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At least 181 records · Page 10

Skeletal Kinetics Reduction for Astrophysical Reaction Networks

A novel methodology is developed to extract accurate skeletal reaction models for nuclear combustion. Local sensitivities of isotope mass fractions with respect to reaction rates are modeled based on the forced optimally time-dependent (f-OTD) scheme. These sensitivities are then analyzed temporally to generate skeletal models. The methodology is demonstrated by conducting skeletal reduction of constant density and temperature burning of carbon and oxygen relevant to Type Ia supernovae (SNe Ia). The 495-isotopes Torch model is chosen as the detailed reaction network. A map of maximum production of 56 Ni in SNe Ia is produced for different temperatures, densities, and proton-to-neutron ratios. The f-OTD simulations and the sensitivity analyses are then performed with initial conditions from this map. A series of skeletal models are derived and their performances are assessed by comparison against currently existing skeletal models. Previous models have been constructed intuitively by assuming the dominance of α-chain reactions. The comparison of the newly generated skeletal models against previous models is based on the predicted energy release and 44 Ti and 56 Ni abundances by each model. The consequences of ye ≠ 0.5 in the initial composition are also explored where ye is the electron fraction. The simulated results show that 56 Ni production decreases by decreasing ye as expected, and that the 43 Sc is a key isotope in proton and neutron channels toward 56 Ni production. It is shown that an f-OTD skeletal model with 150 isotopes can accurately predict the 56Ni abundance in SNe Ia for ye ≲ 0.5 initial conditions.

79 ASTRONOMY AND ASTROPHYSICS↗

Precision Mass Measurements Reveal Low Neutron Pairing in Tin beyond 𝑁=82 and Its Impact on Stellar Nucleosynthesis

We present a study on neutron-rich tin (𝑍 =50) isotopes beyond the doubly closed shell of 𝑁 = 82 through high-precision mass measurements, including the first-ever measurements of the masses of 136 Sn, 137 Sn, and 138 Sn isotopes. These measurements enhance our understanding of the nuclear structure and astrophysical nucleosynthesis in this previously unexplored region. The new mass data are used for evaluation of the final abundances of mass numbers 𝐴 =135 and 137 in 𝑟-process network calculations. Our findings reveal a notable change in the empirical pairing gap for tin isotopes beyond the 𝑁 = 82 closed shell and a shift in the two-neutron-separation energy slope compared to heavier elements above the shell closure. A new set of ab initio calculations effectively describes these observed trends.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Nanoscale wetting controls reactive Pd ensembles in synthesis of dilute PdAu alloy catalysts

The performance of bimetallic dilute alloy catalysts is largely determined by the size of minority metal ensembles on the nanoparticle surface. By analyzing the synthesis of catalysts comprising Pd 8 Au 92 nanoparticles supported on silica using surface-sensitive techniques, we report that whether Pd overgrowth occurs before or after Au nanoparticle deposition onto the support controls the surface Pd ensemble size and abundance. These differences in Pd ensembles influence catalytic reactivity in H 2 –D 2 isotope exchange and benzaldehyde hydrogenation, which, in correlation with theoretical calculations, is used to elucidate the active site(s) in each reaction. To clarify how the synthetic sequence controls the formation of Pd ensembles, we combine numerical wetting calculations and molecular dynamics simulations (with a machine-learned force field) to visualize Pd deposition and migration on the nanoparticle surface, respectively. Our results suggest that the nanoparticle–support interface restricts nanoparticle accessibility to Pd deposition, which consequently controls the Pd ensemble size, illustrating the critical role of nanoscale wetting phenomena during bimetallic catalyst preparation.

36 MATERIALS SCIENCE↗

Ablation loading of barium ions into a surface-electrode trap

Trapped-ion quantum information processing may benefit from qubits encoded in isotopes that are practically available in only small quantities, e.g., due to low natural abundance or radioactivity. Laser ablation provides a method of controllably liberating neutral atoms or ions from low-volume targets, but energetic ablation products can be difficult to confine in the small ion-electrode distance, micron-scale microfabricated traps amenable to high-speed, high-fidelity manipulation of ion arrays. Here, we investigate ablation-based ion loading into surface-electrode traps of different sizes to test a model describing ion loading probability as a function of effective trap volume and other trap parameters. We characterize loading of ablated barium from a metallic source in two cryogenic surface-electrode traps with 730 and 50 μm ion-electrode distances. Furthermore, our loading rate agrees with a predictive analytical model, providing insight for the confinement of limited-quantity species of interest for quantum computing, simulation, and sensing.

