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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 163 records · Page 9

A recirculation system for concentrating CO 2 electrolyzer products

Electrochemical carbon dioxide reduction represents a promising path to utilize CO 2 as a feedstock for generating valuable products such as fuels and chemicals. Faradaic efficiencies near 100% have been achieved for certain CO 2 reduction products such as CO, but the electrolyzer outlet streams usually contain large fractions of unreacted CO 2 , dropping the product concentrations below 1% in many cases. The system disclosed here recycles the unreacted CO 2 together with the products and flows them back into the CO 2 reduction reactor, enabling much higher CO 2 conversion rates without dropping the gas flow rate. However, simple recirculation is shown to accumulate significant amounts of hydrogen, impeding effective CO 2 reduction. In this looped system, an electrochemical H 2 pump is placed in series with the CO 2 reactor, which effectively removes all the H 2 from the recycled gas stream, increasing the concentrations of carbon-containing products. Here, the system was initially tested with a CO-generating catalyst and CO concentrations above 70% were achieved in the recycled gas stream, compared to a maximum CO concentration of 8% in single-pass configuration. Results with a CO 2 reactor targeting ethylene as the main product show that ethylene concentrations of at least 10% can be achieved, which is roughly 20 times higher compared to a single-pass system.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Acid–base concentration swing for direct air capture of carbon dioxide

This work demonstrates the first experimental evidence of the acid–base concentration swing (ABCS) for direct air capture of CO 2 . This process is based on the effect that concentrating particular acid–base chemical reactants will strongly acidify solution, through Le Chatelier's principle, and result in outgassing absorbed CO 2 . After collecting the outgassed CO 2 , diluting the solution will result in a reversal of the acid–base reaction, basifying the solution and allowing for atmospheric CO 2 absorption. The experimental study examines a system that includes sodium cation as the alkalinity carrier, boric acid, and a polyol complexing agent that reversibly reacts with boric acid to strongly acidify solution upon concentration. Though the tested experimental system faces absorption rate and water capacity limitations, the ABCS process described here provides a basis for further process optimization. A generalized theoretical ABCS reaction framework is developed and different reaction orders and conditions are studied mathematically. Higher order reactions yield favorable cycle output results, reaching volumetric cycle capacity above 50 mM for third-order and 80 mM for fourth-order reactions. Optimal equilibrium constants are determined in order to guide alternative chemical searches and synthetic chemistry design targets. There is a substantial energetic benefit for reaction orders above the first, with second- and third-order ABCS cycles exhibiting a thermodynamic minimum work for the concentrating and outgassing steps around 150 kJ per mole of CO 2 . A significant advantage of the ABCS is that it can be driven through well-developed and widely-deployed desalination technologies, such as reverse osmosis, with opportunities for energy recovery when recombining the concentrated and diluted streams, and extraction can occur directly from the liquid phase upon vacuum application.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The critical role of synthesis conditions on small polaron carrier concentrations in hematite—A first-principles study

Achieving highly efficient energy conversion with transition metal oxides necessitates overcoming conductivity limitations due to the formation of small polarons. Detailed understanding of the interplay among intrinsic defects, dopants, and electron polarons can help devise strategies for achieving higher carrier concentrations, therefore improving carrier conductivity. This work employs first-principles calculations to reliably predict electron polaron concentrations in a prominent polaronic oxide, hematite (Fe 2 O 3 ), by resolving interactions between charged defects and electron polarons and keeping charge neutrality condition among all charged species. This work addresses that both V O and Fe i can be primary donors in undoped hematite depending on the synthesis conditions, such as synthesis temperature and oxygen partial pressure, despite the fact that V O owns an extremely high ionization energy compared to k B T. Furthermore, from calculations of a plethora of n-type dopants (group IV and V elements), we find that Ti, Ge, Sb, and Nb are able to raise electron polaron concentrations in hematite significantly without considering dopant clustering. However, the magnitude of electron polaron concentration increase would be smaller if the dopant has a high tendency of clustering, such as Ti. Here we reveal the critical role of synthesis conditions on tuning electron polaron concentrations of both undoped and doped hematite. Our theoretical analysis provides important insights and general design principles for engineering more conductive polaronic oxides.

