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At least 469 records · Page 26

A Unified Interpretation of Variability in Precipitation Isotope Ratios

Abstract Several mechanisms have been proposed to explain why the isotope ratios of precipitation vary in space and time and why they correlate with other climate variables like temperature and precipitation. Here, we argue that this behavior is best understood through the lens of radiative transfer, which treats the depletion of atmospheric vapor transport by precipitation as analogous to the attenuation of light by absorption or scattering. Building on earlier work by Siler et al., we introduce a simple model that uses the equations of radiative transfer to approximate the two-dimensional pattern of the oxygen isotope composition of precipitation ( δ p ) from monthly mean hydrologic variables. The model accurately simulates the spatial and seasonal variability in δ p within a state-of-the-art climate model and permits a simple decomposition of δ p variability into contributions from gradients in evaporation and the length scale of vapor transport. Outside the tropics, δ p is mostly controlled by gradients in evaporation, whose dependence on temperature explains the positive correlation between δ p and temperature (i.e., the temperature effect). At low latitudes, δ p is mostly controlled by gradients in the transport length scale, whose inverse relationship with precipitation explains the negative correlation between δ p and precipitation (i.e., the amount effect). This suggests that the temperature and amount effects are both mostly explained by the variability in upstream rainout, but they reflect distinct mechanisms governing rainout at different latitudes. Significance Statement The isotopic composition of precipitation has long been used to make inferences about past climates based on its observed relationship with precipitation in the tropics and with temperature at higher latitudes. These relationships—known as the “amount effect” and “temperature effect,” respectively—have been attributed to many different mechanisms, most of which are thought to operate at either high or low latitudes but not both. Here, we present a unified framework for interpreting the isotope variability that can explain the latitude dependence of the temperature and amount effects despite making no distinction between high and low latitudes. Although our results are generally consistent with certain interpretations of the amount effect, they suggest that the temperature effect is widely misunderstood.

54 ENVIRONMENTAL SCIENCES↗

Predicting the heat release variability of Li-ion cells under thermal runaway with few or no calorimetry data

Accurate measurement of the variability of thermal runaway behavior of lithium-ion cells is critical for designing safe battery systems. However, experimentally determining such variability is challenging, expensive, and time-consuming. Here, we utilize a transfer learning approach to accurately estimate the variability of heat output during thermal runaway using only ejected mass measurements and cell metadata, leveraging 139 calorimetry measurements on commercial lithium-ion cells available from the open-access Battery Failure Databank. We show that the distribution of heat output, including outliers, can be predicted accurately and with high confidence for new cell types using just 0 to 5 calorimetry measurements by leveraging behaviors learned from the Battery Failure Databank. Fractional heat ejection from the positive vent, cell body, and negative vent are also accurately predicted. We demonstrate that by using low cost and fast measurements, we can predict the variability in thermal behaviors of cells, thus accelerating critical safety characterization efforts.

25 ENERGY STORAGE↗

Stragglers of the thick disc

Young alpha-rich (YAR) stars have been detected in the past as outliers to the local age - [α/Fe] relation. These objects are enhanced in α-elements, but they are apparently younger than typical thick disc stars. Here, we study the global kinematics and chemical properties of YAR giant stars in the APOGEE DR17 survey and show that they have properties similar to those of the standard thick disc stellar population. This leads us to conclude that YAR are rejuvenated thick disc objects, and the most likely explanation is that they are evolved blue stragglers. This is confirmed by their position in the Hertzsprung–Russel diagram (HRD). Extending our selection to dwarfs allowed us to obtain the first general straggler distribution in an HRD of field stars. We also compared the elemental abundances of our sample with those of standard thick disc stars and found that our YAR stars are shifted in oxygen, magnesium, sodium, and the slow neutron-capture element cerium. Although we detected no sign of binarity for most objects, the enhancement in cerium may be a signature of a mass transfer from an asymptotic giant branch companion. The most massive YAR stars suggest that mass transfer from an evolved star may not be the only plausible formation pathway and that other scenarios, such as collision or coalescence, should be considered.

