Mass-independent Isotope Research Articles

Sulfur isotope anomalies in coal combustion: Applications to the present and early Earth environments

The observation of mass-independent sulfur isotope fractionations (S-MIF) in Archean-Paleoproterozoic rocks has been instrumental in constraining oxygen levels on early Earth. The S-MIF effect, experimentally demonstrated to result from photochemical reactions, has now been observed in coal combustion, expanding our understanding of this phenomenon. Our study reveals that the negative Δ33S anomalies produced by coal combustion are consistent with similar anomalies observed in present-day sulfate aerosols in Beijing, China, and the black crust sulfates formed on building stones, monument walls, and sculptures in Europe that contribute to carbonate stone deterioration and cultural heritage damage. This finding provides independent evidence for a critical role of atmospheric sulfate from coal combustion in maintaining isotopic balance and offers an effective method for tracing sulfate aerosol sources. These insights are vital for developing more effective regulatory policies to control air pollution and protect public health. Given that coal energy production remains a significant issue in climate science, accurately mapping the global distribution of its by-products is imperative.

Primitive asteroids as a major source of terrestrial volatiles.

The origins of Earth's volatiles are debated. Recent studies showed that meteorites display unique mass-independent isotopic signatures of the volatile element Zn, suggesting that Earth's Zn originated from materials derived from different regions of the Solar System. However, these studies largely omitted meteorites from the differentiated planetesimals thought to represent the Earth's building blocks, which underwent melting and substantial volatile loss. Here, we characterize the mass-independent Zn isotope compositions of meteorites from such planetesimals. We incorporate these results in mixing models that aim to reproduce Earth's abundance and isotope compositions of Zn and other elements. Our results suggest that, while differentiated planetesimals supplied ~70% of Earth's mass, they provided only ~10% of its Zn. The remaining Zn was supplied by primitive materials that did not experience melting and associated volatile loss. Combined with other findings, our results imply that an unmelted primitive material is likely required to establish the volatile budgets of the terrestrial planets.

A new Re-Os age constraint informs the dynamics of the Great Oxidation Event

Abstract The early Paleoproterozoic (ca. 2.5–2.2 Ga) represents a critical juncture in Earth history, marking the inception of an oxygenated atmosphere while bearing witness to potentially multiple widespread and severe glaciations. Deciphering the nature of this glacial epoch and its connection with atmospheric oxygenation has, however, proven difficult, hindered by a reliance on disputed stratigraphic correlations given the paucity of direct radiometric age constraints. Nowhere is this more acute than within the South African Transvaal Supergroup: Here, while the loss of oxygen-sensitive mass-independent sulfur isotope fractionation (S-MIF) has been reported from both the Duitschland and Rooihoogte formations, divided opinion surrounding the time-equivalence of these units has prompted authors to argue for vastly different oxygenation trajectories. Addressing this debate, we present a depositional Re-Os age (2443 ± 33 Ma) from diamictite samples preserved in drillcore of the upper Duitschland Formation. The 100-million-year separation between the Duitschland Formation and its previously presumed equivalent reveals at least two isolated disappearances of S-MIF, requiring that the Great Oxidation Event was dynamic and proceeded via discrete oxygenation episodes whose structure remains incompletely understood. Importantly, our revised framework aligns the lower Duitschland diamictite with the low-latitude glacigenic Makganyene Formation, supporting hypotheses of widespread regional, and potentially global, early Paleoproterozoic glaciation.

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.

Forging inner-disk Al-rich chondrules by interactions of CAI-like melt and ambient gas

