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At least 1,243 records · Page 69

Haze processing of atmospheric particles during wintertime in the Indo-Gangetic Plains

The impacts of haze on visibility, air quality, and climate are not well quantified due to a lack of understanding of the evolution of the mixing state and phase state of atmospheric particles during haze processing. The variability of the mixing state of atmospheric particles contributes significantly to uncertainties associated with the estimated aerosol radiative forcing. We collected particle samples in January 2018 from the highly polluted Indo-Gangetic plain during hazy conditions to study haze-processed particles. Single particle analysis using multi-modal micro-spectroscopy techniques revealed an abundance (40–70% by number) of potassium-rich sulfate particles from biomass-burning influenced smoke. Tilted view imaging showed that most of the organic particles that had inorganic potassium and sulfate inclusions were liquid-like while those without inclusions were more semi-solid. High-resolution mass spectrometry analysis revealed a significant presence of organosulfates and nitroxy-organosulfates in the morning samples (24%) compared to the afternoon samples (9%), despite higher relative humidity in the afternoon. Overall, our results highlight the significant contribution of both organic and inorganic sulfate to the total particulate sulfur budget during haze processing in winter, when anthropogenic emissions such as household burning, agricultural burning, and vehicular emissions are major contributors to particle mass.

Mathai, Susan [Pacific Northwest National Laborato↗

Engineering Scale Drying of Aluminum-Clad Spent Nuclear Fuel: Experiment Report

Engineering-scale tests were performed to evaluate the relative effectiveness of forced gas and vacuum-drying processes on aluminum-clad spent nuclear fuel (ASNF) in preparation for extended dry storage. Drying models were developed to improve confidence in the likely range of conditions at the start of dry storage and to understand the factors most significant to each process. Testing was performed at the Holtec International Forced Helium Dehydration training facility in Camden, New Jersey, by students from the University of South Carolina in collaboration with Idaho National Laboratory. A full-size Type 1a basket, with a full-diameter vessel configuration (based on the Department of Energy standardized canister design), was used in combination with a 10 assembly surrogate ASNF arrangement to provide a proxy for geometry. A resistance heater incorporated in one assembly simulated the influence of 100 W decay heat. This instrumented chamber allowed testing of the removal of bulk water, physisorbed water, and chemisorbed water over a range of operating parameters with either drying process. Thick oxide films were grown on aluminum test plates to mimic the ASNF surface chemistry. These one-use test plates were housed within select assemblies during drying. Post-test analysis of these plates gave a measure of the moisture removed during each test, which was compared to a control. Instrumentation provided detailed thermal, humidity, and gas or pressure data relevant to each test. Model simulations generally compared favorably to instrument data for the tests. While both processes were able to remove bulk water, removal of chemisorbed water was shown to depend heavily on local temperature. To the disadvantage of vacuum drying, operations approaching or exceeding 220°C achieved consistently more dehydroxylation.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Reactive transport modeling for supporting climate resilience at groundwater contamination sites

Abstract. Climate resilience is an emerging issue at contaminated sites and hazardous waste sites, since projected climate shifts (e.g., increased/decreased precipitation) and extreme events (e.g., flooding, drought) could affect ongoing remediation or closure strategies. In this study, we develop a reactive transport model (Amanzi) for radionuclides (uranium, tritium, and others) and evaluate how different scenarios under climate change will influence the contaminant plume conditions and groundwater well concentrations. We demonstrate our approach using a two-dimensional (2D) reactive transport model for the Savannah River Site F-Area, including mineral reaction and sorption processes. Different recharge scenarios are considered by perturbing the infiltration rate from the base case as well as considering cap-failure and climate projection scenarios. We also evaluate the uranium and nitrate concentration ratios between scenarios and the base case to isolate the sorption effects with changing recharge rates. The modeling results indicate that the competing effects of dilution and remobilization significantly influence pH, thus changing the sorption of uranium. At the maximum concentration on the breakthrough curve, higher aqueous uranium concentration implies that sorption is reduced with lower pH due to remobilization. To better evaluate the climate change impacts in the future, we develop the workflow to include the downscaled CMIP5 (Coupled Model Intercomparison Project) climate projection data in the reactive transport model and evaluate how residual contamination evolves through 2100 under four climate Representative Concentration Pathway (RCP) scenarios. The integration of climate modeling data and hydrogeochemistry models enables us to quantify the climate change impacts, assess which impacts need to be planned for, and therefore assist climate resiliency efforts and help guide site management.

