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All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Climatology of Cloud‐Land‐Surface Coupling Across Different ARM Sites

Land-atmosphere interactions play a critical role in the evolution and formation of low-level clouds. The different states of coupling between low-level clouds and the surface are uncertain, primarily over continental regions, where complex thermodynamics complicates their investigation. This study uses observations from the Atmospheric Radiation Measurement User Facility to explore cloud-surface coupling and perform a climatological analysis of this interaction in five countries across three continents. The results reveal consistent coupling thresholds and average percentages across the five sites, with coupled clouds accounting for 66% of the cases and decoupled clouds for 34%. Thermodynamic and dynamic evaluations show distinct differences between coupled and decoupled clouds. Coupled clouds are characterized by humid environments, in which vertical motions connect the surface and lower atmosphere to the cloud base, conditions that favor the formation of boundary layer clouds. Decoupled clouds prefer to occur in a drier and colder environment with vertical motions inside the boundary layer being detached from the cloud base, under which boundary layer clouds are hard to form. Coupled clouds peak during warmer hours and seasons, and vice versa for decoupled clouds. This study underscores the complexity of cloud-land-surface interactions and paves the way for further investigations into cloud formation and evolution under different atmospheric environments.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Spectral Induced Polarization-Biogeochemical Relationships for Remediation Amendment Monitoring

Geophysical tools such as electrical resistivity (ER) can indirectly monitor subsurface changes in response to remedial injections. These methods exhibit relatively low spatial resolution compared to sediment core characterization but are advantageous due to the ability to collect measurements non-intrusively over time across large volumes of the subsurface. Moreover, along with confirmatory groundwater or core sampling, geophysical methods can be used during active biogeochemical remedies to monitor short-term contaminant transformations and mobility, as well as part of an overall strategy for long-term monitoring of subsurface contaminated sites. The use of alternating current spectral induced polarization (SIP) provides significantly more information than conventional geophysical methods like direct current ER. SIP allows for monitoring changes in both solution and surface conductivity by separation of real and imaginary conductivity, respectively, as well as surface capacitance. In principle, SIP can measure indicators of remedy progression such as precipitation reactions that sequester contaminants, potentially providing a better indication of amendment delivery and reactivity as compared to conventional ER methods. However, multiple processes and material properties have overlapping (interacting) electrical responses across a range of frequencies. Hence, the purpose of this scoping study was to evaluate if SIP can be used to monitor (a) amendment delivery and (b) precipitation and reactivity of amendments under consideration at Hanford. SIP measurements were collected in fully saturated columns packed with sand and Hanford formation sediments containing (a) amendments that were highly conductive with significant capacitance (zero valent iron – ZVI, sulfur modified iron – SMI) and (b) amendments that exhibited low electrical conductivity with a small capacitance (calcite, apatite, bismuth). The sand was a quartz material with homogenous particle size that exhibited a relatively low surface conductivity. It was used as a control for comparison with the sediments from the Hanford Site, which have a greater surface conductivity because of their complex mineralogy and heterogeneous particle size distribution and may have complex interactions with amendments. The amendment mass fraction was varied to represent the different stages and subsurface locations associated with the delivery of a remedy. The primary objective was to identify the solution and solid surface changes associated with the delivery amendments and their secondary reactions within the subsurface. The figure below summarizes results for the amendments tested through this project. The SIP phase shift or imaginary conductivity change for the high conductivity amendments was more than 10 times that of the low conductivity amendments, highlighting the relative ease of detection of ZVI and SMI independent of the background signal from sand or Hanford sediments. The ZVI phase shift and imaginary conductivity changes occur primarily at high frequency (> 100 Hz) whereas SMI changes were at low frequency (0.01 to 10 Hz). SIP signals of SMI also increased over time and the maximum shifted to lower frequencies. The low conductivity amendments (calcite, abiotic and biotic apatite, bismuth subnitrate) exhibited relatively small phase and imaginary conductivity changes when added to sediments. The changes were above minimum detection limits (0.5 mrad for phase shift, 0.03 µS/cm for imaginary conductivity) for the highest concentration except for the commercial bismuth material. The lowest amendment concentration that can be detected is likely sediment specific, as minerals in sediments (clays, magnetite, Fe-oxides) have some capacitance and, therefore, exhibit a variable phase shift.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2019

