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At least 973 records · Page 54

Molecular Models of Atomically Dispersed Uranium at MoS 2 Surfaces Reveal Cooperative Mechanism of Water Reduction

Single atoms of uranium supported on molybdenum sulfide surfaces (U@MoS 2 ) have been recently demonstrated to facilitate the hydrogen evolution reaction (HER) through electrocatalysis. Theoretical calculations have predicted uranium hydroxide moieties bound to edge-sulfur atoms of MoS 2 as a proposed transition state involved in the HER process. However, the isolation of relevant intermediates involved in this process remains a challenge, rendering mechanistic hypotheses unverified. The present work describes the isolation and characterization of a uranium-hydroxide intermediate on molybdenum sulfide surfaces using [(Cp* 3 Mo 3 S 4 )UCp*], a molecular model of a reduced uranium center supported at MoS 2 . Mechanistic investigations highlight the metalloligand cooperativity with uranium involved in the water activation pathway. The corresponding uranium-oxo analogue, [(Cp* 3 Mo 3 S 4 )Cp*U(═O)], was also accessed from the hydroxide cluster via hydrogen atom transfer and from [(Cp* 3 Mo 3 S 4 )UCp*] through an alternative direct oxygen atom transfer. These results provide an atomistic perspective on the reactivity of low-valent uranium at molybdenum sulfide surfaces toward water, modeling key intermediates associated with the HER of U@MoS 2 catalysts.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

GCAM–GLORY v1.0: representing global reservoir water storage in a multi-sector human–Earth system model

Abstract. Reservoirs play a significant role in modifying the spatiotemporal availability of surface water to meet multi-sector human demands, despite representing a relatively small fraction of the global water budget. Yet the integrated modeling frameworks that explore the interactions among climate, land, energy, water, and socioeconomic systems at a global scale often contain limited representations of water storage dynamics that incorporate feedbacks from other systems. In this study, we implement a representation of water storage in the Global Change Analysis Model (GCAM) to enable the exploration of the future role (e.g., expansion) of reservoir water storage globally in meeting demands for, and evolving in response to interactions with, the climate, land, and energy systems. GCAM represents 235 global water basins, operates at 5-year time steps, and uses supply curves to capture economic competition among renewable water (now including reservoirs), non-renewable groundwater, and desalination. Our approach consists of developing the GLObal Reservoir Yield (GLORY) model, which uses a linear programming (LP)-based optimization algorithm and dynamically linking GLORY with GCAM. The new coupled GCAM–GLORY approach improves the representation of reservoir water storage in GCAM in several ways. First, the GLORY model identifies the cost of supplying increasing levels of water supply from reservoir storage by considering regional physical and economic factors, such as evolving monthly reservoir inflows and demands, and the leveled cost of constructing additional reservoir storage capacity. Second, by passing those costs to GCAM, GLORY enables the exploration of future regional reservoir expansion pathways and their response to climate and socioeconomic drivers. To guide the model toward reasonable reservoir expansion pathways, GLORY applies a diverse array of feasibility constraints related to protected land, population, water sources, and cropland. Finally, the GLORY–GCAM feedback loop allows evolving water demands from GCAM to inform GLORY, resulting in an updated supply curve at each time step, thus enabling GCAM to establish a more meaningful economic value of water. This study improves our understanding of the sensitivity of reservoir water supply to multiple physical and economic dimensions, such as sub-annual variations in climate conditions and human water demands, especially for basins experiencing socioeconomic droughts.

54 ENVIRONMENTAL SCIENCES↗

Multi-model analysis of the impact of water vapor on the radiative forcing of volcanic aerosols after the 2022 Hunga Eruption

