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NASA NTRS1973

Recent results from satellite beacon measurements

The techniques are reviewed for measuring ionospheric electron content, the most important parameter in the study of transionospheric propagation. Data collected since 1964 have yielded a synoptic description of the behavior of the electron content in midlatitudes. Empirical relationships between the level of solar activity and the electron content were developed permitting the prognostication of the electron content values. Construction of such prognostication schemes was stimulated by current efforts to create accurate satellite borne navigation systems. Gravity waves propagating in the thermosphere leave a signature in the electron content records. Studies of such records have allowed the identification of the position of the gravity wave source, and its radiation pattern. A one-to-one relationship between these waves and polar substorms was revealed. Electron content measurements were used to monitor the protonosphere with good time resolution. Protonospheric storms were observed with this technique. Slab thickness data obtained from content measurements were used to determine the neutral air temperature in the thermosphere.

Darosa, A. V.↗
NASA NTRS1998

Solar Irradiance and Thermospheric Airglow Rocket Experiments

This report describes work done in support of the Solar Irradiance and Thermospheric Air-glow Rocket Experiments at the University of Colorado for NASA grant NAG5-5021 under the direction of Dr. Stanley C. Solomon. (The overall rocket program is directed by Dr. Thomas N. Woods, formerly at the National Center for Atmospheric Research, and now also at the University of Colorado, for NASA grant NAG5-5141.) Grant NAG5-5021 provided assistance to the overall program through analysis of airglow and solar data, support of two graduate students, laboratory technical services, and field support. The general goals of the rocket program were to measure the solar extreme ultraviolet spectral irradiance, measure the terrestrial far-ultraviolet airglow, and analyze their relationship at various levels of solar activity, including near solar minimum. These have been met, as shown below. In addition, we have used the attenuation of solar radiation as the rocket descends through the thermosphere to measure density changes. This work demonstrates the maturity of the observational and modeling methods connecting energetic solar photon fluxes and airglow emissions through the processes of photoionization and photoelectron production and loss. Without a simultaneous photoelectron measurement, some aspects of this relationship remain obscure, and there are still questions pertaining to cascade contributions to molecular and atomic airglow emissions. However, by removing the solar irradiance as an "adjustable parameter" in the analysis, significant progress has been made toward understanding the relationship of far-ultraviolet airglow emissions to the solar and atmospheric conditions that control them.

Solomon, Stanley C.↗
NASA NTRS1998

Relationship of Topside Ionospheric Ion Outflows to Auroral Forms and Precipitation, Plasma Waves, and Convection Observed by Polar

The POLAR satellite often observes upflowing ionospheric ions (UFIs) in and near the aurora] oval on southern perigee (approx. 5000 km altitude) passes. We present the UFI features observed by the thermal ion dynamics experiment (TIDE) and the toroidal imaging mass angle spectrograph (TIMAS) in the dusk-dawn sector under two different geomagnetic activity conditions in order to elicit their relationships with auroral forms, wave emissions, and convection pattern from additional POLAR instruments. During the active interval, the ultraviolet imager (UVI) observed a bright discrete aurora on the duskside after the substorm onset and then observed a small isolated aurora form and diffuse auroras on the dawnside during the recovery phase. The UFIs showed clear conic distributions when the plasma wave instrument (PWI) detected strong broadband wave emissions below approx. 10 kHz, while no significant auroral activities were observed by UVI. At higher latitudes, the low-energy UFI conics gradually changed to the polar wind component with decreasing intensity of the broadband emissions. V-shaped auroral kilometric radiation (AKR) signatures observed above -200 kHz by PWI coincided with the region where the discrete aurora and the UFI beams were detected. The latitude of these features was lower than that of the UFI conics. During the observations of the UFI beams and conics, the lower-frequency fluctuations observed by the electric field instrument were also enhanced, and the convection directions exhibited large fluctuations. It is evident that large electrostatic potential drops produced the precipitating electrons and discrete auroras, the UFI beams, and the AKR, which is also supported by the energetic plasma data from HYDRA. Since the intense broadband emissions were also observed with the UFIs, the ionospheric ions could be energized transversely before or during the parallel acceleration due to the potential drops.