36 MATERIALS SCIENCE↗

Beyond the Debye–Hückel limit: Toward a general theory for concentrated electrolytes

The phenomenon of underscreening in concentrated electrolyte solutions leads to a larger decay length of the charge–charge correlation than the prediction of Debye–Hückel (DH) theory and has found a resurgence of both theoretical and experimental interest in the chemical physics community. To systematically understand and investigate this phenomenon in electrolytes requires a theory of concentrated electrolytes to describe charge–charge correlations beyond the DH theory. We review the theories of electrolytes that can transition from the DH limit to concentrations where charge correlations dominate, giving rise to underscreening and the associated Kirkwood Transitions (KTs). In this perspective, we provide a conceptual approach to a theoretical formulation of electrolyte solutions that exploits the competition between molecular-informed short-range (SR) and long-range interactions. We demonstrate that all deviations from the DH limit for real electrolyte solutions can be expressed through a single function ΣQ that can be determined both theoretically and numerically. Importantly, ΣQ can be directly related to the details of SR interactions and, therefore, can be used as a tool to understand how differences in representations of interaction can influence collective effects. The precise function form of ΣQ can be inferred through a Gaussian field theory of both the number and charge densities. The resulting formulation is validated by experiment and can accurately describe the collective phenomenon of screening in concentrated bulk electrolytes. Importantly, the Gaussian field theory predictions of the screening lengths appear to be less than ∼1 nm at concentrations above KTs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Modeling the behavior of concentrated aqueous HNO 3 using machine learning interatomic potentials

We develop two multi-defect machine learning interatomic potentials (MLIPs) trained at the BLYP-D2 and PBE-D3 density functional theories using the DeepMD-kit, allowing for the investigation of structural and thermodynamic properties of nitric acid over a wide range of concentrations via molecular dynamics (MD) simulations. We directly compute the degree of dissociation, α, and pK a from MD simulations, revealing that HNO 3 behaves as a weaker acid at higher concentrations, noting that our standard-state pK a value is in excellent agreement with the experimental one. In general, good agreement is observed with experimental results such as α and density outside the training dataset, with only modest deviations at low-to-medium concentrations. We benchmark our custom multi-defect DeepMD MLIPs against foundational models MACE-MP0 and MACE-OFF23. The foundation models capture some aspects of HNO 3 /NO 3 − solvation in concentrated nitric acid but show noticeable density errors and miss subtle structural features relevant to spectroscopy, whereas the bespoke DeepMD MLIPs yield more compact solvation shells, reproduce density-concentration trends, and run ∼12–15× faster than MACE-MP0. Although classical FFs are still more efficient and match experimental densities better, they lack chemical reactivity and thus cannot predict α or pK a , underscoring the need for system-specific reactive MLIPs beyond universal MLIPs.

Dinpajooh, Mohammadhasan [Pacific Northwest Nation↗

Fire reduces riverine DOC concentration draining a watershed and alters post-fire DOC recovery patterns

Abstract The loading of dissolved organic carbon (DOC) from soils to inland waters and ultimate transport to the ocean is a critical flux pathway in the terrestrial biosphere carbon cycle. Fires can significantly affect this flux through biogeochemical processes related to oxidation and mobilization of DOC in the soil. Therefore, in order to accurately estimate and model terrestrial carbon storage and export to the marine environment, we need to better understand the effects of fire on DOC flux. In this analysis, we compiled available observational data sets from seven watersheds across the conterminous United States generally spanning the years 1999–2019. We used these data sets to examine the effects of fire on riverine DOC concentration draining a watershed to study both the immediate impacts and the post-fire recovery patterns. Our results suggest that these fires result in an immediate decrease in riverine DOC concentration draining the watershed by 26 ± 15%, and the time required for DOC concentrations to recover to pre-fire levels was estimated to be, on average, approximately 9 months. During recovery, DOC concentration was 24 ± 11% lower than the long-term average for the watershed. In addition, the larger the proportion of the watershed that burned, the greater the concentration decrease and the longer the time period for post-fire recovery.

