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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 505 records · Page 28
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Xylan-cellulose core structure of oat water-extractable β-glucan macromolecule: Insight into interactions and organization of the cell wall complex

Water-extractable β-glucan with high molar mass (HM) determines health benefits of oat food. Oat β-glucan was extracted by a standardized in vitro digestion method and co-existing water-extractable polysaccharide (WEP) fraction and its HM-arabinoxylan (HM-AX) subfraction were isolated to identify their highly acid-resistant subunit and investigate molecular interactions between constituent polymers. The WEP and HM-AX samples consisted of arabinoxylans (AXs) (74 and 76 %, respectively), however, cellulose constituted the secondary component (6.6 and 12.8 %, respectively). Multi-detection HPSEC along with specific enzymatic hydrolysis of AXs revealed the presence of the HM-xylan domain (16 and 34 %, respectively) built of numerous single- and multi-component populations with random coil and rod-like conformations, which were embedded in a xylan matrix with spherical conformation and controlled the macromolecular shape. Unlike single-component populations, the multi-component ones were resistant to hydrolytic action of AX-hydrolyzing enzymes and represented the subunits that anchor matrix polysaccharides onto cellulose surface. These results indicate that water-extractable β-glucan macromolecule comprises as integral element a cellulose core with two linking populations, HM-xylan and low molar mass glucomannan, which are surrounded by a feruloylated AX-arabinan-arabinogalactan composite and next laminated by β-glucan matrix. Here, the stiff cellulose-xylan backbone is the basis of HM β-glucan organization, controlled by its cellulose-like segments.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Feature extraction for subtle anomaly detection using semi-supervised learning

The demand for automated and effective monitoring techniques has soared with the increased digitization of industrial monitoring systems. State-of-the-art machine learning methods are effectively detecting abrupt changes in system states. However, these methods lack comparable maturity in detecting subtle changes that may be signs of incipient faults. This manuscript argues that the current anomaly detection methods can be enhanced by exploring weak patterns to enable subtle variation detection. Specifically, the concept of semi-supervised learning is employed, with labels representing knowledge about some anomalous conditions of a system. The basic idea is to extract a candidate set of weak patterns discarded by state-of-the-art baselining algorithms. With few labeled anomalous data, the algorithm selects the weak patterns and allows for their possible fusion using the highest sensitivity to the labeled anomalies. Here, the method’s applicability is demonstrated using a representative pressurized water reactor (PWR) model simulated by Dymola.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2020

Detecting Thermally Induced Spinodal Decomposition with Picosecond Ultrasonics in Cast Austenitic Stainless Steels

Given the existential climate crisis faced by mankind and the world, the lifetime and sustainability of nuclear reactors as a carbon-free source of renewable energy depend on the susceptibility of their structural components to environmental degradation. In particular, critical components for light water reactors (LWRs) evolve over decades in service, losing ductility and toughness due to thermal and irradiation aging. Techniques to monitor their health cannot be easily applied in the field due to their destructive, expensive, or immobile nature. Thus, non-destructive evaluation (NDE) methods are sought to monitor and evaluate the health of major LWR components such as core barrels, steam generator tubes, or primary coolant pipes and are often required by policy, such as NRC policy #10-CFR-50.65. In this work we demonstrate the use of gigahertz, non-contact ultrasonics to gauge the state of cast austenitic stainless steels (CASS), used in some of the largest components in LWR primary systems. We do so by linking changes in their surface acoustic wave (SAW) characteristics using transient grating spectroscopy (TGS) to transmission electron microscopy (TEM)-verified evidence of spinodal decomposition and G-phase precipitation. In this thesis, thermal aging is shown to induce SAW peak splitting in spinodally decomposed CASS alloys, correlated strongly with lowered toughness and decreased ductility. Furthermore, statistical testing on the number of SAW peak splits observed show that the second SAW peak significantly appears more frequently and is significantly different in frequency in comparison to counts and frequencies measured in unaged specimens. The ability of this technique to non-destructively detect microstructural degradation at a distance in a predictive manner in the case of CASS motivates extending gigahertz ultrasonics to detect other LWR material degradation modes as an in-vessel inspection technique, such as reactor pressure vessel (RPV) embrittlement. This allows for the greater use of NDE techniques for confident monitoring of LWR structural material health to 80 years and beyond, saving costs by minimizing structural replacements until needed and maximizing energy production by preventing early decommission until necessary.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Particulate and dissolved metabolite distributions along a latitudinal transect of the western Atlantic Ocean