Hirahara, M.↗
NASA NTRS1997

Relationship of Topside Ionospheric Ion Outflows to Auroral Forms and Precipitations, Plasma Waves, and Convection Observed by POLAR

The POLAR satellite often observes upflowing ionospheric ions (UFls) in and near the auroral oval on southern perigee (approximately 5000 km altitude) passes. We present the UFI features observed by the thermal ion dynamics experiment (TIDE) and the toroidal imaging mass-angle spectrograph (TIMAS) in the dusk-dawn sector under two different geomagnetic activity conditions in order to elicit their relationships with auroral forms, wave emissions, and convection pattern from additional POLAR instruments. During the active interval, the ultraviolet imager (UVI) observed a bright discrete aurora on the dusk side after the substorm onset and then observed a small isolated aurora form and diffuse auroras on the dawn side during the recovery phase. The UFls showed clear conic distributions when the plasma wave instrument (PWI) detected strong broadband wave emissions below approximately 10 kHz, while no significant auroral activities were observed by UVI. At higher latitudes, the low-energy UFI conics gradually changed to the polar wind component with decreasing intensity of the broadband emissions. V-shaped auroral kilometric radiation (AKR) signatures observed above approximately 200 kHz by PWI coincided with the region where the discrete aurora and the UFI beams were detected. The latitude of these features was lower than that of the UFI conics. During the observations of the UFI beams and conics, the lower-frequency fluctuations observed by the electric field instrument (EFI) were also enhanced, and the convection directions exhibited large fluctuations. It is evident that large electrostatic potential drops produced the precipitating electrons and discrete auroras, the UFI beams, and the AKR, which is also supported by the energetic plasma data from HYDRA. Since the intense broadband emissions were also observed with the UFIs. the ionospheric ions could be energized transversely before or during the parallel acceleration due to the potential drops.

Hirahara, M.↗
DOE OSTI2025

Computational insights into hydrogen adsorption energies on medium-entropy oxides

High entropy oxides (HEOs) have emerged as promising catalysts for several important chemical transformations including alkane activation. Hydrogen adsorption energy (HAE) has been used as a key descriptor for many reactions including methane C–H activation and hydrogen evolution reactions. Hence, understanding the relationship between HAEs and the surface chemistry of HEO surfaces could lay the foundation for meaningful correlations among methane C–H activation, HAE, and the complex, local environment of HEO surfaces. Here, we used a medium-entropy oxide as a prototypical system – Mg 0.25 Ni 0.25 Cu 0.25 Zn 0.25 O with a rock-salt structure – to interrogate these relationships. We sampled 2000 different surfaces of its (100) plane and calculated the HAEs at randomly chosen surface O sites using density functional theory (DFT). Our analysis of the 2000 data points reveals that the HAEs at the surface O sites are significantly influenced by the local environment around the adsorption sites, particularly the nature of the metal atom directly below the surface O site where H adsorbs. After comparing several popular graph-neural-network-based machine learning models, we found that the DimeNet++ model performed best achieving satisfactory accuracy in predicting HAEs for both Mg 0.25 Ni 0.25 Cu 0.25 Zn 0.25 O and slightly varied compositions. Our work underscores the promise of such models and the need for further refinement to address the complexity of HEOs.

Song, Haohong [Vanderbilt Univ., Nashville, TN (Un↗
NASA NTRS1993

Establishing a relationship between maximum torque production of isolated joints to simulate EVA ratchet push-pull maneuver: A case study

As manned exploration of space continues, analytical evaluation of human strength characteristics is critical. These extraterrestrial environments will spawn issues of human performance which will impact the designs of tools, work spaces, and space vehicles. Computer modeling is an effective method of correlating human biomechanical and anthropometric data with models of space structures and human work spaces. The aim of this study is to provide biomechanical data from isolated joints to be utilized in a computer modeling system for calculating torque resulting from any upper extremity motions: in this study, the ratchet wrench push-pull operation (a typical extravehicular activity task). Established here are mathematical relationships used to calculate maximum torque production of isolated upper extremity joints. These relationships are a function of joint angle and joint velocity.

