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At least 397 records · Page 22

A Case for Nebula Scale Mixing Between Non-Carbonaceous and Carbonaceous Chondrite Reservoirs: Testing the Grand Tack Model with Chromium Isotopic Composition of Almahata Sitta Stone 91A

There is an increasing number of Cr-O-Ti isotope studies that show solar system materials are divided into two main populations, one carbonaceous chondrite (CC)-like and the other is non-carbonaceous (NC)-like, with minimal mixing attributed to a gap opened in the protoplanetary disk due to Jupiter's formation. The Grand Tack model suggests there should be large-scale mixing between S- and C-type asteroids, an idea supported by our recent work on chondrule (Delta)17O-ε54Cr isotope systematics. The Almahata Sitta (AhS) meteorite provides a unique opportunity to test the Grand Tack model. The meteorite fell to Earth in October 2008 and has been linked to the asteroid 2008 TC3 which was discovered just prior to the fall of the AhS stones. The AhS meteorite is composed of up to 700 individual pieces with approx.140 of those pieces having some geochemical and/or petrologic studies. Almahata Sitta is an anomalous polymict ureilite with other meteorite components, including enstatite, ordinary, and carbonaceous chondrites with an approximate abundance of 70% ureilites and 30% chondrites. This observation has lead to the suggestion that TC3 2008 was a loosely aggregated rubble pile-like asteroid with the non-ureilite sample clasts within the rubble-pile. Due to the loosely-aggregated nature of AhS, the object disintegrated during atmospheric entry resulting in the weakly held clasts falling predominantly as individual stones in the AhS collection area. However, recent work has identified one sample of AhS, sample 91A, which may represent two different lithologies coexisting within a single stone. The predominate lithology type in 91A appears to be that of a C2 chondrite based on mineralogy but also contains olivine, pyroxene, and albite that have ureilite-like compositions. Previous Cr isotope investigations into AhS stones are sparse and what data is available show nearly uniform isotopic composition similar to that of typical ureilites with negative ε54Cr values.

Sanborn, M. E.↗

Large Sulphur Isotope Fractionations in Martian Sediments at Gale Crater

Variability in the sulfur isotopic composition in sediments can reflect atmospheric, geologic and biological processes. Evidence for ancient fluvio-lacustrine environments at Gale crater on Mars and a lack of efficient crustal recycling mechanisms on the planet suggests a surface environment that was once warm enough to allow the presence of liquid water, at least for discrete periods of time, and implies a greenhouse effect that may have been influenced by sulfur-bearing volcanic gases. Here we report in situ analyses of the sulfur isotopic compositions of SO2 volatilized from ten sediment samples acquired by NASA's Curiosity rover along a 13 km traverse of Gale crater. We find large variations in sulfur isotopic composition that exceed those measured for Martian meteorites and show both depletion and enrichment in S-34. Measured values of δS-34 range from -47 +/- 14% to 28 +/- 7%, similar to the range typical of terrestrial environments. Although limited geochronological constraints on the stratigraphy traversed by Curiosity are available, we propose that the observed sulfur isotopic signatures at Gale crater can be explained by equilibrium fractionation between sulfate and sulfide in an impact-driven hydrothermal system and atmospheric processing of sulfur-bearing gases during transient warm periods.

Curiosity↗

D/H Isotope Fractionation During H Diffusion Loss from Clinopyroxene Evidenced in Martian Nakhlites

