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At least 235 records · Page 13

Assessment of the Effect of Prototypic High-Burnup Operating Conditions of Fuel Fragmentation, Relocation, and Dispersal Susceptibility

The US nuclear energy industry is investigating strategies that further reduce the cost of energy production by using its existing fleet of nuclear generating stations. Most nuclear power plant operating costs are associated with purchasing fresh fuel assemblies or the efficiency of the reactor core design. Material costs are typically beyond the operator’s control; however, the core design optimizations offer potential operational savings. The core design envelope available to operators is constrained by two primary regulatory criteria: an enrichment limit of 5% 235 U and a burnup limit of 62 GWD/tU. These constraints have resulted in renewed efforts by the nuclear industry to pursue extending the peak rod-average burnup beyond 62 GWd/tU. This effort will likely require additional safety analyses beyond what is currently accepted by the US Nuclear Regulatory Commission. The purpose of this work is to demonstrate a best estimate plus uncertainty pin-by-pin high-burnup loss of coolant accident analysis technique to assess full-core high-burnup fuel fragmentation, relocation, and dispersal (FFRD) and identify approaches for minimizing or potentially mitigating FFRD through core design optimizations.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Deciphering Fingerprints of Stellar Nucleosynthesis Through Nuclear Reaction Rate Measurements and Isotopic Analyses of Stardust

Microscopic stardust grains, found in trace amounts in primitive meteorites, afford a unique opportunity to study stellar nucleosynthesis in the laboratory by measuring their heavy element isotopic compositions. Applying LLNL’s state-of-the art material characterization capabilities to these micrometer-sized grains yields large new datasets with unprecedented precision. However, the astrophysical models necessary to interpret the isotopic record require improved nuclear physics data to constrain stellar nucleosynthesis conditions. For example, the branch point in the s-process path at 95 Zr controls the relative amounts of heavier nuclides but is poorly understood. We conducted a coordinated effort across disciplines to combine a new determination of the neutron capture cross section of 95 Zr with the laboratory analysis of hundreds of stardust grains to yield a view into stellar interiors. We developed new methods to quantify multiple isotopic systems simultaneously (e.g., Zr, Ba, and W) in stardust grains and improved the determination of the neutron capture cross section of unstable 95 Zr via the surrogate reaction method. This interdisciplinary approach is allowing us to fill gaps in our understanding of the environments in which elements are produced while enhancing LLNL’s experimental and theoretical capabilities relevant to nuclear threat reduction missions.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Deciphering Fingerprints of Stellar Nucleosynthesis Through Nuclear Reaction Rate Measurements and Isotopic Analyses of Stardust

Microscopic stardust grains, found in trace amounts in primitive meteorites, afford a unique opportunity to study stellar nucleosynthesis in the laboratory by measuring their heavy element isotopic compositions. Applying LLNL’s state-of-the art material characterization capabilities to these micrometer-sized grains yields large new datasets with unprecedented precision. However, the astrophysical models necessary to interpret the isotopic record require improved nuclear physics data to constrain stellar nucleosynthesis conditions. For example, the branch point in the s-process path at 95 Zr controls the relative amounts of heavier nuclides but is poorly understood. We conducted a coordinated effort across disciplines to combine a new determination of the neutron capture cross section of 95 Zr with the laboratory analysis of hundreds of stardust grains to yield a view into stellar interiors. We developed new methods to quantify multiple isotopic systems simultaneously (e.g., Zr, Ba, and W) in stardust grains and improved the determination of the neutron capture cross section of unstable 95 Zr via the surrogate reaction method. This interdisciplinary approach is allowing us to fill gaps in our understanding of the environments in which elements are produced while enhancing LLNL’s experimental and theoretical capabilities relevant to nuclear threat reduction missions.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Neural network approaches for parameterized optimal control

Here, we consider numerical approaches for deterministic, finite-dimensional optimal control problems whose dynamics depend on unknown or uncertain parameters. We seek to amortize the solution over a set of relevant parameters in an offline stage to enable rapid decision-making and be able to react to changes in the parameter in the online stage. To tackle the curse of dimensionality arising when the state and/or parameter are high-dimensional, we represent the policy using neural networks. We compare two training paradigms: First, our model-based approach leverages the dynamics and definition of the objective function to learn the value function of the parameterized optimal control problem and obtain the policy using a feedback form. Second, we use actor-critic reinforcement learning to approximate the policy in a data-driven way. Using an example involving a two-dimensional convection-diffusion equation, which features high-dimensional state and parameter spaces, we investigate the accuracy and efficiency of both training paradigms. While both paradigms lead to a reasonable approximation of the policy, the model-based approach is more accurate and considerably reduces the number of PDE solves.

