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All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Thermodynamics of Minerals Stable near Earth's Surface

Project “Thermodynamics of Minerals Stable Near the Earth’s Surface” uses specialized calorimetric techniques to obtain new thermochemical data for solid phases of interest in the Earth’s “critical zone”, the near surface regions of the planet most directly affecting and affected by human activity. Major activity was in three areas: manganese oxide materials, aluminum clusters which are precursors to aluminum oxyhydroxide precipitates, and zeolites. All these classes of minerals are potential carriers of heavy metals and radionuclides in the environment, both within their crystal structures and as adsorbed layers or colloids. Their thermodynamic stability, as well as the sequence of stability of competing phases, governs the aqueous solubility of contaminants (and nutrients) in soil, groundwater, and sediments. The thermodynamics of these phases is strongly affected by particle size and crystallinity, since they often occur as very fine particles which do not coarsen in the near-surface environment. Many of these materials exhibit extensive polymorphism, multicomponent solid solution, and variable hydration states. Thus, one must define and systematize important thermodynamic variables, since one cannot make measurements on each and every possible phase, particle size, and composition. A major finding of the work on manganese oxides was labile water-induced oxidation-reduction reactions. These will be studied further by a combination of thermodynamic and synchrotron-based spectroscopic methods, the latter in collaboration with Peggy O’Day at UC Merced. The adsorption of other species, including simple organics, on such redox-active surfaces will also be investigated by a combination of thermochemical and spectroscopic studies. Studies of the energetics of water adsorption on mineral surfaces will be expanded to emphasize the adsorption of CO2 and small organic molecules, relevant to soil, groundwater, and the subsurface environment. Gas adsorption calorimetry, immersion calorimetry, and solution calorimetry will be combined with appropriate analytical and spectroscopic techniques to obtain a comprehensive picture of the interactions and their energetics. The evolution of aqueous aluminum clusters to form aluminum oxyhydroxide precipitates will be studied in detail by a combination of calorimetric and structural methods applied to aqueous samples aged at room temperature. The energetics of new classes of clusters will be explored. The project addresses several common themes relevant to the broad mission of the Department of Energy. Thermochemical data for minerals stable near the Earth’s surface, though still incomplete, are essential for understanding both natural and anthropogenic processes that affect our very existence on this planet. Such data contribute to the fundamental underpinning for mitigation and management strategies for the extraction and use of energy. Fundamental thermodynamic and mechanistic understanding is required to model processes ranging from heavy metal pollution to nuclear waste disposal to climate change.

58 GEOSCIENCES↗
NASA NTRS1989

Theoretical spectroscopic constants for the low-lying states of the oxides and sulfides of Mo and Tc

Spectroscopic results were determined for the ground and low-lying states of the oxides and sulfides of Mo and Tc, using the single-reference-based modified coupled pair functional method of Ahlrichs et al. (1985) and Chong et al. (1986) and the multireference-based state-averaged CASSCF/MRCI method. Spectroscopic constants, dipole moments, Mulliken populations, and radiative lifetimes were calculated for selected low-lying states of these molecular systems. The spectroscopy of the MoS and TcS molecules was found to be quite analogous to the corresponding oxides.

Langhoff, Stephen R.↗
DOE OSTI2022

Observation of a linked-loop quantum state in a topological magnet

Quantum phases can be classified by topological invariants, which take on discrete values capturing global information about the quantum state. Over the past decades, these invariants have come to play a central role in describing matter, providing the foundation for understanding superfluids, magnets, the quantum Hall effect, topological insulators, Weyl semimetals and other phenomena. Here we report an unusual linking-number (knot theory) invariant associated with loops of electronic band crossings in a mirror-symmetric ferromagnet. Using state-of-the-art spectroscopic methods, we directly observe three intertwined degeneracy loops in the material's three-torus, T 3 , bulk Brillouin zone. We find that each loop links each other loop twice. Through systematic spectroscopic investigation of this linked-loop quantum state, we explicitly draw its link diagram and conclude, in analogy with knot theory, that it exhibits the linking number (2, 2, 2), providing a direct determination of the invariant structure from the experimental data. Here we further predict and observe, on the surface of our samples, Seifert boundary states protected by the bulk linked loops, suggestive of a remarkable Seifert bulk-boundary correspondence. Our observation of a quantum loop link motivates the application of knot theory to the exploration of magnetic and superconducting quantum matter.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Variation in surface properties as error sources in dynamic temperature measurements