Knowing the distribution and origin of water in terrestrial planets is crucial to understand their formation, evolution and the source of their atmospheres and surface water. Mantle D/H ratios may be used to determine what type of material contributed water to the terrestrial planets [1]. However, other processes, magmatic or surface alteration processes, can also modify D/H ratios, and for Mars, we only have samples from the crust, as meteorites. The D/H ratio of igneous phases of Martian meteorites is generally explained in terms of the mixing contributions of two reservoirs: surficial with high D/H (dD > 700 ‰) related to interaction with the martian atmosphere (dD ~ 5000‰), and mantle-derived with lower D/H (dD < 500 ‰ but the exact value is still debated)[2]. However, our present study evidences that H loss in clinopyroxene during degassing can significantly fractionate H isotopes and increase their D/H ratios. In situ analyses of H isotopes, and of water, major and trace element contents were performed on the pyroxenes of 5 nakhlites. Nakhlites are clinopyroxenites that likely originated from the same lava flow or shallow magma chamber. Water contents decrease (380 to <5 ppm H2O) with increasing dD (-268 to 4860 ‰). Significant influence from spallation, exchange with the martian atmosphere, shock, surface alteration, and hydrothermal processes is ruled out. Together with the evidence of less water at the edge of individual pyroxene grains compared to their interior, we interpret this correlation as the result of preferential diffusive loss of H relative to D from the already crystallized pyroxenes during ascent of the partially-crystallized magma. Similar H isotope fractionations have been observed in another nominally anhydrous mineral, garnet, during experimental dehydration [3]. These results emphasize that caution is warranted when interpreting H isotope analyses of igneous, nominally anhydrous minerals in terms of planetary processes.

Peslier, A. H.↗

Volcanic Eruption Signatures in the Isotope Enabled Last Millennium Ensemble

Explosive volcanic eruptions are one of the largest natural climate perturbations, but few observational constraints exist on either the climate responses to eruptions or the properties (size, hemispheric aerosol distribution, etc.) of the eruptions themselves. Paleoclimate records are thus important sources of information on past eruptions, often through the measurement of oxygen isotopic ratios (𝛿18O) in natural archives. However, since many processes affect 𝛿18O, the dynamical interpretation of these records can be quite complex. Here we present results from new, isotope-enabled members of the Community Earth System Model Last Millennium Ensemble, documenting eruption-induced 𝛿18O variations throughout the climate system. Eruptions create significant perturbations in the 𝛿18O of precipitation and soil moisture in central/eastern North America, via excitation of the Atlantic Multidecadal Oscillation. Monsoon Asia and Australia also exhibit strong precipitation and soil 𝛿18O anomalies; in these cases, 𝛿18O may reflect changes to El Niño-Southern Oscillation phase following eruptions. Salinity and seawater 𝛿18O patterns demonstrate the importance of both local hydrologic shifts and the phasing of the El Niño-Southern Oscillation response, both along the equator and in the subtropics. In all cases, the responses are highly sensitive to eruption latitude, which points to the utility of isotopic records in constraining aerosol distribution patterns associated with past eruptions. This is most effective using precipitation 𝛿18O; all Southern eruptions and the majority (66%) of Northern eruptions can be correctly identified. This work thus serves as a starting point for new, quantitative uses of isotopic records for understanding volcanic impacts on climate.

Stevenson, S.↗

Bulk Oxygen Isotopic Compositions of Anhydrous Interplanetary Dust Particles: Indication of an 16O-Poor Reservoir In The Outer Solar System

The oxygen isotopic ratios of ancient solar system materials reflect the isotopically distinct reservoirs in which they formed or were altered. These compositions are generally explained by mixing of material derived from an 16O-rich reservoir and material from an 16O-poor reservoir thought to be isotopically heavy H2O. Evidence of this 16O-poor reservoir is scarce and includes cosmic symplectite (COS), probable silicates in an interplanetary dust particle (IDP), and sulfates in a cometary xenolith. These materials have 17O and 18O enrichments between ~150–200 ‰, which agree with predictions for self-shielding and photodissociation of CO. The ‘cometary’ 16O-poor materials indicate alteration or formation in the outer solar system. The bulk O isotopic compositions of IDPs thought to have cometary origins may also harbor evidence of this primordial 16O-poor reservoir. Here we report the bulk O compositions of anhydrous IDPs and discuss the nebular reservoirs from which they derived

A N Nguyen↗

Development Towards Stable Chlorine Isotope Measurements of Astromaterials Using the Modified Middleton Source of an Accelerator Mass Spectrometer

