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Fingerprints of carbon, nitrogen, and silicon isotopes in small interstellar SiC grains from the Murchison meteorite

We report ion microprobe determinations of the carbon, nitrogen, and silicon isotopic compositions of small SiC grains from the Murchison CM2 chondrite. Analyses were made on samples containing variable numbers of grains and on 14 individual grains. In some cases the multiple-grain sample compositions were probably dominated by only one or two grains. Total ranges observed are given. Only a few grains show values near the range limits. Both the total ranges of carbon and nitrogen isotopic compositions, and even the narrower ranges typical for the majority of the grains, are similar to those observed for larger SiC grains. Two rare components appear to be present in the smaller-size fraction, one characterized by C-12/C-13 about 12-16 and the other by very heavy nitrogen. The carbon and nitrogen isotopic compositions qualitatively may reflect hydrostatic H-burning via the CNO cycle and He-burning in red giants, as well as explosive H-burning in novae. The silicon isotopic compositions of most grains qualitatively show what is the signature of He-burning. The silicon isotopic composition of one grain, however, suggests a different process.

Hoppe, Peter↗

Magnesium and Titanium Isotopic Compositions of an Unusual Hibonite-Perovskite Refractory Inclusion from Allende: It Is Fun

Introduction: Hibonite-rich refractory inclusions are among the first solids that formed in the solar nebula, and thus provide constraints on the earliest environment in the Solar System. An unusual hibonite-perovskite inclusion from Allende, SHAL, consists of a large (approximately 500 by 200 microns) single hibonite crystal and coexisting blocky perovskite (approximately 200 microns in size). The hibonite is characterized by chemical and oxygen isotopic compositions similar to those in the FUN (Fractionated and Unknown Nuclear anomalies) inclusion HAL. However, the rare earth element (REE) patterns measured at different spots of SHAL hibonite are highly variable, ranging from Group II-like (light REEs enriched relative to heavy REEs) to Group III-like (relatively flat with slight Eu depletions), but overall contrast largely with that of HAL, especially in the Ce and Yb abundances. This implies that SHAL hibonite formed and underwent distillation processes under more reducing conditions. Interestingly, the accompanying perovskite has uniform, unfractionated oxygen isotopic compositions (averaging delta (sup 17) O equals delta (sup 18) O equals −7 per mille) and REE abundances that are completely different from those of SHAL hibonite. This has been interpreted that perovskite and hibonite may not be co-genetic. Here we performed Al-Mg and Ti isotopic measurements of SHAL hibonite and perovskite to determine if the FUN characteristics are observed in these two isotope systems, and to further constrain the origin and evolution of SHAL. Results: Isotopic measurements of Al-Mg and Ti in SHAL were performed on the UCLA CAMECA ims-1290 ion microprobe by following the analytical protocols described in [1]. The Al-Mg and Ti data obtained in both terrestrial standards and SHAL hibonite and perovskite are shown below. Both SHAL hibonite and perovskite, despite very high (sup 27) Al to (sup 24) Mg ratios, are devoid of (sup 26) Mg excesses that can be attributed to the decay of (sup 26) Al. Delta (sup 25) Mg (mass-dependent fractionation) in hibonite is approximately −5 per mille per atomic mass unit relative to Madagascar hibonite, but is not well constrained for perovskite due to very large uncertainties owing to extremely low Mg contents. Similar to Mg isotopes, SHAL hibonite and perovskite show essentially the same Ti isotopic compositions, with anomalies in (sup 50) Ti of approximately 14 per mille, but the former shows greater Ti isotope fractionation than the latter (2.5 per mille per atomic mass unit versus 0 per mille). Discussion and Conclusions: The Al-Mg and Ti isotopic compositions of SHAL hibonite are consistent with those of HAL, suggesting that SHAL hibonite is a FUN inclusion and likely formed prior to homogenization of (sup 26) Al and Ti isotope variations in the solar nebula. However, the formation mechanisms for SHAL and HAL differ, given the differences in the REE patterns and degrees of oxygen mass-dependent fractionation. The Group-II to Group-III like REE patterns, the Yb depletions, and negative delta (sup 25) Mg observed in SHAL hibonite are all consistent with condensation of the hibonite precursor in a reducing environment.. The lack of large Ce depletions in SHAL hibonite implies that distillation processes that fractionated hibonite's oxygen isotopes must have taken place under a reducing condition, but the extent to which SHAL hibonite was distilled appears to be less than HAL because of the smaller degree of oxygen mass-dependent fractionation. The perovskite shares essentially the same Ti and Mg isotopic compositions as hibonite and probably formed in the same reservoir.. The ultrarefractory REE pattern seen in perovskite likely resulted from gas-solid fractionation which depleted HREEs in this reservoir. This process also explains why SHAL hibonite is generally depleted in HREEs relative to LREEs.