79 ASTRONOMY AND ASTROPHYSICS↗

Investigating biomass composition and size effects on fast pyrolysis using global sensitivity analysis and CFD simulations

It is notoriously difficult to build an accurate universal model for biomass pyrolysis due to its sensitivity to a wide number of critical material attributes such as chemical species and physical sizes. In this work, a biomass pyrolysis kinetics with 32 heterogeneous reactions and 59 species was implemented in an open-source multiphase computational fluid dynamics (CFD) software MFiX and validated against two different experimental pyrolysis data sets that provided detailed data describing chemical component yields. The reaction scheme was then used to build a surrogate model and assess the sensitivity of pyrolysis yields to feedstock compositions. The sensitivity analysis determined that the yield of bio-char showed a strong positive sensitivity to the carbon-rich lignin and tannin pseudo-species in the reaction scheme while the bio-oil and bio-gas were correlated to oxygen-rich lignin pseudo-species. The reaction scheme was then integrated into a coarse-grained discrete element model to simulate fast pyrolysis in a bubbling fluidized bed over a range of feedstock particle sizes. The reactor simulations showed further sensitivity to particle size and hydrodynamics. Notably, particles under 0.5 mm have small heat transfer limitations but left the reactor before completely converting and thus reduced the bio-oil yield. Results from this study can be used to guide future development of highly accurate models for fast pyrolysis reactors with a variety of feedstock properties and operating conditions.

09 BIOMASS FUELS↗

Real-Space Quantification of Exciton Localization in Acene Crystals Using Wannier Function Decomposition

Here, we introduce the Wannier function decomposition of excitons (WFDX) method to quantify exciton localization in solids within the ab initio Bethe-Salpeter equation framework. By decomposing each Bloch exciton wave function into products of single-particle electron and hole maximally localized Wannier functions, this real-space approach provides well-defined orbital- and spatial-resolved measures of both Frenkel and charge-transfer excitons at low computational cost. We apply WFDX to excitons in acene crystals, quantifying how the number of rings, the exciton spin state, and the center-of-mass momentum affect spatial localization. Additionally, we show how this real-space representation reflects structural nonsymmorphic symmetries that are hidden in standard reciprocal-space descriptions. We demonstrate how the WFDX framework can be used to efficiently interpolate exciton expansion coefficients in reciprocal-space and outline how it may facilitate evaluation of observables involving position operators, highlighting its potential as a general tool for both analyzing and computing excitonic properties in solids.

Tao, Zui [University of California, Berkeley, CA (↗

Modulating physicochemical interfaces enables li-rich oxides based ceramic solid-state li batteries under ambient conditions

Li-rich layered oxides exhibit promising potential applications in high-energy-density solid-state lithium metal batteries. Nevertheless, the strong oxidative oxygen species generate at high voltage, which poses great challenges to positive electrode-side interface stability. Herein, a robust in-situ polymerization gel polymer electrolyte with bifunctional additives is designed for interface modification. These additives, include lithium difluoro(oxalate) borate and LiPO 2 F 2 , regulate the Li + chemical environment in gel polymer electrolyte to enhance crosslink density without residual oligomer, which reduce gas generation and suppress contact loss, thus avoiding interfacial impedance divergence. Concurrently, the designed gel polymer electrolyte enables a wide electrochemical stability window (up to 4.7 V) and a high Li + transference number (0.82). Additionally, the additives induced F- and B-rich inorganic cathode-electrolyte interphase inhibits side reactions and oxygen/transition metal loss effectively, stabilizing the chemical interface. The as-constructed Li-rich layered oxides-based ceramic solid-state lithium metal batteries with gel polymer electrolyte interface modification exert a high discharge capacity of 276.5 mAh g -1 at 30 °C without external pressure, delivering a retention of 81.7% after 100 cycles at 25 mA g -1 during 2.0-4.7 V. This work provides a guideline for developing high-voltage solid-state lithium metal batteries via interfacial design.