The volatile element Cl can be lost during the formation and evolution of planetary bodies, leading to fractionation of its two stable isotopes 35Cl and 37Cl. Chlorine isotope variations (reported as δ37Cl in parts per thousand (‰) relative to Standard Mean Ocean Chloride, SMOC) are documented to exceed 80‰ between different lunar rock samples and have been variably interpreted as the fingerprint of degassing during accretion, magma ocean, or volcanic portions of lunar history. The large intersample and intrasample variations observed by both bulk isotope ratio mass spectrometry (IRMS) and in-situ secondary ion mass spectrometry (SIMS) methods are difficult to interpret in part because of a paucity of bulk Cl isotope measurements. This lack of high-precision bulk data is due to the relative rarity of IRMS laboratories capable of making these high precision measurements on small samples of precious planetary materials such as those returned by human or robotic exploration. Here we present a new method for performing high precision δ37Cl measurements using the modified Middleton ion source of an existing accelerator mass spectrometer. For samples with as little as 1 μg Cl–the equivalent of 2–4 mm3 of a typical lunar rock sample–the average cathode accuracy is ∼1‰. Cathode reproducibility is typically ∼1‰ (2σ) for samples with at least 10 μg of Cl, increasing to ∼3–6‰ for aliquots with ∼1–2 μg Cl, similar to published SIMS results and sufficient to study astromaterials from the Moon, Mars, or 4 Vesta, which have tens of ‰ observed variations.

Tyler S. Anderson↗

Interpretable Machine Learning Models for Autonomous Characterization of Analogue Ocean World Seawater Chemistry and Biosignature Potential Using Isotope Ratio Data

Background: Future missions to ocean worlds, such as Enceladus and Europa, will attempt to characterize the subsurface seawater chemistry and assess the potential for life. Such missions will be equipped with capabilities to precisely measure volatile isotopes in plumes, atmospheres, and exospheres. Motivation: While large isotopic fractionations can indicate a biological source, there are signatures resulting from abiotic geochemical processes that mimic isotopic biosignatures. While machine learning (ML) has the potential to disentangle competing effects and biotic mimicry, high-dimensional isotope ratio mass spectrometry (IRMS) data is likely to contain noise/irrelevant features and involve complex statistical interactions that make human inference and interpretation difficult. Further, ML predictions with as far-reaching implications as an extraterrestrial biosignature on an ocean world requires the use of interpretable models (i.e., not “black box” models) with physically and mathematically meaningful feature spaces along with false positive diagnostics. Methods: We use volatile CO2 IRMS data of analogue ocean world seawaters to validate an ML approach to provide biogeochemical context for biosignature detection. We employ a feature selection method called nearest-neighbor projected distance regression (NPDR) that detects statistical interactions and helps elucidate the mechanisms of the Random Forest classification models. Results: We train and validate predictive ML models on volatile CO2 IRMS data of analogue ocean world seawaters to predict major salt components (e.g., MgSO4, NaHCO3), pH, ionic strength, and the presence of biosignatures. Features derived from IRMS measurements are augmented with extracted time-series features. Our results show high test accuracy and interpretability, which is increased by interaction network visualization, sample-wise variable importance scores, and single-sample class probability estimates. We demonstrate an ML mission software solution that triggers autonomous data transmission and biogeochemical sample prediction.

geochemistry↗

Bulk Oxygen Isotope Composition of Aggregate Samples From Asteroid Bennu Returned By OSIRIS-REx

On 24 September 2023, the OSIRIS-REx spacecraft delivered to Earth material collected from the surface of the B-type asteroid Bennu. During its ~2.5-year encounter with the asteroid, OSIRIS-REx made many important discoveries, including establishing its extremely primitive chemical composition, the presence of at least two lithologies, and evidence of fluid flow on its parent asteroid. One of the driving hypotheses of the Sample Analysis Plan is that Bennu’s dominant lithologies are comparable to the most aqueously altered carbonaceous chondrites. Oxygen three-isotope analysis is a powerful tool for defining the relationship between different meteorite groups and can be used to understand the nature of the returned Bennu samples. The O isotope signatures reflect the materials that parent asteroids accreted from and the geological processes that operated during asteroidal evolution. Aggregate samples of particles (typically <500 μm) likely sampled many different larger stones and boulders, and their composition may therefore represent the average composition of Bennu. Fractionation of the sample, e.g. comparison of aliquots of finer material with coarser particles within the aggregate samples, offers the opportunity to identify different isotopic reservoirs within the returned material. The average O isotope composition will also provide a baseline from which to identify and characterize any exogenous clasts present in the sample.