97 MATHEMATICS AND COMPUTING↗

Constraining the Reaction Rate of Criegee Intermediates with Carboxylic Acids during the Multiphase Ozonolysis of Aerosolized Alkenes

Criegee intermediates (CIs) are central to the ozonolysis of unsaturated organic compounds, controlling the formation of small fragmentation reaction products and higher molecular weight oligomeric compounds through competing unimolecular and bimolecular pathways. In particular, the reaction of thermalized CI with carboxylic acids (RCOOH) to produce oligomeric α-acyloxyalkyl hydroperoxides (AAHPs) is of interest to the chemical transformation of organic compounds in the atmosphere. In the gas phase, the CI + RCOOH reaction proceeds at supercollisional rates, consistent with a barrierless reaction mechanism. However, the rate of this reaction in condensed phases remains uncertain. Here, we report the results of aerosol flow tube studies of the ozonolysis of submicron organic aerosol containing mixtures of an internal n-alkene (Z-9-tricosene, tri) and a saturated acid (2-hexyldecanoic acid, HDA). The decay of the reactants and formation of reaction products are monitored using atmospheric pressure chemical ionization mass spectrometry (APCI–MS). A 6-fold decrease in the reactive uptake of ozone is observed with increasing acid concentration, consistent with a previous study using alcohol additives. The decay of HDA with ozone exposure shows that HDA scavenges CIs at rates comparable to competing unimolecular pathways involving CIs. The decay kinetics of HDA are analyzed using a simple kinetic model in order to constrain the ratio of the CI + RCOOH and unimolecular CI rate constants. Empirical fitting to this model, combined with theoretical estimates of the unimolecular loss rate, yields a CI + RCOOH rate constant of 1.85 ± 0.27 × 10 –19 cm 3 molec –1 s –1 , which is six orders of magnitude slower than the expected diffusion limit in a liquid organic matrix. Stochastic kinetic simulations are conducted with different values of the CI + RCOOH rate constant to validate this result and show that the diffusion-limited rate is indeed much too rapid to reproduce the experimental results.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Spatial access and resource limitations control carbon mineralization in soils

Core-scale soil carbon fluxes are ultimately regulated by pore-scale dynamics of substrate availability and microbial access. These are constrained by physicochemical and biochemical phenomena (e.g. spatial access and hydrologic connectivity, physical occlusion, adsorption-desorption with mineral surfaces, nutrient and resource limitations). We conducted an experiment to determine how spatial access and resource limitations influence core-scale SOM mineralization, and how these are regulated by antecedent moisture conditions. Intact soil cores were incubated at field-moist vs. drought conditions, after which they were saturated from above (to simulate precipitation) or below (to simulate groundwater recharge). Soluble C (acetate) and N (nitrate) forms were added to some cores during the rewetting process to alleviate potential nutrient limitations. Respiration showed evidence of C-limitation, as C amendments increased the cumulative CO 2 evolved. Drought and rewetting increased soil respiration, and these soils also exhibited increased complex aromatic molecules in porewater. This newly available substrate appeared to alleviate nutrient limitations on respiration, because there were no further respiration increases with subsequent C and N amendments. We expected that respiration would be influenced by wetting direction, as simulated precipitation would mobilize C from the surface. However, as a main effect, this response was seen only in the C-amended soils, indicating that surface-C may not have been bioavailable. At the pore scale (porewater samples), compared to the baseline soils, drought and the C, N amendments caused a net loss of identified molecules when the soils were rewet from below, whereas wetting from above caused a net increase in identified molecules. This indicates that as soils were wet from below, the fresh inputs simulated the C-and N-limited microbial populations present deeper in the soil profile. Furthermore, our experiment highlights the complex and interactive role of antecedent moisture conditions, wetting direction, and resource limitations in driving core-scale C fluxes.

