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At least 775 records · Page 43

Kinetically versus thermodynamically controlled factors governing elementary pathways of GaP(111) surface oxidation

GaP and related III-V semiconductors have attracted interest as high-efficiency photoelectrochemical electrodes for solar water splitting. However, their efficacy is linked to the presence, identity, and integrity of native surface oxides, which are structurally and chemically complex and evolve during operation. Using ambient pressure X-ray photoelectron spectroscopy (APXPS) coupled with ab initio simulations, we track key chemical motifs expressed during evolution of GaP(111) surface oxides, their associated reaction kinetics, and their correlations with electronic properties. We identify two distinct thermal regimes corresponding to kinetically and thermodynamically controlled oxidation. Below 600 K, exposure to O2 generates kinetically facile Ga-O-Ga configurations, whereas higher temperatures cause activated oxygen to insert into Ga–P bonds as part of a thermodynamically driven transformation into a complex, heterogeneous 3D network of surface POx (1≤x ≤ 4) groups and Ga2O3 species, the latter of which eventually dominates upon depletion of surface phosphorus. Here our study highlights the critical competition between kinetic and thermodynamic factors during GaP oxidation, yielding insights for fabricating stable III-P-based photoelectrodes with precisely engineered surface properties.

08 HYDROGEN↗

Arctic Deployment of a Fully Integrated Self-Powered Drifting Buoy Harvesting Wave Energy via a Triboelectric Nanogenerator

The Arctic Ocean remains one of the most poorly sampled regions on Earth, where improved in situ environmental monitoring is vital for advancing oceanographic and atmospheric studies. However, data collection efforts are constrained by the short operational lifespans and high costs of conventional systems. Drifting buoys powered by pendulum-driven wave energy harvesters offer a cost-effective alternative, yet earlier designs have neither been optimized for real-world wave conditions nor validated in the Arctic. In this study, we develop a self-powered drifting buoy that integrates a pendulum-driven triboelectric nanogenerator (TENG) system with a mechanical motion rectifier, a high-gear-ratio transmission, and power management circuits. Through coupled buoy–pendulum dynamic simulations and laboratory testing using a motion simulator, we identify an optimal pendulum mass of 1.6 kg (12.7% of total buoy weight) that maximizes energy output while maintaining buoy stability. Laboratory experiments achieved average power outputs of 12.7 mW under Arctic-like wave and temperature conditions. The system was successfully deployed in the Bering Sea, where it generated 11 J of energy in 3.1 m waves, marking the first Arctic deployment of a TENG-based drifting buoy for sea surface temperature monitoring. This work establishes a cost-effective framework for designing self-powered Arctic monitoring platforms and advances the feasibility of long-term environmental observations in real Arctic waters.

marine enerby↗

Benchmark of interfacial area concentration approaches for the two-fluid model in gas-dispersed condensing flow

Accurate predictions of interfacial area concentration (IAC) are required for closure of the condensation phase change term. The interfacial area transport equation (IATE) can dynamically predict interfacial area concentration and is increasingly being used in the benchmarking of phase change flows over static based correlations which require a flow regime map. For higher flow regimes, the two-group two-fluid IATE model can separately model the transport of spherical bubbles and cap/slug bubbles. Recently, a modified formulation of the one-group and two-group two-fluid model with interfacial area transport equation was proposed for gas-dispersed condensing flows. Three datasets have been used for validation consisting of condensing two-phase flow data in the unheated section of a vertical annulus with conditions spanning a range of pressures, inlet subcoolings and mass fluxes for benchmarking the various IAC approaches. For bubbly flows, the coupled void transport - IATE simulation results in good agreement in the predictions of the void fraction and the interfacial area concentration under nearly all sixty conditions. Considering the proposed two-group two-fluid IATE model formulation, the group-2 Nusselt number correlation is investigated to account for the appropriate heat transfer length scale for group-2 bubbles. Validation of the proposed two-group two-fluid model against the new dataset shows good agreement with experimental data with significant improvement over the one-group IATE model for conditions with substantial group-2 void fraction throughout the simulation domain.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Axial H-Bonding Solvent Controls Inhomogeneous Spectral Broadening, While Peripheral H-Bonding Solvent Controls Vibronic Broadening: Cresyl Violet in Methanol