Pandya, Abhilash↗
NASA NTRS1991

Assessment of regional biomass-soil relationships using vegetation indexes

The development of photosynthetic active biomass in different ecological conditions, as indicated by normalized difference vegetation indices (NDVIs) is compared by performing a stratified sampling (based on soil assocations) on data acquired over Indiana. Data from the NOAA-10 AVHRR were collected for the 1987 and 1988 growing seasons. An NDVI transformation was performed using the two optical bands of the sensor (0.58-0.68 microns and 0.72-1.10 microns). The NDVI is related to the amount of active photosynthetic biomass present on the ground. Samples of NDVI values over 45 fields representing eight soil associations throughout Indiana were collected to assess the effect of soil conditions and acquisition date on the spectral response of the vegetation, as shown by the NDVIs. Statistical analysis of results indicate that land-cover types (forest, forest/pasture, and crops), soil texture, and soil water-holding capacity have an important effect on vegetation biomass changes as measured by AVHRR data. Acquisition dates should be selected with condideration of the phenological stages of vegetation. Sampling of AVHRR data over extended areas should be stratified according to physiographic units rather than man-made boundaries. This will provide more homogeneous samples for statistical analysis.

Lozano-Garcia, D. Fabian↗
NASA NTRS2014

On the Relationship Between Global Land-Ocean Temperature and Various Descriptors of Solar-Geomagnetic Activity and Climate

Examined are sunspot cycle- (SC-) length averages of the annual January-December values of the Global Land-Ocean Temperature Index ( ) in relation to SC-length averages of annual values of various descriptors of solar-geomagnetic activity and climate, incorporating lags of 0-5 yr. For the overall interval SC12-SC23, the is inferred to correlate best against the parameter incorporating lag = 5 yr, where the parameter refers to the resultant aa value having removed that portion of the annual aa average value due to the yearly variation of sunspot number (SSN). The inferred correlation between the and is statistically important at confidence level cl > 99.9%, having a coefficient of linear correlation r = 0.865 and standard error of estimate se = 0.149 degC. Excluding the most recent cycles SC22 and SC23, the inferred correlation is stronger, having r = 0.969 and se = 0.048 degC. With respect to the overall trend in the , which has been upwards towards warmer temperatures since SC12 (1878-1888), solar-geomagnetic activity parameters are now trending downwards (since SC19). For SC20-SC23, in contrast, comparison of the against SC-length averages of the annual value of the Mauna Loa carbon dioxide ( ) index is found to be highly statistically important (cl >> 99.9%), having r = 0.9994 and se = 0.012 degC for lag = 2 yr. On the basis of the inferred preferential linear correlation between the and , the current ongoing SC24 is inferred to have warmer than was seen in SC23 (i.e., >0.526 degC), probably in excess of 0.68 degC (relative to the 1951-1980 base period).

Wilson, Robert M.↗
DOE OSTI2020

Continental-scale patterns of extracellular enzyme activity in the subsoil: an overlooked reservoir of microbial activity

Abstract Chemical stabilization of microbial-derived products such as extracellular enzymes (EE) onto mineral surfaces has gained attention as a possibly important mechanism leading to the persistence of soil organic carbon (SOC). While the controls on EE activities and their stabilization in the surface soil are reasonably well-understood, how these activities change with soil depth and possibly diverge from those at the soil surface due to distinct physical, chemical, and biotic conditions remains unclear. We assessed EE activity to a depth of 1 m (10 cm increments) in 19 soil profiles across the Critical Zone Observatory Network, which represents a wide range of climates, soil orders, and vegetation types. For all EEs, activities per mass of soil correlated positively with microbial biomass (MB) and SOC, and all three of these variables decreased logarithmically with depth ( p < 0.05). Across all sites, over half of the potential EE activities per mass soil consistently occurred below 20 cm for all measured EEs. Activities per unit MB or SOC were substantially higher at depth (soils below 20 cm accounted for 80% of whole-profile EE activity), suggesting an accumulation of stabilized (i.e. mineral sorbed) EEs in subsoil horizons. The pronounced enzyme stabilization in subsurface horizons was corroborated by mixed-effects models that showed a significant, positive relationship between clay concentration and MB-normalized EE activities in the subsoil. Furthermore, the negative relationships between soil C, N, and P and C-, N-, and P-acquiring EEs found in the surface soil decoupled below 20 cm, which could have also been caused by EE stabilization. This finding suggests that EEs may not reflect soil nutrient availabilities deeper in the soil profile. Taken together, our results suggest that deeper soil horizons hold a significant reservoir of EEs, and that the controls of subsoil EEs differ from their surface soil counterparts.