Hu, Xinchao [Xiamen University (China)]↗

FY2024 Mid-Year Report: Verification of Spent Fuel Inside Dry Storage Casks by Cask Top Fast Neutron Mapping

This project is developing a prototype scanner array verification system for detection of missing fuel assemblies in spent-fuel storage casks. The prototype consists of six fast-neutron scintillator detectors mounted to a linear actuator frame that is placed on the top of a spent fuel cask to scan across all fuel assembly positions. The scanner array was assembled and tested at LLNL in prior years. A field test schedule has been requested at the Idaho National Laboratory (INL) Cask Farm site for FY2024. Following the Field Test, we will present results and discuss the technology with the IAEA. The IAEA may have special requirements for portability, shipping, lifting, and installation. We will incorporate additional improvements to the system based on lessons learned from the Field Test and feedback from the IAEA. If successful, the technology can be transferred to the IAEA or other stakeholders for assessment.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Automated characterization of spatial and dynamical heterogeneity in supercooled liquids via implementation of machine learning

Abstract A computational approach by an implementation of the principle component analysis (PCA) with K -means and Gaussian mixture (GM) clustering methods from machine learning algorithms to identify structural and dynamical heterogeneities of supercooled liquids is developed. In this method, a collection of the average weighted coordination numbers ( W C N s ‾ ) of particles calculated from particles’ positions are used as an order parameter to build a low-dimensional representation of feature (structural) space for K -means clustering to sort the particles in the system into few meso-states using PCA. Nano-domains or aggregated clusters are also formed in configurational (real) space from a direct mapping using associated meso-states’ particle identities with some misclassified interfacial particles. These classification uncertainties can be improved by a co-learning strategy which utilizes the probabilistic GM clustering and the information transfer between the structural space and configurational space iteratively until convergence. A final classification of meso-states in structural space and domains in configurational space are stable over long times and measured to have dynamical heterogeneities. Armed with such a classification protocol, various studies over the thermodynamic and dynamical properties of these domains indicate that the observed heterogeneity is the result of liquid–liquid phase separation after quenching to a supercooled state.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Initial use of Nek5000/Cardinal to improve closure models in Pronghorn

Heat transfer coefficient closure models for pebble bed reactors are built using a data-driven approach by leveraging the capabilities of an Evolutionary Algorithm entitled Particle Swarm Optimization (PSO). In the present work, the Computational Fluid Dynamics code nekRS was used in order to collect the high-fidelity flow data for a core with 1,568 pebbles. To characterize the heat transfer, multiple concentric regions were considered to extract the physical quantities of interest, e.g./ the Reynolds number. The PSO algorithm is employed as part of an inverse problem targeting determine what are the coefficients for a Nusselt number correlation to match the collected data. Such correlation should follow any given format that is defined a priori. Finally, two correlations are proposed, one with an implicit dependence on the pebbles’ wall temperatures and another expressed as a fully explicit correlation depending on the flow conditions and the position within the core. Anyway, given the generic nature of the proposed approach, correlations following different formats could be tested. Preliminary results for the high-fidelity simulation of a fast MSR core are presented. The target Reynolds number is currently 20K, with the expectation that this will increase, pending the availability of further computational resources. These simulations will be used to inform lower fidelity models, including a coarse CFD turbulence model in Pronghorn. Additionally, they will serve as a reference for the RANS models in Nek5000/NekRS.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

ORBIT CORRECTION STUDIES ON THE ELECTRON TRANSPORT LINE FROM RCS TO ESR

A dedicated electron transfer line from Rapid Cycling Synchrotron (RCS) to Electron Storage Ring (ESR), referred to as the RTE line has been designed for the Electron-Ion Collider (EIC). The beamline follows a straight-line geometry, with a length of 133 m, and is consists with two matching sections and a FODO section for beam diagnostics. Imperfections with magnet alignments introduce orbit distortions, making orbit correction scheme a critical component in the design. To facilitate orbit correction, each quadrupole magnet is equipped with a pair of beam position monitors (BPMs) and kickers. The Singular Value Decomposition (SVD) algorithm is used for orbit correction and tolerance studies. This paper presents the ongoing progress in the optics design and error correction scheme of the RTE line.

