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All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

A Combined Wave Function and Density Functional Approach for K-Edge X-ray Absorption Near-Edge Spectroscopy: A Case Study of Hydrated First-Row Transition Metal Ions

The prediction of X-ray absorption spectra (XAS) of transition metal complexes has important and broad application areas in chemistry and biology. In this letter, we have investigated the predictive ability of multiconfiguration pair-density functional theory (MC-PDFT) for X-ray absorption spectra by calculating the metal K pre-edge features of aquated 3d transition metal ions in common oxidation states. MC-PDFT results were compared with experimentally measured spectra as well as analyzed against results from restricted active-space second-order perturbation theory (RASPT2) and time-dependent density functional theory (TDDFT). As expected, TDDFT performs well for excited states that can be accurately represented by singly excited configurations but fails for excited states where higher order excitations become important. On the other hand, both RASPT2 and MC-PDFT provide quantitatively accurate results for all excited states irrespective of their character. While core-level spectroscopy with RASPT2 is accurate, it is computationally expensive. Finally, our results show that MC-PDFT performs equally well with significantly lower computational cost and is an encouraging alternate approach for X-ray spectroscopies.

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

Modeling the Behavior of Complex Aqueous Electrolytes Using Machine Learning Interatomic Potentials: The Case of Sodium Sulfate

Understanding the structure and thermodynamics of solvated ions is essential for advancing applications in electrochemistry, water treatment, and energy storage. While ab initio molecular dynamics methods are highly accurate, they are limited by short accessible time and length scales whereas classical force fields struggle with accuracy. Herein, we explore the structure and thermodynamics of complex monovalent-divalent ion pairs using Na 2 SO 4 (aq) as a case study by applying a machine learning interatomic potential (MLIP) trained on density functional theory (DFT) data. Our MLIP-based approach reproduces key bulk properties such as density and radial distribution functions of water. We provide the hydration structure of the sodium and sulfate ions in the 0.1–2 M concentration range and the one-dimensional and two-dimensional potentials of mean force for the sodium–sulfate ion pairing at the low concentration limit (0.1 M), which are inaccessible to DFT. At low concentrations, the sulfate ion is strongly solvated, leading to the stabilization of solvent-separated ion pairs over contact ion pairs. Minimum energy pathway analysis revealed that coordinating two sodium ions with a sulfate ion is a multistep process whereby the sodium ions coordinate to the sulfate ion sequentially. Finally, we demonstrate that MLIPs allow the study of solvated ions beyond simple monovalent pairs with DFT-level accuracy in their low concentration limit (0.1 M) via statistically converged properties from ns-long simulations.

anions↗
DOE OSTI2024

A molecular view of peptoid-induced acceleration of calcite growth

The extensive deposits of calcium carbonate (CaCO 3 ) generated by marine organisms constitute the largest and oldest carbon dioxide (CO 2 ) reservoir. These organisms utilize macromolecules like peptides and proteins to facilitate the nucleation and growth of carbonate minerals, serving as an effective method for CO 2 sequestration. However, the precise mechanisms behind this process remain elusive. In this study, we report the use of sequence-defined peptoids, a class of peptidomimetics, to achieve the accelerated calcite step growth kinetics with the molecular level mechanistic understanding. By designing peptoids with hydrophilic and hydrophobic blocks, we systematically investigated the acceleration in step growth rate of calcite crystals using in situ atomic force microscopy (AFM), varying peptoid sequences and concentrations, CaCO 3 supersaturations, and the ratio of Ca 2+ / HCO 3 − . Mechanistic studies using NMR, three-dimensional fast force mapping (3D FFM), and isothermal titration calorimetry (ITC) were conducted to reveal the interactions of peptoids with Ca 2+ and HCO 3 − ions in solution, as well as the effect of peptoids on solvation and energetics of calcite crystal surface. Our results indicate the multiple roles of peptoid in facilitating HCO 3 − deprotonation, Ca 2+ desolvation, and the disruption of interfacial hydration layers of the calcite surface, which collectively contribute to a peptoid-induced acceleration of calcite growth. These findings provide guidelines for future design of sequence-specific biomimetic polymers as crystallization promoters, offering potential applications in environmental remediation (such as CO 2 sequestration), biomedical engineering, and energy storage where fast crystallization is preferred.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Facile hermetic TEM grid preparation for molecular imaging of hydrated biological samples at room temperature