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

Influence of Proton Activity Gaps between Electrodes on Open-Circuit Potential of H 2 /H 2 and H 2 /Air Cells

Polymer -electrolyte-fuel-cell open-circuit voltages (OCVs) are exactly defined by equation (1), where cathode and anode proton activities [(aH+)cathode and (aH+)anode, respectively] usually are identical, so the third term in the right-hand side of equation (2) is ignored. OCV=E0+RT/2F*ln(a1/2 O2*(a2 H+)cathode/aH2O)-RT/2F*ln((a2 H+)anode/aH2) (1) =E0+RT/2F*ln(a1/2 O2*aH2/aH2O)+RT/2F*ln((a2 H+)cathode/(a2 H+)anode) (2) Water vapor pressure is a colligative property that fundamentally correlates to electrolyte concentrations in aqueous solutions. Proton activity is a function of acid concentration, such as pH, when electrolytes are acids. In polymer-electrolyte membranes, water vapor pressure and acid concentration are understood as relative humidity (RH) and water uptake (λ), respectively, where λ represents number of water molecules per sulfonic acid molecule. Several investigations have reported the relationship between RH and λ, meaning that proton activities and associated water uptakes are intimately related to RH. In actual fuel cell operation, cathode RH is determined by ambient-atmosphere and/or humidifier RH(s), and anode RH depends on hydrogen-circulator RH. Therefore, RH is not always identical at both electrodes, and the difference between electrode RHs is considerable during dry operation of polymer electrolyte fuel cells. Therefore, the third term in the right-hand side of equation (2) may be significant for dry operation. We measured OCVs when hydrogen was supplied to both electrodes at 80°C. One electrode (A) was fixed at 30% RH, while RH at the other electrode (B) was varied (0, 5, 10, 20, and 30%). Measured OCVs varied from 0 to 75 mV. For fuel cell tests, electrode A was supplied with hydrogen at 30% RH; electrode B, oxygen at 0, 5, 10, 20, and 30% RH. OCVs deviated from that measured when RH at electrode B was 30%, increasing from 0 to 60 mV with decreasing RH at electrode B. Results are also shown in Figure 1. Proton activities of both electrodes were thermodynamically calculated. The Gibbs–Duhem relation was applied to obtain molar Gibbs free energies of water and sulfonic acid, and proton activity coefficient was calculated using the Gibbs free energy of sulfonic acid and the relationship between RH and λ1–4, assuming that protons and sulfonic anions show identical ionic-activity coefficients. OCVs were estimated using the third term in the right-hand side of equation (2). Results are shown in Figure 1. Fuel-cell current–voltage performance was poor when RHs at the anode and cathode were 30 and 20%, respectively. To determine kinetic current, we measured the oxygen-reduction reaction (ORR) using a rotating-disk electrode (RDE) in concentrated-acid aqueous solutions, which modeled catalyst-layer ionomers. Kinetic currents decreased with acid concentrations. References T. A. Zawodzinski, Jr., C. Derouin, S. Radzinski, R. J. Sherman, V. T. Smith, T. E. Springer and S. Gottesfeld , J. Electrochem. Soc., 140,1041 (1993) P. K. Das and A. Z. Weber, Proceedings of the ASME 2013 11th Fuel Cell Science, Engineering and Technology Conference, Fuel Cell 18010 (2013) V. A. Sethuraman, J. W. Weidner, A. T. Haug, S. Motupally,b and L. V. Protsailo, J. Electrochem. Soc., 155, B50 (2008) A. Kusoglu and A. Z. Weber, Chem. Rev., 117, 987 (2017) Figure 1

