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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 415 records · Page 23

Rapid loss of complex polymers and pyrogenic carbon in subsoils under whole-soil warming

Subsoils contain more than half of soil organic carbon (SOC) and are expected to experience rapid warming in the coming decades. Yet our understanding of the stability of this vast carbon pool under global warming is uncertain. In particular, the fate of complex molecular structures (polymers) remains debated. Here we show that 4.5 years of whole-soil warming (+4 °C) resulted in less polymeric SOC (sum of specific polymers contributing to SOC) in the warmed subsoil (20–90 cm) relative to control, with no detectable change in topsoil. Warming stimulated the subsoil loss of lignin phenols (–17 ± 0%) derived from woody plant biomass, hydrolysable lipids cutin and suberin, derived from leaf and woody plant biomass (–28 ± 3%), and pyrogenic carbon (–37 ± 8%) produced during incomplete combustion. Given that these compounds have been proposed for long-term carbon sequestration, it is notable that they were rapidly lost in warmed soils. We conclude that complex polymeric carbon in subsoil is vulnerable to decomposition and propose that molecular structure alone may not protect compounds from degradation under future warming.

54 ENVIRONMENTAL SCIENCES↗

Formation of late-generation atmospheric compounds inhibited by rapid deposition

Reactive organic carbon species are important fuel for atmospheric chemical reactions, including the formation of secondary organic aerosol. However, in parallel to atmospheric oxidation processes, deposition can remove compounds from the atmosphere and impact downstream environments. To understand the impact of deposition on atmospheric oxidation, we present a framework for predicting and visualizing the fate of a molecule on the basis of the physicochemical properties of compounds (Henry’s law constant, vapour pressure and reaction rate constants), which are used to estimate timescales for oxidation and deposition. Further, by implementing our deposition rates in chemical models, we show that deposition substantially suppresses atmospheric reactivity and aerosol formation by removing early-generation products and preventing the formation of large fractions (up to 90%) of downstream, late-generation compounds. Deposition is frequently missing in the laboratory experiments and detailed chemical modelling, which probably biases our understanding of atmospheric composition.

54 ENVIRONMENTAL SCIENCES↗

The promise and challenge of therapeutic genome editing

Genome editing, which involves the precise manipulation of cellular DNA sequences to alter cell fates and organism traits, has the potential to both improve our understanding of human genetics and cure genetic disease. Here I discuss the scientific, technical and ethical aspects of using CRISPR (clustered regularly interspaced short palindromic repeats) technology for therapeutic applications in humans, focusing on specific examples that highlight both opportunities and challenges. Further, genome editing is—or will soon be—in the clinic for several diseases, with more applications under development. The rapid pace of the field demands active efforts to ensure that this breakthrough technology is used responsibly to treat, cure and prevent genetic disease.

60 APPLIED LIFE SCIENCES↗

Frustration- and doping-induced magnetism in a Fermi–Hubbard simulator

Geometrical frustration in strongly correlated systems can give rise to a plethora of novel ordered states and intriguing magnetic phases, such as quantum spin liquids. Promising candidate materials for such phases can be described by the Hubbard model on an anisotropic triangular lattice, a paradigmatic model capturing the interplay between strong correlations and magnetic frustration. However, the fate of frustrated magnetism in the presence of itinerant dopants remains unclear, as well as its connection to the doped phases of the square Hubbard model. Here we investigate the local spin order of a Hubbard model with controllable frustration and doping, using ultracold fermions in anisotropic optical lattices continuously tunable from a square to a triangular geometry. At half-filling and strong interactions U/t ≈ 9, we observe at the single-site level how frustration reduces the range of magnetic correlations and drives a transition from a collinear Néel antiferromagnet to a short-range correlated 120° spiral phase. Away from half-filling, the triangular limit shows enhanced antiferromagnetic correlations on the hole-doped side and a reversal to ferromagnetic correlations at particle dopings above 20%, hinting at the role of kinetic magnetism in frustrated systems. Furthermore, this work paves the way towards exploring possible chiral ordered or superconducting phases in triangular lattices and realizing t–t' square lattice Hubbard models that may be essential to describe superconductivity in cuprate materials.