On 15 January 2022, the Hunga volcano eruption released unprecedented amounts of water vapor into the atmosphere alongside a modest amount of SO 2 . In this work we analyse results from multiple Earth system models as part of the Hunga Tonga-Hunga Ha'apai Volcano Impact Model Observation Comparison Project. Our results show a good model agreement over the climatic outcomes of the eruption, overall indicating a significant negative radiative forcing from the Hunga eruption. The multi-model mean of global instantaneous radiative forcing averaged over 2022–2023 is estimated at −0.19 ± 0.06 W m −2 at the top-of-atmosphere (TOA), and −0.16 ± 0.06 W m −2 at the surface. Simulations with free-running meteorology and climatological sea surface temperatures and sea ice yield a global mean TOA forcing of −0.14 ± 0.10 W m −2 across two models for the first 2 years, decreasing to −0.09 ± 0.10 W m −2 on average between 2022 and 2027. However, these global values may be underestimated by about 50 %, considering that recent SO 2 injection retrievals suggest nearly twice the amount than the 0.5 Tg-SO 2 used in the protocol. We also find that the contribution from added stratospheric water vapor is minimal and that the injected SO 2 and the resulting formation of stratospheric sulfate dominate the radiative forcing. However, water vapor played a key role in the initial aerosol growth, leading to a stronger negative radiative forcing during the first 6 months after the eruption compared to simulations without water vapor co-injection.

Geosciences↗

Diagnostic modeling of dimethylsulfide production in coastal water west of the Antarctic Peninsula

The rate of gross biological dimethylsulfide (DMS) production at two coastal sites west of the Antarctic Peninsula, off Anvers Island, near Palmer Station, was estimated using a diagnostic approach that combined field measurements from 1 January 2006 through 1 March 2006 and a one-dimensional physical model of ocean mixing. The average DMS production rate in the upper water column (0-60 m) was estimated to be 3.1 +/- 0.6 nM/d at station B (closer to shore) and 2.7 +/- 0.6 nM/d1 at station E (further from shore). The estimated DMS replacement time was on the order of 1 d at both stations. DMS production was greater in the mixed layer than it was below the mixed layer. The average DMS production normalized to chlorophyll was 0.5 +/- nM/d)/(mg cubic m) at station B and 0.7 +/- 0.2 (nM/d)/(mg/cubic m3) at station E. When the diagnosed production rates were normalized to the observed concentrations of total dimethylsulfoniopropionate (DMSPt, the biogenic precursor of DMS), we found a remarkable similarity between our estimates at stations B and E (0.06 +/- 0.02 and 0.04 +/- 0.01 (nM DMS / d1)/(nM DMSP), respectively) and the results obtained in a previous study from a contrasting biogeochemical environment in the North Atlantic subtropical gyre (0.047 =/- 0.006 and 0.087 +/- 0.014 (nM DMS d1)/(nM DMSP) in a cyclonic and anticyclonic eddy, respectively).We propose that gross biological DMS production normalized to DMSPt might be relatively independent of the biogeochemical environment, and place our average estimate at 0.06 +/- 0.01 (nM DMS / d)/(nM DMSPt). The significance of this finding is that it can provide a means to use DMSPt measurements to extrapolate gross biological DMS production, which is extremely difficult to measure experimentally under realistic in situ conditions.

Dimethylsulfide↗

A Fuzzy Expert System for Fault Management of Water Supply Recovery in the ALSS Project

Modeling with a new software is a challenge. CONFIG is a challenge and is design to work with many types of systems in which discrete and continuous processes occur. The CONFIG software was used to model the two subsystem of the Water Recovery system: ICB and TFB. The model worked manually only for water flows with further implementation to be done in the future. Activities in the models are stiff need to be implemented based on testing of the hardware for phase III. More improvements to CONFIG are in progress to make it a more user friendly software.

Tohala, Vapsi J.↗

Bayesian calibration of bubble size dynamics applied to CO 2 gas fermenters

To accelerate the scale-up of gaseous CO 2 fermentation reactors, computational models need to predict gas-to-liquid mass transfer which requires capturing the bubble size dynamics, i.e. bubble breakup and coalescence. However, the applicability of existing models beyond air–water mixtures remains to be established. Here, an inverse modeling approach, accelerated with a neural network surrogate, calibrates the breakup and coalescence closure models, that are used in class methods for population balance modeling (PBM). The calibration is performed based on experimental results obtained in a CO 2 -air–water-coflowing bubble column reactor. Bayesian inference is used to account for noise in the experimental dataset and bias in the simulation results. To accurately capture gas holdup and interphase mass transfer, the results show that the breakage rate needs to be increased by one order of magnitude. In conclusion, the inferred model parameters are then used on a separate configuration and shown to also improve bubble size distribution predictions.

