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At least 379 records · Page 21

Gaussian Process Emulators for Volcanic Ash Dispersion Model Tephra2

It is necessary to predict volcanic ash deposition since falling ash is harmful to human activities. Because simulators built for this purpose are computationally expensive, it is popular to use statistical emulators for geophysical hazard analyses, where a large number of simulations are required. Gaussian stochastic process emulators are able to approximate expensive simulations in an accurate and efficient way. Using a relatively small number of simulation runs, a well-trained emulator can accurately predict simulation outputs at massive new input points in a few seconds. Under different explosive eruption conditions, we constructed Gaussian stochastic process emulators for Tephra2, a simulation tool for estimating the accumulation of volcanic ash over a region. Historical wind records are used as input wind data, without assuming a Gaussian wind speed profile or common wind direction among elevations. While there are several inputs for Tephra2, we use no more than three physically motivated variables as emulator inputs to reduce the computational cost of emulations. The emulator outputs predict the mass of tephra per unit area at 50281 grid points around a predetermined vent location.

58 GEOSCIENCES↗

Localized material compression to correct distortion in wire arc additive manufacturing

Wire Arc Additive Manufacturing (WAAM) is an advanced manufacturing technology which utilizes welding systems to generate three dimensional geometries in a layer-by-layer fashion. Distortion or warping of a print substrate and WAAM components due to thermally induced residual stresses is an ongoing challenge limiting the widespread adoption of WAAM technologies for producing components. In this manuscript, a novel approach is described to address thermal distortion in deposited components by applying lateral compressions along the length of the deposited material. To demonstrate this method, a series of single-track walls were printed and compressed at evenly spaced intervals using a modified hydraulic cutter tool. The jaws of the tool were modified to compress material rather than to shear it. A mathematical model was developed to relate the curvature of the deposited material to the volume of compression required to eliminate this distortion. Validation of this model was performed using 3D scan data to compare the change in wall curvature induced by compression to the volume of the applied compressions. Substrate deflection was also compared against a control wall, and implementation of wall compression reduced maximum deflections by 93% across a series of four depositions and subsequent compressions. Wall cross sections were also analyzed to determine the impact of compression on material hardness and grain structure. The results demonstrate that successively placed lateral compressions can effectively control and potentially eliminate bending distortion in printed parts. This methodology can be further developed to form a robust model for correction of thermally-induced distortion in WAAM components.

Additive manufacturing↗

Machine Learning Application to Assess Occurrence and Saturations of Methane Hydrate in Marine Deposits Offshore India

Artificial Neural Networks (ANN) were used to assess methane hydrate occurrence and saturation in marine sediments offshore India. The ANN analysis classifies the gas hydrate occurrence into three types: methane hydrate in pore space, methane hydrate in fractures, or no methane hydrate. Further, predicted saturation characterizes the volume of gas hydrate with respect to the available void volume. Log data collected at six wells, which were drilled during the India National Gas Hydrate Program Expedition 02 (NGHP-02), provided a combination of well log measurements that were used as input for machine learning (ML) models. Well log measurements included density, porosity, electrical resistivity, natural gamma radiation, and acoustic wave velocity. Combinations of well logs used in the ML models provide good overall balanced accuracy (0.79 to 0.86) for the prediction of the gas hydrate occurrence and good accuracy (0.68 to 0.92) for methane hydrate saturation prediction in the marine accumulations against reference data. The accuracy scores indicate that the ML models can successfully predict reservoir characteristics for marine methane hydrate deposits. In conclusion, the results indicate that the ML models can either augment physics-driven methods for assessing the occurrence and saturation of methane hydrate deposits or serve as an independent predictive tool for those characteristics.

58 GEOSCIENCES↗

Exploring Ecological, Morphological, and Environmental Controls on Coastal Foredune Evolution at Annual Scales Using a Process-Based Model

Coastal communities commonly rely upon foredunes as the first line of defense against sea-level rise and storms, thus requiring management guidance to optimize their protective services. Here, we use the AeoLiS model to simulate wind-driven accretion and wave-driven erosion patterns on foredunes with different morphologies and ecological properties under modern-day conditions. Additional sets of model runs mimic potential future climate changes to inform how both morphological and ecological properties may have differing contributions to net dune changes under evolving environmental forcing. This exploratory study, applied to represent the morphological, environmental, and ecological conditions of the northern Outer Banks, North Carolina, USA, finds that dunes experiencing minimal wave collision have similar net volumetric growth rates regardless of beach morphology, though the location and density of vegetation influence sediment deposition patterns across the dune profile. The model indicates that high-density, uniform planting strategies trap sediment close to the dune toe, whereas low-density plantings may allow for accretion across a broader extent of the dune face. The initial beach and dune shape generally plays a larger role in annual-scale dune evolution than vegetation cover. For steeper beach slopes and/or low dune toe elevations, the model generally predicts wave-driven dune erosion at the annual scale.