74 ATOMIC AND MOLECULAR PHYSICS↗

Removal of radionuclides from acidic solution by activated carbon impregnated with methyl- and carboxy-benzotriazoles

The removal efficiencies of metals commonly used to model the fate and transport of aqueous uranium and radioactive its daughter products, were observed on activated carbons impregnated with different benzotriazole derivatives. Acidic solutions containing U(VI), Sr(II), Eu(III), and Ce(III) were used to determine the immobilization potential of carboxybenzotriazole (CBT) and methylbenzotriazole (MeBT), where these derivatives were sorbed to different types of granular activated carbon (GAC). This sorption behavior can be predicted by Redlich–Peterson model. Flow-through column tests showed that the immobilization of uranium and some of its daughter products, significantly improves in response to oxidized GACs saturated with carboxybenzotrzole (CBT), which reached a maximum elimination for U(VI) at 260 BV, Eu(III) at 114 BV, Ce(III) at 126 BV, and Sr(II) at 100. MeBT significantly desorbed from GAC under acidic conditions. Trace amounts of CBT were observed in some column effluents, but this did not appear to alter the effectiveness of metal removal, regardless of the model radionuclide studied. These results suggest that enhanced immobilization of selected metals on GAC, can be achieved by impregnating oxidized activated carbon with carboxylated benzotriazoles, and that metal removal efficiency on this media, is related to their valence and ionic radius in acidic environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Contribution of sewage to occurrence of phosphodiesterase-5 inhibitors in natural water

Phosphodiesterase-5 inhibitors (PDE-5i, such as Sildenafil, Tadalafil and Vardenafil, mainly prescribed to treat erectile dysfunction) and their generic drug equivalents have been widely marketed and consumed in Korea. From the concentrations detected in wastewater, we could deduce that relatively large amounts of PDE-5i were consumed without a legal prescription. Thus, PDE-5i’s presence in the environment via sewage is unavoidable, and their environmental fate within a sewage treatment plant (STP) should be evaluated. In this study, we investigated the occurrence of three PDE-5i analogs in the influent and effluent of two STPs and the receiving water bodies. The PDE-5i concentration in total reached 62 ± 12 (STP#1) and 88 ± 37 ng L -1 (STP#2) in the sewage influent; about 70% of it was Sildenafil in both STPs. However, they were hardly removed by the STPs as the removal efficiency of the STPs was less than 10% ± 5%. Therefore, the pharmaceuticals were detected in the receiving water (lower than 7 ng L -1 as a total amount) and the concentration slightly increased downstream of the STPs. A simple mass balance model applied for the compounds in the STP effluent and receiving water bodies also confirmed that the discharged PDE-5i were quite persistent. Lastly, we identified temporal and regional patterns in the consumption of the drugs from daily variations of PDE-5i in the influent to these two STPs. For instance, the levels of PDE-5i in the sewage significantly increased on weekends (from Friday to Saturday), and especially in the area where adult-entertainment businesses are common. We estimated that the amount of PDE-5i consumption in this area was 31% higher than that in the area with fewer nightlife spots. Considering that they are pharmaceutically active and resistant to treatment processes within an STP, it is advised that a regular monitoring and management program for PDE-5i should be developed to prevent the discharge of the pharmaceuticals into the water environment.

54 ENVIRONMENTAL SCIENCES↗

The effect of oxygen concentration on the speciation of laser ablated uranium

Abstract In order to model the fate and transport of particles following a nuclear explosion, there must first be an understanding of individual physical and chemical processes that affect particle formation. One interaction pertinent to fireball chemistry and resultant debris formation is that between uranium and oxygen. In this study, we use laser ablation of uranium metal in different concentrations of oxygen gas, either 16 O 2 or 18 O 2 , to determine the influence of oxygen on rapidly cooling uranium. Analysis of recovered particulates using infrared absorption and Raman spectroscopies indicate that the micrometer-sized particulates are predominantly amorphous UO x (am-UO x , where 3 ≤ x ≤ 4) and UO 2 after ablation in 1 atm of pure O 2 and a 1% O 2 /Ar mixture, respectively. Energy dispersive X-ray spectroscopy (EDS) of particulates formed in pure O 2 suggest an O/U ratio of ~ 3.7, consistent with the vibrational spectroscopy analysis. Both am-UO x and UO 2 particulates convert to α-U 3 O 8 when heated. Lastly, experiments performed in 18 O 2 environments show the formation of 18 O-substituted uranium oxides; vibrational frequencies for am-U 18 O x are reported for the first time. When compared to literature, this work shows that cooling timescales can affect the structural composition of uranium oxides (i.e., crystalline vs. amorphous). This indicator can be used in current models of nuclear explosions to improve our predicative capabilities of chemical speciation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Increased abundance of a common scavenger affects allocation of carrion but not efficiency of carcass removal in the Fukushima Exclusion Zone

