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At least 559 records · Page 31

Crystallographic dependence of CO 2 hydrogenation pathways over HCP-Co and FCC-Co catalysts

We report efficient conversion of CO 2 is of great significance for sustainable supply of chemicals and fuels. While Co-based catalysts are known to be effective for CO hydrogenation in Fischer-Tropsch synthesis, they work very differently in CO 2 hydrogenation. This study reveals a crystallographic dependence of reaction pathways for CO 2 hydrogenation on Co catalyst showing a new type of structure sensitivity and structure-activity-selectivity relationship for CO 2 conversion to chemicals and fuels. The experimental work on CO 2 conversion including steady-state isotopic transient kinetic analysis (SSITKA) using 13 C-labeled CO 2 shows a preferential CH 4 formation over HCP-Co but dominant CO formation over FCC-Co. The density functional theory calculations indicate that CO 2 does dissociate directly into chemisorbed CO * and O * on both HCP-Co and FCC-Co, but the CO * intermediates on HCP-Co prefer to be hydrogenated to form CH 4 whereas the CO* on FCC-Co preferentially desorb to form CO. The significantly altered adsorption strength of CO * due to the presence of chemisorbed O * and CO 2 * species on the catalyst surface is responsible for the mechanistic disconnection in product selectivity between the CO 2 and CO hydrogenation over Co catalysts. This study also shows that the addition of K to Co diminishes the direct impact of Co crystal structure, but improves the selectivity to C 2 + hydrocarbons along with higher CO 2 conversion. This seems to result from another pathway originating from HCOO* intermediate from bonding interaction of surface Co atoms with carbon in CO 2 , leading to the formation of CH x * whose coupling subsequently give rises to C 2 + products. The present study sheds new light into the crystallographic structural sensitivity of CO 2 hydrogenation towards the rational design of more selective catalysts for CO 2 conversion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Direct Geologic Constraints on the Timing of Late Holocene Ice Thickening in the Amundsen Sea Embayment, Antarctica

Abstract Constraining past West Antarctic Ice Sheet (WAIS) change helps validate numerical models simulating future ice sheet dynamics. Following rapid deglaciation during the mid‐Holocene, ice near Thwaites Glacier was ∼35 m thinner than present; however, the timing of ice regrowth to its present configuration remains unknown. To fill this knowledge gap, we present cosmogenic nuclide exposure ages of cobbles from the surface of a moraine situated between Thwaites and Pope glaciers. We infer that the moraine formed and stabilized in the Late Holocene (∼1.4 ka) when a small glacier thickened. We also present a novel reconstruction of WAIS volume constrained by sea‐level data, which demonstrates that moraine formation coincided with a large‐scale WAIS readvance. Our new geologic constraints will help inform models of the solid Earth response to surface mass loading, improving our understanding of ice sheet dynamics in a vulnerable part of WAIS.

Nichols, Keir A. [Imperial College London London U↗

ClimGen: Learning the Forcing-Response Relationship in Climate System

Solar Radiation Management (SRM) is emerging as a potential geoengineering strategy to address the anthropogenic impact on climate, but its effective implementation requires an iterative and large ensemble of highly accurate and efficient climate projections. Traditional climate projections rely on executing computationally demanding and time-consuming numerical climate models. Recent advances in machine learning (ML) aim to enhance these approaches by emulating traditional methods. In this work, we propose a novel framework for directly learning the relationship between solar radiation flux at the top of the atmosphere and the corresponding surface temperature response. To evaluate the feasibility of this direct ML-based projection, we developed a dataset using an intermediate complexity model, incorporating a comprehensive suite of different forcing patterns and evaluation metrics to rigorously assess the ML model’s performance. We introduce a Conditional Denoising Diffusion Probabilistic Model (cDDPM) for this task, which demonstrates encouraging skill in representing climate statistics under previously unseen forcing patterns. This approach provides a promising pathway for direct climate projections by accurately learning the forcing-response relationship, with a wide range of applications in impact mitigation, emissions policy design, and SRM strategies.