The mechanism of gas-melt interactions and the compositions of precursors are key to understanding the formation of chondrules. To shed light on the two enigmas, we studied the petrography, chemistry, and oxygen isotopes of six Al-rich chondrules (ARCs, five glassy and one plagioclase-bearing) in unequilibrated ordinary chondrites (OCs, petrologic subtype: 3.05). The plagioclase-bearing ARC was also investigated with Al-Mg chronology. Elemental zonation and inter-element correlations in glassy mesostasis of two ARCs indicate the condensation of gaseous Mg, SiO, Fe, and Na onto chondrule melt. The plagioclase-bearing ARC appears to display internal mass-independent oxygen isotope fractionation with δ18O increasing following the order of mineral crystallization, suggesting partial oxygen isotope exchange with ambient gas during crystallization. Oxygen isotopes of the six ARCs are distributed along a mixing line of slope = 0.99 ± 0.05, which intersects with calcium-aluminum-rich inclusions (CAIs), consistent with a small portion of OC type IA chondrules, but deviates from other OC ferromagnesium chondrules (FMCs) towards higher δ17O, suggesting that OC ARCs and some IA chondrules were established by interactions between CAI-like melts and 16O-poor ambient gas, rather than simply remelting solid mixtures of CAI and FMC materials.All six ARCs have unfractionated refractory lithophile element patterns with bulk concentrations ranging from ∼7 × CI to ∼15 × CI, indicating ∼ 30–100 % of CAI-like materials in their precursors. Their bulk compositions are linearly evolved toward the Mg: SiO ∼ 3:2 to 2:1 (in atomic) apex, consistent with adding gaseous Mg and SiO to the chondrule bulk via gas–melt interactions. The back-calculated compositions of the recycled CAI-like materials closely overlap with pyroxene-anorthite-rich CAIs, suggesting that extensive interactions between the melt of pyroxene-anorthite-rich CAI-like materials and ambient gas could make OC ARCs. The Al-Mg age of the plagioclase-bearing ARC is ∼2.2 Ma after CAIs, similar to typical OC FMCs, suggesting that the refractory component arrived at the OC reservoirs in the late stage of the chondrule heating events.

Atmospheric oxygenation at the onset of Earth’s Great Oxidation forced enhanced marine anoxia

Abstract Capturing the loss of mass-independent sulphur isotope fractionation (MIF-S), the correlative South African Duitschland and Rooihoogte formations are widely held to bear the isotopic fingerprint of the first atmospheric oxygenation at the onset of the so-called Great Oxidation Event (GOE). Surprisingly, however, while the multiple sulphur isotope systematics of these formations remain central to our understanding of the GOE, until now, comparatively little work has been done to elucidate the repercussions within the marine realm. Here we present chemostratigraphic records from four drill cores covering a large area of the Transvaal Basin, transcending these crucial units and continuing into the overlying Timeball Hill Formation (TBH), that document the immediate, yet counterintuitive, marine response to atmospheric oxygenation. Specifically, irrespective of the interpretative framework employed, our basin-wide redox-sensitive trace element data document an environmental change from oxic/suboxic conditions within the lower and middle parts of the Duitschland and Rooihoogte formations to suboxic/anoxic conditions within their upper reaches. Interestingly, in concert with a ~35‰ negative δ34S excursion that implicates increased sulphate availability and bacterial sulphate reduction, δ98/95Mo3134+0.25 values increase by ~1.0 to 1.5‰. Combining these observations with increased Fe/Mn ratios, elevated total sulphur and carbon contents and a trend towards lower δ13Corg values imply a shift toward less oxygenated conditions across the Transvaal Basin. The combined observations in the mentioned parameters expose a geobiological feedback-driven causality between the earliest oxygenation of the atmosphere and decreased redox potentials of medium to deep marine environments, at least within the Transvaal Basin.

Continuous-Flow Stable Sulfur Isotope Analysis of Organic and Inorganic Compounds by EA-MC-ICPMS.