54 ENVIRONMENTAL SCIENCES↗

Positive correlation between wood δ 15 N and stream nitrate concentrations in two temperate deciduous forests

Abstract A limitation to understanding drivers of long-term trends in terrestrial nitrogen (N) availability in forests and its subsequent influence on stream nitrate export is a general lack of integrated analyses using long-term data on terrestrial and aquatic N cycling at comparable spatial scales. Here we analyze relationships between stream nitrate concentrations and wood δ 15 N records (n = 96 trees) across five neighboring headwater catchments in the Blue Ridge physiographic province and within a single catchment in the Appalachian Plateau physiographic province in the eastern United States. Climatic, acidic deposition, and forest disturbance datasets were developed to elucidate the influence of these factors on terrestrial N availability through time. We hypothesized that spatial and temporal variation of terrestrial N availability, for which tree-ring δ 15 N records serve as a proxy, affects the variation of stream nitrate concentration across space and time. Across space at the Blue Ridge study sites, stream nitrate concentration increased linearly with increasing catchment mean wood δ 15 N. Over time, stream nitrate concentrations decreased with decreasing wood δ 15 N in five of the six catchments. Wood δ 15 N showed a significant negative relationship with disturbance and acidic deposition. Disturbance likely exacerbated N limitation by inducing nitrate leaching and ultimately enhancing vegetative uptake. As observed elsewhere, lower rates of acidic deposition and subsequent deacidification of soils may increase terrestrial N availability. Despite the ephemeral modifications of terrestrial N availability by these two drivers and climate, long-term declines in terrestrial N availability were robust and have likely driven much of the declines in stream nitrate concentration throughout the central Appalachians.

54 ENVIRONMENTAL SCIENCES↗

Topological alloy engineering and locally linearized gap dependence on concentration

Alloy engineering is a well-established approach to tune various materials’ properties, but its application to topological alloys remains rudimentary. Of special interest is the band gap, the most defining property of topological materials; however, the concentration dependence of energy gaps in topological alloys remains unknown. Here we systematically investigate the band gap evolution of a topological alloy as a function of alloy concentration, using KZnSb 1-x Bi x as a prototype, based on first-principles calculations. In contrast to the well-established smooth bowing curve for a trivial gap in semiconductor alloys, we found that the topological gap evolves generally with a complex fragmented pattern due to topological phase transitions, and most strikingly a linear dependence on concentration locally in each distinct phase. Such gap linearization is fundamentally rooted in the linear dependence on alloy concentration of spin-orbit coupling (SOC) that predominantly determines a topological gap. Furthermore, we demonstrate topological alloy engineering as a general approach to tune the topological order by modulating the band edge composition and degeneracy through the alloying-induced interplay of SOC and atomic orbital on-site energy, while the linear gap dependence on alloy concentration remains independent of the degree of topological order.

36 MATERIALS SCIENCE↗

Ion Pairing, Clustering and Transport in a LiFSI-TMP Electrolyte as Functions of Salt Concentration using Molecular Dynamics Simulations

Battery capacity is highly related to ion-pairing mechanisms in electrolytes, since a cluster formation can lead to dead Li formation, reducing the number of charge carriers and leading to capacity fading. We use molecular dynamics simulations to model an electrolyte comprising trimethyl phosphate (TMP) solvent and a lithium bis(fluorosulfonyl)imide (LiFSI) salt, exploring effects of salt concentration on solvation and ion-transport. We simulate the LiFSI-TMP electrolyte for salt concentrations of 0.7, 1.43 and 3.82 molar. A statistical analysis was performed to study ion-pairing, clustering, diffusivity, conductivity, and coordination of Li-ions, providing insights into relations between molecular structures and transport properties. Molecular structure of ionic components changes as concentration increases, from a predominant solvent separated ion pair (SSIP) and contact ion pair (CIP) to aggregate salt (AGG) and ionic cluster formation. Given the formation of the ionic cluster, the diffusion mechanism followed by Li-ions changes from a hopping/exchange to a vehicular mechanism as concentration increases; this is reflected in a decrease of ionic conductivities. Ionicity was also calculated to reveal how the ionic motion changes from an uncorrelated to a correlated one as the salt concentration increases. Furthermore, we also compared our results with experimental calculations performed for similar electrolyte systems