The dynamics of the nuclei of both a chromophore and its condensed-phase environment control many spectral features, including the vibronic and inhomogeneous broadening present in spectral line shapes. For the cresyl violet chromophore in methanol, we here analyze and isolate the effect of specific chromophore–solvent interactions on simulated spectral densities, reorganization energies, and linear absorption spectra. Employing both chromophore and its condensed-phase environment control many spectral features, including the vibronic and inhomogeneous broadening present in spectral line shapes. For the cresyl violet chromophore in methanol, we here analyze and isolate the effect of specific chromophore–solvent interactions on simulated spectral densities, reorganization energies, and linear absorption spectra. Employing both force field and ab initio molecular dynamics trajectories along with the inclusion of only certain solvent molecules in the excited-state calculations, we determine that the methanol molecules axial to the chromophore are responsible for the majority of inhomogeneous broadening, with a single methanol molecule that forms an axial hydrogen bond dominating the response. Furthermore, the strong peripheral hydrogen bonds do not contribute to spectral broadening, as they are very stable throughout the dynamics and do not lead to increased energy-gap fluctuations. We also find that treating the strong peripheral hydrogen bonds as molecular mechanical point charges during the molecular dynamics simulation underestimates the vibronic coupling. Including these peripheral hydrogen bonding methanol molecules in the quantum-mechanical region in a geometry optimization increases the vibronic coupling, suggesting that a more advanced treatment of these strongly interacting solvent molecules during the molecular dynamics trajectory may be necessary to capture the full vibronic spectral broadening.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nanoscopic Imaging of Self-Propelled Ultrasmall Catalytic Nanomotors

Ultrasmall nanomotors (<100 nm) are highly desirable nanomachines for their size-specific advantages over their larger counterparts in applications spanning nanomedicine, directed assembly, active sensing, and environmental remediation. While there are extensive studies on motors larger than 100 nm, the design and understanding of ultrasmall nanomotors have been scant due to the lack of high-resolution imaging of their propelled motions with orientation and shape details resolved. Here, we report the imaging of the propelled motions of catalytically powered ultrasmall nanomotors─hundreds of them─at the nanometer resolution using liquid-phase transmission electron microscopy. These nanomotors are Pt nanoparticles of asymmetric shapes (“tadpoles” and “boomerangs”), which are colloidally synthesized and observed to be fueled by the catalyzed decomposition of NaBH4 in solution. Statistical analysis of the orientation and position trajectories of fueled and unfueled motors, coupled with finite element simulation, reveals that the shape asymmetry alone is sufficient to induce local chemical concentration gradient and self-diffusiophoresis to act against random Brownian motion. Our work elucidates the colloidal design and fundamental forces involved in the motions of ultrasmall nanomotors, which hold promise as active nanomachines to perform tasks in confined environments such as drug delivery and chemical sensing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Life-Cycle Assessment of Sustainable Aviation Fuel Derived from Paper Sludge

Converting waste paper sludge to sustainable aviation fuel (SAF) offers a circular economy strategy to decarbonize the aviation sector. Here, this study develops a life-cycle assessment (LCA) for converting high-ash paper sludge to SAF in the U.S. using a catalytic sugar upgrading system that consists of ash removal, enzymatic hydrolysis, dehydration, aldol condensation, and hydroprocessing. The LCA is coupled with a process simulation for an industrial-scale biorefinery based on experimental data. We quantified the carbon intensity as 35.7–41.8 gCO 2 eq MJ –1 SAF (–636 to –584 gCO 2 eq per dry kg paper sludge) with acetone as a solvent, renewable fuel, and biobased chemicals; this is further reduced to 5.1–11.1 gCO 2 eq MJ –1 (–925 to –873 gCO 2 eq per dry kg paper sludge) if ash is recycled and used for substituting cement. Converting 1 dry kg paper sludge to SAF with acetone, renewable fuel, and biobased chemicals (–925 to –584 gCO 2 eq) is more climate beneficial than landfilling without landfill gas recovery (791 gCO 2 eq) and with landfill gas recovery (–294 gCO 2 eq). More than 330 million gallons of SAF can be produced annually (>4 million dry t paper sludge/year in the U.S.), resulting in a reduction of 2–7 million tCO 2 eq.