Chen, Tse-Chun [BATTELLE (PACIFIC NW LAB)] (ORCID:↗

Experimental assessment of a computer program used in Space Shuttle orbiter entry heating analysis

A high temperature reusable surface insulation (HRSI) tile taken from the Space Shuttle orbiter was subjected to a nominal heating rate of 60 kW/sq m in the laboratory. The surface temperature response to this heating was measured and used as input to a computer program which computed the applied heating rate. The program is part of a software system that is used to infer convective heating rates to the orbiter thermal protection system during entry. The measured and computed heating rates are compared. Results confirm the applicability of this program to the determination of flight heat transfer rates from flight measured surface temperature data.

Wells, W. L.↗

Statistical Multiobjective Optimization of Thiospinel CoNi 2 S 4 Nanocrystal Synthesis via Design of Experiments

Thiospinels, such as CoNi 2 S 4 , are showing promise for numerous applications, including as catalysts for the hydrogen evolution reaction, hydrodesulfurization, and oxygen evolution and reduction reactions; however, CoNi 2 S 4 has not been synthesized as small, colloidal nanocrystals with high surface-area-to-volume ratios. Traditional optimization methods to control nanocrystal attributes such as size typically rely upon one variable at a time (OVAT) methods that are not only time and labor intensive but also lack the ability to identify higher-order interactions between experimental variables that affect target outcomes. Herein, we demonstrate that a statistical design of experiments (DoE) approach can optimize the synthesis of CoNi 2 S 4 nanocrystals, allowing for control over the responses of nanocrystal size, size distribution, and isolated yield. After implementing a 2 5–2 fractional factorial design, the statistical screening of five different experimental variables identified temperature, Co:Ni precursor ratio, Co:thiol ratio, and their higher-order interactions as the most critical factors in influencing the aforementioned responses. Second-order design with a Doehlert matrix yielded polynomial functions used to predict the reaction parameters needed to individually optimize all three responses. A multiobjective optimization, allowing for the simultaneous optimization of size, size distribution, and isolated yield, predicted the synthetic conditions needed to achieve a minimum nanocrystal size of 6.1 nm, a minimum polydispersity (σ/$\bar{d}$) of 10%, and a maximum isolated yield of 99%, with a desirability of 96%. The resulting model was experimentally verified by performing reactions under the specified conditions. Furthermore, our work illustrates the advantage of multivariate experimental design as a powerful tool for accelerating control and optimization in nanocrystal syntheses.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Simulations of x-ray absorption spectra for CO desorbing from Ru(0001) with transition-potential and time-dependent density functional theory approaches

The desorption of a carbon monoxide molecule from a Ru(0001) surface was studied by means of X-ray Absorption Spectra (XAS) computed with Transition Potential (TP-DFT) and Time Dependent (TD-DFT) DFT methods. By unraveling the evolution of the CO electronic structure upon desorption, we observed that at 2.3 Å from the surface, the CO molecule has already predominantly gas-phase character. While C 1s XAS is quite insensitive to changes in the C–O bond length, the O 1s excitation is very sensitive with the π* coming down in energy upon CO bond stretching, which competes with the increase in orbital energy due to the repulsive interaction with the metallic surface. We show in a systematic way that the TP-DFT method can describe the XAS rather well at the endpoints (chemisorbed and gas phase) but is affected by artificial charge transfer and/or incorrect spin treatment in the transition region in cases like CO, where there are low-lying π* orbitals and large exchange interactions between the core 1s and valence-acceptor π* orbitals. As an alternative, we demonstrate by comparing with experimental data that a linear response approach using TD-DFT employing common exchange-correlation functionals and finite-size clusters can yield a good description of the spectral evolution of the 1s → π* transition with correct spin and gas-to-chemisorbed chemical shifts in good agreement with experiment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Environmental stability impacts the differential sensitivity of marine microbiomes to increases in temperature and acidity