54 ENVIRONMENTAL SCIENCES↗

Influence of zwitterionic amphiphilic copolymers on heterogeneous gypsum formation: A promising approach for scaling resistance

Here, this study aims to investigate the influence of zwitterionic amphiphilic copolymers (ZACs) in the nucleation and growth of heterogeneous CaSO4 at the zwitterion-water interface, which is crucial for the prevention of mineral scaling and consequent downtime or suboptimal performance in industries like membrane desalination, heat exchangers, and pipeline transportation. In situ grazing incidence small angle X-ray Scattering (GISAXS), and quartz crystal microbalance with dissipation (QCM-D) techniques were used to analyze the evolution of CaSO 4 particles on two new ZAC coatings: poly-(trifluoroethyl methacrylate-random-sulfobetaine methacrylate) (PTFEMA-r-SBMA, or PT:SBMA) and poly(trifluoroethyl methacrylate-random-2-methacryloyloxyethyl phosphorylcholine) (PTFEMA-r-MPC, or PT:MPC). The results showed that PT:MPC coatings promoted nucleation but inhibited crystal growth, resulting in slower overall reaction kinetics on PT:MPC coatings compared to PT:SBMA coatings. Interfacial interactions involving the substrates, sulfate minerals, and ions were examined, revealing that calcium ion adsorption, primarily governed by electrostatic attraction, played a crucial role in the nucleation and growth processes on both ZAC coatings. The crystal characterization revealed a phase transition from bassanite to gypsum on both ZAC coatings, suggesting that these zwitterionic materials can influence the mineral phase of heterogeneously formed CaSO 4 crystals. These findings enhance our understanding of the fundamental mechanisms underlying heterogeneous CaSO 4 scaling in the presence of zwitterionic materials.

42 ENGINEERING↗

Connecting suborganismal data to bioenergetic processes: killifish embryos exposed to a dioxin-like compound

A core challenge for ecological risk assessment is to integrate molecular responses into a chain of causality to organismal or population level outcomes. Bioenergetic theory may be a useful approach for integrating suborganismal responses to predict organismal level responses that influence population dynamics. In this work, we describe a novel application of Dynamic Energy Budget (DEB), theory in the context of a toxicity framework (Adverse Outcome Pathways, AOP) to make quantitative predictions of chemical exposures to individuals, starting from suborganismal data. We use early life stage exposure of Fundulus heteroclitus to dioxin-like chemicals (DLCs) and connect AOP Key Events (KEs) to DEB processes through “damage” that is produced at a rate proportional to the internal toxicant concentration. We use transcriptomic data of fish embryos exposed to DLCs to translate molecular indicators of damage into changes in DEB parameters (damage increases somatic maintenance costs) and use DEB models to predict sublethal and lethal effects of young fish. By changing a small subset of model parameters, we predict the evolved tolerance to DLCs in some wild F. heteroclitus populations, a data set not used in model parameterization. The differences in model parameters points to reduced sensitivity and altered damage repair dynamics as contributing to this evolved resistance. Our methodology has potential extrapolation to untested chemicals of ecological concern.

63 RADIATION, THERMAL, AND OTHER ENVIRON. POLLUTAN↗

A 1D–0D–3D coupled model for simulating blood flow and transport processes in breast tissue