09 BIOMASS FUELS↗

Water Content of Lunar Alkali Fedlspar

Detection of indigenous hydrogen in a diversity of lunar materials, including volcanic glass, melt inclusions, apatite, and plagioclase suggests water may have played a role in the chemical differentiation of the Moon. Spectroscopic data from the Moon indicate a positive correlation between water and Th. Modeling of lunar magma ocean crystallization predicts a similar chemical differentiation with the highest levels of water in the K- and Th-rich melt residuum of the magma ocean (i.e. urKREEP). Until now, the only sample-based estimates of water content of KREEP-rich magmas come from measurements of OH, F, and Cl in lunar apatites, which suggest a water concentration of < 1 ppm in urKREEP. Using these data, predict that the bulk water content of the magma ocean would have <10 ppm. In contrast, estimate water contents of 320 ppm for the bulk Moon and 1.4 wt % for urKREEP from plagioclase in ferroan anorthosites. Results and interpretation: NanoSIMS data from granitic clasts from Apollo sample 15405,78 show that alkali feldspar, a common mineral in K-enriched rocks, can have approx. 20 ppm of water, which implies magmatic water contents of approx. 1 wt % in the high-silica magmas. This estimate is 2 to 3 orders of magnitude higher than that estimated from apatite in similar rocks. However, the Cl and F contents of apatite in chemically similar rocks suggest that these melts also had high Cl/F ratios, which leads to spuriously low water estimates from the apatite. We can only estimate the minimum water content of urKREEP (+ bulk Moon) from our alkali feldspar data because of the unknown amount of degassing that led to the formation of the granites. Assuming a reasonable 10 to 100 times enrichment of water from urKREEP into the granites produces an estimate of 100-1000 ppm of water for the urKREEP reservoir. Using the modeling of and the 100-1000 ppm of water in urKREEP suggests a minimum bulk silicate Moon water content between 2 and 20 ppm. However, hydrogen loss was likely very significant in the evolution of the lunar mantle. Conclusions: Lunar granites crystallized between 4.3-3.8 Ga from relatively wet melts that degassed upon crystallization. The formation of these granites likely removed significant amounts of water from some mantle source regions, e.g. later mare basalts predicting derivation from a mantle with <10 ppm water. However, this would have been a heterogeneous pro-cess based on K distribution. Thus some, if not most of the mantle may not have been devolatilized by this process; as seen by water in volcanic glasses and melt inclusions.

Mills, R. D.↗

Improved Calibration of Modeled Discharge and Storage Change in the Atchafalaya Floodplain Using SAR Interferometry

This study focuses on the feasibility of using SAR interferometry to support 2D hydrodynamic model calibration and provide water storage change in the floodplain. Two-dimensional (2D) flood inundation modeling has been widely studied using storage cell approaches with the availability of high resolution, remotely sensed floodplain topography. The development of coupled 1D/2D flood modeling has shown improved calculation of 2D floodplain inundation as well as channel water elevation. Most floodplain model results have been validated using remote sensing methods for inundation extent. However, few studies show the quantitative validation of spatial variations in floodplain water elevations in the 2D modeling since most of the gauges are located along main river channels and traditional single track satellite altimetry over the floodplain are limited. Synthetic Aperture Radar (SAR) interferometry recently has been proven to be useful for measuring centimeter-scale water elevation changes over the floodplain. In the current study, we apply the LISFLOOD hydrodynamic model to the central Atchafalaya River Basin, Louisiana, during a 62 day period from 1 April to 1 June 2008 using two different calibration schemes for Manning's n. First, the model is calibrated in terms of water elevations from a single in situ gauge that represents a more traditional approach. Due to the gauge location in the channel, the calibration shows more sensitivity to channel roughness relative to floodplain roughness. Second, the model is calibrated in terms of water elevation changes calculated from ALOS PALSAR interferometry during 46 days of the image acquisition interval from 16 April 2008 to 1 June 2009. Since SAR interferometry receives strongly scatters in floodplain due to double bounce effect as compared to specular scattering of open water, the calibration shows more dependency to floodplain roughness. An iterative approach is used to determine the best-fit Manning's n for the two different calibration approaches. Results suggest similar floodplain roughness but slightly different channel roughness. However, application of SAR interferometry provides a unique view of the floodplain flow gradients, not possible with a single gauge calibration. These gradients, allow improved computation of water storage change over the 46-day simulation period. Overall, the results suggest that the use of 2D SAR water elevation changes in the Atchafalaya basin offers improved understanding and modeling of floodplain hydrodynamics.