I. A. Franchi↗

Xenon Isotopic Analysis of Individual Intermediate Particles From the OSIRIS-REx Sample of Asteroid Bennu

The OSIRIS-REx mission sampled material from the B-type asteroid Bennu and delivered the sample to Earth on 24 September 2023. Here we present initial xenon isotopic analysis of individual intermediate particles of Bennu material collected by the OSIRIS-REx mission. Noble gases are key tracers of Solar System evolution. Xenon is particularly useful among the noble gases because its nine isotopes allow multiple contributing sources to be unambiguously identified. The sun, asteroids (as measured in meteorites), and comets (measured in the coma of comet 67P) have distinct xenon isotopic signatures reflecting different mixtures of nucleosynthetic components. In addition, 129 I, 238 U, and 244 Pu decay with different half-lives, producing characteristic xenon signatures. Exposure of samples containing light rare earth elements and barium to cosmic rays produces xenon from spallation and secondary neutron capture reaction. Noble gas analyses help address several of the driving hypotheses of the mission [9]. Particle-by-particle analysis can elucidate the diversity of material present and reveal distinct noble gas compositions, including the potential to detect presolar or cometary noble gas signatures on a small scale. The isotopic signature provides a fingerprint that can be used to constrain the sources of volatiles in planetary reservoirs and combined with other information (e.g. mineralogy and petrology of the material analyses) contributes to our understanding of the initial constituents, formation, and history of Bennu and its parent asteroid.

S A Crowther↗

A Coordinated Mineralogical and Oxygen Isotopic Study of Refractory Ca-Al-Rich Inclusions

Refractory Ca-Al-rich inclusions (CAIs) in primitive chondritic meteorites represent the oldest solids that formed in our Solar System. Coordinated analyses using multiple ion and electron-beam techniques are vital to fully understand complex nebular and asteroidal processes that CAIs may have experienced in the context of the formation and early evolution of our Solar System. We report the results of a coordinated mineralogical and oxygen isotopic study of unique grossite bearing CAIs from reduced CV (Vigarano type) carbonaceous chondrites using transmission electron microscopy and secondary ion mass spectrometry. Grossite (CaAl 4 O 7 ) occurs in cores of nodules in fine grained CAIs that likely represent aggregates of nebular condensates. In many occurrences, grossite has been partially replaced by hercynite [(Fe,Mg,Zn)Al 2 O 4 ], which displays complex microstructures and compositions, and magnetite nanoparticles. This grossite alteration likely occurred via crystallographically controlled metasomatic reactions with Zn, Fe-rich aqueous fluids on the parent asteroid. The constituent phases of grossite bearing CAIs show heterogeneous oxygen isotopic compositions . That is, grossite and perovskite are 16 O poor and melilite is variably 16 O-depleted in contrast to solar like, 16 O-rich hibonite and spinel. The observed oxygen isotopic distribution is interpreted as a result of mineralogically controlled oxygen isotopic exchange with an 16 O-poor fluid on the parent asteroid. Collectively, we conclude that the presence of limited fluids played an important role in preferential alteration of grossite to hercynite and magnetite and various degrees of 16 O depletion in grossite, perovskite, and melilite during thermal metamorphism on the CV chondrite parent asteroid.

Jangmi Han↗

Geochemical and isotopic evidence for paleoredox conditions during deposition of the Devonian-Mississippian New Albany Shale, southern Indiana

The upper part of the New Albany Shale is divided into three members. In ascending order, these are (1) the Morgan Trail Member, a laminated brownish-black shale; (2) the Camp Run Member, an interbedded brownish-black and greenish-gray shale; and (3) the Clegg Creek Member, also a laminated brownish-black shale. The Morgan Trail and Camp Run Members contain 5% to 6% total organic carbon (TOC) and 2% sulfide sulfur. Isotopic composition of sulfide in these members ranges from -5.0% to -20.0%. C/S plots indicate linear relationships between abundances of these elements, with a zero intercept characteristic of sediments deposited in a non-euxinic marine environment. Formation of diagenetic pyrite was carbon limited in these members. The Clegg Creek Member contains 10% to 15% TOC and 2% to 6% sulfide sulfur. Isotopic compositions of sulfide range from -5.0% to -40%. The most negative values occur in the uppermost Clegg Creek Member and are characteristic of syngenetic pyrite, formed within an anoxic water column. Abundances of carbon and sulfur are greater and uncorrelated in this member, consistent with deposition in as euxinic environment. In addition, DOP (degree of pyritization) values suggest that formation of pyrite was generally iron limited throughout Clegg Creek deposition, but sulfur isotopes indicate that syngenetic (water-column) pyrite becomes an important component in the sediment only in the upper part of the member. At the top of the Clegg Creek Member, a zone of phosphate nodules and trace-metal enrichment coincides with maximal TOC values. During euxinic deposition, phosphate and trace metals accumulated below the chemocline because of limited vertical circulation in the water column. Increased productivity would have resulted in an increased flux of particulate organic matter to the sediment, providing an effective sink for trace metals in the water column. Phosphate and trace metals released from organic matter during early diagenesis resulted in precipitation of metal-rich phosphate nodules.