Liu, M.-C.↗

Micro-photoluminescence mapping and Chemometrics for the rapid classification of rare earth materials

This article introduces advancements in chemically mapping rare earth materials using photoluminescence (PL) and chemometrics. By leveraging the high sensitivity and selectivity of PL compared to alternative optical techniques, as well as its compatibility with microscopy, we present enhanced capabilities for noninvasive material screening and characterization. Exemplary PL spectra of samarium(III) and europium(III) in oxide, nitrate, and chloride forms demonstrated the ability to extract detailed chemical information of diverse rare earth particles. Additionally, we introduced efficient PL mapping sequences capable of covering a 9 mm diameter carbon tab within minutes, which highlighted the benefits of rapid, large-area imaging. Furthermore, an integrated approach combining PL mapping with principal component analysis and a random forest classifier enabled the resolution of overlapping spectral peaks from different chemistries and provided accurate material classification. In conclusion, these advancements underscored the versatility and robustness of PL for chemically mapping rare earth materials, with the potential to support applications in mining, energy, environmental monitoring, isotope production and beyond.

Chemometrics↗

Oxygen isotope evidence from Ryugu samples for early water delivery to Earth by CI chondrites

The delivery of water to the inner Solar System, including Earth, is still a debated topic. A preferential role for hydrated asteroids in this process is supported by isotopic measurements. Carbonaceous chondrite (CC) meteorites represent our main source of information about these volatile-rich asteroids. However, the destruction of weaker materials during atmospheric entry creates a bias in our CC data. The return of surface materials from the C-type asteroid 162173 Ryugu by the Hayabusa2 spacecraft provides a unique opportunity to study high-porosity, low-density, primitive materials, unrepresented in the meteorite record. We measured the bulk oxygen isotope composition from four Ryugu particles and show that they most closely resemble the rare CI (CC Ivuna-type) chondrites, but with some differences that we attribute to the terrestrial contamination of the CI meteorites. We suggest that CI-related material is widespread among carbonaceous asteroids and a more important source of Earth’s water and other volatiles than its limited presence in our meteoritic collection indicates.

58 GEOSCIENCES↗

Apollo 16 returned lunar samples - Lithophile trace-element abundances

Lithium, K, Rb, Sr, Ba, rare-earth, Zr, and Hf abundances have been determined by mass-spectrometric isotope-dilution for Apollo 16 soils, anorthosite 61016, and 'basalt' 68415 whole-rock and separated pyroxene and plagioclase. Our sample of 61016 is similar to some other lunar anorthosites in lithophile trace-element concentrations but at a slightly lower level. It was probably accumulated from a little differentiated basalt. Basalt 68415 might be a homogeneous mixture of KREEP and anorthosite material; it appears to have crystallized under conditions as reducing as those holding for mare-basalts. The soil fines cover only a limited compositional range. No obvious chemical differences were noted between the Descartes and Cayley formations. Most of the compositional variation of the soils can be accounted for in terms of the addition of plagioclase. The existence of very high alumina basalt as an independent magma-type appears debatable in view of its KREEP-like lithophile trace-element relative concentrations and the observed lunar radioactivity distribution.

Philpotts, J. A.↗

Extinct superheavy element in the Allende meteorite

Radiochemical neutron activation analysis of seven Allende samples for 26 trace elements were conducted. In addition, Cr and Fe were studied with the aid of instrumental neutron activation analysis. The investigation had the objective to identify the extinct superheavy element which was present in meteorites and decayed to Xe isotopes by spontaneous fission. The superheavy element was found to reside mainly in a rare mineral (probably a Fe, Ni, Cr, Al-sulfide), comprising only 0.04% of the meteorite. It is pointed out that of the nine volatile superheavy elements 111 to 119, only 115, 114, and 113 are expected to condense as sulfides in the temperature interval between 400 and 500 K corresponding to mineral formation conditions in the solar nebula.

Anders, E.↗

Monte Carlo simulation of turnover processes in the lunar regolith

A Monte Carlo model for the gardening of the lunar surface by meteoritic impact is described, and some representative results are given. The model accounts with reasonable success for a wide variety of properties of the regolith. The smoothness of the lunar surface on a scale of centimeters to meters, which was not reproduced in an earlier version of the model, is accounted for by the preferential downward movement of low-energy secondary particles. The time scale for filling lunar grooves and craters by this process is also derived. The experimental bombardment ages (about 4 x 10 to the 8th yr for spallogenic rare gases, about 10 to the 9th yr for neutron capture Gd and Sm isotopes) are not reproduced by the model. The explanation is not obvious.