Most temperature measurement methods rely upon the assumption of a single uniform source as part of the analysis in inferring an observed temperature T from the surface of a material. This is true for the radiometric and spectroscopic methods we rely upon in shock physics. However, there are obvious cases where this is a poor assumption that can cause large errors in analysis, such as the measurement of emission from a surface composed of more than one material, such as a rusted surface of Fe and Fe 2 O 3 , or a multi-material surface that could be produced through alloying methods (e.g., mokume gane) or 3D printing. Here we perform an initial examination of the effects of varied surface properties upon the analysis using idealized test data to constrain when we may have better confidence in the resulting calculations. We also examine the structures of the fits to test whether, in principle, comparing the fit with ideal gray bodies would reveal such a structure and enable the researcher to identify when a two-temperature fitting model should be used instead of a single- T model or a wavelength-dependent emissivity model.

36 MATERIALS SCIENCE↗
DOE OSTI2021

High Resolution Infrared Spectroscopy of Highly Reactive Chemical Intermediates: Berkeley Inspiration and a C.B. Moore Retrospective

One of the long-standing paradoxes in chemistry is that the molecular species of greatest interest are often highly reactive chemical intermediates and thus present only at vanishingly small concentrations under typical steady state conditions. Here, this has proven both a key frustration and powerful motivation for physical chemists in probing such species, particularly for high resolution laser spectroscopic methods in the infrared. Over the past 4-5 decades, this fundamental sensitivity challenge has stimulated the development of many novel techniques for efficient generation, cooling, and infrared probing of such transient chemical intermediates, achieving increasingly sophisticated levels of spectroscopic detail, chemical insight, and a testbed for comparison with first principles ab initio quantum calculations. Two of the pioneering contributors to this scientific arena have been George Pimentel and C. Bradley Moore, both responsible for nourishing DJN’s own enduring fascination with spectroscopic IR study of elusive chemical intermediates. This chapter is not intended to provide a comprehensive review of this large and enormously successful field, but it rather more simply attempts to capture a few selective “Moore-centric” snapshots of the Nesbitt group scientific evolution, specifically in i) advances by Pimentel for the original development of rapid scan flash kinetic spectroscopy based on spectrometers with rapidly rotating IR gratings, ii) the modernization/extension of these methods in the Moore group toward the first high resolution IR laser spectroscopy of singlet/triplet methylene 1,3 CH 2 diradical, and finally to iii) the development of slit supersonic discharge expansion methods at JILA for sub-Doppler infrared laser study of multiple radicals, jet cooled molecular ions, and highly reactive chemical intermediates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Cold Testing for Characterization of Oxide Feed Impurities in Support of the ARIES Program

The Advanced Recovery and Integrated Extraction System (ARIES) Program converts surplus plutonium metal components into an oxide powder form and packages the material for final disposition. In support of the ARIES program, over a metric ton (MT) of plutonium has been removed from surplus nuclear weapons since 1998 and packaged for long-term storage in 3013 cans. The oxide production rate is anticipated to increase substantially over the next decade in support of dilute and dispose goals. Analytical chemistry data from destructive analysis of the resulting 70+ blend lots to date has been reported for contaminants in the product oxide. Changes in the Pu product specification for Pu oxide product, induced by a different pit mix, the LANL swap program and processing Alternate (non-Pit Pu) Feed Stock (AFS) metals, will affect the level and the mix of these contaminants in the upcoming years. With these changes in feed material, it will be important to provide fast and efficient measurement of elemental impurities in the oxide to be certain that the process is under control and to monitor the anticipated changes from the historical blend lot data. Non-destructive methods need to be evaluated for the characterization of the plutonium oxide product and the quantification of the impurities at the current and anticipated levels. A feasibility study has begun to investigate the applicability of new spectroscopic methods for oxide impurity characterization. To this end, here we describe the preparation of surrogate materials to support these investigations, and the results of a feasibility study investigating the use of LIBS (Laser Induced Breakdown Spectroscopy) to characterize the surrogate materials as calibration standards.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
NASA NTRS1995