59 BASIC BIOLOGICAL SCIENCES↗

Direct Observation of the Depth of Active Groundwater Circulation in an Alpine Watershed

Abstract The depth of active groundwater circulation is a fundamental control on stream flows and chemistry in mountain watersheds, yet it remains challenging to characterize and is rarely well constrained. We collected hydraulic conductivity, hydraulic head, temperature, chemical, noble gas, and 3 H/ 3 He groundwater age data from discrete levels in two boreholes 46 and 81 m deep in an alpine watershed, in combination with chemical and age data from shallow groundwater discharge, to discern groundwater flow rates at different depths and directly observe active and inactive groundwater. Vertical head gradients are steep (average of 0.4) and thermal profiles are consistent with typical linear conductive continental geotherms. Groundwater deeper than ∼20 m is distinct from shallow groundwater and creek water in its chemistry, noble gas signature, and age (dominantly >65 years compared to <9 years). Together these results suggest low vertical groundwater flow velocities and a relatively shallow active circulation depth of ∼20 m. This hypothesis is tested with a simple 2‐D numerical fluid flow and heat transport model representing a hillslope transect through the two boreholes. The modeling indicates that the subhorizontally bedded sedimentary rocks underlying the basin are highly anisotropic with low vertical hydraulic conductivity, and at most ∼10% of bedrock recharge (equivalent to <2% of stream baseflow) flows below a depth of 20 m. The study demonstrates the considerable value of discrete‐depth hydrogeologic, chemical, and age data for determining active circulation depth, and illustrates an approach for maximizing the utility of individual boreholes drilled for mountain bedrock aquifer characterization.

54 ENVIRONMENTAL SCIENCES↗

Optimal Modulation and DM Filter Design for a High Switching Frequency Single-Stage Microinverter

This paper presents an optimal modulation and systematic filter design approach for a single-stage dual-active-bridge (DAB) based dc-ac microinverter to achieve improved differential-mode (DM) noise performance for electromagnetic interference (EMI) tests. As DM filters contribute significantly to the overall converter volume, the main objective of this work is to leverage the degrees of freedom in the DAB converters to effectively attenuate the EMI noise. In addition, the DM filter design method needs to ensure near unity power factor converter operation. To achieve these targets, this paper analyzes three modulation strategies based on fixed or variable switching frequency operation where the different control modulation variables are varied to find the simulated DM noise spectrum. Based on the required DM attenuation, a constrained optimization problem is formulated to determine minimal DM filter parameters. Simulation results show that a spread spectrum approach with variable switching frequency is shown to minimize the DM EMI attenuation effort by spreading the noise profile. A fully GaN 400 W hardware prototype demonstrated the spread-sprectrum approach.

14 SOLAR ENERGY↗

Relationships between Immersion Freezing and Crystal Habit for Arctic Mixed-Phase Clouds—A Numerical Study

Abstract The number concentration of ice particles in Arctic mixed-phase clouds is a major controlling factor of cloud lifetime. The relationships between ice nucleation mode and ice crystal habit development are not yet constrained by observations. This study uses a habit-predicting microphysical scheme within a 3D large-eddy simulation model to evaluate the relationship between immersion freezing and ice habit in a simulated Arctic mixed-phase cloud case. Three immersion freezing parameterizations are considered: a volume-dependent freezing scheme (VF), a parameterization limited to activated droplets (C-AC), and a parameterization limited to coarse aerosol particles (C-CM). Both C-AC and C-CM are based on classical nucleation theory. The freezing rate with VF is found to be greater in downdraft regions than in updraft regions due to the downdraft having a higher number concentration of large droplets. The C-AC cases show active freezing of small droplets near cloud top, whereas in the C-CM cases, mainly the 8–32- μ m-sized droplets freeze in updraft regions near the cloud base. Because the initial crystal size is assumed to affect the axis ratio of hexagonal plates, the VF cases produce crystals with larger axis ratios, resulting in smaller mode radii than the C-AC cases. In all cases, irregular polycrystals dominate near cloud top and a band-like structure develops within the cloud, which qualitatively agrees with previous observations. In the VF and C-CM cases, unactivated large droplets arising from coarse-mode aerosol particles contributed significantly to the freezing rate, producing an important influence on crystal habit.