Abstract The 2011 nuclear accident in Fukushima, Japan caused the evacuation of > 100,000 people and prompted studies on environmental impacts of radiological contamination. However, few researchers have explored how the human evacuation has affected ecosystem processes. Despite contamination, one common scavenger (wild boar, Sus scrofa ) is 2–3× more abundant inside the Fukushima Exclusion Zone (FEZ). Shifts in abundance of some scavenger species can have cascading effects on ecosystems, so our objective was to investigate impacts of the evacuation and the resulting increase in wild boar on vertebrate scavenger communities. We deployed cameras at 300 carcasses in the FEZ and a nearby inhabited area, and quantified carcass fate, scavenger species, and detection/persistence times. We also tested effects of carcass size and habitat on scavenger community composition and efficiency by balancing trials across two carcass sizes and habitats in each zone. Overall scavenger richness and carcass removal rates (73%) were similar in the FEZ and inhabited area, but species-specific carcass removal rates and occurrence differed between zones. Wild boar removed substantially more carcasses inside the FEZ, with implications for nutrient and contaminant distribution. Our results suggest carcass size affects scavenging dynamics more than human activity or habitat, and abundance changes of common scavengers can influence carrion resource allocation.

59 BASIC BIOLOGICAL SCIENCES↗

Physics-informed machine learning with differentiable programming for heterogeneous underground reservoir pressure management

Abstract Avoiding over-pressurization in subsurface reservoirs is critical for applications like CO $$_2$$ 2 sequestration and wastewater injection. Managing the pressures by controlling injection/extraction are challenging because of complex heterogeneity in the subsurface. The heterogeneity typically requires high-fidelity physics-based models to make predictions on CO $$_2$$ 2 fate. Furthermore, characterizing the heterogeneity accurately is fraught with parametric uncertainty. Accounting for both, heterogeneity and uncertainty, makes this a computationally-intensive problem challenging for current reservoir simulators. To tackle this, we use differentiable programming with a full-physics model and machine learning to determine the fluid extraction rates that prevent over-pressurization at critical reservoir locations. We use DPFEHM framework, which has trustworthy physics based on the standard two-point flux finite volume discretization and is also automatically differentiable like machine learning models. Our physics-informed machine learning framework uses convolutional neural networks to learn an appropriate extraction rate based on the permeability field. We also perform a hyperparameter search to improve the model’s accuracy. Training and testing scenarios are executed to evaluate the feasibility of using physics-informed machine learning to manage reservoir pressures. We constructed and tested a sufficiently accurate simulator that is 400 000 times faster than the underlying physics-based simulator, allowing for near real-time analysis and robust uncertainty quantification.

54 ENVIRONMENTAL SCIENCES↗

Spectroscopic identification of Ca-bearing uranyl silicates formed in C–S–H systems

Portland cement-based grouts used for radioactive waste immobilisation contain a Ca- and Si-rich binder phase, known as calcium–silicate–hydrate (C–S–H). Depending on the blend of cement used, the Ca/Si ratio can vary considerably. A range of C–S–H minerals with Ca/Si ratios from 0.6 to 1.6 were synthesised and contacted with aqueous U(VI) at 0.5 mM and 10 mM concentrations. Solid-state 29 Si MAS-NMR spectroscopy was applied to probe the Si coordination environment in U(VI)-contacted C–S–H minerals and, in conjunction with U L III -edge X-ray absorption spectroscopy analysis, inferences of the fate of U(VI) in these systems were made. At moderate or high Ca/Si ratios, uranophane-type uranyl silicates or Ca-uranates dominated, while at the lowest Ca/Si ratios, the formation of a Ca-bearing uranyl silicate mineral, similar to haiweeite (Ca[(UO 2 ) 2 Si 5 O 12 (OH) 2 ]·3H 2 O) or Ca-bearing weeksite (Ca 2 (UO 2 ) 2 Si 6 O 15 ·10H 2 O) was identified. This study highlights the influence of Ca/Si ratio on uranyl sequestration, of interest in the development of post-closure safety models for U-bearing radioactive waste disposal.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Modeling the impact of extreme weather events and future climate on the radiologically contaminated sites of Enewetak Atoll

