ± 0.7) core compositions are more magnesian than in any previously known ureilite and lack the characteristic reduction rims of ureilites. Rounded small olivine grains within NWA 11562 indicate that the meteorite experienced impact and associated melting. Combined with the characteristic Fe/Mn ratio (3.84 ± 0.16) and Mg# (99.0 ± 0.1) of olivine cores, we suggest that NWA 11562 represents a more Mg-rich ureilite than any previously reported. NWA 11562 has a high 55Mn/52Cr ratio, and when combined with literature data, it plots on a well-defined 53Mn–53Cr isochron, providing a more accurate age, i.e., 4566.7 ± 0.8 Ma, overlapping previous work. This age may represent the result of early partial melting of the ureilite parent body.

Petrology, Mineralogy, and Stable Isotopic Composition of NWA 13943 (CK5) Carbonaceous Chondrite

Karoonda-like (CK) carbonaceous chondrites are highly oxidized meteorites, with metal-to-magnetite ratio close to zero. Unlike other carbonaceous chondrites (petrologic type: 1–3), most CK chondrites have undergone thermal metamorphism (550–1270 K) on their parent body with a petrologic type 4 or above. Lines of evidence suggest a genetic relationship between CK chondrites and Vigarano-like (CV) carbonaceous chondrites, which are predominantly type 3. However, observable petrographic distinctions persist between the two groups. Thus, a thorough reevaluation of their geochemical discrepancies is critical to test the CK-CV single parent body hypothesis. Northwest Africa (NWA) 13943, a newly discovered meteorite subjected to intense modification, was classified using scanning electron microscopy and electron microprobe techniques. High-precision measurements of the mass-independent chromium isotope compositions (ε53Cr and ε54Cr) and the mass-dependent oxygen isotope compositions (δ17O and δ18O) of NWA 13943 were reported for the first time. Integrating petrological, mineralogical, oxygen, and chromium isotopic data, it is legitimated to infer that CK and CV chondrites may originate from two proximal but distinct isotopic reservoirs within the protoplanetary disk.

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.

Mineralogical anatomy of the Cr-rich quenched angrite Northwest Africa 12774: Implication to mantle heterogeneity

Angrites are a small group of basaltic meteorites and their origin is currently disputed. Among these, Northwest Africa (NWA) 12774 is a quenched angrite that was reported having an anomalously high bulk Cr2O3 content (∼0.45 wt%). However, the reason behind this anomaly, which is critical for understanding the evolution of the angrite parent body, remains unknown. Here, we performed a detailed petrographic, mineralogical, and bulk oxygen and chromium isotopic composition study on this meteorite. NWA 12774 consists of porous olivine macrocrysts, phenocrysts of olivine and Al-Ti-rich augite, and spinel micro-phenocrysts with fine-grained groundmass. The olivine macrocrysts and the magnesian cores of olivine phenocrysts show compositional correlations distinctly different from typical olivine phenocrysts. The olivine macrocrysts contain small chromite/chrome-spinel inclusions which have the highest Cr2O3 content (53.2 wt%) for chromite/spinel in angrites to date. Based on these textural and chemical features, the olivine macrocrysts and the magnesian cores of olivine phenocrysts are identified as xenocrysts. Some pyroxene phenocrysts contain regions with complexly zoned microtextures, which have much larger chemical variations compared with those with simply zoned microtextures. The regions with complexly zoned microtextures are likely to be of xenocrystic origin. The bulk Cr2O3 content in NWA 12774 was estimated through two approaches, both of which show the bulk Cr2O3 content to be around 0.3 wt% or possibly up to ∼ 0.45 wt%, which is consistent with previously measured values. The high Cr2O3 content in NWA 12774 could be attributed to both the high abundance of spinel micro-phenocrysts and their high Cr2O3 contents, rather than the presence of Cr-rich xenocrysts. The calculated melt rare earth element concentration in NWA 12774 equilibrated with the most Mg-rich augite is essentially identical to those in LEW 87051 and Asuka 881371, which however have Cr2O3 contents much lower than NWA 12774. We suggest that the mantle source of NWA 12774 may not be as depleted in Cr and probably other volatile elements as other angrite sources. The various Cr2O3 contents in different quenched angrites probably reflect that their mantle sources have not been homogenized.