54 ENVIRONMENTAL SCIENCES↗

Approach to Precision and Bias Analysis of Interlaboratory Salt Study Results

An interlaboratory study of salt properties measurements was initiated in 2020 by Raluca Scarlatt of UC Berkley and Jake McMurray of Oak Ridge National Laboratory as a DOE-funded NEUP project. The objective of what is referred to as the interlaboratory salt study (ISS) was to assess the quality of molten salt property data and develop consensus standard methods for measuring key property values. Unlike many interlaboratory studies in which the precision of applying a well-defined and well-constrained method is measured, the methods used to measure property values were not specified nor were the measurement conditions controlled. Instead, the approach was to engage participants in measuring the property values of two commonly-used salt mixtures by using any desired measurement techniques. By including measurements made using the same and different methods across institutions, the precisions achieved using specific techniques can be assessed as well as the confidence in the values measured using different techniques. Details of the calibrations and uncertainty provided by the participants will be useful in establishing a best practice for the application of each technique to molten salts.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Harnessing Peptide Binding to Capture and Reclaim Phosphate

With rising consumer demands, society is tapping into wastewater as an innovative source to recycle depleting resources. Novel reclamation technologies have been recently explored for this purpose, including several that optimize natural biological processes for targeted reclamation. However, this emerging field has a noticeable dearth of synthetic material technologies that are programmed to capture, release, and recycle specified targets; and of the novel materials that do exist, synthetic platforms incorporating biologically inspired mechanisms are rare. We present here a prototype of a materials platform utilizing peptide amphiphiles that has been molecularly engineered to sequester, release, and reclaim phosphate through a stimuli-responsive pH trigger, exploiting a protein-inspired binding mechanism that is incorporated directly into the self-assembled material network. This material is able to harvest and controllably release phosphate for multiple cycles of reuse, and it is selective over nitrate and nitrite. We have determined by simulations that the binding conformation of the peptide becomes constrained in the dense micelle corona at high pH such that phosphate is expelled when it otherwise would be preferentially bound. However, at neutral pH, this dense structure conversely employs multichain binding to further stabilize phosphate when it would otherwise be unbound, opening opportunities for higher-order conformational binding design to be engineered into this controllably packed corona. With this work, we are pioneering a new platform to be readily altered to capture other valuable targets, presenting a new class of capture and release materials for recycling resources on the nanoscale.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nitrogen fixing shrubs advance the pace of tall-shrub expansion in low-Arctic tundra

Abstract Tall deciduous shrubs are critically important to carbon and nutrient cycling in high-latitude ecosystems. As Arctic regions warm, shrubs expand heterogeneously across their ranges, including within unburned terrain experiencing isometric gradients of warming. To constrain the effects of widespread shrub expansion in terrestrial and Earth System Models, improved knowledge of local-to-regional scale patterns, rates, and controls on decadal shrub expansion is required. Using fine-scale remote sensing, we modeled the drivers of patch-scale tall-shrub expansion over 68 years across the central Seward Peninsula of Alaska. Models show the heterogeneous patterns of tall-shrub expansion are not only predictable but have an upper limit defined by permafrost, climate, and edaphic gradients, two-thirds of which have yet to be colonized. These observations suggest that increased nitrogen inputs from nitrogen-fixing alders contributed to a positive feedback that advanced overall tall-shrub expansion. These findings will be useful for constraining and projecting vegetation-climate feedbacks in the Arctic.