Elemental analysis (EA) coupled to isotope ratio mass spectrometry (IRMS) is a well-established method to derive stable isotope ratios of sulfur (34S/32S). Conversion of sulfur to SO2 by EA and measurement of SO2 isotopologues by IRMS represents the simplest and most versatile method to accomplish isotope measurement of sulfur even in bulk samples. Yet, interferences by oxygen isotopes in SO2 often impair the precision and trueness of measured results. In the current study, we coupled EA to multicollector inductively coupled plasma mass spectrometry (MC-ICPMS) to establish a method that avoids such interferences due to direct measurement of S+ ions. In addition, measurement of the 33S/32S isotope ratios is possible, thus representing the first bulk method that is suitable to study mass-independent isotope fractionation (MIF). Analytical precision (σ) of available Ag2S and BaSO4 reference materials (RMs) was, on average, 0.2 mUr for δ33S and δ34S, never exceeding 0.3 mUr within this study (1 mUr = 1‰ = 0.001). Measured δ34S values of reference materials agreed within ±0.2 mUr of officially reported values. Measurement of wood samples yielded good precision (0.2 mUr) for sulfur amounts as low as 3.5 μg, but precision deteriorated for samples at lower sulfur contents due to poor peak shape. Finally, we explored cross-calibration of organic liquids separated via gas chromatography (GC) against solid RMs combusted via EA that avoids challenging offline conversion of RMs. Results indicate good precision (≤0.08 mUr) and acceptable trueness (≤0.34 mUr) for determination of δ34S, demonstrating the future potential of such an approach.

Positive Δ199Hg anomalies in Mesozoic porphyry Mo deposits of Northeastern China and their implications to the metallogeny of arc-related hydrothermal systems at convergent margins

Mercury (Hg) isotopes display unique mass-independent isotope fractionation (MIF, reported as Δ199Hg), which is primarily generated via Hg photochemical processes in the land-ocean-atmosphere system. Magmatic and hydrothermal processes do not trigger MIF of Hg isotopes, therefore, Hg-MIF signals detected in deep reservoirs (mantle and crust) are theoretically sourced from recycled surface materials. Here, we observed positive Δ199Hg signals (0.10 ± 0.07‰, SD) in Mesozoic porphyry Mo deposits of NE China. These values correspond to the recently reported Δ199Hg signature of Mesozoic epithermal AuAg systems in NE China (Δ199Hg: 0.11 ± 0.07‰, SD), suggesting that both mineral systems receive large amounts of Hg from subducted marine materials, given that marine Hg has positive Δ199Hg composition. Our study thus provides novel geochemical evidence on the linkage between oceanic plate subduction and metallogeny of various hydrothermal systems at convergent margins. Subduction contributes large amounts of volatiles to arc magmas, which then release metal-rich magmatic-hydrothermal fluids of the porphyry to epithermal ore deposit spectrum.

Increased Contribution of Circumpolar Deep Water Upwelling to Methylmercury in the Upper Ocean around Antarctica: Evidence from Mercury Isotopes in the Ornithogenic Sediments.

Upwelling plays a pivotal role in supplying methylmercury (MeHg) to the upper oceans, contributing to the bioaccumulation of MeHg in the marine food web. However, the influence of the upwelling of Circumpolar Deep Water (CDW), the most voluminous water mass in the Southern Ocean, on the MeHg cycle in the surrounding oceans and marine biota of Antarctica remains unclear. Here, we study the mercury (Hg) isotopes in an ornithogenic sedimentary profile strongly influenced by penguin activity on Ross Island, Antarctica. Results indicate that penguin guano is the primary source of Hg in the sediments, and the mass-independent isotope fractionation of Hg (represented by Δ199Hg) can provide insights on the source of marine MeHg accumulated by penguin. The Δ199Hg in the sediments shows a significant decrease at ∼1550 CE, which is primarily attributed to the enhanced upwelling of CDW that brought more MeHg with lower Δ199Hg from the deeper seawater to the upper ocean. We estimate that the contribution of MeHg from the deeper seawater may reach more than 38% in order to explain the decline in Δ199Hg at ∼1550 CE. Moreover, we found that the intensified upwelling may have increased the MeHg exposure for marine organisms, highlighting the importance of CDW upwelling on the MeHg cycle in Antarctic coastal ecosystems.

