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At least 739 records · Page 41

Potential bioavailability of representative pyrogenic organic matter compounds in comparison to natural dissolved organic matter pools

Abstract. Pyrogenic organic matter (PyOM) from wildfires impacts river corridors globally and is widely regarded as resistant to biological degradation. Though recent work suggests PyOM may be more bioavailable than historically perceived, estimating bioavailability across its chemical spectrum remains elusive. To address this knowledge gap, we assessed potential bioavailability of representative PyOM compounds relative to ubiquitous dissolved organic matter (DOM) with a substrate-explicit model. The range of potential bioavailability of PyOM was greater than natural DOM; however, the predicted thermodynamics, metabolic rates, and carbon use efficiencies (CUEs) overlapped significantly between all OM pools. Compound type (e.g., natural versus PyOM) had approximately 6-fold less impact on predicted respiration rates than simulated carbon and oxygen limitations. Within PyOM, the metabolism of specific chemistries differed strongly between unlimited and oxygen-limited conditions – degradations of anhydrosugars, phenols, and polycyclic aromatic hydrocarbons (PAHs) were more favorable under oxygen limitation than other molecules. Notably, amino sugar-like, protein-like, and lignin-like PyOM had lower carbon use efficiencies relative to natural DOM of the same classes, indicating potential impacts in process-based model representations. Overall, our work illustrates how similar PyOM bioavailability may be to that of natural DOM in the river corridor, furthering our understanding of how PyOM may influence riverine biogeochemical cycling.

59 BASIC BIOLOGICAL SCIENCES↗

Interrelated structure of high altitude atmospheric profiles

A preliminary development of a mathematical model to compute probabilities of thermodynamic profiles is presented. The model assumes an exponential expression for pressure and utilizes the hydrostatic law and equation of state in the determination of density and temperature. It is shown that each thermodynamic variable can be factored into the produce of steady state and perturbation functions. The steady state functions have profiles similar to those of the 1962 standard atmosphere while the perturbation functions oscillate about 1. Limitations of the model and recommendations for future work are presented.

Engler, N. A.↗

Nonstationary homogeneous nucleation

A computer calculation was made of the relaxation time to steady-state nucleation in a supersaturated vapor. A binary-collision model of nucleation based on classical liquid-drop thermodynamics was used. The nondimensional nucleation relaxation time is plotted as a function of the critical drop size for various values of the surface-tension parameter. The curves permit a rough estimation of the limit of the validity of steady-state nucleation theory.

Harstad, K. G.↗

Utilization of recently developed codes for high power Brayton and Rankine cycle power systems

Two recently developed FORTRAN computer codes for high power Brayton and Rankine thermodynamic cycle analysis for space power applications are presented. The codes were written in support of an effort to develop a series of subsystem models for multimegawatt Nuclear Electric Propulsion, but their use is not limited just to nuclear heat sources or to electric propulsion. Code development background, a description of the codes, some sample input/output from one of the codes, and state future plans/implications for the use of these codes by NASA's Lewis Research Center are provided.

Doherty, Michael P.↗

Thermodynamics of quantum measurement and Maxwell's demon's arrow of time

Here, we discuss the thermodynamic aspects of a single qubit based device, powered by weak quantum measurements, and feedback controlled by a quantum Maxwell's demon. We discuss both discrete and time-continuous operation of the measurement based device at finite temperature of the reservoir. In the discrete example where a demon acquires information via discrete weak measurements, we find that the thermodynamic variables including the heat exchanged, extractable work, and the entropy produced are completely determined by an information theoretic measure of the demon's perceived arrow of time. We also discuss a realistic time-continuous operation of the device where the feedback is applied after a sequence of weak measurements. In the time-continuous limit, we derive the exact finite-time statistics of work, heat and entropy changes along individual quantum trajectories of the quantum measurement process, and relate them to the demon's arrow of time.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Water Interplays during Dysprosium Electrodeposition in Pyrrolidinium Ionic Liquid: Deconvoluting the Pros and Cons for Rare Earth Metallization

