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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 541 records · Page 30
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Mode Specificity in the OH + HO 2 → H 2 O + O 2 Reaction: Enhancement of Reactivity by Exciting a Spectator Mode

A reaction usually involves a few active modes while the other modes are largely preserved throughout the reaction as spectators. Excitation of an active mode is expected to promote the reaction, but depositing energy in a spectator mode typically has no effect, because of the differing ability for energy flow to the reaction coordinate. Here, we report a surprising case of mode specificity in a key radical–radical reaction OH + HO 2 → H 2 O + O 2 , where such canonical expectations fail to hold. Despite its spectator nature, the vibrational excitation of the OH reactant is shown at low collision energies to enhance the reactivity significantly. This unique effect can be attributed to the increased attraction with HO 2 due to the larger dipole of the stretched OH. At low collision energies, the stronger attraction increases the chance of capturing the reactants to form a hydrogen-bonded complex, thus of passing through the submerged barrier. The novel mechanism differs from the conventional vibrational enhancement via coupling to the reaction coordinate at the transition state, enriching our understanding of mode specificity in chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Elucidating the Molecular Origins of the Transference Number in Battery Electrolytes Using Computer Simulations

The rate at which rechargeable batteries can be charged and discharged is governed by the selective transport of the working ions through the electrolyte. Conductivity, the parameter commonly used to characterize ion transport in electrolytes, reflects the mobility of both cations and anions. The transference number, a parameter introduced over a century ago, sheds light on the relative rates of cation and anion transport. This parameter is, not surprisingly, affected by cation–cation, anion–anion, and cation–anion correlations. In addition, it is affected by correlations between the ions and neutral solvent molecules. Computer simulations have the potential to provide insights into the nature of these correlations. We review the dominant theoretical approaches used to predict the transference number from simulations by using a model univalent lithium electrolyte. In electrolytes of low concentration, one can obtain a quantitative model by assuming that the solution is made up of discrete ion-containing clusters–neutral ion pairs, negatively and positively charged triplets, neutral quadruplets, and so on. These clusters can be identified in simulations using simple algorithms, provided their lifetimes are sufficiently long. In concentrated electrolytes, more clusters are short-lived and more rigorous approaches that account for all correlations are necessary to quantify transference. Elucidating the molecular origin of the transference number in this limit remains an unmet challenge.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Large Individual Ion FTICR Measurements from the Mid-1990s Using Reactions for Charge Determination Mass Spectrometry

This article discusses from a personal and present-day perspective the first studies of large highly charged individual molecular ions that were conducted using electrospray ionization (ESI) with Fourier transform ion cyclotron resonance (FTICR) MS in the mid-1990s. These studies are distinguished from current Charge Detection Mass Spectrometry (CDMS) research primarily by their use of individual ion charge state changes due to reactions. Here this work describes the key differences in technologies and methods with present CDMS, and the likely implications of these differences. I also comment on surprising individual ion behavior observed in some measurements involving increases in charge state, as well as their possible basis, and also briefly discuss the potential utility of the reaction-based mass measurement approach used in the context of what might more globally be referred to as ‘Charge Determination Mass Spectrometry’.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Identification of Unique Fragmentation Patterns of Fentanyl Analog Protomers Using Structures for Lossless Ion Manipulations Ion Mobility-Orbitrap Mass Spectrometry

The opioid crisis in the United States is being fueled by the rapid emergence of new fentanyl analogs and precursors that can elude traditional library-based screening methods, which require data from known reference compounds. Since reference compounds are unavailable for new fentanyl analogs, we examined if fentanyls (fentanyl + fentanyl analogs) could be identified in a reference-free manner using a combination of electrospray ionization (ESI), high-resolution ion mobility (IM) spectrometry, high-resolution mass spectrometry (MS), and higher-energy collision-induced dissociation (MS/MS). We analyzed a mixture containing nine fentanyls and W-15 (a structurally similar molecule) and found that the protonated forms of all fentanyls uniquely exhibited two baseline separated IM distributions that produced different MS/MS patterns. Upon fragmentation, both IM distributions of all fentanyls produced two high intensity fragments resulting from amine site cleavages. The higher mobility distributions of all fentanyls also produced several low intensity fragments, but surprisingly, these same fragments exhibited much greater intensities in the lower mobility distributions. This observation demonstrates that many fragments of fentanyls predominantly originate from one of two different gas-phase structures (suggestive of protomers). Furthermore, increasing the water concentration in the ESI solution increased the intensity of the lower mobility distribution relative to the higher mobility distribution, which further supports that fentanyls exist as two gas-phase protomers. In conclusion, our new observations on the IM and MS/MS properties of fentanyls can be exploited to positively identify them as fentanyls without requiring reference libraries and will hopefully assist first responders and law enforcement in combating new and emerging fentanyls.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