Arnold, J. R.↗

Trace element and isotope studies in oxide/phosphate/silicate inclusions of iron meteorites

Under the above grant research was funded in the following areas: 1. Pallasites: Rare earth element measurements in phosphates to determine if all pallasites fit into only two trace element groups. This work has been completed. 2. HIAB irons: To complete work on the only known silicate inclusion in a IIIAB iron meteorite. This work has been completed. 3. IIIAB irons: To continue the search for Cr-53 excesses in IIIAB iron meteorite phosphates. A part of this work has been completed 4. IIIAB irons: To complete the identification of the phosphate minerals in IIIAB iron meteorites and try to determine the phase relations and chemical history of trace element distributions during the core formation process. Work on this has been largely completed and preliminary results have been reported. The final work is being assessed prior to preparation of a manuscript for publication. 5. IIE irons: To complete work on the unique silicate assemblage in the IIE iron meteorite. Work on this was completed and a paper published. 6. Ungrouped irons: A partially devitrified silicate glass inclusion has been found in the ungrouped iron meteorite. Preliminary work on this has been reported. All the work on this has been now completed and a manuscript has been prepared and submitted for publication.

Olsen, Edward J.↗

Abundances in cosmic rays

Elemental, isotopic, and antiproton abundances in cosmic ray sources are examined. The elemental abundances for very rare elements with atomic numbers (Z) greater than 30, for individual elements with Z less than 33, and for even-Z elements with Z less than 60 are compared with elemental abundances in the solar system. The effects of nucleosynthesis of the material and the cosmic ray acceleration process on the abundances of elements is discussed. It is observed that the cosmic ray sources differ in composition from the solar system; however, the abundances are generally the same. The observations of the cosmic ray antiprotons are described.

Israel, M. H.↗

Nd isotopic variations and petrogenetic models

The isotopic composition of Nd in selected terrestrial rocks is investigated to gain information about its implications for petrogenesis and the history of the earth's crust and mantle. Chemical and mass-spectrometric measurements of the Nd-143/Nd-144 ratio in terrestrial rocks of different ages show that the Sm/Nd ratio and the rare-earth-element (REE) abundance pattern are equal within a few per cent to those of chondritic meteorites. Variations in the Nd isotopic ratio in young basalts are found to permit the identification of distinctive mantle sources and to indicate the preservation of significant heterogeneities in the mantle for times of 1 to 4 billion years ago. The isotopic data also show that mantle source regions with a Sm/Nd ratio which differs from the chondritic value by a factor of two are not preserved for more than a few hundred million years. The average continental crust material is found to have a much lower isotopic ratio than the mantle, reflecting the crust's low Sm/Nd ratio resulting from REE fractionation during crust formation from the mantle.

Depaolo, D. J.↗

νi 13/2 structures in 155 Sm and 159 Gd: Supporting evidence of a Z = 60 deformed subshell gap

Maximal ground-state deformation should occur when both proton and neutron Fermi surfaces are located at midshell. However, subshell gaps that stabilize large deformation can exist at proton or neutron values other than midshell. One such gap may occur at Z = 60 in the rare-earth region, as the energy of the first 2 + states in even-even nuclei are often lowest in an isotonic chain for neodymium (Z = 60) rather than the midshell isotopes of dysprosium (Z = 66). Further evidence of this deformed gap has now been observed by investigating the signature splitting systematics of the νi 13/2 bands found in the odd-N, rare-earth nuclei. Furthermore, these were aided by the present observation of the νi 13/2 band in 159 Gd and the confirmation of the same structure in 155 Sm via the transfer of a neutron from a 160 Gd beam to a 154 Sm target.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Expected sensitivity to 128 Te neutrinoless double beta decay with the CUORE TeO 2 cryogenic bolometers