09 BIOMASS FUELS↗

Development and Evaluation of Chemistry‐Aerosol‐Climate Model CAM5‐Chem‐MAM7‐MOSAIC: Global Atmospheric Distribution and Radiative Effects of Nitrate Aerosol

Abstract An advanced aerosol treatment, with a focus on semivolatile nitrate formation, is introduced into the Community Atmosphere Model version 5 with interactive chemistry (CAM5‐chem) by coupling the Model for Simulating Aerosol Interactions and Chemistry (MOSAIC) with the 7‐mode Modal Aerosol Module (MAM7). An important feature of MOSAIC is dynamic partitioning of all condensable gases to the different fine and coarse mode aerosols, as governed by mode‐resolved thermodynamics and heterogeneous chemical reactions. Applied in the free‐running mode from 1995 to 2005 with prescribed historical climatological conditions, the model simulates global distributions of sulfate, nitrate, and ammonium in good agreement with observations and previous studies. Inclusion of nitrate resulted in ∼10% higher global average accumulation mode number concentrations, indicating enhanced growth of Aitken mode aerosols from nitrate formation. While the simulated accumulation mode nitrate burdens are high over the anthropogenic source regions, the sea‐salt and dust modes respectively constitute about 74% and 17% of the annual global average nitrate burden. Regional clear‐sky shortwave radiative cooling of up to −5 W m −2 due to nitrate is seen, with a much smaller global average cooling of −0.05 W m −2 . Significant enhancements in regional cloud condensation nuclei (at 0.1% supersaturation) and cloud droplet number concentrations are also attributed to nitrate, causing an additional global average shortwave cooling of −0.8 W m −2 . Taking into consideration of changes in both longwave and shortwave radiation under all‐sky conditions, the net change in the top of the atmosphere radiative fluxes induced by including nitrate aerosol is −0.7 W m −2 .

54 ENVIRONMENTAL SCIENCES↗

Development and Evaluation of E3SM‐MOSAIC: Spatial Distributions and Radiative Effects of Nitrate Aerosol

Abstract Nitrate aerosol plays an important role in affecting regional air quality as well as Earth's climate. However, it is not well represented or even neglected in many global climate models. In this study, we couple the Model for Simulating Aerosol Interactions and Chemistry (MOSAIC) module with the four‐mode version of the Modal Aerosol Module (MAM4) in DOE's Energy Exascale Earth System Model version 2 (E3SMv2) to simulate nitrate aerosol and its radiative effects. We find that nitrate aerosol simulated by E3SMv2‐MAM4‐MOSAIC is sensitive to the treatment of gaseous HNO 3 transfer to/from interstitial particles related to accommodation coefficients of HNO 3 ( ) on dust and non‐dust particles. We compare three different treatments of HNO 3 transfer: (a) a treatment (MTC_SLOW) that uses a low in the mass transfer coefficient (MTC) calculation; (b) a dust‐weighted MTC treatment (MTC_WGT) that uses a high on non‐dust particles; and (c) a dust‐weighted MTC treatment that also splits coarse mode aerosols into the coarse dust and sea salt sub‐modes in MOSAIC (MTC_SPLC). MTC_WGT and MTC_SPLC increase the global annual mean (2005–2014) nitrate burden from 0.096 (MTC_SLOW) to 0.237 and 0.185 Tg N, respectively, mostly in the coarse mode. MTC_WGT and MTC_SPLC also produce stronger nitrate direct radiative forcing (−0.048 and −0.051 W m −2 , respectively) and indirect forcing (−0.33 and −0.35 W m −2 , respectively) than MTC_SLOW (−0.021 and −0.24 W m −2 ). MTC_WGT and MTC_SPLC improve nitrate surface concentrations over remote oceans based on limited observations and vertical profiles of nitrate concentrations against aircraft measurements below 400 hPa.