Determination of mass-dependent chromium isotopic compositions in geological samples by double spike-total evaporation-thermal ionization mass spectrometry (DS-TE-TIMS)

BackgroundChromium isotopes have been used to trace geochemical and cosmochemical processes in the past. However, the presence of multivalent Cr species has made it difficult to isolate Cr from geological samples, particularly for samples with a low Cr mass fraction. ResultsHere, a simple three-step ion exchange chromatography procedure is presented to separate Cr from various sample matrices, ranging from ultramafic to felsic rocks. Throughout each of the column chromatography step, 1 mL of cation exchange resin AG50W-X8 (200–400 mesh) was used as the stationary phase and oxalic acid as a chelating agent, was used in addition to the inorganic acids. This method yielded high recoveries of Cr [93 ± 8% (2SD, N = 7)] regardless of the lithology. The total procedural blank of Cr was <0.5 ng. We also developed a double spike-total evaporation-thermal ionization mass spectrometry (DS-TE-TIMS) technique that significantly reduced sample consumption to ∼20 ng of Cr per each measurement of mass-dependent 53Cr/52Cr. SignificanceThis study achieved a 2SD external precision of 0.02‰ for the analysis of NIST NBS3112a and of 0.01–0.07‰ for the geological samples. This study enabled high-precision Cr isotope analysis in geological samples with various matrix and Cr compositions using relatively small sample volumes.

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.

Stable chromium isotope compositions of hydrogenetic ferromanganese crusts potentially linked to primary productivity

Stable chromium isotope composition (δ53Cr) is a widely used paleo-redox proxy. However, modern seawater δ53Cr values do not correlate with dissolved O2 concentrations, suggesting that non-O2 factors may influence marine Cr cycling. We present new δ53Cr data for two hydrogenetic ferromanganese (FeMn) crusts deposited in the western- and central-north Pacific Ocean since the late Eocene, a period when the ocean remained largely oxic. Simple isotope mass balance and Rayleigh distillation models suggest that trivalent Cr is likely the major Cr species incorporated from seawater into the Fe phases of hydrogenetic FeMn crusts. The δ53Cr values of FeMn crusts decrease from −0.35‰ in the late Eocene to −0.74‰ in the middle Miocene, followed by increasing to modern values ranging from −0.33 to −0.47‰. The temporal trend of δ53Cr follows that of the regional pelagic sedimentation rate, suggesting that primary productivity may have played a role in shaping the δ53Cr signals recorded in the hydrogenetic FeMn crusts. Our data show that non-O2 factors may influence δ53Cr values recorded in Fe-rich sedimentary archives deposited in a largely oxic ocean, thus adding more complexities to the Cr isotope paleoproxy.

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.

Shidian meteorite, a new fall analog of near‐Earth asteroid (101955) Bennu

AbstractShidian is a recent meteorite which fell in Yunnan province, China, on November 27, 2017, and has been classified as a CM2 chondrite. Petrography, mineralogy, oxygen and chromium isotopic composition, reflectance spectrum, and density studies of Shidian are reported in this study. Clasts with different aqueous alteration degree, two type 1 clasts with nontypical CM petrography, and one metamorphic clast are observed in Shidian. Mineralogically, Shidian main body consists of phyllosilicates (∼70 vol%), forsterite (∼13 vol%), fayalitic olivine, carbonates, sulfide, high‐Ca pyroxene, magnetite framboids, and Fe‐Ni metal. The average electron microprobe analysis (EMPA) analytical totals of phyllosilicates are 84.07 ± 1.75 wt%, with average FeO/SiO2of tochilinite–cronstedtite intergrowths (TCIs) in different clasts ranging from 1.18 to 3.29. The bulk geochemical composition is characterized by flat rare earth element pattern, and by depletion of highly volatile elements. The whole rock oxygen isotopic composition is −0.51 ± 0.73‰, 5.44 ± 1.01‰, and −3.38 ± 0.20‰ for δ17O, δ18O, and Δ17O, respectively, with bulk chromium isotopic composition as ε54Cr = 1.00 ± 0.11. The grain density, bulk density, and porosity are 2.758 ± 0.008 g cm−3, 2.500 ± 0.004 g cm−3, and 9.37 ± 0.59%, respectively. The reflectance spectrum shows “blue” (negative) continuum slope across the visible and near‐infrared range, with characteristic absorption features (such as 0.765, 0.923, and 1.160 μm for phyllosilicates). These characteristics indicate that Shidian is an unheated, brecciated CM chondrite and may be an analog of asteroid Bennu.