Foraging behavior and sea ice-dependent factors affecting the bioaccumulation of mercury in Antarctic coastal waters

To elucidate the potential risks of the toxic pollutant mercury (Hg) in polar waters, the study of accumulated Hg in fish is compelling for understanding the cycling and fate of Hg on a regional scale in Antarctica. Herein, the Hg isotopic compositions of Antarctic cod Notothenia coriiceps were assessed in skeletal muscle, liver, and heart tissues to distinguish the differences in Hg accumulation in isolated coastal environments of the eastern (Chinese Zhongshan Station, ZSS) and the antipode western Antarctica (Chinese Great Wall Station, GWS), which are separated by over 4000 km. Differences in odd mass-independent isotope fractionation (odd-MIF) and mass-dependent fractionation (MDF) across fish tissues were reflection of the specific accumulation of methylmercury (MeHg) and inorganic Hg (iHg) with different isotopic fingerprints. Internal metabolism including hepatic detoxification and processes related to heart may also contribute to MDF. Regional heterogeneity in iHg end-members further provided evidence that bioaccumulated Hg origins can be largely influenced by polar water circumstances and foraging behavior. Sea ice was hypothesized to play critical roles in both the release of Hg with negative odd-MIF derived from photoreduction of Hg2+ on its surface and the impediment of photochemical transformation of Hg in water layers. Overall, the multitissue isotopic compositions in local fish species and prime drivers of the heterogeneous Hg cycling and bioaccumulation patterns presented here enable a comprehensive understanding of Hg biogeochemical cycling in polar coastal waters.

The multiple sulfur isotope architecture of the Kambalda nickel camp, Western Australia

New data on the multiple sulfur isotope signature of Archean sulfides from country rocks and magmatic mineralization at the Moran deposit (Kambalda, Western Australia) were combined with previously published geochemical data to constrain the various stages of the dynamic evolution of this magmatic system, unveiling new insights into the transport mechanisms of sulfide liquids in komatiite magmas. Sulfides in the Archean magmatic and sedimentary host rocks of the komatiites display a unique mass-independent sulfur isotope signature (Δ33S), which records a photochemical reaction of sulfur in an oxygen-poor atmosphere prior to the Great Oxidation Event.Sedimentary rocks that are thought to be assimilated by komatiite show a distinctly positive Δ33S signature (+ 0.9 to + 2.4‰). Early ore sulfides situated above these sedimentary rocks contain relatively few valuable metals and display an overlapping Δ33S range (+ 0.6 to + 1.0‰). Subsequent but still early ore sulfides are situated above basalt, as the sedimentary rocks were thermo-mechanically eroded by the sulfide melt, displaying more mantle-like signatures (+ 0.2 to + 0.3‰) and valuable metal content - indistinguishable from the main ore deposit. This reflects a progressive dilution of the contaminant signature by the magmatic isotope signature of the komatiite liquid. Calculated volumes of the interaction of silicate melt and sulfide melt to explain the metal tenor of the ore and its Δ33S signature indicate a decoupling between chemical and isotopic signatures. This can be explained by upgrading the sulfide melt with valuable metals simultaneously with the dissolution of sulfur in the komatiite melt.

The potassium isotopic composition of CI chondrites and the origin of isotopic variations among primitive planetary bodies