NASA Discipline Exobiology↗

Carbon and nitrogen isotopic compositions of alkyl porphyrins from the Triassic Serpiano oil shale

The carbon and nitrogen isotopic compositions of seven of the most abundant alkylporphyrins from the Serpiano oil shale (marine, Triassic) were determined. For the C31 and C32 butanoporphyrins, values of delta 13CPDB and delta 15NAIR averaged -24.0% and -3.1%. In contrast, the C31 and C32 methylpropanoporphyrins, DPEP, and a C30 13-nor etioporphyrin had delta 13C and delta 15N values averaging -27.5 and -3.3%, respectively. Carbon and nitrogen isotopic values for kerogen averaged -30.8 and -0.9, whereas those for total extract averaged -31.6, and -4.0%. The butanoporphyrins apparently derive from a biological source different from that giving rise to the other porphyrins, their 13C enrichment not being related to carbon isotopic fractionation accompanying diagenetic reactions. The delta 15N values for all the porphyrins indicate that the depletion of 15N observed in the kerogen is of primary origin. Consistent with the very high abundance of hopanoids and methyl hopanoids in the aliphatic hydrocarbon fraction, it is suggested that cyanobacterial fixation of N2 may have been the main cause of 15N depletion.

NASA Discipline Exobiology↗

An experimental study of the isotopic enrichment in Ar, Kr, and Xe when trapped in water ice

The isotopic enrichment of argon, krypton, and xenon, when trapped in water ice, was studied experimentally. The isotopes were found to be enriched according to their (m1/m2)1/2 ratio. These enrichment factors could be useful for comparison among the uncertain cosmic or solar isotopic ratios, the hopeful in situ cometary ratio, and those in Earth's atmosphere, in the context of cometary delivery of volatiles to Earth.

NASA Discipline Exobiology↗

Carbon dioxide in the atmosphere: isotopic exchange with ozone and its use as a tracer in the middle atmosphere

Atmospheric heavy ozone is enriched in the isotopes 18O and 17O. The magnitude of this enhancement, of the order of 100%, is very large compared with that commonly known in atmospheric chemistry and geochemistry. The heavy oxygen atom in heavy ozone is therefore useful as a tracer of chemical species and pathways that involve ozone or its derived products. As a test of the isotopic exchange reactions, we successfully carry out a series of numerical experiments to simulate the results of the laboratory experiments performed by Wen and Thiemens [1993] on ozone and CO2. A small discrepancy between the experimental and the model values for 17O exchange is also revealed. The results are used to compute the magnitude of isotopic exchange between ozone and carbon dioxide via the excited atom O(1D) in the middle atmosphere. The model for 18O is in good agreement with the observed values.

NASA Discipline Exobiology↗

A molecular and isotopic study of the organic matter from the Paris Basin, France

Thirteen Liassic sedimentary rocks of increasing depth and three petroleums from the Paris Basin were studied for 13C/12C isotopic compositions and biological markers, including steranes, sterenes, methylphenanthrenes, methylanthracenes, and triaromatic steroids. The isotopic compositions of n-alkanes from mature sedimentary rocks and petroleums fall in a narrow range (2%), except for the deepest Hettangian rock and the Trias petroleum, for which the short-chain n-alkanes are enriched and depleted in 13C, respectively. Most of the molecular parameters increase over the 2000-2500 m depth range, reflecting the transformation of the organic matter at the onset of petroleum generation. In this zone, carbonate content and carbon isotopic composition of carbonates, as well as molecular parameters, are distinct for the Toarcian and Hettangian source rocks and suggest a migration of organic matter from these two formations. Two novel molecular parameters were defined for this task: one using methyltriaromatic steroids from organic extracts; the other using 1-methylphenanthrene and 2-methylanthracene from kerogen pyrolysates. The anomalous high maturity of the Dogger petroleum relative to the maturity-depth trend of the source rocks is used to estimate the minimal vertical distance of migration of the organic matter from the source rock to the reservoir.

