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All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Signal Differentiation of Moving Magnetic Nanoparticles for Enhanced Biodetection and Diagnostics

Magnetic nanoparticles are extensively utilized as markers/signal labelling in various biomedical applications. Detecting and distinguishing magnetic signals from similarly sized moving magnetic nanoparticles in microfluidic systems is crucial yet challenging for biosensing. In this study, we have developed an original method to detect and differentiate magnetic signals from moving superparamagnetic (SPM) and ferrimagnetic (FM) nanoparticles of comparable sizes. Our approach utilizes a highly sensitive magnetic-coil-based sensor that harnesses the combined effects of giant magnetoimpedance (GMI) and an LC-resonance circuit, offering performance superior to that of conventional GMI sensors. Iron oxide nanoparticles, which have similar particle sizes but differing coercivities (zero for SPM and non-zero for FM) or similar zero coercivities but differing particle sizes, flow through the magnetic coil at controlled velocities. Their distinct effects are analyzed through changes in the complex impedance of the sensing system. Our findings provide a unique pathway for utilizing SPM and FM nanoparticles as innovative magnetic markers to identify specific biological entities, thereby expanding their potential applications.

Hwang, Kee Young↗
NASA NTRS1975

Impact survival conditions for very large meteorites, with special reference to the legendary Chinguetti meteorite

Contrary to popular belief, very large meteorites can be sufficiently slowed by aerodynamic drag to survive impact with the earth's surface provided that they enter the atmosphere at very low angles. This is a stringent requirement and survival probabilities for large, unguided objects are low; but they are not zero. Based on high-velocity impact experiments and published tabulations of the parameters of shallow angle entry trajectories, we estimate the probability of survival for an iron meteorite approximately the size and shape of the legendary Chinguetti meteorite (100 x 40 x 20-40 m) to be between 0.1 and 1 percent. Together with a limiting estimate of the flux of such bodies encountering the earth, this leads to an expected survival rate of one per (0.1-1.0) billion years on the earth's land surface.

Fudali, R. F.↗
NASA NTRS1985

The super-hot thermal component in the decay phase of solar flares

Solar X-ray observations from balloons and from the SMM and Hinotori spacecraft have revealed evidence for a superhot thermal component with a temperature of more than about 3 x 10 to the 7th K in many solar flares, in addition to the usual 10-20 x 10 to the 6th K soft X-ray flare plasma. The decay phase of 35 solar flare X-ray events observed by ISEE-3 during 1980 was systematically studied. Based on fits to the continuum X-ray spectrum in the 4.8-14 keV range and to the intensity of the 1.9 A feature of iron lines, it was found that 15 (about 43) of the analyzed events have a superhot thermla component in the decay phase of the flare. In this paper, the important properties of the superhot thermal component in the decay phase are summarized. It is found that an additional input of energy is required to maintain the superhot thermal components. Finally, it is suggested that the superhot thermal component in the decay phase is created through the reconnection of the magnetic field during the decay phase of solar flares.

Lin, H.-A.↗
NASA NTRS1990

RSRM-13 (360Q013) ballistics mass properties flight designation STS-41

The propulsion performance and reconstructed mass properties data from Thiokol's RSRM-13 motors which were assigned to the STS-41 launch are presented. The SRM propellant, TP-H1148, is a composite type solid propellant, formulated of polybutadiene acrylic acid acryonitrile terpolymer binder, epoxy curing agent, ammonium perchlorate oxidizer, and aluminum powder fuel. A small amount of burning rate catalyst (iron oxide) was added to achieve the desired propellant burn rate. The propellant evaluation and raw material information are also presented. The presented ballistic performance was based on the Operational Flight Instrumentation. The adjustments made to the raw data on this flight include biasing the data to correct ambient pressure before liftoff. The performance from each motor as well as matched pair performance values were well within the CEI Specification requirements.

Laubacher, Brian A.↗
NASA NTRS1993

Assimilation in lunar basalts and volcanic glasses: Implications for a heterogenous mantle source region

Several scientists have called on assimilation of anorthositic crustal material or KREEP compositions to explain various lunar lithologies. In order to address the practicality of such processes, some techniques for calculating how much assimilation is possible in magma chambers and dikes based on thermal energy balances and simple fluid mechanical constraints are outlined. In a previous effort, it was demonstrated that dissolution of plagioclase in an iron-free basalt was too slow to contaminate magmas, and that the energy cost of melting plagioclase-rich crustal material was prohibitive both in magma chambers and in dike conduits. This analysis was extended to include dissolution rates in an orange glass composition and to quantitatively predict the maximum contamination possible due to assimilation of both lunar crustal material and KREEP.