The isotopic analysis of moderately volatile elements such as K have gained significant interest in recent years as they possess the potential to help us better understand solar system formation. Even so, the precise K isotopic composition of CI chondrites, the most chemically primitive chondrite, has remained elusive. As the K elemental composition of CI chondrites matches well with the solar photosphere, it is possible that their K isotopic composition represents the solar system initial value. Here, we investigate the CI chondrite K isotopic composition in order to determine the precise CI chondrite, and thus possibly solar system initial, δ41K value. In addition, we investigate the K isotope compositions of several other chondrite groups, evaluate all available chondrite K isotope data together, and use these data along with data from a range of other isotope systems to assess if nucleosynthetic variations, volatility related processes, or parent body processes can best explain the range of isotope variations. The δ41K composition of all nine CI chondrite pieces analyzed in this study show limited variation, ranging from −0.29‰ to −0.17‰. When combined with the previous CI analysis, an overall mean CI δ41K value of −0.21 ± 0.05‰ (2SE) is obtained. This K isotope composition is distinct from the Bulk Silicate Earth value of −0.43 ± 0.17‰ (2SD), heavier than almost all other chondrite groups, and may represent the solar system initial K isotope composition. When comparing all chondrites broadly, ordinary chondrites show the lightest mean K isotope composition of −0.76 ± 0.06‰ (H = −0.71 ± 0.12‰, L = −0.77 ± 0.04‰, LL = −0.81 ± 0.12‰), enstatite chondrites the middle composition of −0.39 ± 0.11‰ (EH = −0.34 ± 0.05‰, EL = −0.45 ± 0.20‰), and carbonaceous chondrites the heaviest composition of −0.31 ± 0.08‰. For the carbonaceous chondrite groups CK (−0.42 ± 0.11‰), CR (−0.46 ± 0.05‰), and CV (−0.38 ± 0.07‰) chondrites show lighter δ41K compositions compared to CO (−0.20 ± 0.10‰), CM (−0.23 ± 0.11‰), and CI (−0.21 ± 0.05‰) chondrites. When these K isotope group averages are compared against the averages for other mass-dependent moderately volatile element isotope systems (δ87Rb, δ66Zn, δ71Ga, δ128Te) and mass-independent isotope systems (ε54Cr, ε64Ni, ε50Ti, Δ17O, ε40K, and ε66Zn,), a range of correlations are observed. Across all chondrite groups δ41K shows correlations with δ87Rb, δ66Zn, and δ71Ga, and correlations with ε54Cr, ε64Ni, ε50Ti, ε40K, and ε66Zn. When comparing the CCs only, correlations are observed between δ41K and all four of the other moderately volatile elements assessed, while the mass-independent isotope systems show no strong correlations. Regarding the K isotope variations, these observations, along with other textural and chemical data, can be best explained by inherited isotopic variations form different precursor reservoirs (the cause of which is difficult to conclusively determine, though most likely related to the NC-CC dichotomy), and volatility related fractionation processes for the carbonaceous chondrite groups (most likely due to component mixing).

A 1500-year record of mercury isotopes in seal feces documents sea ice changes in the Antarctic

Temporal and spatial variations in sea ice coverage at high Northern Hemisphere latitudes have been shown to affect the photodegradation of methylmercury in seawater and the mercury isotope signatures in biological samples, suggesting the potential of mercury isotopes to reconstruct sea ice variability. Here we study the mercury isotopic composition of a 1500-year sediment profile strongly affected by seal activities on the Fildes Peninsula, King George Island, Antarctic Peninsula. The mass independent isotope fractionation of mercury (represented by Δ199Hg) in sediments dominated by seal feces input reflects the Δ199Hg of marine methylmercury before entering the food web, documenting the changes in the degree of photodemethylation. We found much higher Δ199Hg in sediments deposited during a warm period (~700-1000 years ago), suggesting that reduced sea ice promoted greater photodemethylation. Thus, this study demonstrates the modulation of methylmercury photodegradation by sea ice in the Antarctic, and that mercury isotopes can record historical sea ice changes.

Spurious molybdenum isotope anomalies resulting from non-exponential mass fractionation

Mass-independent (nucleosynthetic) Mo isotope anomalies are uniquely useful for constraining genetic relationships among meteoritic and planetary materials and, by extension, the origin and nature of Earth's late-stage building blocks. The meaningful interpretation of such data, however, critically depends on the accurate correction of any natural and analytical mass-dependent isotope fractionation, which is commonly assumed to follow the ‘exponential law’. Here, using new high-precision Mo isotope data for a diverse set of terrestrial samples, we show that mass-dependent Mo isotope fractionation in nature typically does not adhere to this law, but is instead dominated by equilibrium and Rayleigh processes. We demonstrate that even moderate degrees of such non-exponential fractionation (i.e., mass-dependent isotope fractionation deviating from the exponential law) can result in significant spurious mass-independent Mo isotope anomalies that, when misinterpreted as nucleosynthetic anomalies, can lead to erroneous conclusions, particularly with respect to Earth's accretion history. Consequently, assessing the magnitude and origin of mass-dependent fractionation will be essential for future efforts to precisely determine the mass-independent Mo isotope composition of bulk silicate Earth and to identify potential nucleosynthetic isotope anomalies in terrestrial rocks.