Ambient conditions shape microbiome responses to both short- and long-duration environment changes through processes including physiological acclimation, compositional shifts, and evolution. Here, we predict that microbial communities inhabiting locations with larger diel, episodic, and annual variability in temperature and pH should be less sensitive to shifts in these climate-change factors. To test this hypothesis, we compared responses of surface ocean microbes from more variable (nearshore) and more constant (offshore) sites to short-term factorial warming (+3 °C) and/or acidification (pH –0.3). In all cases, warming alone significantly altered microbial community composition, while acidification had a minor influence. Compared with nearshore microbes, warmed offshore microbiomes exhibited larger changes in community composition, phylotype abundances, respiration rates, and metatranscriptomes, suggesting increased sensitivity of microbes from the less-variable environment. Moreover, while warming increased respiration rates, offshore metatranscriptomes yielded evidence of thermal stress responses in protein synthesis, heat shock proteins, and regulation. Future oceans with warmer waters may enhance overall metabolic and biogeochemical rates, but they will host altered microbial communities, especially in relatively thermally stable regions of the oceans.

54 ENVIRONMENTAL SCIENCES↗

Energy, angle, and temperature dependencies of the sticking of D atoms on Li surfaces

Detailed experimental and computational information on the response of lithium surfaces to irradiation by slow hydrogenic particles (ions, atoms, molecules) is sparse and mainly speculative. In this work, we present a computational study of the reflection and retention of deuterium (D) atoms at crystalline and amorphous lithium surfaces at 300 and 500 K, where the D atoms have an impact energy in the range of 0.025–5 eV and incident angles of 0° (perpendicular incidence) or 85° (near-grazing incidence). Classical molecular dynamics simulations are performed with the reactive bond-order force field (ReaxFF) potentials. This study provides quantitative information on the deuterium sticking probability and recycling coefficient for lithium surfaces. Further, our results support the ongoing work at the Lithium Tokamak eXperiment-β fusion experiment as well as relevant experiments in the laboratory setting.

74 ATOMIC AND MOLECULAR PHYSICS↗

Coupled Land Atmosphere Predictability

We have designed and executed a set of predictability experiments, designed around the driest and wettest June soil moisture anomalies from a CCM3 simulation forced by observed SST for the period from 1958 through 1998. Each set contains an ensemble of five runs, all begun on June I radiation date. One set of these experiments helps to assess the extent to which the wet or dry conditions depend solely on the initial state of the atmosphere. The other set of experiments helps to assess the extent to which the wet or dry conditions depend sole on the initial state of the land surface. Preliminary analysis of these experiments suggests that the initial atmospheric state is more important than the initial state of the surface soil moisture in predicting the occurrence of wet or dry periods. These results suggest that when the atmosphere is inclined to generate dry surface conditions (through reduced moisture availability and increased evaporation) it matters little what initial levels of soil water are at; the soil will rapidly dry out. The ensemble forcing the ensembles with dry soil conditions, but utilizing 'normal' atmospheric conditions show little if any indication of the sharp reduction in soil moisture experienced in the control, indicating that the 'normal' atmospheric state is more important than the initial state of the soil moisture in predicting the occurrence of drought. Our work to date has documented the response of surface hydrologic variability, particularly over North America, to atmospheric forcing. While we have seen some suggestion that pre-existing surface anomalies can affect atmospheric circulation over this region, by far the strongest signal is the atmospheric anomalies leading those of soil moisture and surface energy balance changes. This is not an unexpected result since wintertime NA precipitation links to remote atmospheric forcing by ENSO are known to be statistically significant. While warm season links to remote forcing are more tenuous and not well explored, the present results encourage us to examine in more detail the SST forcing from the tropical and North Pacific.

Roads, John↗

Climate response to off-equatorial stratospheric sulfur injections in three Earth system models – Part 2: Stratospheric and free-tropospheric response