25 ENERGY STORAGE↗

Mapping Spatiotemporal Solvent Velocity from Measured Concentration Gradients in a Polarized Electrolyte

The electric-field induced motion of neutral species impedes the efficacy of electrochemical devices. By combining operando X-ray transmission measurements with continuum mechanics, we have developed a methodology for determining the velocity of neutral solvent molecules under an applied field. The X-ray transmission experiments were used to determine ion concentration profiles as a function of space and time in a polymer electrolyte. The unsteady state solvent mass balance equation was solved numerically with experimental concentration profiles to map spatiotemporal solvent velocities. We compare our experimentally derived results with predictions made with concentrated solution theory. We use the cation transference number as the only adjustable parameter to match experimental measurements of both concentration and solvent velocity. Our approach may be used to determine solvent velocity with any operando technique used to measure time-dependent ion concentration profiles.

Abdo, Emily E↗

Impact of the LiPF6 Concentration on the Interfacial Charge Transfer and Fast-charging Capabilities of Lithium-Ion Batteries

Fast-charging lithium-ion batteries (LIB) demand optimized electrolyte formulations to balance ionic conductivity, viscosity, and interfacial charge transfer kinetics. This study examines how LiPF 6 concentration shapes solvation structure, desolvation energy, charge transfer activation energy, and solid electrolyte interphase (SEI) properties, which are critical for fast-charging performance. Using Raman spectroscopy, electrochemical cycling, X-ray photoelectron spectroscopy, and atomistic modeling, we analyze how varying LiPF 6 concentrations impact interfacial and bulk transport properties. Our findings show that increasing LiPF 6 concentration alters lithium solvation structures, reduces desolvation energy, and accelerates charge transfer at the electrode interface. Higher concentrations lower the activation energy for charge transfer and suppress excessive SEI growth, improving interfacial kinetics. However, concentrations above a certain threshold increase viscosity and reduce ionic conductivity, limiting transport efficiency. These results offer insights into electrolyte solvation and interfacial charge transfer mechanisms, providing guidelines for designing next-generation fast-charging LIB electrolytes with enhanced efficiency, stability, and longevity.

Son, Seoung-Bum [Argonne National Laboratory (ANL)↗

Concentrated radiative cooling and its constraint from reciprocity

Concentrated radiative cooling, an analogous concept of the concentrated solar power technology, has the potential of amplifying both the cooling power and the temperature reduction. However, concentrators have not yet been systematically optimized. Moreover, a widely used theoretical approach to analyze such systems has neglected a fundamental constraint from reciprocity, which can lead to an overestimate of cooling performance and unclarified limits of amplification factors. Here we develop a theoretical framework addressing these shortcomings. Modeling suggests the optimized shape and geometric dimensions of concentrators, as well as the limiting cooling power and temperature reduction. Using an electroplated Al 2 O 3 emitter and an optimized conical concentrator, we experimentally amplify the nighttime radiative cooling by 26%.

Dong, Minghao↗

Chamber Flux and Porewater Concentration of CH4, CO2 and N2O, 2018, Columbia River bank at the Hanford site, WA, USA