74 ATOMIC AND MOLECULAR PHYSICS↗

High-resolution spectroscopy of barium monofluoride: Odd isotopologues, hyperfine structure, and isotope shifts

Barium monofluoride (BaF) is a promising molecular species for precision tests of fundamental symmetries and interactions. We present a combined theoretical and experimental study of BaF spectra and isotope shifts, focusing in particular on the poorly understood odd isotopologues 137 BaF and 135 BaF. By comparing state-of-the-art ab initio calculations with high-resolution fluorescence and absorption spectroscopy data, we provide a benchmark for electronic structure theory and disentangle the hyperfine and rovibrational spectra of the five most abundant isotopologues, from 138 BaF to 134 BaF. The comprehensive knowledge gained enables a King plot analysis of the isotope shifts that reveals the odd-even staggering of the barium nuclear charge radii. It also paths the way for improved laser cooling of rare BaF isotopologues and crucially supports future measurements of nuclear anapole and Schiff moments.

Kogel, Felix [Univ. of Stuttgart (Germany)] (ORCID↗

Oxidized Sulfur Species in Slab Fluids as a Source of Enriched Sulfur Isotope Signatures in Arcs

Recycling of oxidized sulfur from subducting slabs to the mantle wedge provides simultaneous explanations for the elevated oxygen fugacity (fO 2 ) in subduction zones, their high hydrothermal and magmatic sulfur outputs, and the enriched sulfur isotopic signatures (i.e., δ 34 S > 0‰) of these outputs. However, a quantitative understanding of the abundance and speciation of sulfur in slab fluids consistent with high pressure experiments is lacking. Here we analyze published experimental data for anhydrite solubility in H 2 O-NaCl solutions to calibrate a high-pressure aqueous speciation model of sulfur within the framework of the deep earth water model. We characterize aqueous complexes, required to account for the high experimental anhydrite solubilities. We then use this framework to predict the speciation and solubility of sulfur in chemically complex fluids in equilibrium with model subducting mafic and ultramafic lithologies, from 2 to 3 GPa and 400 to 800°C at log fO 2 from FMQ-2 to FMQ+4. We show that sulfate complexes of calcium and sodium markedly enhance the stability of sulfate in moderately oxidized fluids in equilibrium with pyrite at fO 2 conditions of FMQ+1 to +2, causing large sulfur isotope fractionations up to 10‰ in the fluid relative to the slab. Such fluids could impart oxidized, sulfur-rich and high δ 34 S signatures to the mantle wedge that are ultimately transferred to arc magmas, without the need to invoke 34 S-rich subducted lithologies.

58 GEOSCIENCES↗

Reaction Rate Sensitivity of the Production of γ-Ray Emitting Isotopes in Core-collapse Supernovae

Radioactive isotopes produced in core-collapse supernovae (CCSNe) provide useful insights into the underlying processes driving the collapse mechanism and the origins of elemental abundances. Their study generates a confluence of major physics research, including experimental measurements of nuclear reaction rates, astrophysical modeling, and γ-ray observations. Here we identify the key nuclear reaction rates to the nucleosynthesis of observable radioactive isotopes in explosive silicon burning during CCSNe. Using the nuclear reaction network calculator SkyNet and current REACLIB reaction rates, we evolve temperature–density–time profiles of the innermost 0.45 M⊙ ejecta from the core collapse and explosion of a 12 M⊙ star. Individually varying 3403 reaction rates by factors of 100, we identify 141 reactions that cause significant differences in the isotopes of interest, namely, 43 K, 47 Ca, 44,47 Sc, 44 Ti, 48,51 Cr, 48,49 V, 52,53 Mn, 55,59 Fe, 56,57 Co, and 56,57,59 Ni. For each of these reactions, we present a novel method to extract the temperature range pertinent to the nucleosynthesis of the relevant isotope; the resulting temperatures lie within the range T = 0.47–6.15 GK. Limiting the variations to within 1σ of STARLIB reaction rate uncertainties further reduces the identified reactions to 48 key rates, which can be used to guide future experimental research. Complete results are presented in tabular form.