CMIP6 Models Predict Significant 21st Century Decline of the Atlantic Meridional Overturning Circulation

We explore the representation of the Atlantic Meridional Overturning Circulation (AMOC) in 27 models from the CMIP6 multi-model ensemble. Comparison with RAPID and SAMBA observations suggests that the ensemble mean represents the AMOC strength and vertical profile reasonably well. Linear trends over the entire historical period (1850-2014) are generally neutral, but many models exhibit an AMOC peak around the 1980’s. Ensemble-mean AMOC decline in future (SSP) scenarios is stronger in CMIP6 than CMIP5 models. In fact, AMOC decline in CMIP6 is surprisingly insensitive to the scenario at least up to 2060. We find an emergent relationship among a majority of models between AMOC strength and 21st century AMOC decline. Constraining this relationship with RAPID observations suggests that the AMOC might decline between 6 and 8 Sv (34-45%) by 2100. A smaller group of models projects much less AMOC weakening of only up to 30%.

58 GEOSCIENCES↗
DOE OSTI2020

Heat Flow on the U.S. Beaufort Margin, Arctic Ocean: Implications for Ocean Warming, Methane Hydrate Stability, and Regional Tectonics

The Arctic Ocean represents one of the last geological frontiers on Earth. The formation of the Arctic Ocean remains unclear, and although it is well understood that the Arctic surface temperature is warming at a rate approximately twice as fast as the rest of the Earth, it is unclear how deep Arctic Ocean temperatures are changing. Understanding whether deep Arctic Ocean water is warming is important, since it can lead to the breakdown and release of huge quantities of frozen methane molecules trapped below the Arctic seafloor, which can increase ocean acidity and destabilize the seafloor. To understand both Arctic Ocean temperature change and geologic evolution, we collected temperature measurements at 103 sites. These measurements tell us how temperature increases with depth below the seafloor and can be used to understand both ocean temperature change and regional geology. Analysis of our data shows that at depths of 300–900 m below sea level, the Arctic Ocean has been warming steadily for perhaps several decades—nearly twice as deep as previous studies suggest. At ocean depths greater than 1,000 m, our analysis also reveals surprisingly high temperature increases with depth in the seafloor. The cause of these significant increases is unclear.

58 GEOSCIENCES↗
DOE OSTI2020

Observational Constraints on Warm Cloud Microphysical Processes Using Machine Learning and Optimization Techniques

We introduce new parameterizations for autoconversion and accretion rates that greatly improve representation of the growth processes of warm rain. The new parameterizations capitalize on machine‐learning and optimization techniques and are constrained by in situ cloud probe measurements from the recent Atmospheric Radiation Measurement Program field campaign at Azores. The uncertainty in the new estimates of autoconversion and accretion rates is about 15% and 5%, respectively, outperforming existing parameterizations. Our results confirm that cloud and drizzle water content are the most important factors for determining accretion rates. However, for autoconversion, in addition to cloud water content and droplet number concentration, we discovered a key role of drizzle number concentration that is missing in current parameterizations. The robust relation between autoconversion rate and drizzle number concentration is surprising but real, and furthermore supported by theory. Thus, drizzle number concentration should be considered in parameterizations for improved representation of the autoconversion process.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