In this work, we present mixed dimensional models for simulating blood flow and transport processes in breast tissue and the vascular tree supplying it. These processes are considered, to start from the aortic inlet to the capillaries and tissue of the breast. Large variations in biophysical properties and flow conditions exist in this system necessitating the use of different flow models for different geometries and flow regimes. In total, we consider four different model types. First, a system of 1D nonlinear hyperbolic partial differential equations (PDEs) is considered to simulate blood flow in larger arteries with highly elastic vessel walls. Second, we assign 1D linearized hyperbolic PDEs to model the smaller arteries with stiffer vessel walls. The third model type consists of ODE systems (0D models). It is used to model the arterioles and peripheral circulation. Finally, homogenized 3D porous media models are considered to simulate flow and transport in capillaries and tissue within the breast volume. Sink terms are used to account for the influence of the venous and lymphatic systems. Combining the four model types, we obtain two different 1D–0D–3D coupled models for simulating blood flow and transport processes: The first model results in a fully coupled 1D–0D–3D model covering the complete path from the aorta to the breast combining a generic arterial network with a patient specific breast network and geometry. The second model is a reduced one based on the separation of the generic and patient specific parts. The information from a calibrated fully coupled model is used as inflow condition for the patient specific sub-model allowing a significant computational cost reduction. Several numerical experiments are conducted to calibrate the generic model parameters and to demonstrate realistic flow simulations compared to existing data on blood flow in the human breast and vascular system. Moreover, we use two different breast vasculature and tissue data sets to illustrate the robustness of our reduced sub-model approach.

multiscale blood flow models↗

Numerical case study of the aerosol–cloud interactions in warm boundary layer clouds over the eastern North Atlantic with an interactive chemistry module

The presence of warm boundary layer stratiform clouds over the eastern North Atlantic (ENA) region is commonly influenced by the Azores High, especially during the summer season. To investigate comprehensive aerosol–cloud interactions, this study employs the Weather Research and Forecasting model coupled with a chemistry component (WRF-Chem), incorporating aerosol chemical components that are relevant to the formation of cloud condensation nuclei (CCN) and accounting for aerosol spatiotemporal variation. This study focuses on aerosol indirect effects, particularly the long-range transport of aerosols, in the ENA region under three different weather regimes: a ridge with a surface high-pressure system, a post-trough with a surface high-pressure system, and a weak trough. The WRF-Chem simulations conducted at a near-large-eddy scale offer valuable insights into the model's performance, especially in terms of its ability to use high spatial resolution to capture mesoscale cloud features across various weather regimes. Our result shows that introducing 5 times more aerosols to either non-precipitating or precipitating clouds significantly increases ambient CCN numbers, resulting in, to varying degrees, higher liquid water path (LWP) values. The substantial aerosol–cloud interaction especially occurs in the precipitating clouds and demonstrates the susceptibility of the LWP to changes in CCN under different regimes. Conversely, thin, non-rain clouds at the edges of a cloud system are prone to evaporation, exhibiting an aerosol drying effect. The aerosols released during this process transition back to the accumulation mode, facilitating future activation. This dynamic behavior is not adequately represented in prescribed-aerosol simulations.

54 ENVIRONMENTAL SCIENCES↗

The Influence of Mesoscale Particle Structure on the Electrode Degradation and Resultant Electrochemistry of Lithium Ion Cells With Nickel Rich Lithium Nickel Manganese Cobalt Oxide Positive Electrodes

Nickel-rich lithium nickel manganese cobalt oxide, NMC (LiNi x Mn y Co z O 2 ), materials are desirable positive electrodes in lithium ion batteries, providing high capacity and energy density. The mesoscale structure of NMC materials is commonly a polycrystalline aggregate, providing opportunity for short lithium ion transport distance of the small primary particles, yet facile material handling due to the larger secondary particles. On (de)lithiation the NMC unit cell changes volume, where the anisotropic strain can result in secondary particle fracture. This secondary particle fracture process during cycling has been associated with several degradation modes of NMC materials in LIBs. In this work, a milling process was determined whereby the secondary particles could be pre-fractured with retention of the parent primary particle crystallographic structure, crystallite size, and morphology, providing the ability to unambiguously determine the influence of NMC secondary particle size and mesostructure on resultant functional behavior. The bulk and interfacial properties and electrochemistry of as-received commercially obtained polycrystal NMC811 (LiNi 0.8 Mn 0.1 Co 0.1 O 2 , PC NMC) and its milled MPC NMC counterpart were compared. The smaller secondary particle size, higher surface area MPC NMC was found to result in 1) greater cathode tortuosity, 2) reduced surface Ni on the cycled MPC cathodes consistent with surface reconstruction, and 3) increased Ni deposition on the anodes from cathode-anode crosstalk. These factors manifested in unfavorable electrochemical behavior of MPC with lower functional capacity at both 1C and C/10 rates and higher impedance over extended moderate voltage (dis)charge cycling.