Abstract Although structures of vitrified supramolecular complexes have been determined at near-atomic resolution, elucidating in situ molecular structure in living cells remains a challenge. Here, we report a straightforward liquid cell technique, originally developed for real-time visualization of dynamics at a liquid-gas interface using transmission electron microscopy, to image wet biological samples. Due to the scattering effects from the liquid phase, the micrographs display an amplitude contrast comparable to that observed in negatively stained samples. We succeed in resolving subunits within the protein complex GroEL imaged in a buffer solution at room temperature. Additionally, we capture various stages of virus cell entry, a process for which only sparse structural data exists due to their transient nature. To scrutinize the morphological details further, we used individual particle electron tomography for 3D reconstruction of each virus. These findings showcase this approach potential as an efficient, cost-effective complement to other microscopy technique in addressing biological questions at the molecular level.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS1999

Engine Test and Measurements

Although the importance of aerosols and their precursors are now well recognized, the characterization of current subsonic engines for these emissions is far from complete. Furthermore, since the relationship of engine operating parameters to aerosol emissions is not known, extrapolation to untested and unbuilt engines necessarily remains highly uncertain. 1997 NASA LaRC engine test, as well as the parallel 1997 NASA LaRC flight measurement, attempts to address both issues by expanding measurements of aerosols and aerosol precursors with fuels containing different levels of fuel sulfur content. The specific objective of the 1997 engine test is to obtain a database of sulfur oxides emissions as well as the non-volatile particulate emission properties as a function of fuel sulfur and engine operating conditions. Four diagnostic systems, extractive and non-intrusive (optical), will be assembled for the gaseous and particulate emissions characterization measurements study. NASA is responsible for the extractive gaseous emissions measurement system which contains an array of analyzers dedicated to examining the concentrations of specific gases (NO, NO(x), CO, CO2, O2, THC, SO2) and the smoke number. University of Missouri-Rolla uses the Mobile Aerosol Sampling System to measure aerosol/particulate total concentration, size distribution, volatility and hydration property. Air Force Research Laboratory uses the Chemical Ionization Mass Spectrometer to measure SO2, SO3/H2SO4, and HN03 Aerodyne Research, Inc. uses Infrared Tunable Diode Laser system to measure SO2, SO3, NO, H2O, and CO2.

Wey, Chown Chou↗
DOE OSTI2021

Adiabatic quantum decoherence in many non-interacting subsystems induced by the coupling with a common boson bath

Highlights: • System–environment quantum correlation: a main solid state NMR decoherence channel. • Non-separable system–environment model yields realistic spin decoherence rates. • New open quantum system approach explains irreversible decay of refocused NMR echoes. • Adiabatic quantum decoherence is inherently irreversible and eigen-selective. This work addresses adiabatic quantum decoherence of many-body spin systems coupled with a boson field in the framework of open quantum systems theory. We generalize the traditional spin-boson model by considering a system–environment interaction Hamiltonian that represents a partition of non-interacting subsystems and highlights the collective correlation that appears exclusively due to the coupling with a common environment. Remarkably, this simple, exactly solvable model encompasses relevant aspects of a many-body open quantum system and features the subtle quantum effects that arise when the size scales up to a macroscopic level. We derive an analytical expression for the time dependence of the density matrix elements (in the preferred basis) without assuming coarse-graining. The resulting decoherence function is eigen-selective and is a complex exponential whose exponent has a real part that introduces a decay similar to that in the spin-boson model. On the contrary, the imaginary part depends on the quantum numbers and geometry of the whole partition and does not reflect the system temperature. Motivated by decoherence in solid-state NMR, and in search of realistic numerical estimations, we apply the theoretical results to a partition of dipole-coupled spin pairs in contact with a common phonon bath, using typical parameters of hydrated salts. The proposal allows estimating the decoherence time scale in terms of the system physical constants: sound velocity and eigenvalue distribution width. As a significant novelty, the decoherence function phase depends on the eigenvalue distribution throughout the sample. It plays the leading role, overshadowing the mechanism associated with the bath thermal state. Finally, we apply the formalism to describe decoherence in the “magic echo” NMR reversal experiment. We find that the system–environment correlation explains the origin of irreversibility, and both the decoherence rate value and its dependence on the dipolar frequency, are remarkably similar to the experiment.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
NASA NTRS1999