Fermi surface, possible unconventional fermions, and unusually robust resistive critical fields in the chiral-structured superconductor AuBe

The noncentrosymmetric superconductor (NCS) AuBe is investigated using a variety of thermodynamic and resistive probes in magnetic fields of up to 65 T and temperatures down to 0.3 K. Despite the polycrystalline nature of the samples, the observation of a complex series of de Haas–van Alphen (dHvA) oscillations has allowed the calculated band structure for AuBe to be validated. This permits a variety of BCS parameters describing the superconductivity to be estimated, despite the complexity of the measured Fermi surface. In addition, AuBe displays a nonstandard field dependence of the phase of dHvA oscillations associated with a band thought to host unconventional fermions in this chiral lattice. Overall, this result demonstrates the power of the dHvA effect to establish the properties of a single band despite the presence of other electronic bands with a larger density of states, even in polycrystalline samples. In common with several other NCSs, we find that the resistive upper critical field exceeds that measured by heat capacity and magnetization by a considerable factor. We suggest that our data exclude mechanisms for such an effect associated with disorder, implying that topologically protected superconducting surface states may be involved.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

An automated cluster surface scanning method for exploring reaction paths on metal-cluster surfaces

Metal-cluster surfaces present a wide variety of unique coordination environments. This complexity makes it difficult to manually probe the surface reactivity of such clusters. Here, we present a simple and automated method to systematically discover reaction pathways on cluster surfaces, based on the automated cluster surface scanning (ACSS) technique for mapping out potential energy surfaces. We showcase our method on 55-atom icosahedral Cu and Ag clusters, where we determine the activation energies of four elementary steps common in heterogeneous catalysis – hydrogen recombination (H* + H* → H 2 * + *), oxygen recombination (O* + O* → O 2 * + *), water formation (OH* + H* → H 2 O* + *), and CO oxidation (CO* + O* → CO 2 * + *) – with density functional theory calculations (DFT-PBE + D3). We show that the ACSS method requires significantly less human effort than the established manually performed climbing-image nudged elastic band (MP + CI-NEB) technique and locates transition states with comparable accuracy (root-mean-squared error of 0.10 eV) and similar computational cost. Rigorous sampling of the potential energy surface with the ACSS method allows one to locate all lowest-energy reaction pathways obtained via the MP+CI-NEB approach, as well as alternative pathways that one may have missed with the MP+CI-NEB approach due to the many possible pathways available on these clusters. The accuracy and efficiency afforded by the ACSS method could enable high-throughput exploration of the diverse reactivity of metal clusters.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Natural Attenuation Progress, Plume Movement, and Source Reduction for the SRS CMP Pits VOC Plume - 18384