The paper constitutes Part 2 of a study performing a first systematic inter-model comparison of the atmospheric responses to stratospheric aerosol injection (SAI) at various single latitudes in the tropics, as simulated by three state-of-the-art Earth system models – CESM2-WACCM6, UKESM1.0, and GISS-E2.1-G. Building on Part 1 (Visioni et al., 2023) we demonstrate the role of biases in the climatological circulation and specific aspects of the model microphysics in driving the inter-model differences in the simulated sulfate distributions. We then characterize the simulated changes in stratospheric and free-tropospheric temperatures, ozone, water vapor, and large-scale circulation, elucidating the role of the above aspects in the surface SAI responses discussed in Part 1. We show that the differences in the aerosol spatial distribution can be explained by the significantly faster shallow branches of the Brewer–Dobson circulation in CESM2, a relatively isolated tropical pipe and older tropical age of air in UKESM, and smaller aerosol sizes and relatively stronger horizontal mixing (thus very young stratospheric age of air) in the two GISS versions used. We also find a large spread in the magnitudes of the tropical lower-stratospheric warming amongst the models, driven by microphysical, chemical, and dynamical differences. These lead to large differences in stratospheric water vapor responses, with significant increases in stratospheric water vapor under SAI in CESM2 and GISS that were largely not reproduced in UKESM. For ozone, good agreement was found in the tropical stratosphere amongst the models with more complex microphysics, with lower stratospheric ozone changes consistent with the SAI-induced modulation of the large-scale circulation and the resulting changes in transport. In contrast, we find a large inter-model spread in the Antarctic ozone responses that can largely be explained by the differences in the simulated latitudinal distributions of aerosols as well as the degree of implementation of heterogeneous halogen chemistry on sulfate in the models. The use of GISS runs with bulk microphysics demonstrates the importance of more detailed treatment of aerosol processes, with contrastingly different stratospheric SAI responses to the models using the two-moment aerosol treatment; however, some problems in halogen chemistry in GISS are also identified that require further attention. Overall, our results contribute to an increased understanding of the underlying physical mechanisms as well as identifying and narrowing the uncertainty in model projections of climate impacts from SAI.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Developing an Accurate CFD Based Gust Model for the Truss Braced Wing Aircraft

The increased flexibility of long endurance aircraft having high aspect ratio wings necessitates attention to gust response and perhaps the incorporation of gust load alleviation. The design of civil transport aircraft with a strut or truss-braced high aspect ratio wing furthermore requires gust response analysis in the transonic cruise range. This requirement motivates the use of high fidelity nonlinear computational fluid dynamics (CFD) for gust response analysis. This paper presents the development of a CFD based gust model for the truss braced wing aircraft. A sharp-edged gust provides the gust system identification. The result of the system identification is several thousand time steps of instantaneous pressure coefficients over the entire vehicle. This data is filtered and downsampled to provide the snapshot data set from which a reduced order model is developed. A stochastic singular value decomposition algorithm is used to obtain a proper orthogonal decomposition (POD). The POD model is combined with a convolution integral to predict the time varying pressure coefficient distribution due to a novel gust profile. Finally the unsteady surface pressure response of the truss braced wing vehicle to a one-minus-cosine gust, simulated using the reduced order model, is compared with the full CFD.

Bartels, Robert E.↗

Plasma Environments and Spacecraft Charging for Lunar Programs

Space systems interacting with the space plasma environment charge to potentials of a few tens of volts positive in interplanetary space or on the lunar surface in daylight, a few hundred volts negative in the dark lunar plasma wake and in some regions of the Earth s radiation belts, and to multiple kilovolt negative potentials for worst case conditions in the Earth s magnetosphere near geostationary orbit. Good design practices are required to assure that space systems operate successfully in these environments without detrimental effects due to transient currents and insulator failure produced by electrostatic discharges. Cold lunar environments in particular are challenging because detrimental effects of charging are often exacerbated by cold, highly resistive dielectrics which can integrate charge for long periods of time. We will describe the cold plasma and energetic particle environments relevant to lunar missions responsible for surface and bulk charging of space systems and discuss program requirements under development for assuring that systems operate successfully in these environments.

Minow, Joseph I.↗

Characteristics of the East Asian Winter Climate Associated with the Westerly Jet Stream and ENSO