Cosmogenic Radionuclides in Hot Desert Chondrites with Low C-14 Activities: A Progress Report

Terrestrial ages of meteorites from hot deserts provide an important tool to estimate meteorite fluxes to the Earth. Most desert meteorites have terrestrial ages less than 40 ky, but a few achondrites from the Sahara region were recently shown to have significantly higher ages, up to approx. 100 ky. In general, C-14 (half-life = 5730 y) is the most suited radionuclide to determine terrestrial ages for desert meteorites. However for meteorites with ages greater than 35 ky, the concentration of cosmogenic C-14 has decreased to a level at which it becomes difficult to distinguish between cosmogenic C-14 and terrestrial contamination. These meteorites may therefore be much older than 35 ky. We selected chondrites with low C-14 activities (less than or equal to 2 dpm/kg) for measurements of the concentrations of cosmogenic Cl-36 (half-life= 3.01 x 10 (exp 5) y) and Ca-41 (half-life= 1.04 x 10 (exp 5) y) in the metal phase. Since the ratio of Ca-14/Cl-36 in the metal phase of chondrites is relatively constant and well known, the measured ratio is a direct measure of the terrestrial age. A major problem is that most or sometimes all of the metal in these old "hot desert" meteorites has been oxidized to hydrated Fe-Ni-oxides. Therefore, we also measured the concentrations of Be-10, Al-26 and Cl-36 in the stony phase in order to constrain the terrestrial age as much as possible.

Welten, Kees↗
NASA NTRS2000

Cosmogenic Radionuclides in Hot Desert Chondrites With Low C-14 Activities

Terrestrial ages of meteorites from hot deserts provide an important tool to estimate meteorite fluxes to the Earth. Most desert meteorites have terrestrial ages less than 40 ky, but a few achondrites from the Sahara region were recently shown to have significantly higher ages, up to approx.100 ky. In general, C-14 (half-life = 5730 y) is the most suited radionuclide to determine terrestrial ages for desert meteorites. However for meteorites with ages >35 ky, the concentration of cosmogenic C-14 has decreased to a level at which it becomes difficult to distinguish between cosmogenic C-14 and terrestrial contamination. These meteorites may therefore be much older than 35 ky. We selected chondrites with low C-14 activities (less than or equal to 2 dpm/kg) for measurements of the concentrations of cosmogenic Cl-36 (half-life= 3.01 x 10(exp 5) y) and Ca-41 (half-life= 1.04 x 10(exp 5) y) in the metal phase. Since the ratio of Ca-41/Cl-36 in the metal phase of chondrites is relatively constant and well known, the measured ratio is a direct measure of the terrestrial age]. A major problem is that most or sometimes all. of the metal in these old "hot desert" meteorites has been oxidized to hydrated Fe-Ni-oxides. Therefore, we also measured the concentrations of Be-10, Al-26 and Cl-36 in the stony phase in order to constrain the terrestrial age as much as possible.

Welten, K. C.↗
NASA NTRS2001

E057: Renal Stone Risk Assessment During Space Flight: Assessment and Countermeasure Validation