The CUORE experiment is a ton-scale array of TeO 2 cryogenic bolometers located at the underground Laboratori Nazionali del Gran Sasso of Istituto Nazionale di Fisica Nucleare (INFN), in Italy. The CUORE detector consists of 988 crystals operated as source and detector at a base temperature of ~ 10 mK. Such cryogenic temperature is reached and maintained by means of a custom built cryogen-free dilution cryostat, designed with the aim of minimizing the vibrational noise and the environmental radioactivity. The primary goal of CUORE is the search for neutrinoless double beta decay of 130 Te , but thanks to its large target mass and ultra-low background it is suitable for the study of other rare processes as well, such as the neutrinoless double beta decay of 128 Te. This tellurium isotope is an attractive candidate for the search of this process, due to its high natural isotopic abundance of 31.75%. The transition energy at (866.7 ± 0.7) keV lies in a highly populated region of the energy spectrum, dominated by the contribution of the two-neutrino double beta decay of 130 Te. As the first ton-scale infrastructure operating cryogenic TeO 2 bolometers in stable conditions, CUORE is able to achieve a factor > 10 higher sensitivity to the neutrinoless double beta decay of this isotope with respect to past direct experiments.

128-Te↗

Lunar and Planetary Science XXXV: Chondrules and CAIs

The session "Chondrules and CAI's" included the following reports:Metallic Chondrules in NWA 1390 (H3-6): Clues to Their History from Metallic Cu; Relationship Between Bulk Chemical Composition and Formation Age of Chondrules in Bishunpur and Krymka; Relict Forsterite in Chondrules: Implications for Cooling Rates; An Evaluation of Quantitative Methods of Determining the Degree of Melting Experienced by a Chondrule; Rare Earth Element Fractionation in Chondrules; Mineralogy and Petrology of Chondrules in Carbonaceous Chondrite NWA 770; Isotopic Cosmobarometry: A Synthesis of Concepts and Implications for Chondrule and CAI Formation Mechanisms; Further Investigations of Minor Element Distributions in Spinels in Type B CAIs; and Trace Element Compositions of the Sublayers Making Up W-L Rims on CAI .

Source record↗

Pentavalent Uranium Enriched Mineral Surface under Electrochemically Controlled Reducing Environments

Redox reactions of uranium (U) in aqueous environments have important impacts on the mobility and isotopic fractionation of U in the geosphere. Pentavalent U as the cationic uranyl ion, UO 2 +, is rarely observed in naturally occurring samples because of its limited lifetime, but it may be an important intermediate state controlling the redox kinetics between hexavalent and tetravalent U. Increasing evidence has indicated that U(V) can be stabilized under laboratory conditions. Here, we showed that U(V) is the dominant species on the magnetite (Fe 3 O 4 ) surface under reducing conditions controlled by electrochemical methods. Cyclic voltammetry reveals coupled redox peaks corresponding to the U(VI)O 2 2+ /U(V)O 2+ one-electron redox reaction. Magnetite electrodes polarized at a series of potentials to reduce U(VI)O 2 2+ were characterized by X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), and Auger electron mapping. Overall, the results showed that up to twice the amount of U(V) to U(VI) was present on the magnetite surface. U(V) adopted a typical uranyl-type structure, and the U coverage on the magnetite surface increased with decreasing potentials. The formation of mixed-valence U(V)/U(VI) species on the surface of magnetite may hinder the U(V) disproportionation reaction, thereby eliminating the presence of tetravalent U. These results show that U(V) can exist over short time scales as the dominant U species on mineral surfaces under selected reducing conditions by the controlled polarization of a mineral electrode.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Comparing field and lab quantitative stable isotope probing for nitrogen assimilation in soil microbes

ABSTRACT Soil microbial communities play crucial roles in nutrient cycling and can help retain nitrogen in agricultural soils. Quantitative stable isotope probing (qSIP) is a useful method for investigating taxon-specific microbial growth and utilization of specific nutrients, such as nitrogen (N). Typically, qSIP is performed in a highly controlled lab setting, so the field relevance of lab qSIP studies remains unknown. We conducted and compared tandem lab and field qSIP to quantify the assimilation of 15 N by maize-associated soil prokaryotic communities at two agricultural sites. Here, we show that field qSIP with 15 N can be used to measure taxon-specific microbial N assimilation. Relative 15 N assimilation rates were generally lower in the field, and the magnitude of this difference varied by site. Rates differed by method (lab vs field) for 19% of the top N assimilating genera. The field and lab measures were more comparable when relative assimilation rates were weighted by relative abundance to estimate the proportion of N assimilated by each genus with only ~10% of taxa differing by method. Of those that differed, the taxa consistently higher in the lab were inclined to have opportunistic lifestyle strategies, whereas those higher in the field had niches reliant on plant roots or in-tact soil structure (biofilms, mycelia). This study demonstrates that 15 N-qSIP can be successfully performed using field-incubated soils to identify microbial allies in N retention and highlights the strengths and limitations of field and lab qSIP approaches. IMPORTANCE Soil microbes are responsible for critical biogeochemical processes in natural and agricultural ecosystems. Despite their importance, the functional traits of most soil organisms remain woefully under-characterized, limiting our ability to understand how microbial populations influence the transformation of elements such as nitrogen (N) in soil. Quantitative stable isotope probing (qSIP) is a powerful tool to measure the traits of individual taxa. This method has rarely been applied in the field or with 15 N to measure nitrogen assimilation. In this study, we measured genus-specific microbial nitrogen assimilation in two agricultural soils and compared field and lab 15 N qSIP methods. Our results identify taxa important for nitrogen assimilation in agricultural soils, shed light on the field relevance of lab qSIP studies, and provide guidance for the future application of qSIP to measure microbial traits in the field.