In this study, the influences of the East Asian jet stream (EAJS) and El Nino/Southern Oscillation (ENSO) on the interannual variability of the East Asian winter climate are examined with a focus on the relative climate impacts of the two phenomena. Although the variations of the East Asian winter monsoon and the temperature and precipitation of China, Japan, and Korea are emphasized, the associated changes in the broad-scale atmospheric circulation patterns over Asia and the Pacific and in the extratropical North Pacific sea surface temperature (SST) are also investigated. It is demonstrated that there is no apparent relationship between ENSO and the interannual variability of EAJS core. The EAJS and ENSO are associated with distinctly different patterns of atmospheric circulation and SST in the Asian-Pacific regions. While ENSO causes major climate signals in the Tropics and over the North Pacific east of the dateline, the EAJS produces significant changes in the atmospheric circulation over East Asia and western Pacific. In particular, the EAJS explains larger variance of the interannual signals of the East Asian trough, the Asian continental high, the Aleutian low, and the East Asian winter monsoon. When the EAJS is strong, all these atmospheric systems intensify significantly. The response of surface temperature and precipitation to EAJS variability and ENSO is more complex. In general, the East Asian winter climate is cold (warm) and dry (wet) when the EAJS is strong (weak) and it is warm during El Nino years. However, different climate signals are found during different La Nina years. In terms of linear correlation, both the temperature and precipitation of northern China, Korea, and central Japan are more significantly associated with the EAJS than with ENSO.

Yang, Song↗

Toward Understanding Wake Vortices and Atmospheric Turbulence Interactions Using Large-Eddy Simulation

The vortices produced by an aircraft in flight are a complex phenomena created from a 'sheet of vorticity' leaving the trailing edge of the aircraft surfaces. This sheet tends to roll-up into two counter-rotating vortices. After a few spans downstream of the aircraft, the roll-up process is complete and the vortex pair may be characterized in a simple manner for modeling purposes. Our research will focus on what happens to these post roll-up vortices in the vicinity of an airport terminal. As the aircraft wake vortices descend, they are transported by the air mass which they are embedded and are decayed by both internal and external processes. In the vicinity of the airport, these external influences are usually due to planetary boundary layer (PBL) turbulence. Using large-eddy simulation (LES), one may simulate a variety of PBL conditions. In the LES method, turbulence is generated in the PBL as a response to surface heat flux, horizontal pressure gradient, wind shear, and/or stratification, and may produce convective or unstably stratified, neutral, or stably stratified PBL's. Each of these PBL types can occur during a typical diurnal cycle of the PBL. Thus it is important to be able to characterize these conditions with the LES method. Once this turbulent environment has been generated, a vortex pair will be introduced and the interactions are observed. The objective is to be able to quantify the PBL turbulence vortex interaction and be able to draw some conclusions of vortex behavior from the various scale interactions. This research is ongoing, and we will focus on what has been accomplished to date and the future direction of this research. We will discuss the model being used, show results that validate its use in the PBL, and present a nested-grid method proposed to analyze the entire PBL and vortex pair simultaneously.

DeCroix, David↗

Quantifying the effect of tow architecture variability on the performance of biaxially braided composite tubes

Targeted experiments are performed with stereoscopic digital image correlation to quantify the effect of irregular braid structure on the local surface mechanical response of carbon-fiber reinforced epoxy composite tubes. Virtual models comparing both nonuniform and uniform tow structure of the outer braid of each specimen are integrated into numerical simulations similar to experiments. Experimental and numerical results agree well. Statistical tests are used to support correlations between as-manufactured braid variation ranges to local increases in stress up to 18% compared to an ideal, uniform structure in the elastic regime. Results support improved manufacturing and modeling efforts of defect sensitive braided composites.

36 MATERIALS SCIENCE↗

Methods for LWIR Radiometric Calibration and Characterization

The utility of a remote sensing system increases with its ability to retrieve surface temperature or radiance accurately. Research applications, such as sea temperature and power plant discharge, require a 0.2 C resolution or better for absolute temperature retrievals. Other applications, including agriculture water stress detection, require at least a 1 C resolution. To achieve these levels of accuracy routinely, scientists must perform laboratory and onboard calibration, as well as in-flight vicarious radiometric characterization. A common approach used for in-flight radiometric characterization incorporates a well-calibrated infrared radiometer that is mounted on a bouy and placed on a uniform water body. The radiometer monitors radiant temperature along with pressure, humidity, and temperature measurements of an associated column of atmosphere. On very still waters, however, a buoy can significantly distrub these measurements. Researchers at NASA's Stennis Space Center (SSC) have developed a novel approach of using an uncooled infrared camera mounted on a boom to quantify buoy effects. Another critical aspect of using buoy-mounted infrared radiometers is the need for extensive laboratory characterization of the instruments' radiometric sensitivity, field of view, and spectral response. Proper surface temperature retrieval also requires detailed knowledge of both the upward emission and the reflected sky emission. Recent work at SSC has demonstrated that the use of a polarization-based radiometer operating at the Brewster angle can greatly simplify temperature retrieval as well as improve overall accuracy.