Neththikumara, I. [Thomas Jefferson National Accel↗

A Simple, Revolutionary Approach to Waste Packaging Utilizing Proven Technology - 20201

Historically, removing hazardous waste from gloveboxes involves the use of bags as the primary containment method. This method can prove tedious, repetitive, and time consuming to ensure the process follows all safeguards required to contain the waste and mitigate any breach of containment. Layers of bags, yards of tape, and multiple filters are added to the waste stream in order to transfer the hazardous waste from the glovebox safely into the drum package. Then, finally, it can be shipped and disposed of. The process to cut, tie, and tape each bag for disposal involves manual effort by multiple operators. Following Administrative Safety Controls, good operators are able to safely perform those tasks; but, since the bag is the only confinement layer, incidents can occur. Operators, in some cases, are also at close proximity to this waste which may increase the risk of radiation exposure. Once the waste is transferred out through these bags, it is nearly impossible to remove packaged waste that may contain higher dosage levels, thus increasing drum disposal costs incurred by the facility. Exceeding the allowable radiation levels, and drums not fully filled, both contribute significantly to excess disposal costs. Central Research Laboratories (CRL), based in Red Wing Minnesota, has developed the Waste Drum Transfer System (WDTS) building upon the proven technology and containment of the Rapid Transfer Port (RTP) as an alternate, more efficient method of waste transfer. This solution consists of an RTP Alpha port mounted inside a glovebox and Beta assembly unit composed of a drum liner fitted inside a standard 55 gallon drum. The use of the Beta drum liner bypasses the typical use of bags, sleeves or tape to provide leak tight containment. The process to connect and disconnect a drum from the glovebox is achieved by the self-docking and rotating system controls of the RTP Alpha, all done with only one operator standing in an upright ergonomic position. This system also allows for greater flexibility in available Beta connection options, expanding the overall functionality of the system. This system can be disconnected and reconnected multiple times to maximize volume containment. This will minimize drum disposal costs and reduce the overall volume of waste output by more efficiently filling the drums. Radiation levels inside each drum can be monitored and adjusted more efficiently by operators utilizing the reconnect option. Minimal As Low As Reasonably Achievable (ALARA) levels are also achievable with this system. This paper will show how highly efficient packaging and disposal of hazardous waste can be accomplished in a cost-effective manner utilizing the proven RTP technology. Maximized operator productivity and safety, as well as minimized radiation dose exposure, are all attainable through the system's engineered controls. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Probing basal planes and edge sites in polygranular nuclear graphite by gas adsorption: Estimation of active surface area

Polygranular nuclear graphite, manufactured at 2800–3000 °C from a carbonized filler and binder mix, has high graphitization degree, crystalline structure close to perfect graphite, and about 20% porosity. The pore surfaces expose large regions of rough, defective prismatic edges of graphite crystallites which are the locus of graphite materials surface sites active for oxidation, chemisorption, and electron transfer. However, we show that high-resolution N 2 and Kr first monolayer adsorption on polygranular graphite (P/P 0 < 0.015) occurs in many ways like adsorption on graphitized carbon blacks. This proves the presence of energetically homogeneous basal planes domains in graphite porosity, which was not fully acknowledged before. Using classical analysis methods (Langmuir, Hill-de Boer, adsorption potential distribution) we quantity the basal plane area (BPA) of several polygranular graphite types and correlate it with their microstructure. Finally, we propose that gas adsorption is uniquely positioned to reliably estimate the active surface area of graphite by subtracting BPA from the BET total surface area. Direct estimation based on adsorption is preferable to indirect calculations based on microstructural information.