Exposure to the microgravity environment results in many metabolic and physiological changes to humans. Body fluid volumes, electrolyte levels, and bone and muscle undergo changes as the human body adapts to the weightless environment. Changes in the urinary biochemistry occur as early as flight day 3-4 in the short duration Shuttle crewmembers. Significant decreases were observed both in fluid intake and urinary output. Other significant changes were observed in the urinary pH, calcium, potassium and uric acid levels. During Shuttle missions, the risk of calcium oxalate stone formation increased early in the flight, continued at elevated levels throughout the flight and remained in the increased risk range on landing day. The calcium phosphate risk was significantly increased early in-flight and remained significantly elevated throughout the remainder of the mission. Results from the long duration Shuttle-Mir missions followed a similar trend. Most long duration crewmembers demonstrated increased urinary calcium levels despite lower dietary calcium intake. Fluid intake and urine volumes were significantly lower during the flight than during the preflight. The calcium oxalate risk was increased relative to the preflight levels during the early in-flight period and continued in the elevated risk range for the remainder of the space flight and through two weeks postflight. Calcium phosphate risk for these long duration crewmembers increased during flight and remained in the increased risk range throughout the flight and following landing. The complexity, expense and visibility of the human space program require that every effort be made to protect the health of the crewmembers and ensure the success of the mission. Results from our early investigations clearly indicate that exposure to the microgravity environment of space significantly increases the risk of renal stone formation. The early studies have indicated specific avenues for development of countermeasures for the increased renal stone risk observed during and following space flight. Increased hydration and implementation of pharmacological countermeasures are being tested for their efficacy in mitigating the in-flight risk of renal stones. Maintaining the health and well-being of crewmembers during space flight requires a means of minimizing potential detrimental health effects of microgravity. The formation of a renal stone during flight obviously has severe consequences for the affected crewmember as well as the success of the mission.

Whitson, Peggy A.↗
DOE OSTI2020

Threshold Collision-Induced Dissociation of Hydrated Thorium(IV) Trihydroxide Cation: Experimental and Theoretical Investigation of the Binding Energies for Th(OH) 3 + (H 2 O) n Complexes ( n = 1–4)

Threshold collision-induced dissociation of Th(OH) 3 + (H 2 O) n Complexes ( n = 1–4) with xenon was performed using a guided ion beam tandem mass spectrometer. The primary dissociation pathway for all complexes is a loss of a single water molecule followed by the sequential loss of additional water molecules at higher collision energies. Here, the data were analyzed using a statistical model after accounting for lifetime effects and reactant internal and kinetic energy distributions to obtain 0 K bond dissociation energies (BDEs). These were also converted using rigid rotor/harmonic oscillator approximations to yield thermodynamic values at room temperature. The 0 K BDEs of H 2 O ligands to Th(OH) 3 + (IV) are experimentally determined for the first time as 106 ± 6, 89 ± 6, 76 ± 4, and 51 ± 4 kJ/mol for the first, second, third, and fourth water ligand added. These values agree reasonably well with values calculated at the B3LYP, B3PW91, and PBE0 levels of theory with aug-cc-pVQZ basis sets, whereas B3LYP-GD3BJ, MP2, and CCSD(T) single point energies with (without) counterpoise corrections systematically overestimate the bond energies by about 15 (20), 19 (25), and (18) kJ/mol, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1993

Crustal structure and igneous processes in a chondritic Io

Liquid sulfur can form when metal-free C1 or C2 chondrites are heated. It may be obtained either by direct melting of native sulfur in disequilibrated C1 or C2 chondrites or by incongruent melting of pyrite and other sulfides in thermodynamically equilibrated rocks of the same composition. Hence, Lewis considered C2 chondrites to be the best meteoritic analog for Io's bulk composition. Metal-bearing C3 and ordinary chondrites are too chemically reduced to yield liquid sulfur and are not thought to represent plausible analogs of Io's bulk composition. An important aspect of Lewis' work is that CaSO4 and MgSO4 are predicted to be important in Io. Real C1 and C2 chondrites contain averages of, respectively, 11 percent and 3 percent by mass of salts (plus water of hydration). The most abundant chondritic salts are magnesium and calcium sulfates, but other important components include sulfates of sodium, potassium, and nickel and carbonates of magnesium, calcium, and iron. It is widely accepted that chondritic salts are formed by low-temperature aqueous alteration. Even if Io originally did not contain salts, it is likely that aqueous alteration would have yielded several percent sulfates and carbonates. In any event, Io probably contains sulfates and carbonates. This report presents the results of a model of differentiation of a simplified C2 chondrite-like composition that includes 1.92 percent MgSO4, 0.56 percent CaSO4, 0.53 percent CaCO3, and 0.094 percent elemental sulfur. The temperature of the model is gradually increased; ensuing fractional melting results in these components extruding or intruding at gravitationally stable levels in Io's crust. Relevant phase equilibria were reviewed. A deficiency of high-pressure phase equilibria renders the present model qualitative.