Abstract Metabolites, or the small organic molecules that are synthesized by cells during metabolism, comprise a complex and dynamic pool of carbon in the ocean. They are an essential currency in interactions at the population and community levels of biological organization. Characterizing metabolite distributions inside microbial cells and dissolved in seawater is essential to understanding the controls on their production and fate, as well as their roles in shaping marine microbial food webs. Here, we apply a targeted metabolomics method to quantify particulate and dissolved distributions of a suite of biologically relevant metabolites including vitamins, amino acids, nucleic acids, osmolytes, and intermediates in biosynthetic pathways along a latitudinal transect in the western Atlantic Ocean. We find that, in the upper 200 m of the water column, most particulate or intracellular metabolites positively covary with the most abundant microbial taxa. In contrast, dissolved metabolites exhibited greater variability with differences in distribution between ocean regions. Although fewer particulate metabolites were detected below 200 m, the particulate metabolites identified in the deep ocean may be linked to adaptive physiological strategies of deep‐sea microbes. Based on the identified metabolite distributions, we propose relationships between certain metabolites and microbial populations, and find that dissolved metabolite distributions are not directly related to their particulate abundances.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Size-Dependent Characteristics of Surface-Rooted Three-Dimensional Convective Objects in Continental Shallow Cumulus Simulations

A segmentation algorithm is applied to high resolution simulations of shallow continental convection to identify individual convective 3D objects within the convective boundary layer, in order to investigate which properties of the objects vary with the object width. The study analyses the geometry of the objects, along with their profiles of vertical velocity and total water, to assess various assumptions often used in spectral mass-flux convection schemes. The methodology of this paper is unique in that we use (a) a novel application of the watershed algorithm to detect individual objects in the constantly evolving continental boundary layer efficiently, and (b) an unprecedentedly large number of simulations being analyzed. In total, 26 days of LASSO simulations at the Atmospheric Radiation Measurement Southern Great Plains site are analyzed, yielding roughly one million objects. Plume-like surface-rooted objects are found to be omnipresent, the vertical extent of which is strongly dependent on the object width. The vertical velocity and moisture anomaly profiles of the widest objects are roughly consistent with the classic buoyancy-driven rising plume model. The kinematic and thermodynamic properties of the objects vary with object width. This width dependence is strongest above cloud base, but much weaker below. Finally the impact of neglecting the contribution of covariances to the vertical moisture flux, which is commonly used in mass-flux parameterizations, is investigated. The average effect of neglecting covariances increases linearly with object width, leading to a 20% flux underestimation for 2 km wide objects. Implications of the results for spectral convection scheme development are briefly discussed.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

The hard x-ray nanotomography microscope at the advanced light source

Beamline 11.3.1 at the Advanced Light Source is a tender/hard (6–17 keV) x-ray bend magnet beamline recently re-purposed with a new full-field, nanoscale transmission x-ray microscope. The microscope is designed to image composite and porous materials possessing a submicrometer structure and compositional heterogeneity that determine materials’ performance and geologic behavior. The theoretical and achieved resolutions are 55 and <100 nm, respectively. The microscope is used in tandem with a <25 nm eccentricity rotation stage for high-resolution volume imaging using nanoscale computed tomography. The system also features a novel bipolar illumination condenser for the illumination of an ~100 μm spot of interest on the sample, followed by a phase-type zone plate magnifying objective of ~52 µm field of view and a phase detection ring. The zone plate serves as the system objective and magnifies the sample with projection onto an indirect x-ray detection system, consisting of a polished single crystal CsI(Tl) scintillator and a range of high-quality Plan Fluorite visible light objectives. The objectives project the final visible light image onto a water-cooled CMOS 2048 × 2048-pixel 2 detector. Here, in this paper, we will discuss the salient features of this instrument and describe early results from imaging the internal three-dimensional microstructure and nanostructure of target materials, including fiber-reinforced composites and geomaterials.