36 MATERIALS SCIENCE↗

Searching for correlations between vibrational spectral features and structural parameters of silicate glass network

Infrared (IR) and Raman spectroscopic features of silicate glasses are usually interpreted based on the analogy with those of smaller molecules, molecular clusters, or crystalline counterparts; this study tests the accuracy and validity of these widely cited peak assignment schemes by comparing vibrational spectral features with bond parameters of the glass network created by molecular dynamics (MD) simulations. A series of sodium silicate glasses with compositions of [Na 2 O] x [Al 2 O 3 ] 2 [SiO 2 ] 98- x with x = 7, 12, 17, and 22 were synthesized and analyzed with IR and Raman. A silica glass substrate and a crystalline quartz were also analyzed for comparison. Glass structures with the same compositions were generated with MD simulations using three types of potentials: fixed partial charge pairwise (Teter), partial diffuse charge potential (MGFF), and bond order-based charge transfer potential (ReaxFF). The comparison of simulated and experimental IR spectra showed that, among these three potentials tested, ReaxFF reproduces the concentration dependence of spectral features closest to the experimentally observed trend. Hence, the bond length and angle distributions as well as Si– Q n species and ring size distributions of silica and sodium silicate glasses were obtained from ReaxFF-MD simulations and further compared with the peak assignment or deconvolution schemes—which have been widely used since 1970s and 1980s—(a) correlation between the IR peak position in the Si–O stretch region (1050-1120 cm -1 ) and the Si–O–Si bond angle; (b) deconvolution of the Raman bands in the Si–O stretch region with the Q n speciation; and (c) assignment of the Raman bands in the 420-600 cm -1 region to the bending modes of (SiO) n rings with different sizes (typically, n = 3-6). The comparisons showed that none of these widely used methods is congruent with the bond parameters or structures of silicate glass networks produced via ReaxFF-MD simulations. This result invokes that the adequacy of these spectral interpretation methods must be questioned. Alternative interpretations are proposed, which are to be tested independently in future studies.

36 MATERIALS SCIENCE↗

Reductive chemistry of pyrrolic macrocycles: A PCET dichotomy between metal and ligand

Proton-coupled electron transfer (PCET) is central to the reactivity of porphyrins. The coupling of the electron to the proton is central to a porphyrin’s ability to catalyze energy conversion reactions of which the hydrogen evolution reaction (HER) is exemplary. To understand the mechanistic details of the PCET chemistry of porphyrins and related macrocyclic congeners, we have designed hangman constructs that allow a proton, placed in the secondary coordination sphere (off of the hangman backbone), to be coupled to redox transformations at the macrocycle. For metals whose reduction potentials are positive of the porphyrin macrocycle, such as Co and Fe, HER catalysis is confined to PCET transformations of the metal center where the active catalyst for HER is a reduced metal hydride. Alternatively, the reduction potentials of Ni, Zn, and 2H (freebase) porphyrins allow for redox non-innocence of the macrocycle; here the active “hydridic” catalyst is a phlorin, which gives rise to elaborate HER reaction sequences. Beyond HER catalysis, redox non-innocence of Ni, Zn, and 2H porphyrins and related compounds has been informative for providing detailed mechanistic insight into the multi-site PCET hydrogenation of olefinic bonds of the macrocycle. This mini-review unravels the PCET dichotomy between the metal and macrocycle in promoting HER catalysis and novel chemical transformations that give rise to unusual macrocyclic structures.

Chemistry↗

Selective cysteine-to-selenocysteine changes in a [NiFe]-hydrogenase confirm a special position for catalysis and oxygen tolerance

Significance Substitution of cysteine by selenocysteine is held responsible for the increased performance of many enzymes: The higher activity of [NiFeSe]-hydrogenases compared with their [NiFe] counterparts is often attributed to the Sec replacement of one active-site cysteine ligand. Replacing each of the four active-site cysteine residues in an O 2 -tolerant [NiFe]-hydrogenase by selenocysteine shows that this substitution alone does not overcome the inability to evolve H 2 that is a characteristic of the group 1d hydrogenases. A nonbridging cysteine lying on the direct path between the Ni and an adjacent proton-relaying glutamic acid emerges as being very special: Its substitution by selenocysteine confers extreme tolerance to O 2 but disrupts the proton transfer pathway, providing an example of where sulfur is superior to selenium.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evaluation of satellite Leaf Area Index in California vineyards for improving water use estimation