Jung, Hahn Chul↗

Thermal Model of Ice Growth in Vacuum for Lunar Water Production

To support NASA’s goal of sustained lunar presence, the use of in-situ resource utilization will reduce launch weight and frequency of resupply missions. With the discovery of water in the permanently shadowed regions of the moon, the prospect of harvesting water has generated particular interest. A more fundamental understanding of water storage and capture in lunar conditions is necessary for effective and efficient water capture and transport. The present study derives a thermal model for ice height, heat flux, chamber pressure, and mass flow rate in sub-atmospheric pressures below the triple point. The thermal model compares ice layer height against the results of the experiment at two pressures (300 Pa and 500 Pa) and temperatures from -18°C to -3°C. The thermal model predicts the trends seen experimentally with an overall root mean square error of 0.1135 cm and coefficient of efficiency of 0.994, indicating the model predicts the experimental results. The thermal model can be utilized to examine the impacts of varying pressure, temperature, and cold plate area to determine the most effective ice growth conditions for efficient capture of water on the lunar surface. The thermal model will provide a useful tool for NASA in the design of the lunar ice tanker and shows the promise of effective capture water on the lunar surface.

Ice growth↗

Thermal Model of Ice Growth in Vacuum for Lunar Water Production

To support NASA’s goal of sustained lunar presence, the use of in-situ resource utilization will reduce launch weight and frequency of resupply missions. With the discovery of water in the permanently shadowed regions of the moon, the prospect of harvesting water has generated particular interest. A more fundamental understanding of water storage and capture in lunar conditions is necessary for effective and efficient water capture and transport. The present study derives a thermal model for ice height, heat flux, chamber pressure, and mass flow rate in sub-atmospheric pressures below the triple point. The thermal model compares ice layer height against the results of the experiment at two pressures (300 Pa and 500 Pa) and temperatures from -18°C to -3°C. The thermal model predicts the trends seen experimentally with an overall root mean square error of 0.1135 cm and coefficient of efficiency of 0.994, indicating the model predicts the experimental results. The thermal model can be utilized to examine the impacts of varying pressure, temperature, and cold plate area to determine the most effective ice growth conditions for efficient capture of water on the lunar surface. The thermal model will provide a useful tool for NASA in the design of the lunar ice tanker and shows the promise of effective capture water on the lunar surface.

Ice growth↗

Hyporheic-zone Processes and Stream Oxygen Dynamics: Insights from a Multiscale Reactive Transport Model: Modeling Archive

This archive contains the data and Python scripts required to reproduce the analyses and figures in the study: Gomez-Velez, J. D., Rathore, S. S., Cohen, M. J., & Painter, S. L. (2025). Hyporheic-zone Processes and Stream Oxygen Dynamics: Insights from a Multiscale Reactive Transport Model. Submitted to Water Resources Research. The analysis utilizes the subgrid model Advection Dispersion Equation with Lagrangian Subgrids (ADELS) implemented in the Advanced Terrestrial Simulator (ATS; https://amanzi.github.io/ats/stable/). In this case, the ATS and Amanzi versions are (1) ATS version 1.5.1_f5ba18f8 and (2) Amanzi version 1.6-dev_53444cca4. The repository includes a Jupyter Notebook and the necessary data (Pandas DataFrames stored as pickle files) to generate the figures for the manuscript. Additionally, it contains Python scripts to create ATS input files, run the ATS simulations, and post-process the results. Finally, it provides routines for parameter estimation using the Single-Station Metabolism (SSM) model with the Differential Evolution Adaptive Metropolis (DREAM) Markov Chain Monte Carlo (MCMC) algorithm with ZS enhancements (DREAM-ZS).