54 ENVIRONMENTAL SCIENCES↗

Coupled Chemical and Mechanical Control of Phase Stability in Lanthanide-Substituted BiVO 4

Doping is widely used to enhance the photoelectrochemical performance of BiVO 4 , yet solubility limits and polymorphic stability constrain compositional tuning. Here, in this study, the role of trivalent cation substitution (Ln = La, Nd, Dy, Ho, Y) on pressure-induced phase transformations in Bi 1–x Ln x VO 4 (x ≤ 0.5) is described. Powder X-ray and neutron diffraction reveal that increasing Ln content stabilizes the tetragonal zircon-type polymorph under ambient conditions, while applied pressures of up to ∼5 GPa promote conversion to the monoclinic fergusonite-type polymorph. In-situ neutron diffraction on Bi 0.8 La 0.2 VO 4 shows a reversible monoclinic to tetragonal transition near 2–3 GPa with a bulk modulus of 147 GPa. The extent of conversion depends strongly on dopant identity, concentration, and synthetic route, with mixed-phase solid-state samples converting more efficiently than phase-pure coprecipitated materials. These results demonstrate pressure as a viable pathway to access metastable, doped BiVO 4 compositions beyond conventional solubility limits.

Sypkes, Kathryn I. [University of Sydney, NSW (Aus↗

Water and vapor transport in algal‐fungal lichen: Modeling constrained by laboratory experiments, an application for Flavoparmelia caperata

ABSTRACT Algal‐fungal symbionts share water, nutrients, and gases via an architecture unique to lichens. Because lichen activity is controlled by moisture dynamics, understanding water transport is prerequisite to understand their fundamental biology. We propose a model of water distributions within foliose lichens governed by laws of fluid motion. Our model differentiates between water stored in symbionts, on extracellular surfaces, and in distinct morphological layers. We parameterize our model with hydraulic properties inverted from laboratory measurements of Flavoparmelia caperata and validate for wetting and drying. We ask: (1) Where is the bottleneck to water transport? (2) How do hydration and dehydration dynamics differ? and (3) What causes these differences? Resistance to vapor flow is concentrated at thallus surfaces and acts as the bottleneck for equilibrium, while internal resistances are small. The model captures hysteresis in hydration and desiccation, which are shown to be controlled by nonlinearities in hydraulic capacitance. Muting existing nonlinearities slowed drying and accelerated wetting, while exaggerating nonlinearities accelerated drying and slowed wetting. The hydraulic nonlinearity of F. caperata is considerable, which may reflect its preference for humid and stable environments. The model establishes the physical foundation for future investigations of transport of water, gas, and sugar between symbionts.

Potkay, Aaron↗

A Model Intercomparison Study of Aerosol‐Cloud‐Turbulence Interactions in a Cloud Chamber: 1. Model Results

This study presents the first model intercomparison of aerosol‐cloud‐turbulence interactions in a controlled cloudy Rayleigh‐Bénard Convection chamber environment, utilizing the Pi Chamber at Michigan Technological University. We analyzed simulated cloud chamber‐averaged statistics of microphysics and thermodynamics in a warm‐phase, cloudy environment under steady‐state conditions at varying aerosol injection rates. Simulation results from seven distinct models (DNS, LES, and a 1D turbulence model) were compared. Our findings demonstrate that while all models qualitatively capture observed trends in droplet number concentration, mean radius, and droplet size distributions at both high and low aerosol injection rates, significant quantitative differences were observed. Notably, droplet number concentrations varied by over two orders of magnitude between models for the same injection rates, indicating sensitivities to the model treatments in droplet activation and removal and wall fluxes. Furthermore, inconsistencies in vertical relative humidity profiles and in achieving steady‐state liquid water content suggest the need for further investigation into the mechanisms driving these variations. Despite these discrepancies, the models generally reproduced consistent power‐law relationships between the microphysical variables. This model intercomparison underscores the importance of controlled cloud chamber experiments for validating and improving cloud microphysical parameterizations. Recommendations for future modeling studies are also highlighted, including constraining wall conditions and processes, investigating droplet/aerosol removal (including sidewall losses), and conducting simplified experiments to isolate specific processes contributing to model divergence and reduce model uncertainties.