54 ENVIRONMENTAL SCIENCES↗

Atmospheric Feedbacks Reverse the Sensitivity of Modeled Photosynthesis to Stomatal Function

Stomata mediate fluxes of carbon and water between terrestrial plants and the atmosphere. These fluxes are governed by stomatal function and can be modulated in many Earth system models by an empirical parameter within the calculation of stomatal conductance, the stomatal slope (𝑔 1⁢𝑀 ). Intuitively, 𝑔 1⁢𝑀 represents the marginal water cost of carbon, relating it to the emergent plant property of water use efficiency. Observations show that 𝑔 1⁢𝑀 can range widely across and within plant types in varying environments, and this distribution of 𝑔 1⁢𝑀 is not captured within Earth system models which represent each plant type with a single 𝑔 1⁢𝑀 value. Here we examine how 𝑔 1⁢𝑀 influences photosynthesis using coupled Earth system model simulations by perturbing 𝑔 1⁢𝑀 to observed 5⁢t⁢h and 95⁢t⁢h percentiles for each plant type. We find that high 𝑔 1⁢𝑀 reduces photosynthesis nearly everywhere, while low 𝑔 1⁢𝑀 has regionally dependent responses. Under fixed atmospheric conditions, low 𝑔 1⁢𝑀 increases photosynthesis in the Amazon and central North America but decreases photosynthesis in boreal Canada. These responses reverse when the atmosphere responds interactively due to spatially differing sensitivity to increases in temperature and vapor pressure deficit. Choice of 𝑔 1⁢𝑀 also influences photosynthetic response to changes in atmospheric carbon dioxide (CO 2 ), with lower and higher 𝑔1⁢𝑀 modifying total global response to elevated 2x preindustrial CO 2 by +6.4% and −9.6%, respectively. Our work demonstrates that atmospheric feedbacks are critical for determining the photosynthetic response to 𝑔 1⁢𝑀 assumptions and some regions are particularly sensitive to choice of 𝑔 1⁢𝑀 .

Liu, Amy X. [University of Washington, Seattle, WA↗

More frequent central Pacific El Niño and stronger eastern pacific El Niño in a warmer climate

El Niño events exhibit rich diversity in their spatial patterns, which can lead to distinct global impacts. Therefore, how El Niño pattern diversity will change in a warmer climate is one of the most critical issues for future climate projections. Based on the sixth Coupled Model Intercomparison Project simulations, we report an inter-model consensus on future El Niño diversity changes. Central Pacific (CP) El Niño events are projected to occur more frequently compared to eastern Pacific (EP) El Niño events. Concurrently, EP El Niño events are projected to increase in amplitude, leading to higher chances of extreme EP El Niño occurrences. We suggest that enhanced upper-ocean stability due to greenhouse warming can lead to a stronger surface-layer response for increasing positive feedbacks, more favorable excitation of CP El Niño. Whereas, enhanced nonlinear atmospheric responses to EP sea surface temperatures can lead to a higher probability of extreme EP El Niño.

54 ENVIRONMENTAL SCIENCES↗

Interannual fires as a source for subarctic summer decadal climate variability mediated by permafrost thawing

Climate model simulations run under the Coupled Model Intercomparison Project Phase 6 (CMIP6) use an inhomogeneous biomass burning aerosol (BBA) emission dataset, which exhibits pronounced interannual variability from 1997–2014 due to the infusion of satellite data. Using the Community Earth System Model version 2 Large Ensemble (CESM2-LE) with original and smoothed CMIP6 BBA forcings, we show that the CMIP6 data inhomogeneity causes spurious decadal subarctic land warming. During years with reduced aerosol concentrations, increased solar radiation can trigger abrupt subarctic permafrost thawing, increased soil water drainage, upper soil drying, and subsequent surface warming. This slow process, which is further amplified by nonlinear cloud-aerosol interactions, cannot be completely offset during years of increased aerosol fluxes, thereby reddening surface temperature spectra in response to large-amplitude interannual aerosol forcing. More generally, our CESM2 experiments identify a pathway for generating decadal variability in high latitudes, involving interannual shortwave forcing and slow nonlinear soil responses.