Abundance ratios of oxygen, neon, and magnesium in solar active regions and flares: The FIP effect

Relative abundances of oxygen, neon, and magnesium have been derived for a sample of nine solar active regions, flares, and an erupting prominance by combining plots of the ion differential emission measures. The observations were photographed in the 300-600 A range by the Naval Research Laboratory (NRL) spectroheliograph on Skylab. Methods for deriving the Mg/Ne abundance ratio-which measures the separation between the low- first ionization potential (FIP) and high-FIP abundnace plateaus-have been described in previous papers. In this paper we describe the spectroscopic methods for deriving the O/Ne abundance ratio, which gives the ratio between two high-FIP elements. The plot of the O/Ne ratio versus the Mg/Ne ratio in the sample of nine Skylab events is shown. The variation in the Mg/Ne ratio by a factor of 6 is associated with a much smaller range in the O/Ne ratio. This is broadly consistent with the presence of the standard FIP pattern of abundances in the outer atmosphere of the Sun. However, a real change in the relative abundances of oxygen and neon by a factor of 1.5 cannot be excluded.

Widing, K. G.↗
NASA NTRS1985

Instrumentation for Application Number 1: Mass Spectrometric Analysis of the Boundary Layer Associated with the Tethered Satellite

Knowledge about the boundary layer associated with high enthalpy flow fields has mostly been derived from measurements of physical properties. To further this understanding, the chemistry of the gaseous layer must be studied as well. This requires that instrumentation and measurement methods be developed that can analyze the gases while having a minimal effect on the flow field and composition. Because of its sensitivity and ability to identify species, the mass spectrometer is the most promising instrument for this application, although other spectroscopic methods are being evaluated as well. There are, however, several non-trivial problems that must be solved in order to apply the mass spectrometer, including the obtaining of a representative sample from near the model surface. These problems are being addressed in a research program to develop qualitative and quantitative measurement methods to examine the gas chemistry in several large hot-gas blowdown facilities, and to study the aerodynamics of the boundary layer associated with models in these facilities and in instrumented hypersonic vehicles. These methods can also be applied to the tethered satellite, which will provide a unique opportunity to obtain aerothermodynamic data that is unaltered by effects from the test facility.

Wood, G. M.↗
NASA NTRS2003

Microcrack Quantification in Composite Materials by a Neural Network Analysis of Ultrasound Spectral Data

Intra-ply microcracking in unlined composite pressure vessels can be very troublesome to detect and when linked through the thickness can provide leak paths that may hinder mission success. The leaks may lead to loss of pressure/propellant, increased risk of explosion and possible cryo-pumping into air pockets within the laminate. Ultrasonic techniques have been shown capable of detecting the presence of microcracking and in this work they are used to quantify the level of microcracking. Resonance ultrasound methods are utilized with artificial neural networks to build a microcrack prediction/measurement tool. Two networks are presented, one unsupervised to provide a qualitative measure of microcracking and one supervised which provides a quantitative assessment of the level of microcracking. The resonant ultrasound spectroscopic method is made sensitive to microcracking by tuning the input spectrum to the higher frequency (shorter wavelength) components allowing more significant interaction with the defects. This interaction causes the spectral characteristics to shift toward lower amplitudes at the higher frequencies. As the density of the defects increases more interactions occur and more drastic amplitude changes are observed. Preliminary experiments to quantify the level of microcracking induced in graphite/epoxy composite samples through a combination of tensile loading and cryogenic temperatures are presented. Both unsupervised (Kohonen) and supervised (radial basis function) artificial neural networks are presented to determine the measurable effect on the resonance spectrum of the ultrasonic data taken from the samples.