A detailed record of early solar system melting in the carbonaceous achondrites Northwest Africa 7680 and 6962

AbstractDetailed textural and geochemical analyses of the carbonaceous achondrites Northwest Africa (NWA) 7680 and NWA 6962 support a rapid progression of thermal events, by similar processes, on the same parent body. The achondrites have olivine compositions of Fa44.8 and Fa47.4 for NWA 7680 and NWA 6962, respectively. Replicate oxygen isotope analyses of grains and bulk powders from NWA 7680 yielded average Δ17O values of −1.04 ± 0.03‰ and −1.00 ± 0.05‰, respectively, which is identical to that reported for NWA 6962. The whole rock ɛ54Cr compositions are also equivalent for NWA 7680 and NWA 6962 (1.36 ± 0.05 and 1.30 ± 0.05, respectively). Both meteorites are plagioclase‐rich, and NWA 7680 is also Fe‐metal‐rich, suggesting they both formed via differentiation processes that resulted in the pooling of partial melt products. Major element geochemical trends show that both rocks could be formed through the melting of chondritic material on a CR chondrite‐like parent body. This is consistent with oxygen isotope and chromium isotope compositions. Intrusion of a late‐stage melt is evident in both meteorites and the crystallization products include silica‐rich, alkali‐deficient nepheline. The late‐stage liquid has partially melted and mixed with primary plagioclase in NWA 6962. In contrast, the late‐stage liquid was often restricted to grain boundaries in NWA 7680, leaving some of the primary plagioclase crystals intact. In situ dating of NWA 7680 phosphate minerals (merrillite and fluorapatite) reveals that it has not experienced long duration thermal metamorphism, or impact‐related Pb loss and age resetting since 4578 ± 17 Ma (207Pb/206Pb age ± 2σ, within error of solar system age). Phosphates associated with the late‐stage melt in NWA 6962 yield a 207Pb/206Pb age of 4556.6 ± 8.0 Ma (2σ) within 2σ of the NWA 7680 age. These early dates indicate that the observed chromium isotope signatures in these meteorites were not introduced by a later high‐temperature event, such as late impact accretion processes. These data are consistent with a rapid separation of inner and outer solar system chemical reservoirs, planetesimal melting, differentiation, and cooling, all within several million years of calcium‐aluminum‐rich inclusion formation.

Determination of chromium isotopic composition in various geological material by thermal ionization mass spectrometry

We present a new method for the chemical purification and the measurement of the isotopic composition of Cr by Thermal-Ionization Mass Spectrometry in various geological materials. The separation and purification protocol was adapted to match a wide range of geological and cosmochemical matrices and was tested with terrestrial reference materials, uranium-rich samples and meteorites. The total Cr yield was at least 86% and the Cr/U ratio went from 7.84 × 10−5 to 5.72 × 103 after purification for uranium-rich materials. It also permitted an efficient removal of matrix elements such as Na and Mg and interfering elements such as Fe, Ti and V. Cr isotopic composition was measured using multistatic and multidynamic modes. The multidynamic mode displayed no improvement of the external reproducibility and internal precision compared with the multistatic mode, in contrast with what has been found with other isotope systems. This method gave a reproducibility of 5 ppm and 13 ppm (2 s.d.) for the 53Cr/52Cr and 54Cr/52Cr ratios respectively, over a period of several months, which represents an improvement of the long-term reproducibility compared with the other published methods. The accuracy of the protocol was tested by measuring terrestrial reference materials (AGV-1, AGV-2, BHVO-1 and BHVO-2) as well as extra-terrestrial samples (Bouvante, Stannern and Waconda), displaying good agreement with published data. This method is thus suited to detect any mass-independent fractionation or nucleosynthetic anomalies in geological materials.