47 OTHER INSTRUMENTATION↗
DOE OSTI2022

Metal-organic frameworks as effective sensors and scavengers for toxic environmental pollutants

Abstract Metal-organic frameworks (MOFs) constructed from a rich library of organic struts and metal ions/clusters represent promising candidates for a wide range of applications. The unique structure, porous nature, easy tunability and processability of these materials make them an outstanding class of materials for tackling serious global problems relating to energy and environment. Among them, environmental pollution is one aspect that has increased at an alarming rate in the past decade or so. With rapid urbanization and industrialization, toxic environmental pollutants are constantly released and accumulated leading to serious contamination in water bodies and thereby having adverse effects on human health. Recent studies have shown that many toxic pollutants, as listed by the World Health Organization and the US Environmental Protection Agency, can be selectively detected, captured, sequestered and removed by MOFs from air and aquatic systems. Most of these sensing/capture processes in MOFs are quantifiable and effective for even a trace amount of the targeted chemical species. The functional sites (ligands and metals) play a critical role in such recognition processes and offer an extensive scope of structural tunability for guest (pollutants, toxic entities) recognition. Whereas on the one hand, the underlying mechanisms governing such sensing and capture are important, it is also crucial to identify MOFs that are best suited for commercial applications for the future. In this review article, we provide an overview of the most recent progress in the sensing, capture and removal of various common toxic pollutants, including neutral and ionic, inorganic and organic species, with brief discussions on the mechanism and efficacy of selected MOFs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Probing the pH Effect on Boehmite Particles in Water Using Vacuum Ultraviolet Single-Photon Ionization Mass Spectrometry

Boehmite has been widely used in theoretical research and industry, especially for hazardous material processing. For the liquid-phase treating process, the interfacial properties of boehmite are believed to be affected by pH conditions, which change its physicochemical behavior. However, molecular-level detection on cluster ions is challenging when using bulk approaches. Herein we employ in situ vacuum ultraviolet single-photon ionization mass spectrometry (VUV SPI-MS) coupled with a vacuum-compatible microreactor system for analysis at the liquid–vacuum interface (SALVI) to investigate the solute molecular composition of boehmite under different pH conditions for the first time. The mass spectral results show that more complex clustering of solute molecules exists at the solid–liquid (s–l) interface than conventionally perceived in a “simple” aqueous solution. Besides solute ions, such as boehmite molecules and fragments, the composition and appearance energies of these newly discovered solvated cluster ions are determined by VUV SPI-MS in different pH solutions. We offer new results for the pH-dependent effect of boehmite and provide insights into a more detailed solvation mechanism at the s–l interface. By comparing the key products under different pH conditions, fundamental understanding of boehmite dissolution is revealed to assist the engineering design of waste processing and storage solutions.

SALVI↗
DOE OSTI2025

Development of an ERT‐Based Framework for Bentonite Buffers Monitoring From Laboratory Tests: 1. Characterizing Thermal–Hydrological–Mechanical Processes