Monitoring the effectiveness of natural attenuation for remediating the Savannah River Site (SRS) Chemical, Metals, and Pesticides (CMP) Pits plume fringe has focused intensive sampling of shallow groundwater for different reaches of Pen Branch from 2005 to 2017. Volatile organic compounds (VOCs) were analyzed for the critical hyporheic zone beneath Pen Branch and adjacent floodplain. These sampling efforts assisted larger-scale compliance monitoring in accordance with US Environmental Protection Agency (EPA) guidelines. When applicable, EPA has found natural attenuation to be an acceptable mode of achieving regulatory compliance. While natural attenuation can include any ecosystem function that reduces contaminant loads, it is focused on microbial biochemical pathways. The study plume originated from CMP Pits, a waste disposal area in operation from 1971 to 1979, when the pits were closed and backfilled. In 1984, excavations of source material and contaminated soils were removed up to a depth of 7.6 m below the trenches. However, monitoring well data indicated that perchloroethylene (PCE) and trichloroethylene (TCE) had seeped beneath the vadose zone and formed groundwater plumes reaching the Pen Branch valley below. Although 'hot spots' of TCE were found within the Pen Branch floodplain, it was unknown just how the flow pattern was entering Pen Branch and to what degree natural attenuation was reducing the contaminant load. For this reason, our stations were located along the Pen Branch reach bordering the modelled plume fringe. In general, VOCs were highest at station piezometer holes in the middle study zone. Moderate VOC levels were detected at upstream stations and lowest VOC levels were found at downstream stations. Electrical resistance heating (ERH) with soil vapor extraction (SVE) conducted by Savannah River Nuclear Solutions (SRNS) from 2008 to 2009 at the filled CMP Pits helped to remove contaminants trapped in clay horizons beneath the CMP Pits and to reduce overall new plume concentrations. Collectively PCE, TCE, and their degradation products displayed a favorable yearly trend of contaminant natural attenuation. Additionally, phytoremediation actions by native bamboo, Arundinaria gigantea, added to VOC removal from wetlands soils. Total VOC concentrations at some stations declined by >25% and concentrations of vinyl chloride (VC), a nearly-final stage degradation product increased from 0.0 ppb to >20 ppb. Temporal patterns displayed a continued reduction of VOCs, while spatial patterns indicated a possible slow progression of the plume downstream along Pen Branch. Conclusions about plume export into surface waters must address the seasonal and geological complexities of this system. Hydrological patterns are complex and plumes do not directly outcrop into Pen Branch surface waters, but emerge into the stream through pathways in the porous hyporheic zone. For this reason, continued sampling must identify critical depths and downstream locations where plume flows may be more intense. During drought periods with no surface flow in Pen Branch, subsurface plume flows may be flowing downslope in the hyporheic zone. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2024

Enhanced rare earth element recovery with cross-linked glutaraldehyde-lanthanide binding peptides in foam-based separations

Lanthanide Binding Tag (LBT) peptides that coordinate selectively with lanthanide ions can be used to replace the energy intensive processes used for the separation of rare earth elements (REEs). These surface-active biomolecules, once selectively complexed with the trivalent REE cations, can adsorb to air/aqueous interfaces of bubbles for foam-based REEs recovery. Glutaraldehyde, an organic compound that is a homobifunctional crosslinker for proteins and peptides, can be used to enhance the adsorption and interfacial stabilization of lanthanide-bound peptides films. The stability of the interfacial cross-linked films was tested by measuring their dilational and shear surface rheological properties. Surface activity of the adsorbed species was analyzed using pendant drop tensiometry, while surface density and molecular arrangement were determined using x-ray reflectivity and x-ray fluorescence near total reflection. Glutaraldehyde cross-linked REE-peptide complexes enhance the adsorption of lanthanides to air-water interfaces, resulting in thicker interfacial structures. Subsequently, these thicker layers enhance the dilational and shear interfacial rheological properties. The interfacial film stabilization and REEs extraction promoted by the cross-linker presented in this work provides an approach to integrate glutaraldehyde as a substitute of common foam stabilizers such as polymers, surfactants, and particles to optimize the recovery of REEs when using biomolecules as extractants.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Intersystem crossing in the exit channel

We report that intersystem crossing (ISC), plays an important role in photochemistry. It is understood to be efficient when heavy atoms are present due to strong spin–orbit coupling, or when strongly bound long-lived complexes are formed that increase the chance of finding the singlet–triplet intersection seam. Here we present evidence for a different ISC mechanism in the bimolecular reaction of O( 3 P) with alkylamines. In crossed-beam experiments, product velocity-flux maps are measured for aminoalkyl radicals produced from H-abstraction from the methyl group, which also gives OH radicals as co-fragments. The low translational-energy release and isotropic angular distributions of the products indicate that such reactions undergo the formation of a complex before OH and aminoalkyl are produced. However, there is no well on the triplet potential-energy-surface that could support such a complex. Multireference ab initio calculations suggest, instead, that ISC occurs in the exit-channel region due to the long-range dipole–dipole interaction between the nascent radical product pair coupled with the vanishing singlet–triplet splitting at long range. Finally, ISC then leads to a deep hydroxylamine well before OH elimination.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2020