A New Crater Near InSight: Implications for Seismic Impact Detectability on Mars

A new 1.5 m diameter impact crater was discovered on Mars only ~40 km from the InSight lander. Context camera images constrained its formation between 21 February and 6 April 2019; follow-up High Resolution Imaging Science Experiment images resolved the crater. During this time period, three seismic events were identified in InSight data. In this paper, we derive expected seismic signal characteristics and use them to evaluate each of the seismic events. However, none of them can definitively be associated with this source. Atmospheric perturbations are generally expected to be generated during impacts; however, in this case, no signal could be identified as related to the known impact. Using scaling relationships based on the terrestrial and lunar analogs and numerical modeling, we predict the amplitude, peak frequency, and duration of the seismic signal that would have emanated from this impact. The predicted amplitude falls near the lowest levels of the measured seismometer noise for the predicted frequency. Hence, it is not surprising this impact event was not positively identified in the seismic data. Finding this crater was a lucky event as its formation this close to InSight has a probability of only ~0.2, and the odds of capturing it in before and after images are extremely low. We revisit impact-seismic discriminators in light of real experience with a seismometer on the Martian surface. Using measured noise of the instrument, we revise our previous prediction of seismic impact detections downward, from ~a few to tens, to just ~2 per Earth year, still with an order of magnitude uncertainty.

58 GEOSCIENCES↗
DOE OSTI2021

Snow Reconciles Observed and Simulated Phase Partitioning and Increases Cloud Feedback

The surprising increase of Earth's climate sensitivity in the most recent coupled model intercomparison project (CMIP) models has been largely attributed to extratropical cloud feedback, which is thought to be driven by greater supercooled water in present-day cloud phase partitioning (CPP). Here, we report that accounting for precipitation in the Goddard Institute for Space Studies ModelE3 radiation scheme, neglected in more than 60% of CMIP6 and 90% of CMIP5 models, systematically changes its apparent CPP and substantially increases its cloud feedback, consistent with results using CMIP models. Including precipitation in the comparison with cloud–aerosol lidar and infrared pathfinder satellite observations (CALIPSO) measurements and in model radiation schemes is essential to faithfully constrain cloud amount and phase partitioning, and simulate cloud feedbacks. Our findings suggest that making radiation schemes precipitation-aware (missing in most CMIP6 models) should strengthen their positive cloud feedback and further increase their already high mean climate sensitivity.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Investigating Tropical Versus Extratropical Influences on the Southern Hemisphere Tropical Edge in the Unified Model

Abstract Since the late 1970s, observations have shown a widening of the tropical Hadley cell (HC) circulation. State‐of‐the‐art climate models reproduce the general trend along with a projected continuous expansion. Discrepancies in expansion rates of observation‐ and model‐based studies have been attributed to differences in applied methods, natural variability and model shortcomings. Furthermore, the driving influence of tropical or extratropical processes on these changes is not well understood. All of this highlights the dynamical mechanisms and the region of origin controlling the tropical width are still insufficiently understood. Here we examine the influence of systematic model biases of the atmosphere‐only Unified Model (UM) onto the simulation of the Southern Hemisphere (SH) tropical edge. We utilize nudged experiments with prescribed sea surface temperatures, where potential temperature and horizontal winds are relaxed back to ERA‐Interim reanalysis for a 20‐year period in selected regions. Correcting model biases in the tropics and extratropics separately allows us to dissect the dominant remote impacts of present model errors onto the SH tropical edge simulation. The experiments are applied to established tropical width metrics ranging from near‐surface to upper‐level metrics capturing the poleward flank of the HC. We find both regions work remotely to reduce errors in the UM fields and location of the tropical edge. Surprisingly, correcting the extratropical biases, south of 45°S, more consistently improves the tropical width across the metrics and seasons than nudging the tropics (10°N–10°S). These findings demonstrate the substantial role of extratropical influences in locating the SH tropical edge.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Mineral Protection and Resource Limitations Combine to Explain Profile-Scale Soil Carbon Persistence

The fate of soil carbon (C) is largely controlled by microbial oxidation of organic matter (OM), which is constrained by a variety of mechanisms. OM association with soil minerals provides pronounced protection against microbial decomposition. However, factors such as climate, occlusion, and resource limitations also contribute to OM preservation. Here, we explore the factors explaining C distribution and age within an upland rainforest soil in Hawai'i, a site with abundant preferential flow paths (PFPs) and high short-range order (SRO) mineral content. We characterized lateral and vertical changes in Δ 14 C, SRO mineral content, C-functional group chemistry, and microbial community composition to elucidate the contributions of multiple protection mechanisms to OM preservation. Consistent with our expectation, SRO mineral content and Δ 14 C were strongly correlated (R 2 = 0.95), indicating strong mineral protection of OM throughout the profile. Surprisingly, distance from PFP was also a significant predictor of Δ 14 C and improved model fit, particularly in the shallow horizons (R 2 = 0.97). Elevated C/N ratios, decreased microbial abundance, and greater SRO mineral content suggest nitrogen limitations and enhanced mineral protection constrain OM turnover with distance from PFPs in deep, subsurface mineral horizons. Steady microbial abundance, increasing putative anaerobe abundance, and changes in C-functional group chemistry indicate oxygen limitations constrain OM turnover in the matrix of shallow mineral horizons. Given that oxygen and nutrient limitations contribute to OM preservation in this high SRO system—an exemplar of mineral protection—resource limitations may play an even more important role in OM preservation in other well-structured soils.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Differential Trends in Iron Concentrations of Boreal Streams Linked to Catchment Characteristics