79 ASTRONOMY AND ASTROPHYSICS↗

The nature and origins of decametre-scale porosity in Ordovician carbonate rocks, Halahatang oilfield, Tarim Basin, China

At >7 km depths in the Tarim Basin, hydrocarbon reservoirs in Ordovician rocks of the Yijianfang Formation contain large cavities ( c . 10 m or more), vugs, fractures and porous fault rocks. Although some Yijianfang Formation outcrops contain shallow (formed near surface) palaeokarst features, cores from the Halahatang oilfield lack penetrative palaeokarst evidence. Outcrop palaeokarst cavities and opening-mode fractures are mostly mineral filled but some show evidence of secondary dissolution and fault rocks are locally highly ( c . 30%) porous. Cores contain textural evidence of repeated formation of dissolution cavities and subsequent filling by cement. Calcite isotopic analyses indicate depths between c . 220 and 2000 m. Correlation of core and image logs shows abundant cement-filled vugs associated with decametre-scale fractured zones with open cavities that host hydrocarbons. A Sm–Nd isochron age of 400 ± 37 Ma for fracture-filling fluorite indicates that cavities in core formed and were partially cemented prior to the Carboniferous, predating Permian oil emplacement. Repeated creation and filling of vugs, timing constraints and the association of vugs with large cavities suggest dissolution related to fractures and faults. In the current high-strain-rate regime, corroborated by velocity gradient tensor analysis of global positioning system (GPS) data, rapid horizontal extension could promote connection of porous and/or solution-enlarged fault rock, fractures and cavities. Supplementary material: Stable isotopic analyses and the velocity gradient tensor and principal direction and magnitude calculation are available at https://doi.org/10.6084/m9.figshare.c.4946046 Thematic collection: This article is part of the The Geology of Fractured Reservoirs collection available at: https://www.lyellcollection.org/cc/the-geology-of-fractured-reservoirs

Geology↗

Chemical characteristics of iron meteorite parent bodies

The projected relative abundances of the highly siderophile elements (HSE; Re, Os, Ir, Ru, Pt, and Pd) for bulk parent bodies of 10 magmatic iron meteorite groups/grouplet (IC, IIAB, IIC, IID, IIF, IIIAB, IIIF, IVA, IVB, and South Byron Trio) are broadly similar and show no resolvable differences between noncarbonaceous (NC) and carbonaceous (CC) genetic heritage. The processes driving genetic isotopic heterogeneity in the early Solar System, therefore, evidently did not leave discernable chemical fingerprints with respect to HSE relative abundances on the bulk planetesimal scale. By contrast, the absolute abundances of HSE projected for parent body cores, which reflect core size, are more variable and, on average, higher in CC bodies compared to NC bodies. Overall, bulk core chemical compositions, as well as core size, are linked to the distribution of Fe within a parent body, which is controlled by its oxidation state. The CC parent bodies are constrained to have formed under heterogeneous oxidizing conditions which were, on average, more oxidizing than those of the NC environment.

Hilton, Connor D.↗

A case study on the use of carbon sticky tabs for microbeam uranium isotope measurement with an emphasis on understanding the influence of subtle variations in substrate composition

In this paper we integrate laser induced breakdown spectroscopy (LIBS), large geometry secondary ion mass spectrometry (LG-SIMS), laser ablation—multi collector—inductively coupled plasma—mass spectrometry (LA-MC-ICP-MS), and trace elemental compositions obtained by bulk digestion from a suite of commercially available carbon sticky tabs to determine if subtle variations in the tab’s composition can be tied to shifts in the observed uranium isotopic composition of the IRMM-2020 standard relative to its ‘true’ value. The results suggest that, although clear differences exist in the relative abundances of carbon and hydrogen across the various carbon sticky tabs examined, as well as differences in their trace elemental and total uranium concentrations, these differences do not appear to influence the LG-SIMS or LA-MC-ICP-MS uranium isotope ratio measurements, or the appearance of the uranium mass spectrum scans. Instead, the quality (i.e., precision and accuracy) of the LG-SIMS and LA-MC-ICP-MS results are directly proportional to the observed signal intensity at the time of analysis. For the LG-SIMS measurements, there does appear to be a direct correlation between 235U1H hydride formation rates and vacuum conditions within the instrument’s analytical chamber. Furthermore, none of the carbon sticky tabs examined by LG-SIMS displayed evidence of elevated background uranium content. While a preliminary correlation was observed between the uranium isotope background signal during LA-MC-ICP-MS and the total uranium concentrations determined by isotope dilution, none of the tabs displayed a high enough analytical background to affect the isotope ratio measurements.