Ryan, Robert↗

Arctic Warming in Response to Regional Aerosol Emissions Reductions

This study examines the Arctic surface air temperature response to regional aerosol emissions reductions using three fully coupled chemistry–climate models: National Center for Atmospheric Research-Community Earth System Model version 1, Geophysical Fluid Dynamics Laboratory-Coupled Climate Model version 3 (GFDL-CM3) and Goddard Institute for Space Studies-ModelE version 2. Each of these models was used to perform a series of aerosol perturbation experiments, in which emissions of different aerosol types (sulfate, black carbon (BC), and organic carbon) in different northern mid-latitude source regions, and of biomass burning aerosol over South America and Africa, were substantially reduced or eliminated. We find that the Arctic warms in nearly every experiment, the only exceptions being the U.S. and Europe BC experiments in GFDL-CM3 in which there is a weak and insignificant cooling. The Arctic warming is generally larger than the global mean warming (i.e. Arctic amplification occurs), particularly during non-summer months. The models agree that changes in the poleward atmospheric moisture transport are the most important factor explaining the spread in Arctic warming across experiments: the largest warming tends to coincide with the largest increases in moisture transport into the Arctic. In contrast, there is an inconsistent relationship (correlation) across experiments between the local radiative forcing over the Arctic and the simulated Arctic warming, with this relationship being positive in one model (GFDL-CM3) and negative in the other two. Our results thus highlight the prominent role of poleward energy transport in driving Arctic warming and amplification, and suggest that the relative importance of poleward energy transport and local forcing/feedbacks is likely to be model dependent.

Arctic↗

Leveraging Pre-storm Soil Moisture Estimates for Enhanced Land Surface Model Calibration in Ungauged Hydrologic Basins

Despite long-standing efforts, hydrologists still lack robust tools for calibrating land surface model (LSM) streamflow estimates within ungauged basins. Using surface soil moisture estimates from the Soil Moisture Active Passive Level 4 Soil Moisture (L4_SM) product, precipitation observations, and streamflow gauge measurements for 617 medium-scale (200-10,000 km2) basins in the contiguous United States, we measure the temporal (Spearman) rank correlation between antecedent (i.e., pre-storm) surface soil moisture (ASM) and the storm-scale runoff coefficient (RC; the fraction of storm-scale precipitation accumulation converted into streamflow). In humid and semi-humid basins, this rank correlation is shown to be sufficiently strong to allow for the substitution of storm-scale RC observations (available only in basins that are both lightly regulated and gauged) with high-quality ASM values (available quasi-globally from L4_SM) in streamflow calibration procedures. Using this principle, we define a new, basin-wise LSM streamflow calibration approach based on L4_SM alone and successfully apply it to identify LSM configurations that produce a high rank correlation with observed RC. However, since the approach cannot detect RC bias, it is less successful in identifying LSM configurations with low mean-absolute error. Plain Text Summary Accurately forecasting the fraction of rainfall that runs off into streams, as opposed to infiltrates into the soil, is critical for flash-flood prediction, water-resource monitoring, and tracking the transport of nutrients from agricultural fields into local waterways. Such forecasting is typically performed by hydrologic models that attempt to represent the physical processes responsible for surface runoff generation. However, to provide accurate streamflow forecasts, these models typically need to be calibrated against actual streamflow observations. This is problematic given the relatively poor, and declining, global availability of stream gauges. This paper presents a novel model calibration strategy that uses soil moisture from remote sensing and numerical modeling in place of streamflow observations during calibration. This transition has significant practical advantages because, unlike streamflow observations, the soil moisture data are continuously available across space. Our results demonstrate that this new approach can significantly improve hydrologic models within humid and semi-humid basins lacking sufficient ground-based instrumentation for traditional streamflow calibration.

hydrologic models↗