This is the corresponding observations data for the paper: Jorge A Villa; Garrett J Smith; Yang Ju; Lupita Renteria; Jordan C Angle; Evan Arntzen; Samuel F Harding; Huiying Ren; Xingyuan Chen; Audrey H Sawyer; Emily B Graham; James C Stegen; Kelly C Wrighton; Gil Bohrer (2020) Methane and nitrous oxide porewater concentrations and surface fluxes of a regulated river. Science of the Total Environment.Greenhouse gas (GHG) emissions from rivers are a critical missing component of current global GHG models. Their exclusion is mainly due to a lack of in-situ measurements and a poor understanding of the spatiotemporal dynamics of GHG production and emissions, which prevents optimal model parametrization. We combined simultaneous observations of porewater concentrations along different beach positions and depths, and surface fluxes of methane and nitrous oxide at a plot scale in a large regulated river during three water stages: rising, falling, and low. Our goal was to gain insights into the interactions between hydrological exchanges and GHG emissions and elucidate possible hypotheses that could guide future research on the mechanisms of GHG production, consumption, and transport in the hyporheic zone (HZ). Results indicate that the site functioned as a net source of methane. Surface fluxes of methane during river water stages at three beach positions (shallow, intermediate and deep) correlated with porewater concentrations of methane. However, fluxes were significantly higher in the intermediate position during the low water stage, suggesting that low residence time increased methane emissions. Vertical profiles of methane peaked at different depths, indicating an influence of the magnitude and direction of the hyporheic mixing during the different river water stages on methane production and consumption. The site acted as either a sink or a source of nitrous oxide depending on the elevation of the water column. Nitrous oxide porewater concentrations peaked at the upper layers of the sediment throughout the different water stages. River hydrological stages significantly influenced porewater concentrations and fluxes of GHG, probably by influencing heterotrophic respiration (production and consumption processes) and transport to and from the HZ. Our results highlight the importance of including dynamic hydrological exchanges when studying and modeling GHG production and consumption in the HZ of large rivers.

54 ENVIRONMENTAL SCIENCES↗

2019 Results for Avian Monitoring of Inorganic and Organic Element Concentrations in Passerine Eggs and a Nestling Collected from Technical Area 16 Burn Grounds, Technical Area 36 Minie, and Technical Area 39 Point 6 at Los Alamos National Laboratory

In 2019, non-viable avian eggs and one nestling were opportunistically collected at Los Alamos National Laboratory (LANL) near open detonation sites located at Technical Area (TA) 16 burn grounds, TA-36 Minie, and TA-39 Point 6. These samples were evaluated for inorganic elements (mostly metals), polychlorinated biphenyls (PCBs), dioxins, and furans. A total of 26 western bluebird (Sialia mexicana) and five mountain bluebird (Sialia currucoides) egg samples and one non-viable ash-throated flycatcher (Myiarchus cinerascens) nestling were collected among the three locations of interest. Concentrations of inorganic elements observed in this study were compared with the regional statistical reference level (RSRL) which is the upper-level bounds of background concentrations (mean + three standard deviations = 99% confidence interval). Several inorganic elements were not detected in avian eggs and the majority of inorganic elements detected were below the RSRL. The few elements that exceeded the RSRL were below the lowest observable adverse effect level (LOAEL), when available. One nestling collected from TA-16 contained detectable concentrations of some dioxin and furan congeners. Octachlorodibenzodioxin-1,2,3,4,6,7,8,9 concentration exceeded the RSRL, but did not exceed the calculated tetrachlorodibenzodioxin-2,3,7,8 (TCDD) toxic equivalent LOAEL. PCBs were also detected in the nestling sample and were above the RSRL but below the LOAEL. These data suggest that inorganic and organic element concentrations in eggs and nestlings are not of ecological concern. More data are needed to make a robust assessment and to evaluate trends over time.

54 ENVIRONMENTAL SCIENCES↗

Modeling the Destruction of Glycolate in the Defense Waste Processing Facility (DWPF) Recycle Stream and Concentration Factors for Glycolate in the 2H Evaporator

Two models were developed to predict maximum glycolate concentrations in the Savannah River Site (SRS) Concentration, Storage, and Transfer Facility (CSTF) from implementation of the Nitric-Glycolic flowsheet at the Defense Waste Processing Facility (DWPF). One model describes the kinetics of glycolate destruction via chemical oxidation with sodium permanganate. This model conservatively predicts glycolate concentration delivered to the CSTF with a high probability the actual glycolate concentration is lower than predicted. The second model describes the potential concentration of said residual glycolate within the 242-16H (i.e., “2H”) Evaporator system.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

2020 Results for Avian Monitoring of Inorganic and Organic Element Concentrations in Passerine Eggs and Nestlings Collected from Technical Area 16 Burn Grounds, Technical Area 36 Minie, and Technical Area 39 Point 6 at Los Alamos National Laboratory