Increasing iron (Fe) concentrations have been reported for freshwaters across northern Europe over the last decades. This increase, together with elevated concentrations of dissolved organic carbon (DOC), leads to browning of freshwaters, which affects aquatic organisms, ecosystem functioning, biogeochemical cycles, and brings challenges to drinking water production. However, how such increasing trends in stream Fe concentrations reflect the contribution of different catchment sources remains poorly resolved. Here, we explored how catchment characteristics, that is, mires and coniferous soils, regulate spatial and temporal patterns of Fe in a boreal stream network. For this, we determined Fe speciation in riparian and mire soils, and studied temporal Fe dynamics in soil-water and stream-water over a span of 18 years. Positive Fe trends were found in the solution of the riparian soil, while no long-term trend was observed in the mire. These differences were reflected in stream-water, where three headwater streams dominated by coniferous cover also displayed positive Fe trends, whereas the mire dominated stream showed no trend. Surprisingly, the majority of higher order streams showed declining Fe trends, despite long-term increases in DOC. In addition, we found that an extreme drought event led to a prolonged release of Fe and DOC from the riparian soils, that could have long-term effects on stream Fe concentrations. Our results show that riparian forest soils can be major contributors to ongoing increases in freshwater Fe concentrations and that drought can further promote the release of Fe from organic soils.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Unexpected Changes of Aerosol Burdens With Decreased Convection in the Context of Scale-Aware Convection Schemes

Atmospheric aerosols in global climate models (GCMs) can be removed by both large-scale and convective precipitation. As the horizontal resolution of GCMs increases, it is expected that large-scale precipitation increases and convective precipitation decreases if scale-aware convection schemes are well developed. Here, to explore its impact on aerosol burdens, this study develops a novel method and applies it to the National Center for Atmospheric Research Community Atmosphere Model version 5.3 to mimic the behavior of scale-aware convective schemes. Surprisingly, it is found that aerosol burden increases globally as convective precipitation decreases and large-scale precipitation increases, which can be attributed to the reduced light rain. In the light-rain intensity category, the decreased frequency of convective precipitation is not offset by the increased frequency of large-scale precipitation. Therefore, for aerosol simulations in high-resolution GCMs using scale-aware convection schemes, subgrid convection and large-scale condensation should be coordinated to assure light rain stays the same.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Characterization of Aquifer Poroelastic Response to Impulse and Oscillatory Well Pressure Using Distributed Acoustic Sensing

Abstract The storage of fluids in the subsurface is critical for a broad spectrum of applications including managed aquifer recharge, storage of liquefied carbon dioxide and hydrogen, geothermal heat extraction and exploitation of hydrocarbon. It is surprising then, that there has been relatively little measurement of the vertical distribution of poroelastic storage in geologic formations as compared with permeability. We present experiments in which fluid was injected into an important regional aquifer and the depth‐dependent strain response measured using fiber optic distributed acoustic sensing. The formation expansion and contraction in response to fluid injection were several 100 nanostrain. Strain, and the implied storage distribution, was highly localized in specific strata and demonstrated complex, hydromechanical behavior. This new window into fluid‐geomechanical coupling undermines some typically use models and observations currently in practice, but provides potential for complete representation and prediction of fluid storage in the subsurface.