Environmental Sciences & Ecology↗

Methodologies for Design, Characterization and Testing of Electrolytes that Enable Extreme Fast Charging of Lithium-ion Cells

Selection, testing and validation of electrolyte candidates for Li-ion cells are discussed, based on a 10-minute target for extreme fast charge (XFC). A combination of modeling and laboratory measurements create a timely and synergistic approach to identifying candidate electrolyte formulations. Multi-solvent systems provide a balanced set of properties, wherein lower molecular-weight solvents offer reduced viscosity, increased species diffusivity, and mitigation of concentration polarization at high charge rates. Carefully selected formulations can exhibit peak conductivity and usable conductivity range of two to three times that of the baseline EC-EMC (3:7, wt.) + LiPF 6 . Candidates are also chosen based on stability and longevity within the cell environment. Lab testing coincides with property predictions from the Advanced Electrolyte Model (AEM) and a macro-scale cell model. Furthermore, cell testing utilized coin and pouch cells having NMC532 or NMC811 cathodes with graphite electrodes. Results indicate combinations of low-molecular weight solvents are key for fast-charge electrolytes as they extend the useful conductivity range to both low and higher salt concentrations, and possess higher self-diffusivities compared to conventional solvents. This reduces impacts from concentration polarization. The choice of electrolyte also influences the tendency for lithium metal deposition at the anode, as showcased by experimental and modeling results herein.

25 ENERGY STORAGE↗

Sulfur isotopes from the Paleoproterozoic Francevillian Basin record multigenerational pyrite formation, not depositional conditions

Bulk-rock sulfur isotope data from pyrite in the ~2.1 billion-year sedimentary rocks of the Francevillian Basin, Gabon, have underpinned ideas about initial oxygenation of Earth’s surface environments and eukaryote evolution. In this paper, we show, using micro-scale analytical methods, that the bulk sulfur isotope record represents progressive diagenetic modification. Our findings indicate no significant change in microbial sulfur cycling processes and seawater sulfate composition throughout that initial phase of atmosphere-ocean oxygenation of Paleoproterozoic time. This offers an alternative view of Earth system evolution during the transition from an anoxic to an oxic state and highlights the need for a judicious reappraisal of conceptual models using sulfur isotope data as primary depositional signals linked to global-scale biogeochemical processes.

58 GEOSCIENCES↗

New Approach Methodology for Assessing Inhalation Risks of a Contact Respiratory Cytotoxicant: Computational Fluid Dynamics-Based Aerosol Dosimetry Modeling for Cross-Species and In Vitro Comparisons

Regulatory agencies are considering alternative approaches to assessing inhalation toxicity that utilizes in vitro studies with human cells and in silico modeling in lieu of additional animal studies. In support of this goal, computational fluid-particle dynamics models were developed to estimate site-specific deposition of inhaled aerosols containing the fungicide, chlorothalonil, in the rat and human for comparisons to prior rat inhalation studies and new human in vitro studies. Under bioassay conditions, the deposition was predicted to be greatest at the front of the rat nose followed by the anterior transitional epithelium and larynx corresponding to regions most sensitive to local contact irritation and cytotoxicity. For humans, simulations of aerosol deposition covering potential occupational or residential exposures (1–50 µm diameter) were conducted using nasal and oral breathing. Aerosols in the 1–5 µm range readily penetrated the deep region of the human lung following both oral and nasal breathing. Under actual use conditions (aerosol formulations >10 µm), the majority of deposited doses were in the upper conducting airways. Beyond the nose or mouth, the greatest deposition in the pharynx, larynx, trachea, and bronchi was predicted for aerosols in the 10–20 µm size range. Only small amounts of aerosols >20 µm penetrated past the pharyngeal region. Using the ICRP clearance model, local retained tissue dose metrics including maximal concentrations and areas under the curve were calculated for each airway region following repeated occupational exposures. These results are directly comparable with benchmark doses from in vitro toxicity studies in human cells leading to estimated human equivalent concentrations that reduce the reliance on animals for risk assessments.