Kargel, J. S.↗
DOE OSTI2025

In situ Raman investigation of Dy complexation in Cl-bearing aqueous solutions at 20–300 °C

Raman spectroscopy provides a versatile tool for in situ characterization of aqueous rare earth elements (REE) speciation at the molecular level. Complexation of REE with ligands such as Cl – and OH – is of particular interest for understanding the mobility of REE in NaCl-bearing hydrothermal fluids responsible for enriching REE to economic levels in nature. Raman spectroscopic studies of REE speciation in Cl-bearing aqueous fluids are primarily conducted at ambient temperature, whereas natural systems indicate temperatures of >100–600 °C. In this study, the speciation of Dy in acidic chloride-bearing hydrothermal solutions was investigated using confocal Raman spectroscopy with a new capillary Raman heating stage at 20–300 °C. Background solutions (pure water, NaCl-solutions) and solutions with 0.14–1.8 mol kg –1 dissolved DyCl 3 were sealed in quartz capillary cells. Comparison of the spectra for Dy chloride solutions with those for background solutions and the spectra for reference Dy-bearing solids was used to identify Raman bands specific to Dy–O and Dy–Cl bonds. The Raman band for the Dy–O stretching mode of hydrated Dy 3+ aqua ions was measured at 365–384 cm –1 and a Raman band for the Dy–Cl stretching modes of Dy chloride complexes was measured near 240 cm –1 . The Dy–O band decreases systematically with temperature, whereas the Dy–Cl band systematically increases, indicating a systematic increase in the stability of Dy chloride complexes with temperature. Here, this study provides the framework for expanding the use of in situ Raman spectroscopy to investigate the speciation of REE in aqueous solutions to hydrothermal conditions.

58 GEOSCIENCES↗
DOE OSTI2026

Molecular insights into CO 2 -to-bicarbonate transformation in functionalized anion exchange ionomers for electrochemical separations

Bipolar membrane (BPM) electrochemical processes are a promising platform for carbon dioxide (CO 2 ) separations, but the molecular level thermodynamic and kinetic understanding of CO 2 -to-bicarbonate (HCO 3 − ) transformation remain poorly understood. This study employs a multiscale computational approach to systematically explore the adsorption and reactive transformation of CO 2 in five anion exchange ionomer systems. Classical molecular dynamics (MD) simulation results demonstrate that polymers with imidazolium groups significantly reduce CO 2 diffusion and enhance (OH − )–CO 2 interactions due to stronger electrostatic and π-interactions. Compared to the commonly used quaternary ammonium ionomers, imidazolium-functionalized ionomers show improved CO 2 proximity and interaction strength. Ab initio MD and density functional theory (DFT) calculations reveal that the benzyl-substituted imidazolium (IM-Ben) substantially reduces the energy barrier for HCO 3 − formation (∼72 meV lower) compared to the alkyl-substituted IM-nBu, while also mitigating imidazolium deprotonation under moderate hydration conditions. Transition state analysis shows IM-Ben forms more extensive hydrogen-bonding networks, which stabilize the transition state structure and contribute to a lower energy barrier for bicarbonate formation. These findings highlight the advantage of the adjacent benzyl moiety in enabling efficient CO 2 -to-bicarbonate transformation via hydrated hydroxide ion counterions, offering mechanistic insights and clear molecular design principles for optimizing anion exchange ionomers at bipolar membrane interfaces for electrochemical CO 2 separation applications.