Finnila, A. B.↗
NASA NTRS1998

The Generation of Lighting in the Solar Nebula

The process that melted and formed the chondrules, mm-sized glassy beads within meteorites, has not been conclusively identified. Origin by lightning in the solar nebula is consistent with many features of chondrules, but no viable model of lightning has yet been advanced. We present a model demonstrating how lightning could be generated in the solar nebula which differs from previous models in three important aspects. First, we identify a new', powerful charging mechanism that is based on the differences in contact potentials between particles of different composition, a form of triboelectric charging. In the presence of fine silicate grains and fine iron metal grains, large silicate particles (the chondrules) can acquire charges of +10(exp 5) e. Second, we assume that the chondrule precursor particles are selectively concentrated in clumps 1 - 100 km in size by the turbulent concentration mechanism described by Cuzzi et al. (1996). The concentration of these highly charged particles into clumps, in a background of negatively charged metal grains, is what generates the strong electric fields. Third, we make refinements in the estimates of the breakdown electric field and the ionization rate. We calculate that electric fields large enough to trigger breakdown easily could have existed over regions large enough (approx. 100km) to generate very large discharges of electrical energy (approx. 10(exp 16)erg). The discharges would have been sufficiently energetic and frequent to have formed the chondrules. We place constraints on the generation of lightning and conclude that it could not be generated if the abundance of Al-26 in chondrules was as high as the level in the CAls. This conclusion is consistent with isotopic analyses of chondrules. This possibly implies that Al-26 was non-uniformly distributed in the solar nebula or that the chondrules formed several Myr after the CAIs.

Cuzzi, Jeffrey↗
NASA NTRS2016

Deposition, Accumulation, and Alteration of Cl(-), NO3(-), ClO4(-) and ClO3(-) Salts in a Hyper-Arid Polar Environment: Mass Balance and Isotopic Constraints

The salt fraction in permafrost soils/sediments of the McMurdo Dry Valleys (MDV) of Antarctica can be used as a proxy for cold desert geochemical processes and paleoclimate reconstruction. Previous analyses of the salt fraction in MDV permafrost soils have largely been conducted in coastal regions where permafrost soils are variably affected by aqueous processes and mixed inputs from marine and stratospheric sources. We expand upon this work by evaluating permafrost soil/sediments in University Valley, located in the ultraxerous zone where both liquid water transport and marine influences are minimal. We determined the abundances of Cl(-), NO3(-, ClO4(-)and ClO3(-)in dry and ice-cemented soil/sediments, snow and glacier ice, and also characterized Cl(-) and NO3(-) isotopically. The data are not consistent with salt deposition in a sublimation till, nor with nuclear weapon testing fall-out, and instead point to a dominantly stratospheric source and to varying degrees of post depositional transformation depending on the substrate, from minimal alteration in bare soils to significant alteration (photodegradation and/or volatilization) in snow and glacier ice. Ionic abundances in the dry permafrost layer indicate limited vertical transport under the current climate conditions, likely due to percolation of snowmelt. Subtle changes in ClO4(-)/NO3(-) ratios and NO3(-) isotopic composition with depth and location may reflect both transport related fractionation and depositional history. Low molar ratios of ClO3(-)/ClO4(-) in surface soils compared to deposition and other arid systems suggest significant post depositional loss of ClO3(-), possibly due to reduction by iron minerals, which may have important implications for oxy-chlorine species on Mars. Salt accumulation varies with distance along the valley and apparent accumulation times based on multiple methods range from approximately 10 to 30 kyr near the glacier to 70-200 kyr near the valley mouth. The relatively young age of the salts and relatively low and homogeneous anion concentrations in the ice-cemented sediments point to either a mechanism of recent salt removal, or to relatively modern permafrost soils (less than 1 million years). Together, our results show that near surface salts in University Valley serve as an end-member of stratospheric sources not subject to biological processes or extensive remobilization.

cold desert geochemical processes↗
DOE OSTI2024

Portable Luminescent Sensor Technologies for Economically Critical Metals

Presentation on the development of sensing materials and compact platforms for the photoluminescence-based detection of economically critical metals, including rare earth elements, cobalt, and aluminum. The important of detecting metals that interfere with critical metal processing, such as iron and aluminum, are also discussed. The presented results represent a significant step forward in reducing the economic and time costs associated with the characterization of metals during prospecting and downstream processing.