36 MATERIALS SCIENCE↗

Magnetic Field Strength Effects on Nucleosynthesis from Neutron Star Merger Outflows

Abstract Magnetohydrodynamic turbulence drives the central engine of post-merger remnants, potentially powering both a nucleosynthetically active disk wind and the relativistic jet behind a short gamma-ray burst. We explore the impact of the magnetic field on this engine by simulating three post-merger black hole accretion disks using general relativistic magnetohydrodynamics with Monte Carlo neutrino transport, in each case varying the initial magnetic field strength. We find increasing ejecta masses associated with increasing magnetic field strength. We find that a fairly robust main r -process pattern is produced in all three cases, scaled by the ejected mass. Changing the initial magnetic field strength has a considerable effect on the geometry of the outflow and hints at complex central engine dynamics influencing lanthanide outflows. We find that actinide production is especially sensitive to magnetic field strength, with the overall actinide mass fraction calculated at 1 Gyr post-merger increasing by more than a factor of 6 with a tenfold increase in magnetic field strength. This hints at a possible connection to the variability in actinide enhancements exhibited by metal-poor, r -process-enhanced stars.

79 ASTRONOMY AND ASTROPHYSICS↗

Signal Origin of Electrochemical Strain Microscopy and Link to Local Chemical Distribution in Solid State Electrolytes

Electrochemical strain microscopy (ESM) is a distinguished method to characterize Li-ion mobility in energy materials with extremely high spatial resolution. The exact origin of the cantilever deflection when the technique is applied on solid state electrolytes (SSEs) is currently discussed in the literature. Under-standing local properties and influences on ion mobility in SSEs is of utmost importance to improve such materials for next generation batteries. Here, the exact signal formation process of ESM when applied on sodium super ionic conductor (NASICON)-type SSE containing Na- and Li-ions is investigated. Changes in the dielectric properties, which are linked to the local chemical composition, are found to be responsible for the observed contrast in the deflection of the cantilever instead of a physical volume change as a result of Vegard´s Law. The cantilever response is strongly reduced in areas of high sodium content which is attributed to a reduction of the tip-sample capacitance in comparison to areas with high lithium content. This is the first time a direct link between electrostatic forces in contact mode and local chemical information is demonstrated on SSEs. Furthermore, the results open up new possibilities in information gain since dielectric proper-ties are sensitive to subtle changes in local chemical composition.

36 MATERIALS SCIENCE↗

The critical role of lignin in lignocellulosic biomass conversion and recent pretreatment strategies: A comprehensive review

Heterogeneity and rigidity of lignocellulose causing resistance to its deconstruction have provided technical and economic challenges in the current biomass conversion processes. Lignin has been considered as a crucial recalcitrance component in biomass utilization. An in-depth understanding of lignin properties and their influences on biomass conversion can provide clues to improve biomass utilization. Also, utilization of lignin can significantly increase the economic viability of biorefinery. Recent lignin-targeting pretreatments have aimed not only to overcome recalcitrance for biomass conversion but also to selectively fractionate lignin for lignin valorization. Numerous studies have been conducted in biomass characteristics and conversion technologies, and the role of lignin is critical for lignin valorization and biomass pretreatment development. In this review, we provide a comprehensive review of lignin-related biomass characteristics, the impact of lignin on the biological conversion of biomass, and recent lignin-targeting pretreatment strategies. The desired lignin properties in biorefinery and future pretreatment directions are also discussed.

09 BIOMASS FUELS↗

Cleavage at the nsp5–nsp6 site of SARS-CoV-2 main protease intermediate precursor is faster from a monomer than a dimer form