Walker, James L.↗
NASA NTRS1977

Laboratory studies of lean combustion

The fundamental processes controlling lean combustion were observed for better understanding, with particular emphasis on the formation and measurement of gas-phase pollutants, the stability of the combustion process (blowout limits), methods of improving stability, and the application of probe and optical diagnostics for flow field characterization, temperature mapping, and composition measurements. The following areas of investigation are described in detail: (1) axisymmetric, opposed-reacting-jet-stabilized combustor studies; (2) stabilization through heat recirculation; (3) two dimensional combustor studies; and (4) spectroscopic methods. A departure from conventional combustor design to a premixed/prevaporized, lean combustion configuration is attractive for the control of oxides of nitrogen and smoke emissions, the promotion of uniform turbine inlet temperatures, and, possibly, the reduction of carbon monoxide and hydrocarbons at idle.

Sawyer, R. F.↗
DOE OSTI2021

The Story of 5d Metallocorroles: From Metal–Ligand Misfits to New Building Blocks for Cancer Phototherapeutics

Porphyrin chemistry is Shakespearean: over a century of study has not withered the field’s apparently infinite variety. Heme proteins continually astonish us with novel molecular mechanisms, while new porphyrin analogues bowl us over with unprecedented optical, electronic, and metal-binding properties. Within the latter domain, corroles occupy a special place, exhibiting a unique and rich coordination chemistry. The 5d metallocorroles are arguably the icing on that cake. New Zealand chemist Penny Brothers has used the word “misfit” to describe the interactions of boron, a small atom with a predilection for tetrahedral coordination, and porphyrins, classic square-planar ligands. Steve Jobs lionized misfits as those who see things differently and push humanity forward. Both perspectives have inspired us. The 5d metallocorroles are misfits in that they encapsulate a large 5d transition metal ion within the tight cavity of a contracted porphyrin ligand. Given the steric mismatch inherent in their structures, the syntheses of some 5d metallocorroles are understandably capricious, proceeding under highly specific conditions and affording poor yields. Three broad approaches may be distinguished. (a) In the metal–alkyl approach, a free-base corrole is exposed to an alkyllithium and the resulting lithio-corrole is treated with an early transition metal chloride; a variant of the method eschews alkyllithium and deploys a transition metal–alkyl instead, resulting in elimination of the alkyl group as an alkane and insertion of the metal into the corrole. This approach is useful for inserting transition metals from groups 4, 5, and, to some extent, 6, as well as lanthanides and actinides. (b) In our laboratory, we have often deployed a low-valent organometallic approach for the middle transition elements (groups 6, 7, 8, and 9). The reagents are low-valent metal–carbonyl or −olefin complexes, which lose one or more carbon ligands at high temperature, affording coordinatively unsaturated, sticky metal fragments that are trapped by the corrole nitrogens. (c) Finally, a metal acetate approach provides the method of choice for gold and platinum insertion (groups 10 and 11). This Account provides a first-hand perspective of the three approaches, focusing on the last two, which were largely developed in our laboratory. In general, the products were characterized with X-ray crystallography, electrochemistry, and a variety of spectroscopic methods. The physicochemical data, supplemented by relativistic DFT calculations, have provided fascinating insights into periodic trends and relativistic effects. An unexpected feature of many 5d metallocorroles, given their misfit character, is their remarkable stability under thermal, chemical, and photochemical stimulation. Many of them also exhibit long triplet lifetimes on the order of 100 μs and effectively sensitize singlet oxygen formation. Many exhibit phosphorescence in the near-infrared under ambient conditions. Furthermore, water-soluble ReO and Au corroles exhibit impressive photocytotoxicity against multiple cancer cell lines, promising potential applications as cancer phototherapeutics. We thus envision a bright future for the compounds as rugged building blocks for new generations of therapeutic and diagnostic (theranostic) agents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Enzymes and Models. In: XAFS Techniques for Catalysts, Nanomaterials, and Surfaces

Many important redox-active metalloenzymes consist of 3d transition metals in their active sites. They catalyze multi-electron reactions in aqueous solution, under ambient temperature and pressure. To understand the functionality of the catalytic sites of these enzymes, X-ray spectroscopy methods provide important information of the electronic structure of the metal of interest and its local structural information, as well as their changes during the catalysis. Studying model compounds, that mimic enzyme catalytic site structures or their functional mimics, is as critical as studying enzymes themselves, in order to interpret X-ray spectroscopic data. In this chapter, various X-ray spectroscopic methods that are useful for structural and electronic structural studies of enzymes and model compounds are described.