Bipolar membranes, Reactive transformation of CO2,↗
NASA NTRS2020

Impact of Convectively Detrained Ice Crystals on the Tropical Upper Troposphere and Lower Stratosphere

The role of convectively detrained ice crystals on the humidity of the tropical upper troposphere and lower stratosphere (UTLS) is investigated in simulations of cirrus clouds along trajectories launched from the 378K potential temperature level in the tropics. The one-dimensional (vertical) cloud model tracks individual ice crystals through their lifecycle beginning with detrainment from convection, followed by deposition growth, sedimentation and sublimation. Convective influence of the parcels is diagnosed by tracing the trajectories through time-dependent fields of convective cloud-top height adjusted to match the CloudSAT and CALIPSO statistics. Model simulations of UTLS water vapor and cloud fields are evaluated and constrained by comparison with Aura MLS and CALIPSO measurements. Preliminary results indicate sensitivity of the detrained ice crystal lifecycle to atmospheric conditions downstream of convection. Specifically, cooling (high relative humidity and supersaturation) downstream of convection leads to deposition growth and sedimentation of detrained ice crystals, resulting in net dehydration of the UTLS. In contrast, warming (low relative humidity and subsaturation) downstream of convection leads to sublimation of detrained ice crystals and subsequent hydration. As such, the impact of detrained ice crystals on the humidity of the UTLS exhibits distinct spatial variability. Detrained ice crystals predominantly dehydrate the UTLS in the tropical mean. Sensitivities to the convectively detrained ice crystal size and concentration are also examined using measurements from the StatoClim aircraft campaign. The importance of convectively detrained ice crystals will be discussed within the context of the overall contribution of convection to the lower stratospheric humidity.

Ueyama, Rei↗
DOE OSTI2023

Facile hyperpolarization chemistry for molecular imaging and metabolic tracking of [1– 13 C]pyruvate in vivo

Hyperpolarization chemistry based on reversible exchange of parahydrogen, also known as Signal Amplification By Reversible Exchange (SABRE), is a particularly simple approach to attain high levels of nuclear spin hyperpolarization, which can enhance NMR and MRI signals by many orders of magnitude. SABRE has received significant attention in the scientific community since its inception because of its relative experimental simplicity and its broad applicability to a wide range of molecules, however, in vivo detection of molecular probes hyperpolarized by SABRE has remained elusive. Here we describe a first demonstration of SABRE-hyperpolarized contrast detected in vivo, specifically using hyperpolarized [1– 13 C]pyruvate. Biocompatible formulations of hyperpolarized [1– 13 C]pyruvate in, both, methanol-water, and ethanol-water mixtures followed by dilution with saline and catalyst filtration were prepared and injected into healthy Sprague Dawley and Wistar rats. Effective hyperpolarization-catalyst removal was performed with silica filters without major losses in hyperpolarization. Metabolic conversion of pyruvate to lactate, alanine, and bicarbonate was detected in vivo. Pyruvate-hydrate was also observed as a minor byproduct. Measurements were performed on the liver and kidney at 4.7 T via time-resolved spectroscopy and chemical-shift-resolved MRI. In addition, whole-body metabolic measurements were obtained using a cryogen-free 1.5 T MRI system, illustrating the utility of combining lower-cost MRI systems with simple, low-cost hyperpolarization chemistry to develop safe and scalable molecular imaging.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2011

Compositional Impact of Io Volcanic Emissions on Jupiter's Magnetosphere and the Icy Galilean Moons