Observing the three-dimensional dynamics of supported metal complexes

Dynamics are intricately linked with activity and selectivity when it comes to catalysis, as noted for instance in the enzymatic principles of induced fit and allostery, and yet the range of motions heterogeneous catalytic sites are able to undergo is poorly understood. Solid-state nuclear magnetic resonance (NMR) spectroscopy is perhaps the only tool capable of probing the rapid conformational dynamics found in heterogeneous catalysts but has historically been restricted by its low sensitivity, limiting the detail with which structures can be resolved. In this work, we apply solid-state NMR and dynamic nuclear polarization, in combination with density functional theory modeling, to reveal the high-resolution structure and motional freedom of a scandium supported complex in three dimensions. The results are contrasted with the study of the analogous homoleptic complex in the crystalline state, highlighting the impacts that surface structure may have on the dynamics of supported complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Cyber Attack Sequences Generation for Electric Power Grid

Security assessment of cyber-physical energy systems (CPESs) such as the electric power grid is a critical operation to maintain availability, reliability, and quality of service in the presence of persistent threats from malicious cyber actors. Existing security assessment approaches such as penetration testing and red teaming rely on subject matter expert experience and forensic cyber analysis of historical events to perform realistic, threat-informed assessments of CPES defense. CPESs have a large attack surface because of the heterogeneity and complexity of underlying topology, devices, measurements, and vulnerabilities. The aforementioned approaches lead to partial coverage of the attack surface with a large set of unknown but possible exploits. There is a need to automate the CPES attack surface discovery and contextualize it for relevant, highly probable, real-world attack scenarios. We propose a methodology and framework to facilitate the discovery of the CPES attack surface. We present a multilayer attack graph with ranked attack sequences to describe CPES failure scenarios. We present a work-in-progress framework that lists key components to automate the attack modeling and sequence generation. We demonstrate the published National Electric Sector Cybersecurity Organization Resource CPES failure scenario to highlight the trustworthiness of generated attack sequences.

Dutta, Ashutosh↗
DOE OSTI2024

Size matters: altering the metal-surface coordination in micropores via structural confinement effects

Solid-state NMR experiments were used to investigate the dynamics of supported complexes grafted to a series of silica gel materials of varied pore sizes. Through dipolar recoupling measurements, we found that ligand dynamics were impeded in the more confined environments, as would be expected. A new form of motion involving the complex as a whole, however, appeared in the most restricted environment consisting of 22 Å diameter pores. These motions persisted down to –100 °C at which point the ligands were frozen on the NMR timescale. The newly observed dynamics could only result from the breaking of secondary dative metal–siloxane interactions that otherwise lock the complex in a preferred orientation on the surface. Crucially, these results show that confinement effects alone can be sufficient to reduce a grafted metal's effective coordination number in direct analogy to the synthesis of undercoordinated complexes using bulky ligands. Finally, this finding could have important implications in the synthesis of more active heterogeneous catalysts.

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

An Experimental Method to Measure Gaseous Diffusivity in Tight and Partially Saturated Porous Media via Continuously Monitored Mass Spectrometry

Detection of radioxenon and radioargon produced by underground nuclear explosions is one of the primary methods by which the Comprehensive Nuclear-Test–Ban Treaty (CTBT) monitors for nuclear activities. However, transport of these noble gases to the surface via barometric pumping is a complex process relying on advective and diffusive processes in a fractured porous medium to bring detectable levels to the surface. To better understand this process, experimental measurements of noble gas and chemical surrogate diffusivity in relevant lithologies are necessary. However, measurement of noble gas diffusivity in tight or partially saturated porous media is challenging due to the transparent nature of noble gases, the lengthy diffusion times, and difficulty maintaining consistent water saturation. Here, the quasi-steady-state Ney–Armistead method is modified to accommodate continuous gas sampling via effusive flow to a mass spectrometer. An analytical solution accounting for the cumulative sampling losses and induced advective flow is then derived. Experimental results appear in good agreement with the proposed theory, suggesting the presence of retained groundwater reduces the effective diffusivity of the gas tracers by 10–1000 times. Finally, by using a mass spectrometer, the method described herein is applicable to a broad range of gas species and porous media.