Yachandra, VK↗
NASA NTRS2004

Remote Sensing of the Haughton Impact Structure (HIS): A Terrestrial Proof of Concept for Using the Remote Sensing of Martian Craters as a Probe of Subsurface Composition

Impact cratering is the most widespread geological process in the Solar System. Impact craters can provide 'windows' into the subsurfaces of planetary bodies through excavation and uplift. By utilizing remote methods in the visible and near infrared (VNIR; 0.4-1.4 micron), short-wavelength infrared (SWIR; 1.4-2.5 micron) and thermal infrared (TIR 7-14 micron), subsurface mineral compositions may be identified and mapped via impact craters. Complex craters in particular, expose minerals from both the shallow and deep-seated subsurface, which may be identified spectroscopically. Complex craters have morphological features such as central peaks or peak rings, which are composed of relatively coherent lithologies tapped from deep-seated crustal components. While near-surface crustal components can be observed as coherent rocks uplifted and exposed in the rim and the crater walls, and from the ejecta deposits. Only two previously published studies using this approach have been successful on large planetary bodies. Tompkins and Pieters utilized ultraviolet and VNIR from Clementine to characterize near- and deep-subsurface materials in and around lunar craters. The work of Ramsey and Wright was the first remote spectroscopic study to successfully identify near-subsurface materials in the ejecta and crater wall of a terrestrial impact structure, namely Meteor Crater. Here we present early results of a third such study, a remote spectroscopy evaluation of the Haughton impact structure (HIS). The purpose of this study is to serve as terrestrial proof of concept that remote visible/infrared spectroscopic methods in this case, analysis of LANDSAT 7 ETM+ and ASTER data of the well-preserved HIS can be utilized in deciphering the subsurface composition of planetary crusts. This technique is particularly promising for Mars were limited tectonic uplift and ubiquitous dust-mantling offer few opportunities to access subsurface information.