54 ENVIRONMENTAL SCIENCES↗

Assimilation of GRACE Terrestrial Water Storage Observations into a Land Surface Model for the Assessment of Regional Flood Potential

We evaluate performance of the Catchment Land Surface Model (CLSM) under flood conditions after the assimilation of observations of the terrestrial water storage anomaly (TWSA) from NASA's Gravity Recovery and Climate Experiment (GRACE). Assimilation offers three key benefits for the viability of GRACE observations to operational applications: (1) near-real time analysis; (2) a downscaling of GRACE's coarse spatial resolution; and (3) state disaggregation of the vertically-integrated TWSA. We select the 2011 flood event in the Missouri river basin as a case study, and find that assimilation generally made the model wetter in the months preceding flood. We compare model outputs with observations from 14 USGS groundwater wells to assess improvements after assimilation. Finally, we examine disaggregated water storage information to improve the mechanistic understanding of event generation. Validation establishes that assimilation improved the model skill substantially, increasing regional groundwater anomaly correlation from 0.58 to 0.86. For the 2011 flood event in the Missouri river basin, results show that groundwater and snow water equivalent were contributors to pre-event flood potential, providing spatially-distributed early warning information.

flood↗

How Accurately Do Maize Crop Models Simulate the Interactions of Atmospheric CO2 Concentration Levels With Limited Water Supply on Water Use and Yield?

This study assesses the ability of 21 crop models to capture the impact of elevated CO2 concentration [CO2] on maize yield and water use as measured in a 2-year Free Air Carbon dioxide Enrichment experiment conducted at the Thunen Institute in Braunschweig, Germany (Manderscheid et al. 2014). Data for ambient [CO2] and irrigated treatments were provided to the 21 models for calibrating plant traits, including weather, soil and management data as well as yield, grain number, above ground biomass, leaf area index, nitrogen concentration in biomass and grain, water use and soil water content. Models differed in their representation of carbon assimilation and evapotranspiration processes. The models reproduced the absence of yield response to elevated [CO2] under well-watered conditions, as well as the impact of water deficit at ambient [CO2], with 50 percent of models within a range of plus/minus 1 Mg ha(exp. -1) around the mean. The bias of the median of the 21 models was less than 1 Mg ha(exp. -1). However under water deficit in one of the two years, the models captured only 30 percent of the exceptionally high [CO2] enhancement on yield observed. Furthermore the ensemble of models was unable to simulate the very low soil water content at anthesis and the increase of soil water and grain number brought about by the elevated [CO2] under dry conditions. Overall, we found models with explicit stomatal control on transpiration tended to perform better. Our results highlight the need for model improvement with respect to simulating transpirational water use and its impact on water status during the kernel-set phase.

grain number↗

Improving Short Term Predictability of Hydrologic Models with Deep Learning

Focal Area: Focal Area 2. Predictive modeling through the use of AI techniques and AI-derived model components; the use of AI and other tools to design a prediction system comprising of a hierarchy of models (e.g., AI driven model/component/parameterization selection). Science Challenge: A major challenge exists in the lack of reliable predictive modeling of water-cycle extremes using macro-scale hydrologic models that are driven by atmospheric climate data. This causes a critical knowledge gap in understanding the magnitudes, probabilities, and severity of droughts, rainfall, and flooding. Improved understanding of these extreme events requires more accurate modeling at high spatial and temporal resolutions. This shortcoming is especially apparent when complex couplings between atmospheric quantities and engineered systems emerge, such as during extreme precipitation or drought events and at intersections of atmospheric-land-fluvial-ocean systems. Added complexity around representing operations of engineered infrastructure leads to a limited capability to analyze the temporal and spatial implications of compounding extreme events across inland and coastal regions. This results in profound challenges for water and power systems operators, agriculture production, and regional infrastructure planning. The science challenge can be summarized as How can we use AI/ML to improve short term predictability of extreme water-cycle events and associated risk, especially compounding events and extreme rainfall patterns that result in flooding, to inland and coastal communities under different climate scenarios?