63 RADIATION, THERMAL, AND OTHER ENVIRON. POLLUTAN↗

A cleaner snow future mitigates Northern Hemisphere snowpack loss from warming

Abstract Light-absorbing particles (LAP) deposited on seasonal snowpack can result in snow darkening, earlier snowmelt, and regional climate change. However, their future evolution and contributions to snowpack change relative to global warming remain unclear. Here, using Earth System Model simulations, we project significantly reduced black carbon deposition by 2081-2100, which reduces the December-May average LAP-induced radiative forcing in snow over the Northern Hemisphere from 1.3 Wm −2 during 1995-2014 to 0.65 (SSP126) and 0.49 (SSP585) Wm −2 . We quantify separately the contributions of climate change and LAP evolution on future snowpack and demonstrate that projected LAP changes in snow over the Tibetan Plateau will alleviate future snowpack loss due to climate change by 52.1 ± 8.0% and 8.0 ± 1.1% at the end of the century for the two scenarios, mainly due to reduced black carbon contamination. Our findings highlight a cleaner snow future and its benefits for future water supply from snowmelt especially under the sustainable development pathway of SSP126.

54 ENVIRONMENTAL SCIENCES↗

Deconvolution of Water-Splitting on the Triple-Conducting Ruddlesden–Popper-Phase Anode for Protonic Ceramic Electrolysis Cells

Triple-conducting materials have been proved to improve the performance of popular protonic ceramic electrolysis cells. However, partially because of the complexity of the water splitting reaction involving three charge carriers, that is, oxygen (O 2– ), proton (H + ), and electron (e – ), the triple-conducting reaction mechanism was not clear, and the reaction conducting pathways have seldom been addressed. In this study, the triple conducting Ruddlesden–Popper phase Pr 1.75 Ba 0.25 NiO 4+δ as an anode on the BaCe 0.7 Zr 0.1 Y 0.1 Yb 0.1 O 3–δ electrolyte was fabricated and its electroresponses were characterized by electrochemical impedance spectroscopy with various atmospheres and temperatures. The impedance spectra are deconvoluted by means of the distribution of the relaxation time method. The surface exchange rate and chemical diffusivity of H + and O 2– are characterized by electrical conductivity relaxation. The physical locations of electrochemical processes are also identified by atomic layer deposition with a surface inhibitor. A microkinetics model is proposed toward conductivities, triple-conducting pathways, reactant dependency, surface exchange and bulk diffusion capabilities, and other relevant properties. Lastly, the rate-limiting steps and suggestions for further improvement of electrode performance are presented.

25 ENERGY STORAGE↗

Electrode roughness dependent electrodeposition of sodium at the nanoscale

Na metal is an attractive anode material for rechargeable Na ion batteries, however, the dendritic growth of Na can cause serious safety issues. Along with modifications of solid-electrolyte interphase (SEI), engineering the electrode has been reported to be effective in suppressing Na dendritic growth, likely by reducing localized current density accumulation. However, fundamental understanding of Na growth at the nanoscale is still limited. Here, we report an in-situ study of Na electrodeposition in electrochemical liquid cells with the electrodes in different surface roughness, e.g., flat or sharp curvature. Real time observation using transmission electron microscopy (TEM) reveals the Na electrodeposition with remarkable details. Relatively large Na grains (in the micrometer scale) are achieved on the flat electrode surface. The local SEI thickness variations impact the growth rate, thus the morphology of individual grains. In contrast, small Na grains (in tens of nanometers) grow explosively on the electrode at the point with sharp curvature. The newly formed Na grains preferentially deposit at the base of existing grains close to the electrode. Further studies using continuum-based computational modeling suggest that the growth mode of an alkali metal (e.g. Na) is strongly influenced by the transport properties of SEI. Our direct observation of Na deposition in combination with the theoretical modeling provides insights for comprehensive understanding of electrode roughness and SEI effects on Na electrochemical deposition.