Tornabene, L. L.↗
DOE OSTI2017

New approaches for metabolomics by mass spectrometry

Small molecules constitute a large part of the world around us, including fossil and some renewable energy sources. Solar energy harvested by plants and bacteria is converted into energy rich small molecules on a massive scale. Some of the worst contaminants of the environment and compounds of interest for national security also fall in the category of small molecules. The development of large scale metabolomic analysis methods lags behind the state of the art established for genomics and proteomics. This is commonly attributed to the diversity of molecular classes included in a metabolome. Unlike nucleic acids and proteins, metabolites do not have standard building blocks, and, as a result, their molecular properties exhibit a wide spectrum. This impedes the development of dedicated separation and spectroscopic methods. Mass spectrometry (MS) is a strong contender in the quest for a quantitative analytical tool with extensive metabolite coverage. Although various MS-based techniques are emerging for metabolomics, many of these approaches include extensive sample preparation that make large scale studies resource intensive and slow. New ionization methods are redefining the range of analytical problems that can be solved using MS. This project developed new approaches for the direct analysis of small molecules in unprocessed samples, as well as pushed the limits of ultratrace analysis in volume limited complex samples. The projects resulted in techniques that enabled metabolomics investigations with enhanced molecular coverage, as well as the study of cellular response to stimuli on a single cell level. Effectively individual cells became reaction vessels, where we followed the response of a complex biological system to external perturbation. We established two new analytical platforms for the direct study of metabolic changes in cells and tissues following external perturbation. For this purpose we developed a novel technique, laser ablation electrospray ionization (LAESI), for metabolite profiling of functioning cells and tissues. The technique was based on microscopic sampling of biological specimens by mid-infrared laser ablation followed by electrospray ionization of the plume and MS analysis. The two main shortcomings of this technique had been limited specificity due to the lack of a separation step, and limited molecular coverage, especially for nonpolar chemical species. To improve specificity and the coverage of the metabolome, we implemented the LAESI ion source on a mass spectrometer with ion mobility separation (IMS). In this system, the gas phase ions produced by the LAESI source were first sorted according to their collisional cross sections in a mobility cell. These separated ion packets were then subjected to MS analysis. By combining the atmospheric pressure ionization with IMS, we improved the metabolite coverage. Further enhancement of the non-polar metabolite coverage resulted from the combination of laser ablation with vacuum UV irradiation of the ablation plume. Our results indicated that this new ionization modality provided improved detection for neutral and non-polar compounds. Based on rapid progress in photonics, we had introduced another novel ion source that utilized the interaction of a laser pulse with silicon nanopost arrays (NAPA). In these nanophotonic ion sources, the structural features were commensurate with the wavelength of the laser light. The enhanced interaction resulted in high ion yields. This ultrasensitive analytical platform enabled the MS analysis of single yeast cells. We extended these NAPA studies from yeast to other microorganisms, including green algae (Chlamydomonas reinhardtii) that captured energy from sunlight on a massive scale. Combining cellular perturbations, e.g., through environmental changes, with the newly developed single cell analysis methods enabled us to follow dynamic changes induced in the cells. In effect, we were able to use individual cells as a “laboratory,” and approached the long-standing goal of establishing a “lab-in-a-cell.” Model systems for these studies included cells of cyanobacteria (Anabaena), yeast (Saccharomyces cerevisiae), green algae (C. reinhardtii) and Arabidopsis thaliana.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Disordered TiO x –SiO x Nanocatalysts Using Bioinspired Synthetic Routes

Metal oxide nanomaterials have increasing significance and broad applications in catalysis, ranging from support materials to active catalysts. Here, we have demonstrated a facile synthetic strategy to create disordered, high-surface-area metal oxide nanomaterials using biomineralization-inspired methods. Using protamine as a protein template, a range of TiO x –SiO x nanomaterials were synthesized and implemented for catalytic CO 2 thermal reduction reactions. The modularity of synthetic options afforded via biomineralization enables increases in surface area, which are ideally suited for subsequent modification to regulate catalytic performance. All materials were thoroughly characterized using a suite of synchrotron scattering and spectroscopic methods. Through these techniques, we have demonstrated that protamine-induced biomineralization results in largely disordered materials with changes in the local atomic structure dependent on the applied synthetic conditions. Protamine removal with treatment under acidic conditions greatly increased material surface area while causing measurable changes in the structure as revealed by X-ray absorption spectroscopy. Upon subsequent hydrogenation, Ti- and Si-based defects were induced in the materials while the disordered nature of the material was still largely retained. Furthermore, we found that the incorporation of Si into TiO x was able to mitigate the known anatase to rutile phase change during the reaction while stabilizing the defect sites. The synthetic strategies described in this work are expected to be translatable to other metal oxide nanomaterial chemical structures, providing a means to control catalytic properties using benign synthetic strategies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Resonant Polarization Spectroscopy for Hot X-ray Plasmas

X-ray line polarization spectroscopy is a method of choice for probing hot plasma conditions. The precise roles of resonant structures in this method have not been realized and fully understood. With a sophisticated relativistic close coupling Dirac R-matrix calculation of polarized radiation of the quadrupole magnetic M2 line at 2.717 Å in Ba 46+ , we revealed the nature of resonant structures in x-ray line polarization spectroscopy. We found that signatures with a heavy resonance forest imprinting on polarization may be used for a sensitive new spectroscopic method. The resonant polarization spectrum was used to determine or constrain the directional beam electron distribution of the laboratory Ba plasma. Lastly, our results provide a start of resonant polarization spectroscopy as a method for diagnostics of laboratory, fusion and astrophysical plasma source conditions.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