Our previous studies of severe acute respiratory syndrome coronavirus 2 main protease (MPro) precursor monomer indicate that the initial N-terminal nonstructural protein (nsp)4/nsp5 cleavage occurs intramolecularly, with a small fraction of the active site loop equilibrium being in the active state. To understand the influence of dimer formation of MPro upon N-terminal cleavage on the subsequent C-terminal nsp5/nsp6 intermolecular cleavage kinetics, the stepwise processing of a monomeric, inactive precursor containing the native terminal cleavage sites of MPro (MBP- (−6) MPro C145A(+3) -GB1-6H, 86.2 kDa) by mature WT MPro (MPro WT ) was investigated. Differential scanning fluorimetry and analytical ultracentrifugation measurements of various MPro constructs suggest that the C145A mutation decreases the dimer dissociation constant (K dimer ) by ∼26-fold, relative to WT C145 and H41A. The monomeric precursor’s nsp4–nsp5 site appears to saturate MProWT’s active sites and cleave faster, followed by a slower first-order cleavage at the C-terminal site. No detectable product resulting from the C-terminal cleavage is observed until most of the N-terminal cleavage is complete. The initial intermediate product (termed MPro C145A-IP ) is a homodimer with an estimated K dimer of <0.05 μM. In contrast, the first-order kinetics observed for the cleavage of the monomeric form of the intermediate product is at least 300 times faster than that of the dimer form. Room-temperature X-ray structure of the MPro C145A-IP –ensitrelvir complex is like that of the MPro WT –ensitrelvir complex and reveals a dynamic C-terminal region including MPro residues 302 to 306. These results are interpreted from the point of view of a mechanism in which nsp5–nsp6 cleavage may occur from a monomeric intermediate, and dimer formation restricts this cleavage.

60 APPLIED LIFE SCIENCES↗

Enhancing 2D hydrodynamic flood models through machine learning and urban drainage integration

Two-dimensional hydrodynamic flood models are commonly employed for simulating flood extent and inundation depth. However, the influence of urban drainage network (UDN) is frequently overlooked in these models, potentially compromising their accuracy. Furthermore, the expensive computational costs and longer processing times make them challenging for large-scale hydrodynamic simulation. To address these challenges, this paper develops a machine learning (ML)-driven emulator for an open-source flood model, the Two-dimensional Runoff Inundation Toolkit for Operational Needs (TRITON). A TRITON-ML Emulator (TR-Emulator) that utilizes Convolutional Long Short-Term Memory is developed to capture the spatiotemporal features of flood events based on the outputs from TRITON. We further enhance the emulator by integrating UDN parameters (TR-UDN), such as the flow capacity of drainage pipes, pipe size, and pipe length, via an ML stacking technique to improve the water surface elevation (WSE) simulation. Hurricane Harvey 2017 in Houston, TX is used as the case study. We compare WSE results from TRITON, TR-Emulator, TR-UDN, and the United States Geological Survey (USGS) observations to evaluate the performance of these models. The results indicate that the TR-Emulator effectively replicates the WSE simulated by TRITON. Additionally, TR-UDN performs well in capturing WSE patterns and peak flows, aligning more closely with USGS observations, except in areas with milder slopes where conveyance discrepancies are observed. We further test the generalizability of our ML-based models using another smaller event. This paper shows that the TR-Emulator is effective for users and engineers to emulate a 2D hydrodynamic model, and the enhanced version of the TR-Emulator, TR-UDN, can be an efficient tool for predicting WSEs during urban flooding.

54 ENVIRONMENTAL SCIENCES↗

The Complexation Properties of Self-Defensive Microgel-Modified Antimicrobial Surfaces

The complexation of cationic antimicrobials with polyanionic microgels on a biomaterial surface can render that surface self-defensive against bacteria by killing those bacteria which physically contact the antimicrobial-loaded microgels. This killing has been attributed to the contact-driven transfer of antimicrobial from a microgel to a challenging bacterium, though much remains unknown about this process. Here, in this study, we use a combination of experiments and computational modeling to identify key aspects of the complexation phenomena which influence the self-defensive properties. We synthesize poly(acrylic acid) (PAA) microgels (∼2–5 μm diameter) via membrane emulsification and electrostatically deposit them onto polycaprolactone (PCL) coupons or onto glass to form a discontinuous submonolayer. Subsequent microgel loading with colistin or with Sub5 antimicrobial peptide (AMP) causes microgel deswelling. Under physiological conditions Sub5 remains stably sequestered whereas colistin is quickly released. Coarse-grained molecular dynamics (CGMD) simulations confirm stronger Sub5/PAA complexation. CGMD calculations also indicate that Sub5 forms dimers and higher-order structures, a prediction confirmed experimentally by Small-Angle X-ray Scattering (SAXS). Supramolecular structure entropically enhances the complexation strength because of enhanced counterion release per complexation event, and this finding can help identify other antimicrobials well suited for such a nonelutive yet self-defensive strategy. CGMD simulations also show that Sub5 has a higher complexation strength with the Staphylococcus aureus membrane than it does with PAA, confirming that there is a thermodynamic driving force for antimicrobial transfer. Such self-defensive surfaces significantly reduce S. aureus colonization (over 90% reduction relative to unmodified controls) in an in vitro hematogenous contamination model and remain cyto-compatible as evidenced by mesenchymal stem cell spreading and proliferation.