25 ENERGY STORAGE↗

Computational Fluid Dynamic Modeling of Dry Cask Simulator with Crosswind

The purpose of this study is to create a STAR-CCM+ model of a Belowground Vertical Dry Cask Simulator (BVDCS) at Sandia National Laboratories (SNL) and validate the model with SNL’s experimental results. The BVDCS consists of a single boiling water reactor assembly fitted with electric heaters encompassed by a containment vessel and shell to represent a belowground spent nuclear fuel (SNF) dry storage system. Blowers are located near the inlet and outlet of the BVDCS to simulate crosswind conditions. In addition to the experimental results, the STAR-CCM+ model developed for this study is compared with a previous computational fluid dynamics (CFD) model in a different software program, which is used as a software-to-software benchmark. The experimental results provide a dataset to compare the STAR-CCM+ model results for a variety of different conditions. The main objective is to validate and improve STAR-CCM+ CFD models for spent nuclear fuel storage systems with explicitly modeled external environments and “wind driven” crossflows. These CFD models aide in the study of external particle deposition in spent nuclear fuel storage systems, which is important to predicting the significance of chloride induced stress corrosion cracking (CISCC). In addition to experimental comparison, a sensitivity analysis study is performed using the STAR-CCM+ model. The sensitivity analysis provides a quantitative assessment of the sensitivity of various parameters. This helps provide information on various parameters that are of particular importance to constructing a model representative of real life systems. The STAR-CCM+ model compared well to the experimental results showing similar responses to changes in cross wind flow, and a number of parameters are identified for model improvement.

Jensen, Ben J.↗

A DFT-based kinetic Monte Carlo simulation of multiphase oxide-metal thin film growth

Functional thin films of nanoscale metal pillars in oxide or nitride matrices known as vertically aligned nanocomposite (VAN) have gained much interest owing to their unique strain-coupled and highly anisotropic properties. So far, the deposition of these films has been explored mostly experimentally. In this work, a density functional theory (DFT)-based kinetic Monte Carlo simulation model using Bortz–Kalos–Lebowitz algorithm was developed to understand the growth of VAN films deposited by pulsed laser technique on mismatching substrates. The model has been parameterized and applied to understand the kinetics of growth thin films consisting of Au pillars in CeO2 matrix deposited on SrTiO3 substrates. The effects of pulsed laser deposition (PLD) conditions including the pulse frequency, deposition flux, and substrate temperature were explored. The simulations indicate that the Au pillar size and shape exhibit significant dependence on the PLD conditions. Namely, increasing the temperature increases the average pillar size and lowers the pillar density, and vice versa. In addition, the simulations revealed that increasing the deposition rate results in lowering the average pillar size and increasing the density. Particularly, the DFT results suggest that Au pillar size can be tuned during the initial growth of the first monolayer due to the significantly low activation barrier. Our analysis showed that the relationship between the average pillar size and pillar density is influenced by the kinetics. Furthermore, autocorrelation analysis showed that pillars self-organize in quasi-ordered patterns at certain windows of the deposition conditions, which is attributed to the complex nature of the chemical interactions in the system, the kinetics, and the deposition parameters.

Physics↗

Harmonizing tau positron emission tomography in Alzheimer's disease: The CenTauR scale and the joint propagation model

Abstract INTRODUCTION Tau‐positron emission tomography (PET) outcome data of patients with Alzheimer's disease (AD) cannot currently be meaningfully compared or combined when different tracers are used due to differences in tracer properties, instrumentation, and methods of analysis. METHODS Using head‐to‐head data from five cohorts with tau PET radiotracers designed to target tau deposition in AD, we tested a joint propagation model (JPM) to harmonize quantification (units termed “CenTauR” [CTR]). JPM is a statistical model that simultaneously models the relationships between head‐to‐head and anchor point data. JPM was compared to a linear regression approach analogous to the one used in the amyloid PET Centiloid scale. RESULTS A strong linear relationship was observed between CTR values across brain regions. Using the JPM approach, CTR estimates were similar to, but more accurate than, those derived using the linear regression approach. DISCUSSION Preliminary findings using the JPM support the development and adoption of a universal scale for tau‐PET quantification. Highlights Tested a novel joint propagation model (JPM) to harmonize quantification of tau PET. Units of common scale are termed “CenTauRs”. Tested a Centiloid‐like linear regression approach. Using five cohorts with head‐to‐head tau PET, JPM outperformed linearregressionbased approach. Strong linear relationship was observed between CenTauRs values across brain regions.