The electrochemical production of rare earth metals (REMs) in ionic liquids (ILs) has received much attention as a promising, sustainable and replacement to the molten salt electrolysis. Water additives have been recently suggested as a strategy to overcome the limitations of the ionic liquid process, but without complete assessment of its overall viability for the REMs production. In this regard, a full investigation of water impact on dysprosium (Dy) electrodeposition in pyrrolidinium triflate (BMPyOTf) ionic liquid was carried out. Water introduction was revealed to involve an interplay of implications on the electrodeposition process, including coordination, speciation, reduction pathways, interfacial dynamics, nucleation and metal stability and purity. In highly dry conditions, the reduction occurs at very negative potentials (-3.3V) in a consecutive pathway, resulting in negligible metal electrodeposition (low rate and efficiency) at the electrode surface. Initial water introduction (<30% molar fraction) leads to partitioning of the Dy complex between water and IL coordinated speciation, giving rise to an additional wave at more positive potentials (-2.4V). Probing and quantification of the heterogeneous Dy speciation by spectroscopic analyses enabled the uncovering of the reduction mechanism and accurate evaluation of the mass transport properties. While lowering the reduction thermodynamics, water addition also improved the nucleation, deposition rate and faradaic efficiency. In spite of these benefits, stripping voltammetric analysis also indicated substantial chemical reactivity of the deposited Dy metal with water additives and/or electrolyte components, under extended timescales. Surface characterization of the obtained product confirmed limited Dy metal stability (mostly oxidized/fluorinated) and purity (~60%) in the studied system. Moreover, high water introduction (>30% molar fraction) was shown to trigger a fast hydrogen evolution reaction (HER), downgrading the robustness of system efficiency. We report the overall impact of water additives seems to engender both promoting and mitigating effects on the Dy electrodeposition process, making the case for more innovative strategies to be sought.

36 MATERIALS SCIENCE↗

Assessing the impact of substrate-level enzyme regulations limiting ethanol titer in Clostridium thermocellum using a core kinetic model

Clostridium thermocellum is a promising candidate for consolidated bioprocessing because it can directly ferment cellulose to ethanol. Despite significant efforts, achieved yields and titers fall below industrially relevant targets. This implies that there still exist unknown enzymatic, regulatory, and/or possibly thermodynamic bottlenecks that can throttle back metabolic flow. By (i) elucidating internal metabolic fluxes in wild-type C. thermocellum grown on cellobiose via 13 C-metabolic flux analysis ( 13 C-MFA), (ii) parameterizing a core kinetic model, and (iii) subsequently deploying an ensemble-docking workflow for discovering substrate-level regulations, this paper aims to reveal some of these factors and expand our knowledgebase governing C. thermocellum metabolism. Generated 13 C labeling data were used with 13 C-MFA to generate a wild-type flux distribution for the metabolic network. Notably, flux elucidation through MFA alluded to serine generation via the mercaptopyruvate pathway. Using the elucidated flux distributions in conjunction with batch fermentation process yield data for various mutant strains, we constructed a kinetic model of C. thermocellum core metabolism (i.e. k-ctherm138). Subsequently, we used the parameterized kinetic model to explore the effect of removing substrate-level regulations on ethanol yield and titer. Upon exploring all possible simultaneous (up to four) regulation removals we identified combinations that lead to many-fold model predicted improvement in ethanol titer. In addition, by coupling a systematic method for identifying putative competitive inhibitory mechanisms using K-FIT kinetic parameterization with the ensemble-docking workflow, we flagged 67 putative substrate-level inhibition mechanisms across central carbon metabolism supported by both kinetic formalism and docking analysis.

59 BASIC BIOLOGICAL SCIENCES↗

Augmentation of Rocket Propulsion: Physical Limits

Rocket propulsion is not ideal when the propellant is not ejected at a unique velocity in an inertial frame. An ideal velocity distribution requires that the exhaust velocity vary linearly with the velocity of the vehicle in an inertial frame. It also requires that the velocity distribution variance as a thermodynamic quantity be minimized. A rocket vehicle with an inert propellant is not optimal, because it does not take advantage of the propellant mass for energy storage. Nor is it logical to provide another energy storage device in order to realize variable exhaust velocity, because it would have to be partly unfilled at the beginning of the mission. Performance is enhanced by pushing on the surrounding because it increases the reaction mass and decreases the reaction jet velocity. This decreases the fraction of the energy taken away by the propellant and increases the share taken by the payload. For an optimal model with the propellant used as fuel, the augmentation realized by pushing on air is greatest for vehicles with a low initial/final mass ratio. For a typical vehicle in the Earth's atmosphere, the augmentation is seen mainly at altitudes below about 80 km. When drag is taken into account, there is a well-defined optimum size for the air intake. Pushing on air has the potential to increase the performance of rockets which pass through the atmosphere. This is apart from benefits derived from "air breathing", or using the oxygen in the atmosphere to reduce the mass of an on-board oxidizer. Because of the potential of these measures, it is vital to model these effects more carefully and explore technology that may realize their advantages.