Abstract Bentonite clay is widely used in engineered barrier systems for the permanent disposal of high‐level radioactive waste due to its low permeability, high swelling capacity, and thermal stability. However, the complex thermal‐hydrological‐mechanical (THM) processes induced by heating from decaying radioactive waste and hydration from surrounding rock can lead to heterogeneous changes that are difficult to measure and predict. This study develops an Electrical Resistivity Tomography (ERT)‐based framework for monitoring THM processes, progressing from sample‐scale to bench‐scale tests, to inform field‐scale applications. Sample‐scale tests analyzed small bentonite samples under controlled variations in water content, temperature, and porosity to establish fundamental resistivity relationships. Bench‐scale tests involved larger bentonite columns subjected to heating (up to 200°C) and hydration under controlled pressure, simulating repository conditions. ERT measurements, complemented by X‐ray CT imaging, temperature monitoring, and tracing sensors, revealed coupled THM processes, such as hydration‐induced compression, swelling, and thermal gradients, leading to complex resistivity patterns. The results demonstrate the potential of ERT for capturing THM‐induced resistivity changes, though challenges remain in upscaling and quantitative analysis. This study evaluates laboratory test capabilities and proposes future improvements for understanding THM‐induced resistivity responses. A conceptual framework for ERT implementation in field‐scale monitoring is presented, synthesizing findings from both scales and exploring how ERT data can inform long‐term modeling and reduce prediction uncertainties. Overall, this ERT‐based framework offers a robust method for monitoring bentonite buffers, aiding in early issue detection and supporting the safe long‐term disposal of radioactive waste in geological repositories, while highlighting the need for future development. Plain Language Summary Bentonite clay is crucial in engineered barrier systems (EBS) for containing high‐level radioactive waste due to its ability to absorb water, swell, seal and remain stable under high temperatures. When bentonite absorbs water and heats up from radioactive decay, it experiences complex changes in its physical and mechanical properties. Understanding these changes is important for ensuring the long‐term safety and effectiveness of EBS. This study used Electrical Resistivity Tomography (ERT), a non‐invasive method that measures electrical conductivity to monitor these changes during laboratory experiments. The ERT data revealed significant variations in resistivity corresponding to changes in water content, temperature, and density, providing detailed spatial and temporal insights into the behavior of bentonite. These findings enhance our ability to predict the long‐term performance of bentonite barriers, ensuring the safe containment of radioactive waste. By improving our understanding of bentonite's behavior, this research supports the development of more reliable and effective barrier systems for radioactive waste disposal, protecting the environment and public health. Key Points ERT monitoring was employed to capture resistivity changes in bentonite during controlled heating and hydration experiments, providing insights into THM processes ERT data reveal significant resistivity changes correlated with water content, temperature, and mechanical effects, enhancing the understanding of THM dynamics in bentonite This study explores the potential of the framework for application in field‐scale EBS monitoring, emphasizing the need for integrating additional geophysical methods for comprehensive subsurface imaging

Chen, Hang↗
DOE OSTI2026

A Global Methane Observation System to Reduce Uncertainty for Anthropogenic and Natural Sources and Sinks for Detecting and Attributing Climate Feedbacks

Atmospheric methane (CH4) concentrations are accelerating global warming as net emissions increase. Observing systems that quantify sources remain too sparse and fragmented to detect trends—especially in remote regions where climate‐driven natural emissions may be rising. We provide a framework for quantifying uncertainty reductions through the implementation of a global ecosystem‐methane observing system designed to: (i) substantially lower uncertainty in sectoral and regional emissions, (ii) separate co‐occurring anthropogenic and natural fluxes, and (iii) trend detection at regional scales to verify mitigation progress and provide early warning of natural feedbacks. Using bottom‐up inventories and process‐model ensembles for 2014–2023, we show that anthropogenic emissions remain uncertain by ∼32% globally, while natural sources—tropical and boreal‐arctic wetlands, fires, and inland waters—carry far larger uncertainties (+ 70%) and trend uncertainties reaching ∼200%. Additional observations must match spatial emission structure to increase observability of emissions: high‐resolution satellite constellations for point sources combined with expanded flux networks and wetland mapping for diffuse sources, and denser ground‐based atmospheric column measurements to restore observability in under‐sampled tropics and high latitudes. Notional analyses indicate that targeted additions of flux towers and ∼20 in situ atmospheric column concentration instruments per key tropical region could reduce continental‐scale uncertainties at modest cost. Conceptual illustration of a Global Ecosystem Methane Observing System (GEM‐OS) integrating satellites, aircraft, atmospheric networks, and ecosystem measurements to quantify methane emissions from anthropogenic and natural sources. The multi‐scale observing framework improves source attribution, reduces uncertainty in regional methane budgets, and enables early detection of climate‐driven feedbacks from wetlands, fires, permafrost, agriculture, and fossil‐fuel emissions.