Crawford, Scott↗
DOE OSTI2025

Electron Bifurcating Hydrogenases

The importance of electron-bifurcating enzymes is manifest by their ability to maximize energy efficiency. Specifically, they couple a downhill oxidation-reduction (redox) reaction with an uphill redox reaction. Since the rapid increase in the discovery of bifurcating enzymes starting in 2008, there has been interest in incorporating their mechanistic principles into artificial/semiartificial systems to drive chemically challenging reactions. This has yet to be achieved, partly because the details of electron bifurcation, i.e. mechanisms, are largely elusive. Nevertheless, much progress has been made in understanding reactivities, structures, and some mechanistic aspects of these enzymes. Notable examples are electron-bifurcating hydrogenases, which are the focus of this chapter. The chapter is organized as follows. Section 11.1 provides an overview of hydrogenases and electron bifurcation. In Section 11.2, some physiological roles of electron-bifurcating hydrogenases are highlighted. Additionally, electron-bifurcating subunit compositions and biochemical reactivities are comprehensively tabulated, and some key points/considerations about these are noted. In Section 11.3, we discuss the known structures of these enzymes, which provide insight into their complex arrangements of redox cofactors, such as iron-sulfur clusters. Also provided are tabulations and discussions of some biophysical properties of the cofactors. In Section 11.4, we discuss the mechanistic proposals of these enzymes, which are primarily based on structural information. Areas of research that are much needed are outlined in Section 11.5. We conclude on the note that what is learned from electron-bifurcating hydrogenases has applicability to other bifurcating enzymes, nonbifurcating analogs, and mechanistic enzymology at large.

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

Quantification of Swelling in Hematite Pellets Reduced Using Hydrogen–Nitrogen Gas Mixture

Iron ore pellets are reduced in a 50%H 2 –50%N 2 1 atm gas mixture at 750, 800, 850, 900, and 950 °C while simultaneously documenting swelling (change in pellet radius) and weight change. Swelling increases with increasing temperature, with catastrophic swelling (>20% of reduction swelling index) observed at 850, 900, and 950 °C. As the pellet is reduced, the pellet radius increases until 40–50% reduction is achieved, followed by a decrease in diameter beyond 40–50% reduction at 750 and 850 °C. At 950 °C, the pellet radius continues to increase with additional pellet reduction without any subsequent decrease in diameter. Scanning electron microscopy (SEM) analysis shows that the neighboring grains inside the pellet sinter together at 750 and 850 °C, whereas the individual grains sinter internally at 950 °C. SEM analysis and observations suggest that the reduction process at 750 and 850 °C can be approximated as a topochemical reaction process, while the reduction process at 950 °C can no longer be approximated as a topochemical reaction process. In conclusion, an empirical equation for the radius of the pellet is derived with fitting parameters dependent on temperature and the degree of reduction of the pellet undergoing reduction based on the experimental data.

08 HYDROGEN↗
DOE OSTI2024

Annotation of DOM metabolomes with an ultrahigh resolution mass spectrometry molecular formula library

Current approaches to analyzing metabolomic data often rely on matching MS/MS fragmentation data to sparse libraries or databases. This approach results in limited identification of features, often with less than 10% of the dataset being annotated. A complementary approach is to assign molecular formula to features based on accurate mass measurements, but the platforms commonly used for metabolomics do not have the needed accuracy or resolving power to do this robustly, particularly for larger molecules. Using our newly modified analysis tool, CoreMS, we generated a library of molecular formula from pooled samples analyzed with LC-21T FT-ICR MS. This library successfully annotated approximately 53.2% of features identified from the exometabolome of marine diatom Phaeodactylum tricornutum – a nearly ten-fold increase over the 5.9% annotation rate achieved using a conventional MS/MS library matching approach. Using this FT-ICR MS library approach, we were able to differentiate differences in the exometabolome of P. tricornutum in iron replete and iron limited conditions, with 668 metabolites being differentially expressed (p < 0.05, 2 x intensity difference) under these conditions. The traditional MS/MS fragmentation-based annotation approach only annotated 61 of these metabolites, while our novel pipeline annotated 450 metabolites and revealed 12 metabolites that were significantly more abundant under low iron conditions. Our results demonstrate the utility of ultrahigh resolution mass spectrometry for generating more comprehensive and confident molecular annotations.