36 MATERIALS SCIENCE↗

Amplifying Nanoparticle Reinforcement through Low Volume Topologically Controlled Chemical Coupling

Here, we present a streamlined method to covalently bond hydroxylated carbon nanotubes (CNOH) within a polyphenol matrix, all achieved through a direct, solvent-free process. Employing an extremely small concentration of CNOH (0.01% w/w) along with topologically contrasting linkers led to a maximum of 5-fold increase in modulus and a 25% enhancement in tensile strength compared to the unaltered matrix, an order of magnitude greater reinforcement (w/w) compared to state-of-the-art melt-processed nanocomposites. Through dynamic mechanical analysis, low field solid-state nuclear magnetic resonance spectroscopy, and molecular dynamics simulations, we uncovered the profound influence of linker’s conformational degrees of freedom on the segmental dynamics and therefore the material’s properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mapping Composition Evolution through Synthesis, Purification, and Depolymerization of Random Heteropolymers

Random heteropolymers (RHPs) consisting of three or more comonomers have been routinely used to synthesize functional materials. While increasing the monomer variety diversifies the side-chain chemistry, this substantially expands the sequence space and leads to ensemble-level sequence heterogeneity. Most studies have relied on monomer composition and simulated sequences to design RHPs, but the questions remain unanswered regarding heterogeneities within each RHP ensemble and how closely these simulated sequences reflect the experimental outcomes. Here, we quantitatively mapped out the evolution of monomer compositions in four-monomer-based RHPs throughout a design-synthesis-purification-depolymerization process. By adopting a Jaacks method, we first determined 12 reactivity ratios directly from quaternary methacrylate RAFT copolymerization experiments to account for the influences of competitive monomer addition and the reversible activation/deactivation equilibria. The reliability of in silico analysis was affirmed by a quantitative agreement (<4% difference) between the simulated RHP compositions and the experimental results. Furthermore, we mapped out the conformation distribution within each ensemble in different solvents as a function of monomer chemistry, composition, and segmental characteristics via high-throughput computation based on self-consistent field theory (SCFT). These comprehensive studies confirmed monomer composition as a viable design parameter to engineer RHP-based functional materials as long as the reactivity ratios are accurately determined and the livingness of RHP synthesis is ensured.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Atomic dynamics of electrified solid–liquid interfaces in liquid-cell TEM

Electrified solid–liquid interfaces (ESLIs) play a key role in various electrochemical processes relevant to energy, biology and geochemistry. The electron and mass transport at the electrified interfaces may result in structural modifications that markedly influence the reaction pathways. For example, electrocatalyst surface restructuring during reactions can substantially affect the catalysis mechanisms and reaction products. Despite its importance, direct probing the atomic dynamics of solid–liquid interfaces under electric biasing is challenging owing to the nature of being buried in liquid electrolytes and the limited spatial resolution of current techniques for in situ imaging through liquids. Here, with our development of advanced polymer electrochemical liquid cells for transmission electron microscopy (TEM), we are able to directly monitor the atomic dynamics of ESLIs during copper (Cu)-catalysed CO 2 electroreduction reactions (CO 2 ERs). Our observation reveals a fluctuating liquid-like amorphous interphase. It undergoes reversible crystalline–amorphous structural transformations and flows along the electrified Cu surface, thus mediating the crystalline Cu surface restructuring and mass loss through the interphase layer. Furthermore, the combination of real-time observation and theoretical calculations unveils an amorphization-mediated restructuring mechanism resulting from charge-activated surface reactions with the electrolyte. Our results open many opportunities to explore the atomic dynamics and its impact in broad systems involving ESLIs by taking advantage of the in situ imaging capability.

36 MATERIALS SCIENCE↗