Origin and abundances of volatiles on Mars from the zinc isotopic composition of Martian meteorites

Volatile elements are key to understanding the accretion and differentiation processes that formed the terrestrial planets. Relative to the solar photosphere or carbonaceous Ivuna-type (CI) chondrites, the terrestrial planets are depleted in moderately volatile elements (MVEs), with the Earth being more depleted in MVEs than Mars. Mass-dependent and mass-independent stable isotope variations of MVEs, such as Zn, can be used to determine the origin of volatile depletion on Mars. Here we present Zn isotopic compositions of ten Martian meteorites, spanning the major petrologic groups, and show that the Zn isotope composition of the Martian mantle, representative of the Bulk Silicate Mars (BSM), has a δ66Zn (per mille deviation of the 66Zn/64Zn from the JMC-Lyon standard) of +0.50 ± 0.18. This is distinctly heavier than that of the Earth (+0.16 ± 0.06‰). The BSM Zn isotope composition could partly reflect fractionation during volatile loss by evaporation consistent with the isotopic composition of other volatile elements (e.g., K). The mass-independent Zn isotopic composition of Mars, ε66Zn (per 10,000 deviation of the 66Zn/64Zn from the terrestrial standard JMC-Lyon, normalized to 68Zn/64Zn) is intermediate between carbonaceous chondrites (CC) and non-carbonaceous chondrites (NC), but with stronger affinity to the NC compared to that of the Earth. Therefore, planets further from the Sun are not necessarily made from a higher fraction of CC-like material.

Mass-independent Sn isotope fractionation and radiogenic 115Sn in chondrites and terrestrial rocks

Tin has ten stable isotopes, providing the opportunity to investigate and discriminate nucleosynthetic isotope anomalies from mass-dependent and mass-independent isotope fractionation. Novel protocols for chemical separation (based on TBP-resin) and MC-ICP-MS analyses are reported here for high precision Sn isotope measurements on terrestrial rocks and chondrites. Relative to the Sn reference standard (NIST SRM 3161a), terrestrial basalts and chondrites show isotope patterns that are consistent with mass-dependent and mass-independent isotope fractionation processes as well as with 115Sn radiogenic ingrowth from 115In.Two different mass-independent isotope effects are identified, namely the nuclear volume (or nuclear field shift) and the magnetic isotope effect. The magnetic isotope effect dominates in the two measured ordinary chondrites, while repeated analyses of the carbonaceous chondrite Murchison (CM2) display a pattern consistent with a nuclear volume effect. Terrestrial basalts show patterns that are compatible with a mixture of nuclear volume and magnetic isotope effects. The ultimate origin of the isotope fractionation is unclear but a fractionation induced during sample preparation seems unlikely because different groups of chondrites show distinctly different patterns, hence pointing towards natural geo/cosmochemical processes. Only the carbonaceous chondrite Murchison (CM2) shows a Sn isotope pattern similar to what expected for nucleosynthetic variations. However, this pattern is better reproduced by nuclear volume effects. Thus, after considering mass-independent and mass-dependent effects, we find no evidence of residual nucleosynthetic anomalies, in agreement with observations for most other elements with similar half-mass condensation temperatures.Most chondrites show a deficit in 115Sn/120Sn (typically −150 to −200 ppm) relative to terrestrial samples, with the exception of one ordinary chondrite that displays an excess of about +250 ppm. The 115Sn/120Sn data correlate with In/Sn, being consistent with the β− decay of 115In over the age of the solar system. This represents the first evidence of the 115In-115Sn decay system in natural samples. The radiogenic 115Sn signature of the BSE derives from a suprachondritic In/SnBSE, which reflects preferential partitioning of Sn into the Earth’s core.