Zirakparvar, Alex [ORNL] (ORCID:0000000337797730)↗

Challenges in studying water fluxes within the soil-plant-atmosphere continuum: A tracer-based perspective on pathways to progress

Tracing and quantifying water fluxes in the hydrological cycle is crucial for understanding the current state of ecohydrological systems and their vulnerability to environmental change. Especially the interface between ecosystems and the atmosphere that is strongly mediated by plants is important to meaningfully describe ecohydrological system functioning. Many of the dynamic interactions generated by water fluxes between soil, plant and the atmosphere are not well understood, which is partly due to a lack of interdisciplinary research. This opinion paper reflects the outcome of a discussion among hydrologists, plant ecophysiologists and soil scientists on open questions and new opportunities for collaborative research on the topic "water fluxes in the soil-plant-atmosphere continuum" especially focusing on environmental and artificial tracers. We emphasize the need for a multi-scale experimental approach, where a hypothesis is tested at multiple spatial scales and under diverse environmental conditions to better describe the small-scale processes (i.e., causes) that lead to large-scale patterns of ecosystem functioning (i.e., consequences). Novel in-situ, high-frequency measurement techniques offer the opportunity to sample data at a high spatial and temporal resolution needed to understand the underlying processes. Here we advocate for a combination of long-term natural abundance measurements and event-based approaches. Multiple environmental and artificial tracers, such as stable isotopes, and a suite of experimental and analytical approaches should be combined to complement information gained by different methods. Virtual experiments using process-based models should be used to inform sampling campaigns and field experiments, e.g., to improve experimental designs and to simulate experimental outcomes. On the other hand, experimental data are a pre-requisite to improve our currently incomplete models. Interdisciplinary collaboration will help to overcome research gaps that overlap across different earth system science fields and help to generate a more holistic view of water fluxes between soil, plant and atmosphere in diverse ecosystems.

54 ENVIRONMENTAL SCIENCES↗

Light- and Chemical-Doping-Induced Magnetic Behavior of Eu Molecular Systems

Variable temperature electron paramagnetic resonance (VT-EPR) was used to investigate the role of the environment and oxidation states of several coordinated Eu compounds. We find that while Eu(III) chelating complexes are diamagnetic, simple chemical reduction results in the formation of paramagnetic species. In agreement with the distorted D 3h symmetry of Eu molecular complexes investigated in this study, the EPR spectrum of reduced complexes showed axially symmetric signals (g ⊥ = 2.001 and g ∥ = 1.994) that were successfully simulated with two Eu isotopes with nuclear spin 5/2 ( 151 Eu and 153 Eu with 48% and 52% natural abundance, respectively) and nuclear g-factors 151 Eu/ 153 Eu = 2.27. Illumination of water-soluble complex Eu(dipic) 3 at 4 K led to the ligand-to-metal charge transfer (LMCT) that resulted in the formation of Eu(II) in a rhombic environment (g x = 2.006, g y = 1.995, g z = 1.988). The existence of LMCT affects the luminescence of Eu(dipic) 3 , and pre-reduction of the complex to Eu(II)(dipic) 3 reversibly reduces red luminescence with the appearance of a weak CT blue luminescence. Furthermore, encapsulation of a large portion of the dipic ligand with Cucurbit[7]uril, a pumpkin-shaped macrocycle, inhibited ligand-to-metal charge transfer, preventing the formation of Eu(II) upon illumination.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A new TEVA-DGA chromatography procedure to separate Pu, Am, and Np from bulk U materials