Yoshida, Toshihiko↗
NASA NTRS1983

A design procedure for active control of beam vibrations

The transverse vibrations of beams is discussed and a methodology for the design of an active damping device is given. The Bernoulli-Euler equation is used to derive a transcendental transfer function, which relates a torque applied at one end of the beam to the rotational position and velocity at that point. The active damping device consists of a wire, a linear actuator and a short torque arm attached to one end of the beam. The action of the actuator varies a tension in the wire and creates a torque which opposes the rotation of the beam and thus damps vibration. A design procedure for such an active damper is given. This procedure shows the relationships and trade-offs between the actuator stroke, power required, stress levels in the wire and beam and the geometry of the beam and wire. It is shown that by consideration of the frequency response at the beam natural frequencies, the aforementioned relationships can be greatly simplified. Similarly, a simple way of estimating the effective damping ratios and eigenvalue locations of actively controlled beams is presented.

Dickerson, S. L.↗
DOE OSTI2022

Electronic Structure of Single-Atom Alloys and Its Impact on The Catalytic Activities

Single-atom alloys (SAAs) are promising materials for heterogeneous catalysis due to their unique structure and electronic properties. SAAs have active sites narrowed down to the single-atom level, which combines the advantages of alloy materials and single-site catalysts. Given the unique structural feature of SAAs, their electronic properties can be more flexibly tailored than for their monometallic counterparts, which can be used to effectively control their catalytic activities. One interesting feature commonly observed for SAAs is the lower density of state (DOS) near the Fermi level than their bulk references. Comparing with results for their monometallic bulk reference, the most noticeable electronic property change in SAAs is the narrowing of the valence band, which gives them free-atom-like character. Moreover, the d-band position of both single atoms and their host metals can show a pronounced shift. These changes of electronic structure in SAAs could largely affect the adsorption behavior of adsorbates during the catalytic processes. Close examination of the relationship between electronic structure and catalytic activity can provide useful guidance for rational design of new catalysts with improved performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Oxidation, Oligomerization, Isomerization of Hydrocarbons Using Metal–Organic Frameworks

The selective conversion of hydrocarbons into higher-value fuels and feedstocks is essential to the global energy and chemistry landscape. While porous inorganic materials have enabled significant progress in these transformations, achieving high activity, selectivity, and stability under industrially relevant conditions remains challenging. Metal–organic frameworks (MOFs) are a promising platform to precisely control active-site environments and interrogate structure–function relationships due to their crystallinity, tunability, and porosity. This review highlights relevant hydrocarbon transformations and outlines the general mechanisms for oxidation, oligomerization, and isomerization. Metal node acidity, confinement effects, and active site dispersion are analyzed for their impact on reactivity and selectivity across the three reactions. Lastly, we discuss current limitations in catalyst stability and offer a perspective on integrating reticular chemistry with high-throughput experimentation and machine learning to accelerate the discovery and design of robust, next-generation MOF catalysts.

Catalysts↗
NASA NTRS1975

A subauroral and mid-latitude view of substorm activity

Experimental observations from a variety of sources made during a substorm period near 0900 UT on January 2, 1971 have provided evidence confirming mid-latitude and subauroral phenomena associated with magnetic substorm activity. A review of these observations, including ground and balloon observations made near L=4 at the conjugate stations Siple, Antarctica and Roberval, Canada and data obtained from the synchronous-orbit satellite ATS 5 positioned about 2 hours west of the Siple, Roberval meridian, is presented. During the hour before the reported correlated bursts of X rays and VLF noise (Rosenberg et al., 1971), the plasmapause appears to be displaced towards the equator from Siple; resonance conditions along the field lines at Siple were favorable for the observation of results of magnetospheric wave-particle interactions involving electrons with energies exceeding 30 keV. The correlated observations are a potential source of information concerning the relationship of ULF and VHF noise activity to the magnetospheric particle population at middle latitudes; the injection and subsequent drift of low and medium energy electrons during substorms; and enhanced particle precipitation deep within the plasmasphere during substorms.