Reconciling discrepant minor sulfur isotope records of the Great Oxidation Event

Understanding the timing and trajectory of atmospheric oxygenation remains fundamental to deciphering its causes and consequences. Given its origin in oxygen-free photochemistry, mass-independent sulfur isotope fractionation (S-MIF) is widely accepted as a geochemical fingerprint of an anoxic atmosphere. Nevertheless, S-MIF recycling through oxidative sulfide weathering—commonly termed the crustal memory effect (CME)—potentially decouples the multiple sulfur isotope (MSI) record from coeval atmospheric chemistry. Herein, however, after accounting for unrecognised temporal and spatial biases within the Archaean–early-Palaeoproterozoic MSI record, we demonstrate that the global expression of the CME is barely resolvable; thereby validating S-MIF as a tracer of contemporaneous atmospheric chemistry during Earth’s incipient oxygenation. Next, utilising statistical approaches, supported by new MSI data, we show that the reconciliation of adjacent, yet seemingly discrepant, South African MSI records requires that the rare instances of post-2.3-billion-year-old S-MIF are stratigraphically restricted. Accepting others’ primary photochemical interpretation, our approach demands that these implied atmospheric dynamics were ephemeral, operating on sub-hundred-thousand-year timescales. Importantly, these apparent atmospheric relapses were fundamentally different from older putative oxygenation episodes, implicating an intermediate, and potentially uniquely feedback-sensitive, Earth system state in the wake of the Great Oxidation Event.

High precision nickel isotope measurements of early Solar System materials and the origin of nucleosynthetic disk variability

Various chemical elements including nickel (Ni) exhibit mass-independent isotope heterogeneity on a bulk meteorite level, which is generally accepted to reflect the heterogeneous distribution of presolar carrier(s) from different nucleosynthetic sources. Thus, understanding the nature of the carriers can help decipher the origin of the observed nucleosynthetic variability, which remains elusive. In this study, we present the first high precision measurements of mass-independent and mass-dependent Ni isotope compositions for step-leaches of the CI chondrite Ivuna and Efremovka CAIs supplemented by bulk chondrite measurements. Step-leaches record highly anomalous Ni isotope signatures that can be attributed to at least four diverse nucleosynthetic sources. The most anomalous leachates show either large deficits (up to 0.1 %) in the neutron-poor 58Ni and 60Ni nuclides (L11, thought to contain mainly s-process derived Ni) or minor enrichments and deficits (∼100 ppm) in 60Ni or 64Ni (L6, L8, L9 and L10, all thought to derive mainly from supernovae). Pristine CAIs record Ni isotope compositions typified by enrichments in 58Ni of up to 400 ppm. Our new data for bulk chondrites agree with earlier work and emphasize the appropriateness of using the 62Ni/61Ni ratio for internal normalization. Based on the compositional relations between the step-leaches data, CAIs, and bulk meteorites, we show that 60Ni variability is consistent with being of nucleosynthetic origin as opposed to reflecting variable Fe/Ni ratios in the presence of live 60Fe. Finally, we infer that the observed Ni nucleosynthetic disk variability is predominantly driven by a combination of processes separating different nucleosynthetic carriers in the disk from each other, including thermal processing and size-based sorting.