54 ENVIRONMENTAL SCIENCES↗

AUTOIGNITION DELAY TIMES FOR REFORMATE GAS MIXTURES FROM METHANE GAS ENGINES

Methane slip is a prominent issue in natural gas reciprocating engines that are used in transportation and marine applications. The incomplete combustion that results in methane slip can be resolved with the introduction of hydrogen within the combustion mixture to improve methane oxidation and further enable combustion within the engine crevices where methane has previously remained unreacted. Steam methane reforming (SMR) is a common method used to produce hydrogen and can be used to design an onboard device to reduce methane slip from reciprocating engines. The development of this reformer device requires the validation of high-fidelity chemical kinetic models at the low temperatures of the crevice volumes of these engines. In this work, auto-ignition data is obtained using a shock tube at lean (φ—0.714 or λ—1.4) and stoichiometric (φ, λ = 1) equivalence ratios spanning a temperature range of 1042–1234 K at the 80-bar operating pressure of the test engine. Blends of methane, hydrogen, and reformate products from the SMR reaction are shock-heated in synthetic air, with the ignition delay time measured using an OH* chemiluminescence detector at 310 nm and a CH* detector at 430 nm. The experimental results are compared to several state-of-the-art chemical kinetic mechanisms from the literature. In general, most of the mechanisms show very good agreement with experiments at higher temperatures, with simulation results showing little deviation from experiments at lower temperatures. A sensitivity analysis was conducted, and the results reveal that the reaction H2 + CH3O2 = H + CH3O2H has a very significant role in determining low-temperature ignition delay times (IDTs) of SMR mixtures. These findings provide valuable insights into the chemical kinetics governing methane reformate combustion and contribute to the optimization of onboard reformer designs aimed at mitigating methane slip in natural gas-fueled engines.

Fraze, Matthew↗

Fiber-optic-based laser vapor screen flow visualization system for aerodynamic research in larger scale subsonic and transonic wind tunnels

Laser vapor screen (LVS) flow visualization systems that are fiber-optic based were developed and installed for aerodynamic research in the Langley 8-Foot Transonic Pressure Tunnel and the Langley 7- by 10-Foot High Speed Tunnel. Fiber optics are used to deliver the laser beam through the plenum shell that surrounds the test section of each facility and to the light-sheet-generating optics positioned in the ceiling window of the test section. Water is injected into the wind tunnel diffuser section to increase the relative humidity and promote condensation of the water vapor in the flow field about the model. The condensed water vapor is then illuminated with an intense sheet of laser light to reveal features of the flow field. The plenum shells are optically sealed; therefore, video-based systems are used to observe and document the flow field. Operational experience shows that the fiber-optic-based systems provide safe, reliable, and high-quality off-surface flow visualization in smaller and larger scale subsonic and transonic wind tunnels. The design, the installation, and the application of the Langley Research Center (LaRC) LVS flow visualization systems in larger scale wind tunnels are highlighted. The efficiency of the fiber optic LVS systems and their insensitivity to wind tunnel vibration, the tunnel operating temperature and pressure variations, and the airborne contaminants are discussed.

Gary E Erickson↗

Dynamic modeling of orographically induced precipitation

Local orography governs the triggering of cloud formation and the enhancement of processes such as condensation and hydrometeor nucleation and growth in mountainous regions. Intense, lengthy precipitation events are typical upwind of the topographic divide, with sharply decreasing magnitude and duration on the lee side. Differences in mean annual precipitation of several hundred percent between windward slopes of orographic barriers and adjacent valleys or lee side slopes are not unusual. Because much of the streamflow in areas such as the western United States is derived from mountainous areas that are remote and often poorly instrumented, modeling of orographic precipitation has important implications for water resources management. Models of orographically induced precipitation differ by their treatment of atmospheric dynamics and by the extent to which they rely on bulk parameterization of cloud and precipitation physics. Adiabatic ascent and a direct proportionality between efficiency and orographically magnified updrafts are the most frequent assumptions in orographic precipitation modeling. Space-time discretization (i.e., resolution) is a major issue because of the high spatial variability of orographic precipitation. For a specific storm, relative errors as large as 50 to 100% are common in the forecast/hindcast of precipitation intensity and can be even larger in the case of catastrophic storms. When monthly or seasonal timescales are used to evaluate model performance, the magnitude of such errors decreases dramatically, reaching values as low as 10 to 15%. Current research is focusing on the development of data assimilation techniques to incorporate radar and satellite observations, and on the development of aggregation and disaggregation methodologies to address the implications of modeling a multiscale problem at restricted spatial and temporal resolutions.

Barros, Ana Paula↗