Carpenter, D. L.↗
DOE OSTI2023

Assessing factors that determine adatom migration and clustering on a thin film oxide; Pt 1 and Rh 1 on the “29” Cu x O/Cu(1 1 1) surface

The dynamical nature of single-site catalysts under non-equilibrium conditions poses significant challenges in the full characterization of their active sites. The “29” oxide is a thin Cu x O film grown on Cu(111) which provides a well-defined surface on which to study the structure and chemistry of atomically dispersed precious metals. A combination of experimental and first-principles approaches is used to investigate the factors that influence the mobility of metal adatoms and their clustering tendencies. Our work elucidates how a homogenous coordination environment of neutral single-atoms can be obtained when its tendency to break oxide bonds within its vicinity is low. Herein we demonstrate that this in turn affects the chemical atomically dispersed species on thin-film oxides, as defects on the oxide would in fact allow such species to be more accessible to CO. We thus highlight the importance of understanding the relationship between defects and atomically dispersed active sites upon designing single-site catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1982

Relations between the Birkeland currents, the auroral electrojet indices and high latitude Joule heating

Field-aligned currents were postulated by Birkeland (1908) to explain the magnetic perturbations in the auroral zone. Theoretical models have been developed to examine the effect of these currents on the ionosphere. These models, in general, involve very extensive computer programs, and it is difficult to see how their very complicated boundary conditions and assumptions affect the relationships between the Birkeland currents and magnetic activity. In the present investigation, a simplified analysis is used to study the average behavior of the large-scale ionospheric current paths and to examine the interrelationships of various parameters. The relationship of the parameters of the current deposition regions to the magnetic indices is investigated along with the polar cap potential. Attention is given to the experimental values of coefficients, and relations between the Birkeland current densities, current intensities, currents, and the AL, AU, AE indices are discussed.

Nisbet, J. S.↗
DOE OSTI2022

Strategies for breaking molecular scaling relationships for the electrochemical CO 2 reduction reaction

The electrocatalytic CO 2 reduction reaction (CO 2 RR) is a promising strategy for converting CO 2 to fuels and value-added chemicals using renewable energy sources. Molecular electrocatalysts show promise for the selective conversion of CO 2 to single products with catalytic activity that can be tuned through synthetic structure modifications. However, for the CO 2 RR by traditional molecular catalysts, beneficial decreases in overpotentials are usually correlated with detrimental decreases in catalytic activity. This correlation is sometimes referred to as a “molecular scaling relationship”. Overcoming this inverse correlation between activity and effective overpotential remains a challenge when designing new, efficient molecular catalyst systems. Here, in this perspective, we discuss some of the concepts that give rise to the molecular scaling relationships in the CO 2 RR by molecular catalysts. We then provide an overview of some reported strategies from the last decade for breaking these scaling relationships. We end by discussing strategies and progress in our own research designing efficient molecular catalysts with redox-active ligands that show high activity at low effective overpotentials for the CO 2 RR.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1989

Glycogen supercompensation in rat soleus muscle during recovery from nonweight bearing

Events leading to the normalization of the glycogen metabolism in the soleus muscle of rat, altered by 72-h three days of hind-limb suspension, were investigated during the 72-h recovery period when the animals were allowed to bear weight on all four limbs. Relative importance of the factors affecting glycogen metabolism in skeletal muscle during the recovery period was also examined. Glycogen concentration was found to decrease within 15 min and up to 2 h of recovery, while muscle glucose 6-phosphate, and the fractional activities of glycogen phosphorylase and glycogen synthase increased. From 2 to 4 h, when the glycogen synthase activity remained elevated and the phosphorylase activity declined, glycogen concentration increased, until it reached maximum values at about 24 h, after which it started to decrease, reaching control values by 72 h. At 12 and 24 h, the inverse relationship between glycogen concentration and the synthase activity ratio was lost, indicating that the reloading transiently uncoupled glycogen control of this enzyme.

Henriksen, Erik J.↗