Experimental study of chromium (III) coprecipitation with calcium carbonate

Chromium (Cr) isotope compositions of marine carbonates have widely been used to trace the evolution of oxygen levels in the atmosphere and ocean during geological history. Recent studies have indicated that Cr found in natural carbonates is dominated by trivalent Cr, also known as Cr(III). However, the incorporation behavior of Cr(III) into carbonates remains undefined. Here, we conducted coprecipitation experiments for Cr(III) with calcium carbonate to constrain the behavior of Cr(III) in carbonate deposition environments. Extended X-ray absorption fine structure (EXAFS) results suggest that Cr(III) is incompatible with the calcite crystal lattice. There are likely to be several Cr species in the coprecipitation samples. Most Cr is adsorbed on the crystal surface of calcite or exists as amorphous Cr hydroxide[Cr(OH)3]. A small fraction of Cr can reside in the calcite crystal, but Cr3+ cannot directly substitute for Ca2+. It may exist in interstitial voids in crystals or occupy the position of Ca2+ in the form of divalent Cr hydroxide cation [Cr(OH)2+], leading to a distorted structure. Moreover, we find that Cr(III) can stimulate polymorph selection of vaterite [a metastable polymorph of calcium carbonate (CaCO3)] during CaCO3 precipitation, likely due to the formation of Cr hydroxide on the surface of vaterite crystals, hindering its transformation to calcite. Because Cr(III) is incompatible with the carbonate crystal lattice, we suggest that most Cr in natural carbonates is adsorbed on the crystal surface and may be acquired at water–sediment interfaces after carbonate precipitation. Therefore, Cr isotope compositions of carbonates may easily be affected by post-depositional diagenetic processes, and Cr isotope variations in sedimentary carbonates should not exclusively correspond to changes in oxygen levels in the atmosphere and ocean. Paleoenvironment reconstruction based on Cr isotope compositions of carbonates should take post-depositional processes into consideration.

Chromium isotope fractionation during adsorption of chromium(III) by soils and river sediments

Chromium (Cr) isotope compositions of sedimentary rocks have been widely used to unravel fluctuations in atmospheric oxygen levels during geologic history. A fundamental framework of this application is that any Cr isotope fractionation in natural environments should be related to the redox transformation of Cr species [Cr(VI) and Cr(III)]. However, the behavior of Cr isotopes during non-redox Cr cycling is not yet well understood. Here, we present laboratory experimental results which show that redox-independent adsorption of Cr(III) by natural river sediments and soils can be accompanied by obvious Cr isotope fractionation. The observed Cr isotope fractionation factors (−0.06‰ – −0.95‰, expressed as 10&lt;sup&gt;3&lt;/sup&gt;ln&lt;i&gt;α&lt;/i&gt;) are much smaller than those caused by redox processes. Combined with previous studies on redox-independent Cr isotope fractionation induced by ligand-promoted dissolution, we suggest that the systematic shift to highly fractionated Cr isotope compositions of sedimentary rocks is likely to represent atmospheric oxygenation, but muted signals observed in some geologic periods may be attributed to non-redox Cr cycling and should be interpreted with caution.

Early differentiation of magmatic iron meteorite parent bodies from Mn–Cr chronometry

Magmatic iron meteorite groups such as IIAB, IIIAB and IVA, represent the largest sampling of extraterrestrial core material from the earliest accreted distinct planetary bodies in the solar system. Chromium isotope compositions of chromite/daubreelite from seven samples, translated into 53Cr/52Cr model ages, provide robust time information on planetary core formation. These ages range within 1.5 Ma after formation of calcium-aluminium-rich inclusions (CAIs) and define the time of metal core formation in the respective parent bodies, assuming metal-silicate separation was an instantaneous event that induced strong chemical fractionation of Mn from the more siderophile Cr. The early core formation ages support accretion and differentiation of the magmatic iron meteorite parent bodies to have occurred prior to the chondrule formation interval. The calibration of Mn-Cr ages with established Hf-W ages of samples from the same magmatic iron meteorite groups constrains the initial E53Cr of the solar system to -0.30, and thus lower than previously estimated.