Trace actinides present within uranium (U) material are diagnostic signatures of U processing history. For example, the emplacement of U material within the high neutron-flux environment of a nuclear reactor can cause neutron capture of U to form 241-plutonium ( 241 Pu). Plutonium-241 then decays to progeny isotopes 241-americium ( 241 Am) and 237-neptunium ( 237 Np); therefore, the presence and relative abundances of these trace actinides is indicative of the material’s production history and intended employment (Mayer et al., 2013). During a pre-detonation nuclear forensics investigation, measurement of trace actinide 241 Pu, 241 Am, and 237 Np concentrations by an analytical laboratory may be requested. However, chemically purifying these elements from bulk U is a challenging and involved procedure requiring several sequential chromatography columns across 4+ days. To expedite Pu-Am-Np separation from bulk U material, and to improve the yield recovery of these elements, this DHS Postdoc Fellowship has worked to create a new chromatography separation chemistry.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Implications of the non-observation of 6 Li in halo stars for the primordial 7 Li problem

The primordial Lithium Problem is intimately connected to the assumption that the 7 Li abundance observed in metal-poor halo stars is unchanged from its primordial value, which lies significantly below the predictions of standard big-bang nucleosynthesis. Two key lines of evidence have argued that these stars have not significantly depleted their initial (mostly primordial) 7 Li: i) the lack of dispersion in Li abundance measurements at low metallicity (and high surface temperature); and ii) the detection of the more fragile 6 Li isotope in at least two halo stars. The purported 6 Li detections were in good agreement with predictions from cosmic-ray nucleosynthesis which is responsible for the origin of 6 Li. This concordance left little room for 6 Li depletion, and the apparent 6 Li survival implied that 7 Li largely evaded destruction, because stellar interiors destroy 6 Li more vigorously then than 7 Li. Recent (re)-observations of halo stars challenge the evidence against 7 Li depletion: i) lithium elemental abundances now show significant dispersion, and ii) sensitive 6 Li searches now reveal only upper limits to the 6 Li/ 7 Li ratio. We discuss the consequences of these 6 Li non-detections on the primordial 7 Li Problem, Galactic cosmic-ray nucleosynthesis, and the question of differential depletion of Li in stars. The tight new 6 Li upper limits generally fall far below the predictions of cosmic-ray nucleosynthesis, implying that substantial 6 Li depletion has occurred — by factors up to 50. We show that in stars with 6 Li limits and thus lower bounds on 6 Li depletion, an equal amount of 7 Li depletion is more than sufficient to resolve the primordial 7 Li Problem. This picture is consistent with well-studied stellar models in which 7 Li is less depleted than 6 Li, and strengthen the case that the Lithium Problem has an astrophysical solution. We conclude by suggesting future observations that could test these ideas.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Carbon, Nitrogen, and Sulfur Analysis of the Cetama Viognier Standard Reference Material

The Viognier sample was analyzed for C, N, and S concentrations and stable isotope compositions using an Elementar Vario Isotope Cube Elemental Analyzer (EA) that is coupled to an IsoPrime PrecisION IRMS. Powder samples were placed in tin capsules and then loaded onto a rotary autosampler. The autosampler dropped samples into the EA, and samples were combusted at 1175 °C over tungsten oxide in a continuous stream of helium carrier gas. A pulse of oxygen is added to the gas stream resulting in flash combustion of the tin capsule containing the sample, which raises the reaction temperature to approximately 1800 °C for a few seconds. The combustion reaction produces SO 2 , N 2 and CO 2 from any sulfur, nitrogen and carbon present in the sample. The resulting gases were then passed through a reduced copper reactor that was heated to 850 °C, to reduce NO x to N 2 , reduce SO 3 to SO 2 , and trap any volatile halogen compounds on silver wool. Following water removal using an adsorption tube, the N 2 , CO 2 , and SO 2 analyte gases were separated and purified using purge-trap columns. The purified gases were then carried through a thermal conductivity detector. The detector signal was passed to software that calculated elemental abundances based on integrated peak areas. The sample gases were then passed to the IRMS and stable isotope ratios were measured. Raw sample peak areas were corrected by subtracting the average peak area from blanks consisting of empty tin capsules run using the same EA analysis method. Blanks were also run following each replicate to verify that all the material was combusted. The Viognier sample was analyzed in triplicate on two days (target sample masses: 30, 60 and 90 mg). The following standards were analyzed to calibrate EA-IRMS measurements: IAEA-C6, USGS-40, USGS-41, IAEA-S1, and IAEA-S2.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Rainforest-to-pasture conversion stimulates soil methanogenesis across the Brazilian Amazon