The magnetospheric ion population of Jupiter is dominated by the 1000 kg/s of iogenic material constantly ejected by IO volcanism as neutral gas (approx. 1 kg/s goes out as high speed dust grains), subsequent atmospheric losses to the IO torus, and radial transport of torus ions throughout the magnetosphere. As that magnetosphere is greatly distended in radial size by the iogenic plasma loading, so are surfaces of the other Galilean moons also significantly, and perhaps even dominantly, affected by iogenic plasma bombardment, e.g. at the level up to 0.2 kg/s heavy ions (mostly O and S) onto Europa as per local plasma ion measurements. In comparison, cometary impacts onto IO deliver about 0.02 kg/s of impact ejecta to Europa via ballistic transfer through the Jupiter system. The magnetosphere of this system operates as a powerful engine to produce and transport ions from the IO source to the surfaces of these other moons, and any future orbiter missions to these moons must account for surface distributions of the iogenic material and its chemical effects before real assessments can be made of sensible chemical materials otherwise arising from primordial formation and subsequent evolution of these moons. This is a fundamental problem of space weathering that must be addressed for all planetary bodies with thin atmospheres and direct surface exposure to their space plasma environments. Long-standing debates from Galileo Orbiter measurements about the origins of hydrate sulfates at Europa present examples of this problem, as to whether the sulfates arise from oceanic minerals or from iogenic sulfur chemistry. Any orbiter or landed mission to Europa for astrobiological investigations would further need to separate the potential chemical biosignatures of life or its precursors from the highly abundant background of iogenic material. Although no single ion carries a tag identifying it as of iogenic or other origin, the elemental abundance distributions of ions to be measured throughout the jovian magnetosphere and in the local moon environments can act as tracers if we know from direct measurements and models the distributions at the mostly likely sources, i.e. at IO. However, our knowledge of these abundances are very limited from earlier in-situ and remote measurements, mainly confined to major (S, O) and some minor (Na, K, Cl) species with abundances at or above a few percent relative to O. Future in-situ plasma measurements by the planned Jupiter Europa Orbiter and Jupiter Ganymede Orbiter missions should extend the abundance coverage to minor and even trace elemental species. For Europa astrobiological investigations it is also important to specify iogenic inputs and surface processing of isotopic species. We discuss the range of abundance distributions arising from models for IO hot volcanic emissions, and from the subsequent dynamics of ion injection, magnetospheric transport, and icy moon surface bombardment.

Cooper, John↗
NASA NTRS2021

NASA Engineering and Safety Center Technical Bulletin No. 21-03-1: Best Practices for the Elemental Profiling of High-Purity Hydrazine

Trace contaminants in high-purity hydrazine (HPH) propellant impact a wide variety of commercial, Department of Defense (DoD), and NASA missions. Depending on thruster design, elemental contaminants must be kept at extremely low levels and are verified as such by routine analysis. A number of these contaminants have recently undergone an assessment to shed light on their quantities present following changes in the HPH supply chain. A round robin analysis utilizing four separate laboratories resulted in unacceptably high variability in the quantification of these contaminants. The principal objective of this technical bulletin is to signal the availability of a new analysis methodology which yields accurate and repeatable quantification by providing best practices for both quantitation methodology and strategies for avoiding sample contamination during analysis.

High-Purity Hydrazine↗
DOE OSTI2025

Hydrolysis Reaction Pathways of Thorium Oxide Nanoclusters

Density functional theory benchmarked by correlated molecular orbital theory is used to develop a fundamental and predictive understanding of the interaction of thorium oxide nanoclusters with gas phase water to provide insight into nuclear-waste storage, production of thorium nuclear reactor fuels, and reprocessing of spent fuel. The structures of Th n O 2n (n = 3 – 6) clusters and their interactions with water have been studied at the B3LYP, MP2, and CCSD(T) levels. Hydrolysis is initiated by the formation of Lewis acid-base adducts, with relative H 2 O binding energies (physisorption) ranging from −15 kcal/mol to −22 kcal/mol. The initial H 2 O physisorption energy is ca. −21 kcal/mol regardless of the cluster size and is consistent with the experimentally obtained initial adsorption energy on a thorium dioxide surface. The physisorption enthalpies for additional water molecules can be affected by the presence of terminal groups OH groups generated by proton transfer to a Th-O near the site of adsorption. The hydrolysis products (chemisorption) form either bridging or terminal hydroxides. More exothermic hydrolysis steps were predicted for the formation of terminal hydroxides as compared to the formation of bridging hydroxides. Here, the calculated transition state barriers for transfer of protons from bound water complexes to form the chemisorption products are very low. Overall, water readily reacts with thorium oxide clusters preferring hydroxide products over hydrated complexes. First and second order fits were predicted for the combined physisorption and chemisorption energies for the hydrolysis of thorium oxide clusters. Finally, ionization energies and electron affinities were calculated as were HOMO-LUMO gaps to provide additional insights into the properties of the thorium oxide and hydroxide clusters.

Adsorption↗