Enewetak Atoll underwent 43 historical nuclear tests from 1948 to 1958, including the first hydrogen bomb test, resulting in a substantial nuclear material fallout contaminating the Atoll and the lagoon waters. The radionuclide fallout material deposited in lagoon sediments and land soil will remain for decades to come. With intensifying climate and extreme weather events, the possibility of redistribution of deposited radionuclide material has become a great concern. This study uses a numerical modeling approach to estimate the potential elevated radionuclide concentrations that can be distributed during storm events under current and future climates. We simulated three historical storm scenarios that are most likely to impact Atoll’s environment and remobilize the radionuclide-bound sediments. WRF-ARW was used to reconstruct these storm scenarios under current year (2015) and future year (2090) climates. Storm-induced ocean hydrodynamics conditions were generated using FVCOM. FVCOM-ICM was externally coupled to simulate the fate and transport of radionuclides. Given that the 239 Pu is the largest inventory of the lagoon and Atoll islands, the model results show the highest average 239 Pu concentration that an island may be exposed to is 3.25E-4 Bq/m 3 (becquerel per cubic meters), which is an increase of 84 times the average baseline/existing 239 Pu concentration without the storm conditions. The overall increase in 239 Pu average over all the islands of Atoll is about 20 folds relative to the baseline concentration. Despite the high relative increase ratios, the significantly low activity concentrations may not pose an immediate exposure risk. However, due to the limitations of the study and uncertainties/biases in the historical data used, further research supported by field surveys to better characterize the current contamination level may be needed to make more accurate predictions.

54 ENVIRONMENTAL SCIENCES↗

The iodine-129 paradox in nuclear waste management strategies

Nuclear energy has an important role in the low-carbon energy transition, but the safety of spent nuclear fuel (SNF) management remains a public concern. Here, in this study, we investigate the interplay between waste management strategies and their environmental impacts with a particular focus on a highly mobile and persistent radionuclide, iodine-129 (I-129), which is the dominant risk contributor from SNF disposal and at existing groundwater contamination sites. The results show that the current recycling practice releases more than 90% of I-129 in SNF into the present-day biosphere using an isotropic dilution strategy, whereas the direct disposal of SNF in geological repositories is likely to delay and reduce the release by 8 orders of magnitude. In addition, our data synthesis of surface water concentrations near four nuclear facilities shows that the release-dilution strategy results in lower concentrations than regulatory standards, while insufficient waste isolation in the past has resulted in locally high concentrations within one site. Our analysis suggests that it is essential to consider effluents more explicitly as a part of the waste, that as society moves from dilution to isolation of waste, the potential risks of waste isolation to local regions should be carefully evaluated, and that excessive burdens of proof could hinder or discourage waste isolation. Comprehensive waste management strategies—considering not just volume but also mobility, isolation technologies and ultimate fates—are needed for persistent contaminants. This study offers valuable insights for optimizing the management of SNF and other persistent contaminants.

Wainwright, Haruko M. [Massachusetts Inst. of Tech↗

Senescence-driven solubilization of biomass is the main source of kelp-derived dissolved organic carbon to the coastal ocean

Abstract Kelp forests form some of the most productive areas on earth and are proposed to sequester carbon in the ocean, largely in the form of released dissolved organic carbon (DOC). Here we investigate the role of environmental, seasonal and age-related physiological gradients on the partitioning of net primary production (NPP) into DOC by the canopy forming giant kelp (Macrocystis pyrifera). Rates of DOC production were strongly influenced by an age-related decline in physiological condition (i.e. senescence). During the mature stage of giant kelp development, DOC production was a small and constant fraction of NPP regardless of tissue nitrogen content or light intensity. When giant kelp entered its senescent phase, DOC production increased substantially and was uncoupled from NPP and light intensity. Compositional analysis of giant kelp-derived DOC showed that elevated DOC production during senescence was due to the solubilization of biomass carbon, rather than by direct exudation. We coupled our incubation and physiological experiments to a novel satellite-derived 20-year time series of giant kelp canopy biomass and physiology. Annual DOC production by giant kelp varied due to differences in standing biomass between years, but on average, 74% of the annual DOC production by giant kelp was due to senescence. This study suggests DOC may be a more important fate of macroalgal NPP than previously recognized.