58 GEOSCIENCES↗
DOE OSTI2024

Research to Confront Climate Change Complexity: Intersectionality, Integration, and Innovative Governance

Abstract Climate impacts increasingly unfold in interlinked systems of people, nature, and infrastructure. The cascading consequences are revealing sometimes surprising connections across sectors and regions, and prospects for climate responses also depend on complex, difficult‐to‐understand interactions. In this commentary, we build on the innovations of the United States Fifth National Climate Assessment to suggest a framework for understanding and responding to complex climate challenges. This approach involves: (a) integration of disciplines and expertise to understand how intersectionality shapes complex climate impacts and the wide‐ranging effects of climate responses, (b) collaborations among diverse knowledge holders to improve responses and better encompass intersectionality, and (c) sustained experimentation with and learning about governance approaches capable of handling the complexity of climate change. Together, these three pillars underscore that usability of climate‐relevant knowledge requires transdisciplinary coordination of research and practice. We outline actionable steps for climate research to incorporate intersectionality, integration, and innovative governance, as is increasingly necessary for confronting climate complexity and sustaining equitable, ideally vibrant climate futures.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

The Effect of Indian Ocean Temperature on the Pacific Trade Winds and ENSO

Abstract A notable shift in the El Niño‐Southern Oscillation (ENSO) has been observed in the early 21st century, characterized by an increased prevalence of Central Pacific (CP) events and strengthened Pacific trade winds. This shift may be attributed to the warming tropical Indian Ocean (TIO). To investigate this, we conduct perturbation experiments using the Insitut Pierre Simon Laplace climate model and nudge TIO surface temperatures to induce warming or cooling effects. Our findings reveal that TIO warming (or cooling) leads to amplified (weakened) mean trade winds and surface warming (cooling) in the Pacific region. Surprisingly, ENSO variability increases in both TIO cooling and warming scenarios. This result is linked to stronger positive feedbacks and a less stable Bjerknes index for either TIO forcing. Additionally, we find that TIO warming leads to more frequent CP events, meridional widening of wind anomalies, and broadening of the ENSO power spectrum toward lower frequencies.

Geology↗
DOE OSTI2023

Characterizing the Impacts of Multi-Scale Heterogeneity on Solute Transport in Fracture Networks

We model flow and transport in fracture networks with varying degrees of fracture-to-fracture aperture heterogeneity and network intensity to show how changes in these properties can cause the emergence of anomalous flow and transport behavior. If fracture-to-fracture aperture heterogeneity is increased in sparse networks, velocity fluctuations inhibit high flow rates and solute transport can be delayed. Surprisingly, transport can be slowed even in cases where hydraulic aperture is monotonically increased. As the intensity of the networks is increased, more connected pathways allow for particles to bypass these effects. There exists transition behavior where with relatively few connected pathways in a network, first arrival times of particles are not heavily affected by fracture-to-fracture aperture heterogeneity, but the scaling behavior of the tails is strongly influenced. These results reinforce the importance of considering multi-scale effects in fractured systems and can inform flow and transport processes in both natural and engineered fractured systems.

58 GEOSCIENCES↗
DOE OSTI2024

An Evaluation of Dynamical Downscaling Methods Used to Project Regional Climate Change

In the past decade, dynamical downscaling using “pseudo-global-warming” (PGW) techniques has been applied frequently to project regional climate change. Such techniques generate signals by adding mean global climate model (GCM)-simulated climate change signals in temperature, moisture, and circulation to lateral and surface boundary conditions derived from reanalysis. An alternative to PGW is to downscale GCM data directly. This technique should be advantageous, especially for simulation of extremes, since it incorporates the GCM's full spectrum of changing synoptic-scale dynamics in the regional solution. Here, we test this assumption, by comparing simulations in Europe and Western North America. We find that for warming and changes in temperature extremes, PGW often produces similar results to direct downscaling in both regions. For mean and extreme precipitation changes, PGW generally also performs surprisingly well in many cases. Moisture budget analysis in the Western North America domain reveals why. Large fractions of the downscaled hydroclimate changes arise from mean changes in large-scale thermodynamics and circulation, that is, increases in temperature, moisture, and winds, included in PGW by design. The one component PGW may have difficulty with is the contribution from changes in synoptic-scale variability. When this component is large, PGW performance could be degraded. Global analysis of GCM data shows there are regions where it is large or dominant. Hence, our results provide a road map to identify, through GCM analyses, the circumstances when PGW would not be expected to accurately regionalize GCM climate signals.

54 ENVIRONMENTAL SCIENCES↗