21T-FTICR-MS, CoreMS↗
NASA NTRS2010

Oxidation States of Grim Glasses in EET79001 Based on Vanadium Valence

Gas-rich impact-melt (GRIM) glasses in SNC meteorites are very rich in Martian atmospheric noble gases and sulfur suggesting a possible occurrence of regolith-derived secondary mineral assemblages in these samples. Previously, we have studied two GRIM glasses, 506 and 507, from EET79001 Lith A and Lith B, respectively, for elemental abundances and spatial distribution of sulfur using EMPA (WDS) and FE-SEM (EDS) techniques and for sulfur-speciation using K-edge XANES techniques. These elemental and FE-SEM micro-graph data at several locations in the GRIM glasses from Shergotty (DBS), Zagami 994 and EET79001, Lith B showed that FeO and SO3 are positively correlated (SO3 represents a mixture of sulfide and sulfate). FE-SEM (EDS) study revealed that the sulfur-rich pockets in these glasses contain numerous micron-sized iron-sulfide (Fe-S) globules sequestered throughout the volume. However, in some areas (though less frequently), we detected significant Fe-S-O signals suggesting the occurrence of iron sulfate. These GRIM glasses were studied by K-edge microXANES techniques for sulfur speciation in association with iron in sulfur-rich areas. In both samples, we found the sulfur speciation dominated by sulfide with minor oxidized sulfur mixed in with various proportions. The abundance of oxidized sulfur was greater in 506 than in 507. Based on these results, we hypothesize that sulfur initially existed as sulfate in the glass precursor materials and, on shock-impact melting of the precursor materials producing these glasses, the oxidized sulfur was reduced to predominately sulfide. In order to further test this hypothesis, we have used microXANES to measure the valence states of vanadium in GRIM glasses from Lith A and Lith B to complement and compare with previous analogous measurements on Lith C (note: 506 and 507 contain the largest amounts of martian atmospheric gases but the gas-contents in Lith C measured by are unknown). Vanadium is ideal for addressing this re-dox issue because it has multiple valence states and is a well-studied element. Ferrous-dominated iron valences determined by microXANES on the Lith A and Lith B glasses provide little redox sensitivity. Vanadium valence measurements for impact glass in Lith C at three different locations yielded valence values of 3.1, 3.2 and 3.4 with inferred fO2 values of IW-0.7, IW-0.1 and IW+0.7, respectively. This range of oxygen-fugacity values is understandable because the glasses are shock-molten impact glasses which are heterogeneous in nature. Oxygen fugacity values obtained from the analysis of Fe-Ti oxides and Eu partitioning in pyroxenes from EET79001 Lith A and Lith B (host lithologies) were in the range of IW+0.3 to IW+1.9 suggesting that V in the Lith C impact glass was reduced in the impact process. Here, we examine whether the 506 from Lith A and 507 from Lith B GRIM glasses yield similar or different fO2 values from those of Lith C using the vanadium K-edge microXANES technique.

Sutton, S. R.↗
NASA NTRS2009

Redox Interactions between Iron and Carbon in Planetary Mantles: Implications for Degassing and Melting Processes

Carbon stability in planetary mantles has been studied by numerous authors because it is thought to be the source of C-bearing atmospheres and of C-rich lavas observed at the planetary surface. In the Earth, carbonaceous peridotites and eclogites compositions have been experimentally studied at mantle conditions [1] [2] [3]. [4] showed that the fO2 variations observed in martian meteorites can be explained by polybaric graphite-CO-CO2 equilibria in the Martian mantle. Based on thermodynamic calculations [4] and [5] inferred that the stable form of carbon in the source regions of the Martian basalts should be graphite (and/or diamond), and equilibrium with melts would be a source of CO2 for the martian atmosphere. Considering the high content of iron in the Martian mantle (approx.18.0 wt% FeO; [6]), compared to Earth s mantle (8.0 wt% FeO; [7]) Fe/C redox interactions should be studied in more detail.

Martin, A.↗
DOE OSTI2021

Understanding Reaction Networks through Controlled Approach to Equilibrium Experiments Using Transient Methods

We report a combined experimental/theoretical approach to studying heterogeneous gas/solid catalytic processes using low-pressure pulse response experiments achieving a controlled approach to equilibrium that combined with quantum mechanics (QM)-based computational analysis provides information needed to reconstruct the role of the different surface reaction steps. We demonstrate this approach using model catalysts for ammonia synthesis/decomposition. Polycrystalline iron and cobalt are studied via low-pressure TAP (temporal analysis of products) pulse response, with the results interpreted through reaction free energies calculated using QM on Fe-BCC(110), Fe-BCC(111), and Co-FCC(111) facets. In TAP experiments, simultaneous pulsing of ammonia and deuterium creates a condition where the participation of reactants and products can be distinguished in both forward and reverse reaction steps. This establishes a balance between competitive reactions for D* surface species that is used to observe the influence of steps leading to nitrogen formation as the nitrogen product remains far from equilibrium. Here, the approach to equilibrium is further controlled by introducing delay timing between NH 3 and D 2 which allows time for surface reactions to evolve before being driven in the reverse direction from the gas phase. The resulting isotopic product distributions for NH 2 D, NHD 2 , and HD at different temperatures and delay times and NH 3 /D 2 pulsing order reveal the role of the N 2 formation barrier in controlling the surface concentration of NH x * species, as well as providing information on the surface lifetimes of key reaction intermediates. Conclusions derived for monometallic materials are used to interpret experimental results on a more complex and active CoFe bimetallic catalyst.