Life Sciences & Biomedicine - Other Topics↗

Ion solvation as a predictor of lanthanide adsorption structures and energetics in alumina nanopores

Adsorption reactions at solid-water interfaces define elemental fate and transport and enable contaminant clean-up, water purification, and chemical separations. For nanoparticles and nanopores, nanoconfinement may lead to unexpected and hard-to-predict products and energetics of adsorption, compared to analogous unconfined surfaces. Here we use X-ray absorption fine structure spectroscopy and operando flow microcalorimetry to determine nanoconfinement effects on the energetics and local coordination environment of trivalent lanthanides adsorbed on Al 2 O 3 surfaces. We show that the nanoconfinement effects on adsorption become more pronounced as the hydration free energy, ΔG hydr , of a lanthanide decreases. Neodymium (Nd 3+ ) has the least exothermic ΔG hydr (-3336 kJ·mol -1 ) and forms mostly outer-sphere complexes on unconfined Al 2 O 3 surfaces but shifts to inner-sphere complexes within the 4 nm Al 2 O 3 pores. Lutetium (Lu 3+ ) has the most exothermic ΔG hydr (-3589 kJ·mol -1 ) and forms inner-sphere adsorption complexes regardless of whether Al 2 O 3 surfaces are nanoconfined. Importantly, the energetics of adsorption is exothermic in nanopores only, and becomes endothermic with increasing surface coverage. Changes to the energetics and products of adsorption in nanopores are ion-specific, even within chemically similar trivalent lanthanide series, and can be predicted by considering the hydration energies of adsorbing ions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Wildfire aerosol deposition likely amplified a summertime Arctic phytoplankton bloom

Summertime wildfire activity is increasing in boreal forest and tundra ecosystems in the Northern Hemisphere. However, the impact of long range transport and deposition of wildfire aerosols on biogeochemical cycles in the Arctic Ocean is unknown. Here, we use satellite-based ocean color data, atmospheric modeling and back trajectory analysis to investigate the transport and fate of aerosols emitted from Siberian wildfires in summer 2014 and their potential impact on phytoplankton dynamics in the Arctic Ocean. We detect large phytoplankton blooms near the North Pole (up to 82°N in the eastern Eurasian Basin). Our analysis indicates that these blooms were induced by the northward plume transport and deposition of nutrient-bearing wildfire aerosols. We estimate that these highly stratified surface waters received large amounts of wildfire-derived nitrogen, which alleviated nutrient stress in the phytoplankton community and triggered an unusually large bloom event. Our findings suggest that changes in wildfire activity may strongly influence summertime productivity in the Arctic Ocean.

54 ENVIRONMENTAL SCIENCES↗

Optimization of floodwater redistribution from Lake Nasser could recharge Egypt’s aquifers and mitigate its excessive floods

Extreme precipitation periods, possibly related to climate change, over the Nile River source areas caused flooding in Sudan and excess runoff reaching Lake Nasser in Egypt in 1998–2002 and 2019–2022. Excess water from the 1st event (25.5 × 10 9 m 3 ) was channeled to depressions within the plateau west of the Nile Valley, forming the Tushka Lakes, where it was left to evaporate, a fate that awaits the 53.5 × 10 9 m 3 from the 2nd event while the underlying fossil Nubian Sandstone Aquifer System is being depleted (–0.98 × 10 9 m 3 /yr). We simulated release scenarios of excess Lake Nasser waters (53.5 × 10 9 m 3 ) to proximal lowlands; preference was given to the scenario that recharged the aquifer through infiltration (74.3%) and minimized losses to evaporation (20.1%) and surface runoff (5.6%). Findings serve as an example of adaptations that replace catastrophic consequences of climate change with beneficial and sustainable development opportunities.

54 ENVIRONMENTAL SCIENCES↗

Mechanically robust and reprocessable imine exchange networks from modular polyester pre-polymers

Covalent adaptable networks (CANs) containing reversible cross-links impart recyclability to thermoset materials without sacrificing their desirable properties (e.g. high tensile strength and solvent resistance). In addition to thermal recycling, the sustainability of these materials may be further improved by incorporating bio-sourced monomers or by enabling alternate end-of-life fates, such as biodegradation or recovery of starting materials. The alternating ring-opening copolymerisation of epoxides and cyclic anhydrides permits the modular synthesis of polyester pre-polymers that can then be cross-linked to form dynamic imine-linked networks. In this work, we report the synthesis and characterisation of five imine exchange polyester CANs with varied cross-linking densities and pre-polymer architectures. While the materials exhibit characteristic thermoset properties at service temperatures, differences in pre-polymer architecture produce distinct dynamic mechanical effects at elevated temperatures. The networks may be thermally reprocessed with full recovery of their tensile strengths and cross-linking densities, dissociated to pre-polymer, or hydrolytically degraded.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