Neurosciences & Neurology↗

Process-oriented analysis of dominant sources of uncertainty in the land carbon sink

The observed global net land carbon sink is captured by current land models. All models agree that atmospheric CO 2 and nitrogen deposition driven gains in carbon stocks are partially offset by climate and land-use and land-cover change (LULCC) losses. However, there is a lack of consensus in the partitioning of the sink between vegetation and soil, where models do not even agree on the direction of change in carbon stocks over the past 60 years. This uncertainty is driven by plant productivity, allocation, and turnover response to atmospheric CO 2 (and to a smaller extent to LULCC), and the response of soil to LULCC (and to a lesser extent climate). Overall, differences in turnover explain ~70% of model spread in both vegetation and soil carbon changes. Further analysis of internal plant and soil (individual pools) cycling is needed to reduce uncertainty in the controlling processes behind the global land carbon sink.

54 ENVIRONMENTAL SCIENCES↗

Reactor scale simulations of ALD and ALE: Ideal and non-ideal self-limited processes in a cylindrical and a 300 mm wafer cross-flow reactor

Here, we have developed a simulation tool to model self-limited processes such as atomic layer deposition (ALD) and atomic layer etching inside reactors of arbitrary geometry as well the output of in situ quartz crystal microbalance and mass spectrometry. We have applied this model to two standard types of cross-flow reactors: a cylindrical tube reactor and a model 300 mm wafer reactor, and explored both ideal and nonideal self-limited kinetics. The model results are in agreement with experimental results and analytic expressions obtained using a simple plug-flow model for the cylindrical tube reactor. We also extended the simulations to consider two nonideal self-limited processes: soft-saturating processes characterized by a slow reaction pathway and processes where surface by-products can compete with the precursor for the same pool of adsorption sites. Our results show that it is possible to have a self-limited process with saturated yet inhomogeneous growth profiles due to the competition of reactor by-products. This is in agreement with experimental observations for titanium dioxide ALD from titanium tetraisopropoxide and titanium tetrachloride precursors.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Temporal deposition of copper and zinc in the sediments of metal removal constructed wetlands

The objective of this study was to explore the effects of time, seasons, and total carbon (TC) on Copper (Cu) and Zinc (Zn) deposition in the surface sediments. This study was performed at the H-02 constructed wetland on the Savannah River Site (Aiken, SC, USA). Covering both warm (April-September) and cool (October-March) seasons, several sediment cores were collected twice a year from the H-02 constructed wetland cells from 2007 to 2013. Total concentrations of Cu and Zn were measured in the sediments. Concentrations of Cu and Zn (mean ± standard deviation) in the surface sediments over 7 years of operation increased from 6.0 ± 2.8 and 14.6 ± 4.5 mg kg -1 to 139.6 ± 87.7 and 279.3 ± 202.9 mg kg -1 dry weight, respectively. The linear regression model explained the behavior and the variability of Cu deposition in the sediments. On the other hand, using the generalized least squares extension with the linear regression model allowed for unequal variance and thus produced a model that explained the variance properly, and as a result, was more successful in explaining the pattern of Zn deposition. Total carbon significantly affected both Cu ( p = 0.047) and Zn ( p < 0.001). Time effect on Cu deposition was statistically significant ( p = 0.013), whereas Zn was significantly affected by the season ( p = 0.009).

54 ENVIRONMENTAL SCIENCES↗

Vapor-phase grafting of a model aminosilane compound to Al 2 O 3 , ZnO, and TiO 2 surfaces prepared by atomic layer deposition

Atomic layer deposition (ALD) is a highly versatile surface functionalization technique that can conformally coat both planar and porous substrates. Here we use ALD metal oxide layers to establish a well-defined starting surface for vapor-phase surface organic modification. Vapor-phase (3-aminopropyl)triethoxysilane (APTES) surface silanization of ALD Al 2 O 3 , ZnO and TiO 2 surfaces were studied at 100 °C, 150 °C and 200 °C. In situ quartz crystal microbalance (QCM) and Fourier-transform infrared (FTIR) spectroscopy measurements, and ex situ atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) measurements showed uniform monolayer silane formation through self-limiting APTES reaction. We observed a higher surface density of grafted APTES species following silanization at 100 °C compared to 200 °C, and we attribute this to the temperature-dependent reactivity of the surface hydroxyls and changes in the mode of APTES reaction. The FTIR and XPS measurements revealed that APTES reacts with Al 2 O 3 and ZnO exclusively through metal siloxy bond formation. However, APTES reacts with TiO 2 through both siloxy bond formation and ammonium salt formation via the amine group.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