Ciais, P↗
DOE OSTI2021

The Reactivity of Polyethylene Microplastics in Water under Low Oxygen Conditions Using Radiation Chemistry

Polyethylene (PE) is an intensely utilized polymer, which has consequently led to it becoming a common environmental contaminant. PE and other plastic waste are known to be highly persistent in surface waters; however, chemical and physical changes do take place over time, dependent mostly on highly variable natural conditions, such as oxygen (O2) availability. Gamma radiation was used to generate reactive oxygen species, namely hydroxyl radicals, in initially aerated aqueous solutions to simulate the natural weathering of microplastics in waters where there are fluctuations and often depletions in dissolved O2. The headspace of the irradiated PE-containing solutions was probed for the formation of degradation products using solid-phase microextraction (SPME) fibers in combination with gas chromatography mass spectrometry (GCMS). The major species detected were n-dodecane, with trace levels of tridecane, 2-dodecanone, and hexadecane, which were believed to be predominately adsorbed in the PE microplastics in excess of their aqueous solubility limits. Surface characterization by Raman spectroscopy and light and dark field microscopy indicated no change in the chemical composition of the irradiated PE microplastics under low O2 to anaerobic conditions. However, morphological changes were observed, indicating radical combination reactions.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2023

Development of a Portable In Situ Phosphorous Sensor

While phosphorus is a critical nutrient for all forms of life, runoff leads to phosphorus accumulation in surface water where it can cause a variety of health, environmental, and economic problems. The Department of Energy is interested in conducting long-term field experiments to monitor the impact of phosphorus in terrestrial and aquatic environments, and to better understand a cost vs. benefit analysis of reducing phosphorus pollution. Performing such long-term experiments requires affordable sensors capable of monitoring low-level phosphorus concentrations under challenging environmental conditions. However, such sensors are currently not available. The goal of this proposed project is to develop and demonstrate a low-cost portable phosphorus sensor suitable for in situ measurements. We will determine the technical requirements for a Raman-based sensor system, design and build a signal amplifier, integrate it with a Raman-based sensor, and demonstrate a proof-of-concept level sensor system. The expected accomplishments for Phase I include the identification of the technical requirements of a combined Raman laser/spectrometer and cavity enhancement system, building a proof-of-concept level sensor system capable of detecting orthophosphate compounds at the desired level of 0.25 mg P/L and organic P compounds, and verification of the sensor performance under laboratory and field conditions. In addition, we will identify initial hardening requirements that will need to be implemented during Phase II. While we plan to develop an integrated sensor system for monitoring phosphorus, the cavity-based enhancement system can also be used in combination with other (non-phosphorus) Raman sensors that we plan to develop or that are already commercially available. A recent market report highlights the increasing demand for such environmental monitoring applications, with the market for chemical detection anticipated to grow at a compound annual growth rate of 6.5% (2020-2025). Wide-spread monitoring of phosphorus could reduce the damage from eutrophication in freshwater, which is estimated to be $2.2 billion annually, thereby increasing biodiversity, reducing costs required for drinking water treatment, and decreasing economic losses related to recreation and angling and lake property values.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Initial assessment of second generation of large-area picosecond photodetectors with multi-channel systems-on-a-chip readout