In 2020, non-viable avian eggs and two nestling were opportunistically collected at Los Alamos National Laboratory (LANL) near open detonation sites located at Technical Area (TA) 16 burn grounds, TA-36 Minie, and TA-39 Point 6. These samples were evaluated for inorganic elements (mostly metals), dioxins, and furans. A total of six eggs and two deceased western bluebird (Sialia mexicana) nestling samples were collected among the three locations of interest. Concentrations of inorganic elements observed in this study were compared with the regional statistical reference level (RSRL) which is the upper-level bounds of background concentrations (mean + three standard deviations = 99% confidence interval). Several inorganic elements were not detected in avian eggs and all inorganic elements detected were below the RSRL and the lowest observable adverse effect level (LOAEL), when available. One nestling collected from TA-39 contained detectable concentrations of two dioxin congeners. Heptachlorodibenzodioxin-1,2,3,4,6,7,8 and octachlorodibenzodioxin-1,2,3,4,6,7,8,9 concentration exceeded the RSRL, but did not exceed the calculated tetrachlorodibenzodioxin 2,3,7,8 (TCDD) toxic equivalent LOAEL. These data suggest that inorganic and organic element concentrations in eggs and nestlings are not of ecological concern. More data are needed to make a robust assessment and to evaluate trends over time.

54 ENVIRONMENTAL SCIENCES↗

Microbial Communities Influence Soil Dissolved Organic Carbon Concentration by Altering Metabolite Composition

Rapid microbial growth in the early phase of plant litter decomposition is viewed as an important component of soil organic matter (SOM) formation. However, the microbial taxa and chemical substrates that correlate with carbon storage are not well resolved. The complexity of microbial communities and diverse substrate chemistries that occur in natural soils make it difficult to identify links between community membership and decomposition processes in the soil environment. To identify potential relationships between microbes, soil organic matter, and their impact on carbon storage, we used sand microcosms to control for external environmental factors such as changes in temperature and moisture as well as the variability in available carbon that exist in soil cores. Using Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) on microcosm samples from early phase litter decomposition, we found that protein- and tannin-like compounds exhibited the strongest correlation to dissolved organic carbon (DOC) concentration. Proteins correlated positively with DOC concentration, while tannins correlated negatively with DOC. Through random forest, neural network, and indicator species analyses, we identified 42 bacterial and 9 fungal taxa associated with DOC concentration. The majority of bacterial taxa (26 out of 42 taxa) belonged to the phylum Proteobacteria while all fungal taxa belonged to the phylum Ascomycota. Additionally, we identified significant connections between microorganisms and protein-like compounds and found that most taxa (12/14) correlated negatively with proteins indicating that microbial consumption of proteins is likely a significant driver of DOC concentration. This research links DOC concentration with microbial production and/or decomposition of specific metabolites to improve our understanding of microbial metabolism and carbon persistence.

59 BASIC BIOLOGICAL SCIENCES↗

Emiliania huxleyi —Bacteria Interactions under Increasing CO 2 Concentrations

The interactions established between marine microbes, namely phytoplankton–bacteria, are key to the balance of organic matter export to depth and recycling in the surface ocean. Still, their role in the response of phytoplankton to rising CO 2 concentrations is poorly understood. Here, we show that the response of the cosmopolitan Emiliania huxleyi (E. huxleyi) to increasing CO 2 is affected by the coexistence with bacteria. Specifically, decreased growth rate of E. huxleyi at enhanced CO 2 concentrations was amplified in the bloom phase (potentially also related to nutrient concentrations) and with the coexistence with Idiomarina abyssalis (I. abyssalis) and Brachybacterium sp. In addition, enhanced CO 2 concentrations also affected E. huxleyi’s cellular content estimates, increasing organic and decreasing inorganic carbon, in the presence of I. abyssalis, but not Brachybacterium sp. At the same time, the bacterial isolates only survived in coexistence with E. huxleyi, but exclusively I. abyssalis at present CO 2 concentrations. Bacterial species or group-specific responses to the projected CO 2 rise, together with the concomitant effect on E. huxleyi, might impact the balance between the microbial loop and the export of organic matter, with consequences for atmospheric carbon dioxide.

54 ENVIRONMENTAL SCIENCES↗