Remote sensing estimation of evapotranspiration (ET) directly quantifies plant water consumption and provides essential information for irrigation scheduling, which is a pressing need for California vineyards as extreme droughts become more frequent. Many ET models take satellite-derived Leaf Area Index (LAI) as a major input, but how uncertainties of LAI estimations propagate to ET and the partitioning between evaporation and transpiration is poorly understood. Here we assessed six satellite-based LAI estimation approaches using Landsat and Sentinel-2 images against ground measurements from four vineyards in California and evaluated ET sensitivity to LAI in the thermal-based two-source energy balance (TSEB) model. We found that radiative transfer modeling-based approaches predicted low to medium LAI well, but they significantly underestimated high LAI in highly clumped vine canopies (RMSE ~ 0.97 to 1.27). Cubist regression models trained with ground LAI measurements from all vineyards achieved high accuracy (RMSE ~ 0.3 to 0.48), but these empirical models did not generalize well between sites. Red edge bands and the related vegetation index (VI) from the Sentinel-2 satellite contain complementary information of LAI to VIs based on near-infrared and red bands. TSEB ET was more sensitive to positive LAI biases than negative ones. Positive LAI errors of 50% resulted in up to 50% changes in ET, while negative biases of 50% in LAI caused less than 10% deviations in ET. However, even when ET changes were minimal, negative LAI errors of 50% led to up to a 40% reduction in modeled transpiration, as soil evaporation and plant transpiration responded to LAI change divergently. These findings call for careful consideration of satellite LAI uncertainties for ET modeling, especially for the partitioning of water loss between vine and soil or cover crop for effective vineyard irrigation management.

54 ENVIRONMENTAL SCIENCES↗

Biocatalytic control of site-selectivity and chain length-selectivity in radical amino acid halogenases

Biocatalytic C–H activation has the potential to merge enzymatic and synthetic strategies for bond formation. Fe II /αKG-dependent halogenases are particularly distinguished for their ability both to control selective C–H activation as well as to direct group transfer of a bound anion along a reaction axis separate from oxygen rebound, enabling the development of new transformations. In this context, we elucidate the basis for the selectivity of enzymes that perform selective halogenation to yield 4-Cl-lysine (BesD), 5-Cl-lysine (HalB), and 4-Cl-ornithine (HalD), allowing us to probe how site-selectivity and chain length selectivity are achieved. We now report the crystal structure of the HalB and HalD, revealing the key role of the substrate-binding lid in positioning the substrate for C 4 vs C 5 chlorination and recognition of lysine vs ornithine. Targeted engineering of the substrate-binding lid further demonstrates that these selectivities can be altered or switched, showcasing the potential to develop halogenases for biocatalytic applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

ASAS J071404+7004.3 – a close, bright nova-like cataclysmic variable with gusty winds

ABSTRACT Despite being bright (V ≃ 11.8) and nearby (d = 212 pc) ASAS J071404+7004.3 has only recently been identified as a nova-like cataclysmic variable. We present time-resolved optical spectroscopy obtained at the Isaac Newton and the Hiltner and McGraw-Hill Telescopes, together with Swift X-ray and ultraviolet observations. We combined these with TESS photometry and find a period of 3.28 h and a mass transfer rate of $4\!-\!9\times 10^{-9}\, {\mathrm{M_{\odot }\, yr}^{-1}}$. Historical photometry shows at least one low state establishing the system as a VY Scl star. Our high-cadence spectroscopy also revealed rapidly changing winds emanating from the accretion disc. We have modelled these using the Monte Carlo python code and shown that all the emission lines could emanate from the wind – which would explain the lack of double-peaked lines in such systems. In passing, we discuss the effect of variability on the position of cataclysmic variables in the Gaia Hertzsprung–Russell diagram.

Inight, K. (ORCID:0000000222002416)↗