54 ENVIRONMENTAL SCIENCES↗

Bimodality in simulated precipitation frequency distributions and its relationship with convective parameterizations

Abstract Bimodality in precipitation frequency distributions is often evident in atmospheric models, but rarely in observations. This study i) proposes a metric to objectively quantify the bimodality in precipitation distributions, ii) evaluates model simulations contributed to the Coupled Model Intercomparison Project (CMIP) phase 5 (CMIP5), phase 6 (CMIP6), and the DYnamics of the Atmospheric general circulation Modeled On Non-hydrostatic Domains (DYAMOND) project by comparing them to satellite-based and reanalysis precipitation products, and iii) investigates possible origins of bimodal precipitation distributions. Our results reveal that about 83% (20 out of 24) of CMIP5 and 70% (21 out of 30) of CMIP6 models used in this study exhibit bimodal distributions. The few DYAMOND models that use a deep convective parameterization also show bimodal distributions, while most DYAMOND models do not. Predictably, the bimodality originates from the separation of precipitation process between resolved grid-scale and parameterized subgrid-scale. However, in a larger number of models bimodality arises from the parameterized subgrid-scale convective precipitation alone.

54 ENVIRONMENTAL SCIENCES↗

Anthropogenic sulfate-climate interactions suppress dust activity over East Asia

Observational evidences indicate a significant decline in dust storm frequencies over the East Asian arid-semiarid region during recent decades, which creates a strong contrast with a great increase in sulfate emissions over monsoonal Asia. However, the causes for decline of dust activities are still controversial. Through conducting a set of idealized sensitivity experiments of regional aerosol perturbations, here we show that anthropogenic sulfate aerosols over monsoonal Asia remarkably suppress the regional dust activities over East Asia. Southward shift of Asian westerly jet stream induced by sulfate aerosols results in increasing precipitation and weakening surface wind speeds over the arid-semiarid region, thereby suppressing local dust emission fluxes. Further, the latest Sixth Coupled Model Intercomparison Project simulations indicate that anthropogenic aerosols partly drive the recent weakening in regional dust activities and that future change of regional dust activities will likely depend on emissions scenarios of Asian anthropogenic aerosols and greenhouse gases.

54 ENVIRONMENTAL SCIENCES↗

Cyber‐physical system testbed for power system monitoring and wide‐area control verification

The electric power system is intrinsically a cyber‐physical system (CPS) with power flowing inthe physical system and information flowing in the cyber‐network. Testbeds arecrucial for understanding the cyber‐physical interactions and provideenvironments for prototyping novel applications. This study proposes afour‐layer architecture for CPS testbeds with emphases on communication networkemulation and networked physical components. A configurable software‐definednetwork is employed to bridge physical components with wide‐area applicationsfor closed‐loop control. In order to distribute physically coupled devices intomultiple software simulations, this study proposes a data broker setup based ona distributed messaging environment to achieve low‐latency data streaming. Thedecoupled design with data streaming allows for building testbed components asmodules and running them in a distributed manner. Case studies verify the databroker setup for low‐latency sensing and actuation, as well as the communicationemulation setup for the desired network latency. Also illustrated is a replayattack scenario using synchrophasors in the Western Electricity CoordinatingCouncil (WECC) 181‐bus system for demonstrating the closed‐loop cyber‐physicalsimulation capability of the testbed.

Cui, Hantao↗

Application of sensitivity analysis in DYMOND/Dakota to fuel cycle transition scenarios