Here, we first briefly describe the history and motivation behind Cherenkov and scintillation light detection. We then discuss the instrumentation needed to detect these photons as it applies to both photodetectors and readout electronics. One of the motivations is future large neutrino detectors that could, in principle, differentiate between Cherenkov and scintillation light if using novel water-based scintillators. In this paper, we present the first measurements utilizing the second generation of Large Area Picosecond Photodetectors (LAPPDs) in conjunction with commercial system-on-a-chip readouts from Nalu Scientific—in particular, the High Density System on Chip (HDSoC) and Advanced ASoC Rapid Digitizer, Variable Adaptive Readout Chip (AARDVARC) platforms. These state-of-the-art full-waveform digitizers feature sampling rates on the order of 1 and 10 samples per nanosecond, respectively. Using a picosecond laser, we measured the timing jitter between a pair of LAPPD channels, demonstrating the potential of this setup for precise timing applications.

Li, V. A. [Lawrence Livermore National Laboratory ↗
DOE OSTI2024

Metatranscriptomic analysis reveals dissimilarity in viral community activity between an ice-free and ice-covered winter in Lake Erie

Winter is a relatively under-studied season in freshwater ecology. The paucity of wintertime surveys has led to a lack of knowledge regarding microbial community activity during the winter in Lake Erie, a North American Great Lake. Viruses shape microbial communities and regulate biogeochemical cycles by acting as top-down controls, yet very few efforts have been made to examine active virus populations during the winter in Lake Erie. Furthermore, climate change-driven declines in seasonal ice cover have been shown to influence microbial community structure, but no studies have compared viral community activity between different ice cover conditions. We surveyed surface water metatranscriptomes for viral hallmark genes as a proxy for active virus populations and compared activity metrics between ice-covered and ice-free conditions from two sampled winters. Transcriptionally active viral communities were detected in both winters, spanning diverse phylogenetic clades of putative bacteriophage (Caudoviricetes), giant viruses (Nucleocytoviricota, or NCLDV), and RNA viruses (Orthornavirae). However, viral community activity metrics revealed pronounced differences between the ice-covered and ice-free winters. Viral community composition was distinct between winters and viral hallmark gene richness was reduced in the ice-covered relative to the ice-free conditions. In addition, the observed differences in viral communities correlated with microbial community activity metrics. Overall, these findings contribute to our understanding of the viral populations that are active during the winter in Lake Erie and suggest that viral community activity may be associated with ice cover extent.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Evidence that Ultra-high-energy Gamma Rays Are a Universal Feature near Powerful Pulsars

The highest-energy known gamma-ray sources are all located within 0°5 of extremely powerful pulsars. This raises the question of whether ultra-high-energy (UHE; >56 TeV) gamma-ray emission is a universal feature expected near pulsars with a high spin-down power. Using four years of data from the High Altitude Water Cherenkov Gamma-Ray Observatory, we present a joint-likelihood analysis of 10 extremely powerful pulsars to search for subthreshold UHE gamma-ray emission correlated with these locations. We report a significant detection (>3σ), indicating that UHE gamma-ray emission is a generic feature of powerful pulsars. Finally, we discuss the emission mechanisms of the gamma rays and the implications of this result. The individual environment, such as the magnetic field and particle density in the surrounding area, appears to play a role in the amount of emission.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2020

A Featureless Infrared Transmission Spectrum for the Super-puff Planet Kepler-79d

Extremely low-density planets (“super-puffs”) are a small but intriguing subset of the transiting planet population. With masses in the super-Earth range (1 − 10 M{sub ⊕}) and radii akin to those of giant planets (> 4 R{sub ⊕}), their large envelopes may have been accreted beyond the water snow line and many appear to be susceptible to catastrophic mass loss. Both the presence of water and the importance of mass loss can be explored using transmission spectroscopy. Here, we present new Hubble space telescope WFC3 spectroscopy and updated Kepler transit depth measurements for the super-puff Kepler-79d. We do not detect any molecular absorption features in the 1.1 − 1.7 μm WFC3 bandpass, and the combined Kepler and WFC3 data are consistent with a flat-line model, indicating the presence of aerosols in the atmosphere. We compare the shape of Kepler-79d’s transmission spectrum to predictions from a microphysical haze model that incorporates an outward particle flux due to ongoing mass loss. We find that photochemical hazes offer an attractive explanation for the observed properties of super-puffs like Kepler-79d, as they simultaneously render the near-infrared spectrum featureless and reduce the inferred envelope mass-loss rate by moving the measured radius (optical depth unity surface during transit) to lower pressures. We revisit the broader question of mass-loss rates for super-puffs and find that the age estimates and mass-loss rates for the majority of super-puffs can be reconciled if hazes move the photosphere from the typically assumed pressure of ∼10 mbar to ∼10 μbar.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2023