Reed, Kinsey (ORCID:0000000155178664)↗

Cr-Rich and Al-Rich Oxide Grains With 16O-Rich Compositions in Ryugu Samples

Samples returned from asteroid Ryugu by JAXA’s Hayabusa2 mission are CI-like, with abundant hydrated and secondary phases [1]. Rare anhydrous minerals occur in the matrix of the major lithology and in chemically distinct clasts. Oxygen isotopic analysis of coarse (> 10 µm) anhydrous Mg-rich silicates revealed a bimodal distribution, with some grains having compositions similar to amoeboid olivine aggregates (AOAs) and others having compositions similar to chondrule phenocrysts [2, 3]. We previously analyzed < 2 µm-sized Mg-rich silicates within a clast that also showed a range of O isotopic compositions (δ18O from -38 to +5 ‰) [4]. In this study, we conducted coordinated isotopic and mineralogical analysis of anhydrous oxide grains found in the matrix of Ryugu samples

A. N. Nguyen↗

Oxygen Isotopic Imaging of Refractory Inclusions from the Miller Range (MIL) 090019 CO3 Chondrite: A Perovskite Perspective

Calcium-Aluminum-rich Inclusions (CAIs) in primitive meteorites are the first solids to condense in the Solar System. The oxygen isotopic compositions recorded in various mineral components of CAIs provide clues about their origins and post-formation histories, recording processes such as condensation, melting, nebular alteration, and fluidrock reactions on the parent body. MIL 090019 is similar to some rare carbonaceous chondrites such as Acfer 094, DOM 08004/6 and ALH 77303 that contain high abundances of a variety of refractory inclusions. This provides an opportunity to study the oxygen isotopic record of different types of refractory inclusions within the same meteorite. We analyzed CAIs specifically targeting primary minerals that are direct nebular condensates, such as corundum and perovskite, with the goal of gaining insights into the O isotopic composition of the nebular gas(es) from which these CAIs condensed. As MIL 090019 is a classified as CO3.1, it shows some signs of thermal metamorphism, compared to the more primitive CO3 meteorites (e.g., DOM 08004/06). A second goal of this study is to search for evidence of nebular processes in phases such as perovskite and melilite that are susceptible to parent body alteration to varying degrees. We analyzed the oxygen isotopic compositions of various CAIs from the MIL 090019 CO3 carbonaceous chondrite by ion imaging using the NanoSIMS 50L (Nano Secondary Ion Mass Spectrometer) at JSC following methods described in. An advantage of ion imaging over traditional spot analyses is that it provides spatial context to the oxygen isotopic data. This work builds on previously reported oxygen isotopic composition of two other CAIs (CAI-44 and CAI-E2) from the same meteorite thin section.

Mane, P.↗

East River Watershed Stable Water Isotope Data in Precipitation, Snowpack and Snowmelt 2016-2020

Stable water isotopes (d18O, d2H and d-excess) are important tracers in hydrologic research to understand water partitioning between vegetation, groundwater, and runoff but are rarely applied to large watersheds with persistent snowpack and complex topopgraphy. Data were collected for the Lawrence Berkeley National Laboratory Watershed Function Science Focus Area supported by the U.S Department of Energy in the East River, CO Hydrologic Unit Code (140200010) with limited data also collected in adjacent watersheds Ohio Creek and Taylor River. Data are provided in csv and includes isotopic information for precipitation (years 2014-2016), snowmelt (years 2016-2017) and snowpits (years 2016-2020). Snowpit data contain depth resolved information at 10 cm intervals for density, snow water equivalent (SWE) and stable water isotopes. Bulk isotopic data for 86 snowpits contain depth, SWE, density and SWE-weighted isotope values. Sampling locations and elevations are provided within the data files, while kmz files are provided to view sampling locations using Google Earth software.

54 ENVIRONMENTAL SCIENCES↗