Taylor, Charles R.↗

FSISPH: An SPH formulation for impacts between dissimilar materials

Here, we present an SPH formulation with several new features designed to better model the fully-compressible interaction of dissimilar materials. We developed the new method to simulate the atmospheric entry and break-up of small celestial bodies in planetary atmospheres. The formulation uses a unity-based, density-energy discretization of the hydrodynamic conservation laws with linear-corrected kernel gradients. To account for variations in compressibility, we use an HLLC approximate Riemann solver to adjust the velocity gradient at material interfaces. To handle large transverse velocity discontinuities, we introduce a simple slip interface model that limits the artificial viscosity at material interfaces. Diffusion is optionally applied through the velocity gradient and this allows the density and specific thermal energy to evolve in a manner more consistent with the first law of thermodynamics in comparison to other more direct diffusion schemes. We also introduce a material-local second-order artificial conduction scheme used to smooth the specific thermal energy field. Material damage fits neatly under this framework by treating the damage front as a material interface. The method has been implemented as a solver, FSISPH, within the code, Spheral++, and is publicly available on github. We test our new solver on a number of classic shock, mixing, and multi-material problem. The components we outline can significantly improve accuracy of SPH for problems with sharp contact discontinuities.

79 ASTRONOMY AND ASTROPHYSICS↗

A stress-sensitive precipitate nucleation model beyond classical nucleation theory

The dynamic evolution of precipitates and second phases dictates the strength and stability of most engineering alloys. By design, or as a consequence of thermo-mechanical aging, engineering metals and alloys often form precipitates of second phases when subjecting to diverse thermal and mechanical loads. Precipitation is governed by several factors, including the alloy’s composition, processing/operating temperature, and stresses — either as a result of external loads or from residual stresses. However, state-of-the-art models for precipitate nucleation (i.e., classical nucleation theory) typically lacks consistent method to capture the effects of externally applied and/or internal stresses on nucleation; thereby severely limiting the applicability of these models to complex materials systems and to representative loading scenarios. Here, in this work, we extend upon classical nucleation theory to account for the effect of stresses on precipitation kinetics and thermodynamics. This is achieved via the use of an Eshelbian micromechanics framework keeping track of (i) the stress build up resulting from second phase formation as a function of mechanical load and, (ii) the effects of dislocations on precipitate formation. This new model is applied to σ precipitate in Fe–Cr binary alloys and M 23 C 6 precipitate in 316H stainless steel (SS). Simulations demonstrate the important role of both the remotely applied loads and dislocation pile ups on precipitate nucleation.

36 MATERIALS SCIENCE↗

The Martini 3 Lipidome: Expanded and Refined Parameters Improve Lipid Phase Behavior

Lipid membranes are central to cellular life. Complementing experiments, computational modeling has been essential in unraveling complex lipid-biomolecule interactions, crucial in both academia and industry. The Martini model, a coarse-grained force field for efficient molecular dynamics simulations, is widely used to study membrane phenomena but has faced limitations, particularly in capturing realistic lipid phase behavior. Here, we present refined Martini 3 lipid models with a mapping scheme that distinguishes lipid tails that differ by just two carbon atoms, enhancing the structural resolution and thermodynamic accuracy of model membrane systems including ternary mixtures. The expanded Martini lipid library includes thousands of models, enabling simulations of complex and biologically relevant systems. These advancements establish Martini as a robust platform for lipid-based simulations across diverse fields.

Lipids↗

TIGER, A thermodynamics Equilibrium Tool for Explosives Update: Improved Solver

The thermodynamic equilibrium code known as TIGER has been in use since the 1970s and is designed to calculate the performance of energetic materials during detonation at high temperatures and pressures. The original TIGER code utilized a limited database consisting of 12 gaseous and 3 condensed constituents, which were composed of the elements carbon (C), hydrogen (H), nitrogen (N), oxygen (O), and aluminum (Al). In contrast, the more modern JCZS3 database features a significantly larger dataset, including 756 gaseous species, 189 positive and negative ions, and 496 condensed constituents derived from 62 different elements. While this expanded product species database allows for the exploration of a broader range of problems relevant to our laboratory, it also introduces challenges related to convergence, particularly when both liquid and solid species coexist under a vapor dome. In this work, we present an improved TIGER solution technique aimed at accurately determining the equilibrium state for systems that can produce a diverse array of products, including both solid and liquid condensed species. This report presents the status of the TIGER solver as of the end of FY25. Ongoing efforts are focused on enhancing the solver, and the report outlines several planned improvements. We anticipate that further developments will require additional documentation in the future.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Subsurface mafic and ultramafic rock mapping and analysis for carbon mineralization in the United States (SubMAP-CO 2 )

Achieving durable, gigaton-scale carbon dioxide (CO₂) removal will require the development of storage strategies that are both permanent and scalable. Among the available options, carbon mineralization in mafic and ultramafic rocks offers a uniquely robust pathway for long-term CO₂ sequestration, converting CO₂ into thermodynamically stable carbonate minerals. While surface exposures of these lithologies have been extensively studied, particularly in ophiolitic and volcanic settings, the potential for carbon mineralization in the subsurface remains comparatively underexplored at national scale. This gap limits the ability to assess storage capacity, accessibility, and deployment pathways for mineralization-based carbon management in the United States.