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

Structure and density of silicon carbide to 1.5 TPa and implications for extrasolar planets

There has been considerable recent interest in the high-pressure behavior of silicon carbide, a potential major constituent of carbon-rich exoplanets. In this work, the atomic-level structure of SiC was determined through in situ X-ray diffraction under laser-driven ramp compression up to 1.5 TPa; stresses more than seven times greater than previous static and shock data. Here we show that the B1-type structure persists over this stress range and we have constrained its equation of state (EOS). Using this data we have determined the first experimentally based mass-radius curves for a hypothetical pure SiC planet. Interior structure models are constructed for planets consisting of a SiC-rich mantle and iron-rich core. Carbide planets are found to be ~10% less dense than corresponding terrestrial planets.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2024

Gradient-based surface nuclear magnetic resonance for groundwater investigation

In medical magnetic resonance imaging, spatial localization (imaging) is based upon the application of controlled magnetic field gradients on top of the main magnetic field to spatially modulate the frequency and/or phase of the nuclear magnetic resonance (NMR) signal across the volume of investigation. In this work, we have applied similar physical principles to produce controlled magnetic field gradients during surface NMR-based groundwater investigations. In this approach, a gradient pulse of variable amplitude or duration is applied immediately after the excitation pulse to cause predictable phase encoding of the NMR signal as a function of depth. This approach is also applicable to emerging surface NMR detection methods that use a prepolarization field with fast nonadiabatic turn-off to generate detectable NMR signals from the shallow subsurface. In this case, the gradient pulse is applied after terminating the prepolarization field and provides a heretofore unavailable means of localizing the NMR response as a function of depth. The application of gradients can also be combined with tip-angle-based modulation to yield higher imaging resolution than can be achieved through either gradient- or tip-angle-based imaging alone. We implemented this new gradient-based capability into a surface NMR gradient generation accessory that is compatible with the GMR-Flex instrument and developed surface NMR-specific forward modeling and linear inverse models. We validated the accuracy of this novel gradient-based sNMR technology using computer simulations, experiments using a small pool filled with a discrete layer of bulk water, and field experiments at well-characterized groundwater test sites along Ebey Island, WA, and Larned, KS. The gradient-based sNMR imaging observations were compared with high-resolution direct push NMR results observed at these sites. The results of computer simulations and field experiments indicate improvements in both the detection (signal-to-noise ratio) and spatial resolution of shallow subsurface water content using gradient-based surface NMR, compared with traditional surface NMR imaging methods.

Geochemistry & Geophysics↗
NASA NTRS1973

Ultraviolet photometry from the Orbiting Astronomical Observatory. VII alpha squared Canum Venaticorum.

Far-ultraviolet photometry by OAO-2 is presented for alpha squared CVn covering the entire 5.47-day period of this magnetic Ap variable. The light curves ranging from 1330 to 3320 A indicate that there are two important sources of back warming from far-ultraviolet absorption. Strong line blanketing by the rare earths redistributes flux longward of the Balmer discontinuity, causing the major observed photometric variations. In addition, a second source, which may be due to a combination of continuous opacities and line blanketing from the iron-peak and rare-earth groups below 1600 A, apparently redistributes flux into the region of the Balmer discontinuity. It is also found that ground-based determinations of the effective temperature are overestimated due to the flux redistribution from far-ultraviolet absorption. The effective temperature of alpha squared CVn derived from OAO and ground-based absolute fluxes is found to be 11,200 K, which remains constant over the cycle.

Molnar, M. R.↗
NASA NTRS1975

The University of California Iron Isotope Experiment

We suggest a novel technique for resolving neighboring isotopes of iron-group nuclei with abundance ratios as great as 20:1 over the energy range from about 360 to about 550 MeV/nucleon. The determination of mass is based on the proportionality between mass and range and the negligible magnitude of range straggling. A balloon-borne experiment based on this technique is described which uses active electronic counters to measure particle speed, trajectory, and charge, and a passive polycarbonate plastic stack to measure range.

Ahlen, S. P.↗