The ability to perform sensitivity analysis has been enabled for the nuclear fuel cycle simulator DYMOND through its coupling with the design and analysis toolkit Dakota. To test and demonstrate these new capabilities, a transition scenario and multi-parameter study were devised. The transition scenario represents a partial transition from the US nuclear fleet to a closed fuel cycle with small modular LWRs and fast reactors fueled by reprocessed used nuclear fuel. Four uncertain parameters in this transition were studied – start date of reprocessing, total reprocessing capacity, the nuclear energy demand growth, and the rate at which the fast reactors are deployed – with respect to their impact on four response metrics. The responses – total natural uranium consumed, maximum annual enrichment capacity required, total disposed mass, and total cost of the nuclear fuel cycle – were chosen based on measures known to be of interest in transition scenarios and to be significantly impacted by the varying parameters. Furthermore, analysis of this study was performed both from the direct sampling and through surrogate models developed in Dakota to calculate the global sensitivity measures Sobol’ indices. This example application of this new capability showed that the most consequential parameter to most metrics was the share of new build capacity that is fast reactors. However, for the cost metric, the scaling factor of the energy demand growth was significant and had synergistic behavior with the fast reactor new build share.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Thermal transport modeling of laser-irradiated spheres

Thermal transport of uniformly laser-irradiated spheres of various materials is investigated computationally. One-dimensional simulations of low- to mid-Z materials (Be, Al, and Cu) are performed to evaluate the impact of nonlocal electron transport on experimental observables under laser intensities of relevance to direct-drive inertial confinement fusion. Here we compare thermal transport models of different levels of fidelity: flux-limited Spitzer–Harm diffusion, the Schurtz–Nicolai–Busquet (SNB) reduced-order nonlocal model, and a Fokker–Planck description. Spitzer–Harm diffusion with different flux-limiter factors are compared with different implementations of the SNB model in the HYDRA radiation hydrodynamics code. Under the conditions of interest, the peak heat flux in the thermal front with the SNB model shows good agreement with Fokker–Planck calculations, with the largest errors below 10% at 10 15 W/cm 2 laser intensity. From HYDRA-SNB simulations, two experimentally relevant effects are observed from nonlocal heat transport when compared to flux-limited Spitzer–Harm modeling: coronal temperatures are cooler due to reduced heat fluxes in the expanding plasma and (for mid-Z materials) x-ray emissions are enhanced due to preheating in the dense plasma.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Coupling solidification kinetics with phase-behavior computations in hydrodynamic simulations of high-pressure, dynamic-compression processes

In this study, we report a numerical scheme to integrate models for the kinetics of solidification processes together with phase-behavior computations in the context of continuum-scale hydrodynamic simulations. The objective of the phase-behavior computations is to determine the pressure and temperature, given the following three sets of inputs: (1) an appropriate equation of state to describe our system, (2) the phase fraction(s) produced by the kinetic models, (3) and the volume and internal energy obtained by solving the conservation equations that govern the hydrodynamic behavior. The kinetics are assumed to be governed by the Kolmogorov–Johnson–Mehl–Avrami equation, and the nucleation and growth rates that enter into that equation are functions of the pressure and temperature produced by the phase-behavior computations. Our formulation allows for the fluid and solid phases to be at different temperatures (thermal nonequilibrium) and pressures (arising from surface-tension-induced Laplace contributions). The formulation is presented in a fairly general setting that is independent of any particular material, although we demonstrate it in some examples related to high-energy-density science applications where materials are rapidly compressed to pressures exceeding several gigapascals in less than a microsecond. We conclude with a critical evaluation of our approach and provide suggestions for future work to improve the predictive capabilities and generality of the models.

42 ENGINEERING↗

Role of hot electrons in shock ignition constrained by experiment at the National Ignition Facility

Shock ignition is a scheme for direct drive inertial confinement fusion that offers the potential for high gain with the current generation of laser facility; however, the benefits are thought to be dependent on the use of low adiabat implosions without laser–plasma instabilities reducing drive and generating hot electrons. A National Ignition Facility direct drive solid target experiment was used to calibrate a 3D Monte Carlo hot-electron model for 2D radiation-hydrodynamic simulations of a shock ignition implosion. The α = 2.5 adiabat implosion was calculated to suffer a 35% peak areal density decrease when the hot electron population with temperature T ℎ = 55 keV and energy E ℎ = 13 kJ was added to the simulation. Optimizing the pulse shape can recover ~1/3 of the peak areal density lost due to a change in shock timing. Here, despite the harmful impact of laser–plasma instabilities, the simulations indicate shock ignition as a viable method to improve performance and broaden the design space of near ignition high adiabat implosions.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