Non-NASA Center↗

The effect of aromatization on the isotopic compositions of hydrocarbons during early diagenesis

Polycyclic aromatic hydrocarbons with varying degrees of aromatization were isolated from the Eocene Messel Shale (Rheingraben, Germany). The high abundances of these compounds and their structural resemblances to cyclic triterpenoid lipids are consistent with derivation from microbial rather than thermal processes. Compounds structurally related to oleanane contain from five to nine double bonds; those within a series of aromatized hopanoids contain from three to nine. All are products of diagenetic reactions that remove hydrogen or methyl groups, and, in several cases, break carbon-carbon bonds to open rings. Aromatized products are on average depleted in 13C relative to possible precursors by l.2% (range: l.5% enrichment to 4% depletion, n = 9). The dependence of 13C content on the number of double bonds is not, however, statistically significant and it must be concluded that there is no strong evidence for isotopic fractionation accompanying diagenetic aromatization. Isotopic differences between series (structures related to ursane, des-A-ursane, des-A-lupane, des-A-arborane, and possibly, des-A-gammacerane are present) are much greater, indicating that 13C contents are controlled primarily by source effects. Fractionations due to chromatographic isotope effects during HPLC ranged from 0.1 to 2.8%.

NASA Discipline Exobiology↗

Sulfur isotope effects associated with oxidation of sulfide by O2 in aqueous solution

Normal sulfur isotope effects averaging epsilon = -5.2 +/- 1.4% (s.d.) were consistently observed for the oxidation of sulfide in aqueous solution. Reaction products were sulfate, thiosulfate and sulfite at pH 10.8-11 in distilled water; S0 was formed in two experiments with synthetic seawater at pH 8-9.5. Because the -5.2% normal isotope effect differs significantly from the previously measured +2% inverse effect associated with anaerobic oxidation of sulfide by photosynthetic bacteria, stable sulfur isotopic measurements are potentially useful for distinguishing aerobic vs. anaerobic sulfide oxidation in marine and freshwater sulfureta.

NASA Program Exobiology↗

Factors controlling precision and accuracy in isotope-ratio-monitoring mass spectrometry

The performance of systems in which picomole quantities of sample are mixed with a carrier gas and passed through an isotope-ratio mass spectrometer system was examined experimentally and theoretically. Two different mass spectrometers were used, both having electron-impact ion sources and Faraday cup collector systems. One had an accelerating potential of 10kV and accepted 0.2 mL of He/min, producing, under those conditions, a maximum efficiency of 1 CO2 molecular ion collected per 700 molecules introduced. Comparable figures for the second instrument were 3 kV, 0.5 mL of He/min, and 14000 molecules/ion. Signal pathways were adjusted so that response times were <200 ms. Sample-related ion currents appeared as peaks with widths of 3-30 s. Isotope ratios were determined by comparison to signals produced by standard gases. In spite of rapid variations in signals, observed levels of performance were within a factor of 2 of shot-noise limits. For the 10-kV instrument, sample requirements for standard deviations of 0.1 and 0.5% were 45 and 1.7 pmol, respectively. Comparable requirements for the 3-kV instrument were 900 and 36 pmol. Drifts in instrumental characteristics were adequately neutralized when standards were observed at 20-min intervals. For the 10-kV instrument, computed isotopic compositions were independent of sample size and signal strength over the ranges examined. Nonlinearities of <0.04%/V were observed for the 3-kV system. Procedures for observation and subtraction of background ion currents were examined experimentally and theoretically. For sample/ background ratios varying from >10 to 0.3, precision is expected and observed to decrease approximately 2-fold and to depend only weakly on the precision with which background ion currents have been measured.

NASA Discipline Exobiology↗