Data-Driven Discovery of Linear Molecular Probes with Optimal Selective Affinity for PFAS in Water

Approaches to tackle the wide and growing variety of highly persistent per- and polyfluoroalkyl substances (PFAS) are of pressing global need because of their detrimental human health effects, such as cancer, birth defects, and hormone imbalance. Sensitive, selective, and easy-to-use real-time sensors to monitor and detect PFAS and sorbents to extract them are critical to meeting government-mandated environmental concentrations. In this work, we combine all-atom molecular dynamics simulations, enhanced sampling, deep representational learning, and Bayesian optimization to perform high-throughput virtual screening for highly sensitive and selective molecular probes. Our molecular design space consists of 3850 linear hydrocarbon chains with varying degrees of halogenation with and without amine- and phosphine-based headgroups. By employing a data-driven search process, we efficiently explore the molecular design space to optimize the sensitivity to perfluorooctanesulfonic acid (PFOS) as a prototypical PFAS analyte and selectivity relative to a sodium dodecyl sulfate (SDS) interferent. We calculate 504 Gibbs free energies of probe-analyte and probe-interferent interactions and identify probes with PFOS association free energies of up to (-ΔG PFOS ) = 9.8 ± 0.2 kJ/mol and selectivities relative to SDS of (-ΔΔG PFOS–SDS ) = 3.1 ± 1.5 kJ/mol. A C 11 Br 23 P(CH 3 ) 2 probe containing 11 backbone brominated carbons and a tertiary phosphine headgroup possesses the most sensitive binding constant to PFOS within the defined search space of K b PFOS = 177.4 ± 12.7, and a semibrominated probe C 5 H 11 C 7 Br 14 N(CH 3 ) 2 containing 12 backbone carbons and a tertiary amine headgroup possesses the highest selectivity relative to SDS of K b PFOS /K b SDS = 4.6 ± 1.7. A retrospective analysis of our data to extract interpretable design rules reveals that the sensitivity of linear hydrogenated probes increases by approximately 1 kJ/mol per C–C bond. The addition or removal of halogen atoms and amine or phosphine headgroups produces nonmonotonic changes in both sensitivity and selectivity with changes to the sensitivity of up to 2.5 kJ/mol. Finally, this work places empirical limitations on the performance of a wide range of linear probes for PFOS detection and offers a generic strategy for high-throughput computational screening to promote selective and sensitive binding.

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

How irradiation promotes intergranular stress corrosion crack initiation

Irradiation assisted stress corrosion cracking (IASCC) is a form of intergranular stress corrosion cracking that occurs in irradiated austenitic alloys. It requires an irradiated microstructure along with high temperature water and stress. The process is ubiquitous in that it occurs in a wide range of austenitic alloys and water chemistries, but only when the alloy is irradiated. Despite evidence of this degradation mode that dates back to the 1960s, the mechanism by which it occurs has remained elusive. Here, using high resolution electron backscattering detection to analyze local stress-strain states, high resolution transmission electron microscopy to identify grain boundary phases at crack tips, and decoupling the roles of stress and grain boundary oxidation, we are able to unfold the complexities of the phenomenon to reveal the mechanism by which IASCC occurs. The significance of the findings impacts the mechanical integrity of core components of both current and advanced nuclear reactor designs worldwide.

36 MATERIALS SCIENCE↗