08 HYDROGEN↗

Chandra Discovery of Luminous Supersoft X-Ray Sources in M81

A Chandra ACIS-S imaging observation of the nearby galaxy M81 (NGC 3031) reveals 9 luminous soft X-ray sources. The local environments, X-ray spectral properties, and X-ray light curves of the sources are presented and discussed in the context of prevailing physical models for supersoft sources. It is shown that the sample falls within expectations based on population synthesis models taken from the literature though the high observed luminosities (L approx.2e36 to approx.3e38 ergs in the 0.2--2.0-keV band) and equivalent blackbody temperatures (T approx.40 to 80 eV) place the brightest detected M81 objects at the high luminosity end of the class of supersoft sources defined by previous ROSAT and Einstein studies of nearby galaxies. This is interpreted as a natural consequence of the higher sensitivity of Chandra to hotter and more luminous systems. Most of the sources can be explained as canonical supersoft sources, secreting white dwarfs powered by steady surface nuclear burning, with X-ray spectra well-fit by hot white dwarf local thermodynamic equilibrium atmosphere models. An exceptionally bright source is scrutinized in greater detail as its estimated barometric luminosity, L approx. 1.5e39 ergs, greatly exceeds theoretical estimates for supersoft sources. This source may be beyond the stability limit and undergoing a phase of mass outflow under extreme conditions. Alternatively, a model in which the observed X-ray spectrum arises from an accretion disk around a blacklists of mass approx.1200/sqrt(cosi) solar masses (viewed at an inclination angle 1) cannot be excluded.

Swartz, Douglas A.↗

A Vision of Quantitative Imaging Technology for Validation of Advanced Flight Technologies

Flight-testing is traditionally an expensive but critical element in the development and ultimate validation and certification of technologies destined for future operational capabilities. Measurements obtained in relevant flight environments also provide unique opportunities to observe flow phenomenon that are often beyond the capabilities of ground testing facilities and computational tools to simulate or duplicate. However, the challenges of minimizing vehicle weight and internal complexity as well as instrumentation bandwidth limitations often restrict the ability to make high-density, in-situ measurements with discrete sensors. Remote imaging offers a potential opportunity to noninvasively obtain such flight data in a complementary fashion. The NASA Hypersonic Thermodynamic Infrared Measurements Project has demonstrated such a capability to obtain calibrated thermal imagery on a hypersonic vehicle in flight. Through the application of existing and accessible technologies, the acreage surface temperature of the Shuttle lower surface was measured during reentry. Future hypersonic cruise vehicles, launcher configurations and reentry vehicles will, however, challenge current remote imaging capability. As NASA embarks on the design and deployment of a new Space Launch System architecture for access beyond earth orbit (and the commercial sector focused on low earth orbit), an opportunity exists to implement an imagery system and its supporting infrastructure that provides sufficient flexibility to incorporate changing technology to address the future needs of the flight test community. A long term vision is offered that supports the application of advanced multi-waveband sensing technology to aid in the development of future aerospace systems and critical technologies to enable highly responsive vehicle operations across the aerospace continuum, spanning launch, reusable space access and global reach. Motivations for development of an Agency level imagery-based measurement capability to support cross cutting applications that span the Agency mission directorates as well as meeting potential needs of the commercial sector and national interests of the Intelligence, Surveillance and Reconnaissance community are explored. A recommendation is made for an assessment study to baseline current imaging technology including the identification of future mission requirements. Development of requirements fostered by the applications suggested in this paper would be used to identify technology gaps and direct roadmapping for implementation of an affordable and sustainable next generation sensor/platform system.