54 ENVIRONMENTAL SCIENCES↗

Frequency reproducibility of solid-state thorium-229 nuclear clocks

Solid-state thorium-229 ( 229 Th) nuclear clocks are set to provide new opportunities for precision metrology and fundamental physics. Taking advantage of inherent low sensitivity of a nuclear transition to its environment, orders of magnitude more emitters can be hosted in a solid-state crystal compared with current optical lattice atomic clocks. Furthermore, solid-state systems needing only simple thermal control are key to the development of field-deployable compact clocks. Here we explore and characterize the frequency reproducibility of the 229 Th:CaF 2 nuclear clock transition, a key performance metric for all clocks. We measure the transition linewidth and centre frequency as a function of the doping concentration, temperature and time. We report the concentration-dependent inhomogeneous linewidth of the nuclear transition, limited by the intrinsic host crystal properties. We determine an optimal working temperature for the 229 Th:CaF 2 nuclear clock at 196(5) K, at which the first-order thermal sensitivity vanishes. This would enable in situ temperature co-sensing using different quadrupole-split lines, reducing the temperature-induced systematic shift below the 10 −18 fractional frequency uncertainty level. At 195 K, the reproducibility of the nuclear transition frequency is 220 Hz (fractionally 1.1 × 10 −13 ) for two differently doped 229 Th:CaF 2 crystals over 7 months. Furthermore, these results form the foundation for understanding, controlling and harnessing the coherent nuclear excitation of 229 Th in solid-state hosts and for their applications in constraining temporal variations of fundamental constants.

Atomic and molecular physics↗

Assessing effective radiative forcing from aerosol–cloud interactions over the global ocean

How clouds respond to anthropogenic sulfate aerosols is one of the largest sources of uncertainty in the radiative forcing of climate over the industrial era. This uncertainty limits our ability to predict equilibrium climate sensitivity (ECS)—the equilibrium global warming following a doubling of atmospheric CO 2 . Here, we use satellite observations to quantify relationships between sulfate aerosols and low-level clouds while carefully controlling for meteorology. We then combine the relationships with estimates of the change in sulfate concentration since about 1850 to constrain the associated radiative forcing. We estimate that the cloud-mediated radiative forcing from anthropogenic sulfate aerosols is − 1.11 ± 0.43 W m −2 over the global ocean (95% confidence). This constraint implies that ECS is likely between 2.9 and 4.5 K (66% confidence). Our results indicate that aerosol forcing is less uncertain and ECS is probably larger than the ranges proposed by recent climate assessments.

54 ENVIRONMENTAL SCIENCES↗

Bayesian Exploration and Surrogate Emulation of Nonlinear Beam-Response Geometry in the LBNF Beamline

Next-generation long-baseline neutrino experiments aim to achieve multi-MW proton beam power while reducing accelerator-induced systematic uncertainties. At Fermilab, the LBNF beamline is designed for 1.2 MW operation with PIP-II and is upgradeable to 2.4 MW. DUNE will probe the three-flavor neutrino paradigm and search for CP violation, requiring precise neutrino-flux normalization and improved control of accelerator-related uncertainties. Within the LBNF beamline, the System for On-Axis Neutrino Detection (SAND) will constrain flux uncertainties using precision near-detector measurements, while the Muon Monitor System (MuMS) will provide beamline diagnostics sensitive to the proton beam, target, and horn configuration. However, the pion phase space relevant for DUNE depends simultaneously on many correlated parameters, including beam centroid, beam width, horn current and alignment, target position, optics shifts, and radiation-induced changes. Consequently, MuMS observables exhibit nonlinear and coupled responses that are difficult to characterize using traditional one-parameter scans. To address this challenge, we are developing a Bayesian Exploration framework coupled to physics-informed surrogate emulators trained on Geant4 beamline simulations. Gaussian-process emulators provide both fast predictions and uncertainty estimates, enabling adaptive selection of new simulation points in beam-parameter space. As an initial demonstration, we construct surrogate emulators for MuMS response observables using a verified simulation campaign spanning proton-beam steering conditions. The emulators reproduce the simulated dependence of MuMS centroid and gradient observables while providing predictive uncertainties, and serve as the foundation for future multidimensional exploration including beam width, horn current, and additional beamline parameters. This work establishes a framework for uncertainty-aware beam monitoring, adaptive simulation campaigns, and rapid beam-response inference for future DUNE operations.

Ganguly, Sudeshna [Fermilab] (ORCID:00000003163482↗