Chondrite diversity revealed by chromium, calcium and magnesium isotopes

Chondrites are undifferentiated meteorites that can provide information on the compositions of materials in the early solar System, including the building blocks of the terrestrial planets. While most chondrites belong to well-defined groups based on their mineralogy and chemical composition, a minor fraction have unusual characteristics and are classified as ungrouped chondrites. These ungrouped chondrites reflect the diversity of chondritic materials in the early solar system; however, they are not as well studied as grouped meteorites and their origins are poorly understood. In this study, we present high-precision mass-independent Cr, Ca and Mg isotope data for 17 ungrouped chondrites. The ε54Cr and ε48Ca (ε expresses parts per ten thousand mass-independent isotope deviation) data for ungrouped chondrites also provide important constraints for assessing their relationships to the known chondrite groups, and the radiogenic Mg isotope ratios (μ26Mg*) can be used to track the early solar system history. We also present the first high-precision data for a Kakangari (KC) chondrite, an enstatite chondrite, and for four enstatite-rich meteorites. The ε54Cr and ε48Ca values for the KC are −0.44 ± 0.04 and −1.30 ± 0.25, respectively, and ε48Ca value for SAH 97096 (EH3) is −0.19 ± 0.22 that overlaps with that of those of Earth-Moon system and ordinary chondrites. All the carbonaceous chondrite-like (CC) ungrouped chondrites show positive ε54Cr and ε48Ca values, and all the non-carbonaceous chondrite-like (NC) ungrouped chondrites and KCs (also belong to the NC trend) show zero or negative ε54Cr and ε48Ca values. This observation confirms the CC-NC dichotomy for primitive solar system materials. LEW 87232 (KC) also shows the highest 55Mn/52Cr ratio and ε53Cr value amongst all the chondrites. There is a positive trend between 55Mn/52Cr ratios and ε53Cr values among all the chondrites that mostly reflects a mixing between multiple chondritic components. Previously it has been reported that there is a bulk 26Al-26Mg correlation line amongst chondrites. This correlation has been interpreted as being due to mixing of CAIs (high 27Al/24Mg ratios and μ26Mg* values) and other silicate material (e.g., chondrules and matrix). By providing additional 26Al-26Mg chondrite data, we show that there is no 26Al-26Mg correlation line for the chondrites, ruling out the two-endmember (i.e., CAIs and other silicates) mixing model.

Collision course; high-precision mass-independent and mass-dependent calcium isotope measurements using the prototype collision cell MC-ICPMS/MS, Proteus

This paper reports measurements of mass-independent and mass-dependent Ca isotope variations using the prototype collision cell MC-ICPMS/MS, Proteus. Helium and hydrogen gases are introduced into the collision cell and the well characterised resonant charge exchange and proton transfer reactions between Ar+ ions and H2 molecules results in almost complete removal of the 40Ar+ ions allowing the measurement of the 40Ca isotope by MC-ICPMS without resorting to ‘cold’ plasma.A range of reference materials have been characterised for both their mass-independent and mass-dependent Ca isotope compositions relative to the international reference material NIST SRM 915a. Notably, the radiogenic 40Ca/44Ca isotope ratio (internally normalised to 42Ca/44Ca) can be accurately measured with typical reproducibility better than 40 ppm (pooled 2 SD) for a single measurement using 12 μg of Ca. Reference materials USGS GSP‐2 and CRPG FKN have notably radiogenic 40Ca/44Ca, with values of 434 ± 7 and 5513 ± 17 ppm respectively relative to NIST SRM 915a (pooled 2 SE, n = 35 and 5 respectively). In contrast, multiple repeat measurements of mantle derived reference materials BIR, BHVO-2, BCR-2 and JP-1 yield values that are slightly unradiogenic (mean − 23 ± 5 ppm, pooled 2 SE, n = 71) relative to NIST SRM 915a, bone ash and seawater reference materials, likely reflecting crustal components in the latter. Coupled measurements of the minor 48Ca and 43Ca isotopes give 48Ca/44Ca and 43Ca/44Ca (internally normalised to 42Ca/44Ca) with typical reproducibilities of ± 40 and ± 16 ppm respectively (pooled 2 SD) for single (24 μg Ca) analyses. Multiple repeats yield mean values for terrestrial reference materials that are within their pooled 2 SE uncertainties of SRM 915a, to precisions of ± 15 and ± 6 ppm respectively. Measurements of mass-dependent Ca isotope variations (δ44/40Ca) have been made using a 42Ca-43Ca double spike isotope tracer together with measurements of 40Ca and 44Ca and have typical reproducibilities of ± 0.035 ‰ (pooled 2 SD) for single (12 μg) analyses. Measured δ44/40Ca values for reference materials are within uncertainty of previously reported values. Moreover, given that the double spike inversion uses the same isotopes as the mass independent determinations of 40Ca/44Ca and 43Ca/44Ca, our documentation of the absence of anomalies at a precision of better than 20 ppm in a range of low K/Ca terrestrial reference materials implies that the accuracy of our δ44/40Ca analyses is at this level of uncertainty.