Stable chromium isotopic variations in peridotite mantle xenoliths: Metasomatism versus partial melting

Chromium isotope compositions have been determined for 42 mantle-derived xenoliths from Cameroon, France, Mongolia, Russia and the USA. The samples are mainly spinel and garnet lherzolites, or harzburgites, and yield δ53CrNIST979 from −0.33 to 0.43‰, within the range of previously reported compositions, −0.51 to 0.74‰ (Xia et al., 2017). Partial melting has been proposed as a process that alters the δ53Cr of the mantle residue. New non-modal melting models show that the compatible nature of Cr is inconsistent with large changes in the residue’s isotopic composition. The fractionation during melting is constrained by calculated Δ53Crmantle-melt-values <0.09 and the measured Δ53/52Cr mantle-melt ≈ 0.07‰, which is too small to generate the observed range in δ53Cr at low to medium degrees of melting. Fertile to melt-depleted, unmetasomatised peridotite xenoliths show no correlations between δ53Cr and indicators of partial melting. Almost all LREE-enriched samples studied here define a correlation between δ53Cr and (La/Yb)N. This is consistent with alteration of Cr isotopic compositions by some process that is related to interactions with low degree partial melts. The low Cr content of small degree partial melts renders metasomatism via such liquids a difficult explanation for the isotopic effects found. A possible explanation is some form of disequilibrium loss of isotopically light Cr into such liquids during their percolation through the mantle. This is similar to a previously proposed mechanism of kinetic isotopic fractionation of Cr associated with interactions between silicate melts and peridotitic mantle (Xia et al., 2017).

Olivine-rich achondrites from Vesta and the missing mantle problem

Mantles of rocky planets are dominantly composed of olivine and its high-pressure polymorphs, according to seismic data of Earth’s interior, the mineralogy of natural samples, and modelling results. The missing mantle problem represents the paucity of olivine-rich material among meteorite samples and remote observation of asteroids, given how common differentiated planetesimals were in the early Solar System. Here we report the discovery of new olivine-rich meteorites that have asteroidal origins and are related to V-type asteroids or vestoids. Northwest Africa 12217, 12319, and 12562 are dunites and lherzolite cumulates that have siderophile element abundances consistent with origins on highly differentiated asteroidal bodies that experienced core formation, and with trace element and oxygen and chromium isotopic compositions associated with the howardite-eucrite-diogenite meteorites. These meteorites represent a step towards the end of the shortage of olivine-rich material, allowing for full examination of differentiation processes acting on planetesimals in the earliest epoch of the Solar System.

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.

Accurate Measurement Of Chromium Isotopic Compositions In Geological Reference Materials By Double-Spike MC‐ICP‐MS

Accurate Measurement Of Chromium Isotopic Compositions In Geological Reference Materials By Double-Spike MC‐ICP‐MS

Coupled stable chromium and iron isotopic fractionation tracing magmatic mineral crystallization in Archean komatiite-tholeiite suites

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.

Behaviour of Cr in runoff from two catchments underlain by felsic bedrock

ABSTRACT Chromium isotope and chemical compositions in runoff from two felsic rock catchments, the Lysina (LYS; Czech Republic) and the Neglinka (NEG; northwest Russia), were studied. Three types of water were identified: Na-Ca-SO4 type for the LYS, Mg-Ca-Cl-HCO3 type for the NEG downstream, and Mg-Ca-Cl to Mg-Ca-HCO3 type for the NEG upstream. The Cr (III) liberated during soil/bedrock weathering oxidized to Cr (VI), which was the main dissolved Cr species in both catchments. Variations in δ53Cr values for LYS runoff (–0.07‰ to +0.37‰) reflected a sole Cr source, seasonality of weathering and hydrologically controlled leaching/export processes. In the NEG catchment, back-reduction of Cr (VI) to Cr (III) during riverine transport resulted in a decrease in Cr concentrations (to 10–30%) and in an increase of δ53Cr values (+0.09 to +0.42‰ for the upstream to +0.72 to +1.73‰ for the downstream). Groundwater discharge could have influenced the chemical composition of the downstream NEG runoff to some extent.