The Amazon rainforest is a biodiversity hotspot and large terrestrial carbon sink threatened by agricultural conversion. Rainforest-to-pasture conversion stimulates the release of methane, a potent greenhouse gas. The biotic methane cycle is driven by microorganisms; therefore, this study focused on active methane-cycling microorganisms and their functions across land-use types. We collected intact soil cores from three land use types (primary rainforest, pasture, and secondary rainforest) of two geographically distinct areas of the Brazilian Amazon (Santarém, Pará and Ariquemes, Rondônia) and performed DNA stable-isotope probing coupled with metagenomics to identify the active methanotrophs and methanogens. At both locations, we observed a significant change in the composition of the isotope-labeled methane-cycling microbial community across land use types, specifically an increase in the abundance and diversity of active methanogens in pastures. We conclude that a significant increase in the abundance and activity of methanogens in pasture soils could drive increased soil methane emissions. Furthermore, we found that secondary rainforests had decreased methanogenic activity similar to primary rainforests, and thus a potential to recover as methane sinks, making it conceivable for forest restoration to offset greenhouse gas emissions in the tropics. These findings are critical for informing land management practices and global tropical rainforest conservation.

59 BASIC BIOLOGICAL SCIENCES↗

β Decay of 61 V and its Role in Cooling Accreted Neutron Star Crusts

The interpretation of observations of cooling neutron star crusts in quasipersistent x-ray transients is affected by predictions of the strength of neutrino cooling via crust Urca processes. The strength of crust Urca neutrino cooling depends sensitively on the electron-capture and β -decay ground-state-to-ground-state transition strengths of neutron-rich rare isotopes. Nuclei with a mass number of A = 61 are predicted to be among the most abundant in accreted crusts, and the last remaining experimentally undetermined ground-state-to-ground-state transition strength was the β decay of 61 V. This Letter reports the first experimental determination of this transition strength, a ground-state branching of $8.1^{+4.0}_{- 3.1}%$, corresponding to a log ft value of $5.5^{+0.2}_{-0.2}$. This result was achieved through the measurement of the β -delayed γ rays using the total absorption spectrometer SuN and the measurement of the β -delayed neutron branch using the neutron long counter system NERO at the National Superconducting Cyclotron Laboratory at Michigan State University. This method helps to mitigate the impact of the pandemonium effect in extremely neutron-rich nuclei on experimental results. The result implies that A = 61 nuclei do not provide the strongest cooling in accreted neutron star crusts as expected by some predictions, but that their cooling is still larger compared to most other mass numbers. Finally, only nuclei with mass numbers 31, 33, and 55 are predicted to be cooling more strongly. However, the theoretical predictions for the transition strengths of these nuclei are not consistently accurate enough to draw conclusions on crust cooling. With the experimental approach developed in this work, all relevant transitions are within reach to be studied in the future.

79 ASTRONOMY AND ASTROPHYSICS↗

A window into atmospheric escape on early Mars provided by argon isotopes in a Martian meteorite

Novel analytical approaches to determining the trapped 38 Ar/ 36 Ar ratio of gases contained within Martian meteorites are presented and applied to the Martian regolith breccia Northwest Africa (NWA) 7034 and paired stone NWA 11220. The resulting data indicate that extensive mass-dependent fractionation of atmospheric Ar may have occurred within 150 million years of planetary formation, ostensibly as a result of diffusion-limited hydrodynamic escape. The inferred fractional loss of Ar and lighter atmospheric constituents exceeds 50%. In conclusion, these data suggest that volatiles derived from planetary outgassing and/or impactors may dominate the present abundance of atmospheric Ar.

07 ISOTOPE AND RADIATION SOURCES↗