Horvath, Thomas J.↗

Extreme sparsification of physics-augmented neural networks for interpretable model discovery in mechanics

Data-driven constitutive modeling with neural networks has received increased interest in recent years due to its ability to easily incorporate physical and mechanistic constraints and to overcome the challenging and time-consuming task of formulating phenomenological constitutive laws that can accurately capture the observed material response. However, even though neural network-based constitutive laws have been shown to generalize proficiently, the generated representations are not easily interpretable due to their high number of trainable parameters. Sparse regression approaches exist that allow for obtaining interpretable expressions, but the user is tasked with creating a library of model forms which by construction limits their expressiveness to the functional forms provided in the libraries. Here, in this work, we propose to train regularized physics-augmented neural network-based constitutive models utilizing a smoothed version of $L^0$-regularization. This aims to maintain the trustworthiness inherited by the physical constraints, but also enables interpretability which has not been possible thus far on any type of machine learning-based constitutive model where model forms were not assumed a priori but were actually discovered. During the training process, the network simultaneously fits the training data and penalizes the number of active parameters, while also ensuring constitutive constraints such as thermodynamic consistency. We show that the method can reliably obtain interpretable and trustworthy constitutive models for compressible and incompressible hyperelasticity, yield functions, and hardening models for elastoplasticity, using synthetic and experimental data. This work aims to set a new paradigm for interpretable machine learning models in the broad area of solid mechanics where low and limited data is available along with prior knowledge of physical constraints that the learned maps need to obey. This paradigm can potentially be extended to a broader spectrum of scientific exploration.

Data-driven constitutive models↗

Development and characterization of Nb3Sn/Al2O3 superconducting multilayers for particle accelerators

Abstract Superconducting radio-frequency (SRF) resonator cavities provide extremely high quality factors > 10 10 at 1–2 GHz and 2 K in large linear accelerators of high-energy particles. The maximum accelerating field of SRF cavities is limited by penetration of vortices into the superconductor. Present state-of-the-art Nb cavities can withstand up to 50 MV/m accelerating gradients and magnetic fields of 200–240 mT which destroy the low-dissipative Meissner state. Achieving higher accelerating gradients requires superconductors with higher thermodynamic critical fields, of which Nb 3 Sn has emerged as a leading material for the next generation accelerators. To overcome the problem of low vortex penetration field in Nb 3 Sn, it has been proposed to coat Nb cavities with thin film Nb 3 Sn multilayers with dielectric interlayers. Here, we report the growth and multi-technique characterization of stoichiometric Nb 3 Sn/Al 2 O 3 multilayers with good superconducting and RF properties. We developed an adsorption-controlled growth process by co-sputtering Nb and Sn at high temperatures with a high overpressure of Sn. The cross-sectional scanning electron transmission microscope images show no interdiffusion between Al 2 O 3 and Nb 3 Sn. Low-field RF measurements suggest that our multilayers have quality factor comparable with cavity-grade Nb at 4.2 K. These results provide a materials platform for the development and optimization of high-performance SIS multilayers which could overcome the intrinsic limits of the Nb cavity technology.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Visible-Light-Driven, Iridium-Catalyzed Hydrogen Atom Transfer: Mechanistic Studies, Identification of Intermediates, and Catalyst Improvements

The harvesting of visible light is a powerful strategy for the synthesis of weak chemical bonds involving hydrogen that are below the thermodynamic threshold for spontaneous H 2 evolution. Piano-stool iridium hydride complexes are effective for the bluelight- driven hydrogenation of organic substrates and contrathermodynamic dearomative isomerization. In this work, a combination of spectroscopic measurements, isotopic labeling, structure–reactivity relationships, and computational studies has been used to explore the mechanism of these stoichiometric and catalytic reactions. Photophysical measurements on the iridium hydride catalysts demonstrated the generation of long-lived excited states with principally metal-to-ligand charge transfer (MLCT) character. Transient absorption spectroscopic studies with a representative substrate, anthracene revealed a diffusion-controlled dynamic quenching of the MLCT state. The triplet state of anthracene was detected immediately after the quenching events, suggesting that triplet–triplet energy transfer initiated the photocatalytic process. The key role of triplet anthracene on the post-energy transfer step was further demonstrated by employing photocatalytic hydrogenation with a triplet photosensitizer and a HAT agent, hydroquinone. DFT calculations support a concerted hydrogen atom transfer mechanism in lieu of stepwise electron/proton or proton/electron transfer pathways. Kinetic monitoring of the deactivation channel established an inverse kinetic isotope effect, supporting reversible C(sp 2 )–H reductive coupling followed by rate-limiting ligand dissociation. Mechanistic insights enabled design of a piano-stool iridium hydride catalyst with a rationally modified supporting ligand that exhibited improved photostability under blue light irradiation. The complex also provided improved catalytic performance toward photoinduced hydrogenation with H 2 and contra-thermodynamic isomerization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