47 OTHER INSTRUMENTATION↗
DOE OSTI2018

Characteristics of Hydrogen Sensors Based on Thin Tin Dioxide Films Modified with Platinum, Palladium, Silver, and Yttrium

The dependence of the characteristics of hydrogen sensors based on thin Pt/Pd/SnO{sub 2}:Sb, Ag, Y and Ag/SnO{sub 2}:Sb, Ag, Y films obtained by the method of magnetron sputtering at a direct current on the humidity level of the gas mixture during operation in thermal cyclic mode is investigated. The analysis of the experimental data was carried out using the expressions obtained on the basis of the dissociative adsorption model of hydrogen and water molecules on the SnO{sub 2} surface, taking into account the presence of three types of adsorbed particles: O{sup –}, OH, OН{sup –}. The use of complex modifiers Pt/Pd, Ag on the surface and Ag + Y in the bulk of tin dioxide films allows to reduce the influence of humidity on the characteristics of sensors. The role of these modifying additives in the process of dissociative adsorption of hydrogen molecules on the surface of SnO{sub 2} films in humid environment is established.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2019

Toward Fast and Reliable Potential Energy Surfaces for Metallic Pt Clusters by Hierarchical Delta Neural Networks

Data-driven machine learning force fields (MLF) are more and more popular in atomistic simulations, and exploit machine learning methods to predict energies and forces for unknown structures based on the knowledge learned from an existing reference database. The latter usually comes from density functional theory calculations. One main drawback of MLFs is that physical laws are not incorporated in the machine learning models and instead, MLFs are designed to be very flexible to simulate complex quantum chemistry potential energy surface (PES). In general, MLFs have poor transferability, and hence a very large trainset is required to span all the target feature space to get a reliable MLF. This procedure becomes more troublesome when the PES is complicated, with a large number of degrees of freedom, in which building a large database is inevitable and very expensive, especially when accurate but costly exchange-correlation functionals have to be used. In this manuscript, we exploit a high dimensional neural network potential (HDNNP) on Pt clusters of size 6 to 20 as one example. Furthermore, our standard level of energy calculation is DFT GGA (PBE) using a plane wave basis set. We introduce an approximate but fast level with the PBE functional and a minimal atomic orbital basis set, then a more accurate but expensive level, using a hybrid functional or non-local vdw functional and a plane wave basis set, is reliably predicted by learning the difference with HDNNP. Findings show that such a differential approach (named ΔHDNNP) can deliver very accurate predictions (error < 10 meV/atom) in reference to converged basis set energies as well as more accurate but expensive xc functional. The overall speedup can be as large as 900 for 20 atom Pt cluster. More importantly, ΔHDNNP shows much better transferability due to the intrinsic smoothness of delta potential energy surface, and accordingly one can use much smaller trainset data to obtain better accuracy than the conventional HDNNP. A multi-layer ΔHDNNP is thus proposed to obtain very accurate predictions versus expensive non-local vdW functional calculations in which the required trainset is further reduced. The approach can be easily generalized to any other machine learning methods and opens a path to study the structure and dynamics of Pt clusters and nanoparticles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Modeling of three-dimensional surfaces using high-level canonical piecewise-linear functions in cylindrical coordinates

In this paper, the potential application of the high-level canonical piecewise-linear model in the field of three-dimensional visualization is proposed. This idea emerges from the premise that a three-dimensional surface can be modeled by a continuous two-dimensional function. In this regard, the main contribution consists in providing a methodology for the construction of such function. For this purpose, the well-known algorithm used in the high-level canonical piecewise-linear model has been modified to achieve functions with greater graphing capability. One of the most notorious changes made with respect to the traditional methodology is the use of a new scheme of function domain partition. Contrary to the simplicial partitioning, in our proposal, an equally distributed angular partitioning is considered. With this, the resulting approximate function is expressed in cylindrical coordinates which overcome the typical limitation of graphs in Cartesian coordinates of only representing single-valued surfaces. Another remarkable change can be found in the range of evaluation of the function. Instead of using an open interval, in our approach, a closed interval from 0 to 2π is adopted. To support this proposal, illustrative case studies are reported. Numerical simulations demonstrate the effectiveness of this type of representation model not only in visual perception of three-dimensional surfaces, but also in more complex tasks like volume estimation.

97 MATHEMATICS AND COMPUTING↗