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NASA NTRS1996

Southern Hemisphere In Situ Observations of OH, HO2, CIO and BrO from the ER-2 Aircraft for the 1994 ASHOE Mission

A summary of the first order scientific conclusions that emerged from the research done under this grant are as follows: (1) For the first time, the concentration of the key hydrogen and halogen radicals OH, H02, ClO and BrO were determined on a global scale extending from the arctic circle to the antarctic circle, over the altitude domain of the ER-2. That domain extends from 15-20 km altitude, covering a critical part of the lower stratosphere; (2) Simultaneous, in situ measurements of the concentrations of OH, H02, ClO, BrO, NO and NO2 demonstrate the predominance of odd-hydrogen and halogen free radical catalysis in determining the rate of removal of ozone in the lower stratosphere over the complete ASHOE mission. This extends to the global scale the "first look" data obtained during the NASA Stratospheric Photochemistry and Dynamics Experiment (SPADE), executed out of Ames Research Center in June 1993. This represents a major rearrangement of our understanding with respect to the hierarchy of dominant catalytic cycles controlling ozone loss in the lower stratosphere. For the past twenty years, it has been assumed that nitrogen radicals dominate the destruction rate of ozone in the lower stratosphere; (3) Throughout the altitude and latitude range covered by ASHOE, it was determined that a single catalytic cycle, HO2 + O3 yields OH + 2O2, accounted for one half of the total O3 removal in this region of the atmosphere. Halogen radical catalytic cycles were found to account for one third of the ozone loss, and nitrogen radicals were found to account for 20% of the loss; (4) Simultaneous observations of the full complement of radicals, tracers, ozone, and water vapor during ASHOE demonstrated quantitatively the coupling that exists between the rate limiting radicals and other reactive species in the photochemical reaction network. Specifically, the concentrations of ClO and HO2 are inversely correlated with the concentration of NOx. This carries the implication that the NOx effluent from the proposed High Speed Civil Transport may be less destructive to stratospheric ozone than had previously been thought. ASHOE brought this conclusion forward for the first time on a global basis; and (5) The density of BrO was measured on a global scale during ASHOE in the lower stratosphere. It was found that bromine is responsible for 55-65% of the local rate of catalytic destruction of ozone by reactions involving bromine and chlorine. Normalizing calculated loss rates to total available inorganic bromine and chlorine explicitly demonstrates that bromine is 60-80 times more efficient than chlorine in removing ozone in the lower stratosphere. An inferred value of total inorganic bromine is in excellent agreement with measurements of their source species, organic bromine compounds in the troposphere.

Anderson, James G.↗

NASA NTRS1991

Design and performance of a high-Tc superconductor coplanar waveguide filter

The design of a coplanar waveguide low-pass filter made of YBa2Cu3O(7-delta) (YBCO) on an LaAlO3 substrate is described. Measurements were incorporated into simple models for microwave CAD analysis to develop a final design. The patterned and packaged coplanar waveguide low-pass filter of YBCO, with dimensions suited for integrated circuits, exhibited measured insertion losses when cooled in liquid nitrogen superior to those of a similarly cooled thin-film copper filter throughout the 0 to 9.5 GHz passband. Coplanar waveguide models for use with thin-film normal metal (with thickness either greater or less than the skin depth) and YBCO are discussed and used to compare the losses of the measured YBCO and copper circuits.

Chew, Wilbert↗

DOE OSTI2021

Investigation on Light Stability of Injected Charge in α- SiN x : H by Plasma Charge Injection Technology

The plasma charge injection technology reported earlier can be a low-cost alternative to the Al 2 O 3 passivation technology. The charge stability under sunlight exposure is a key concern. We investigated the light-induced loss of injected charge for different nitrogen-to-silicon atomic ratios (x=N/Si) of SiN x , and found drastic improvements in charge loss with increasing x-value and logarithmic time dependent charge decays. The best result indicated a sufficient charge amount can sustain over the module lifetime (25 years). Here, the charge loss is likely related to photo-generated free carriers and atomic hydrogens in SiN x .

14 SOLAR ENERGY↗

DOE OSTI2023

Root litter decomposition rates and impacts of drought are regulated by ecosystem legacy

In grassland ecosystems, about two-thirds of productivity is in roots, and therefore roots constitute a major soil organic matter input. However, influences on the rate of root litter decomposition remain unresolved, especially in the context of land-use conversion and climate change. Ecosystem legacy can affect root decomposition rates via impacts on substrate chemistry and soil environments, and this may manifest in responses of decomposition to changing temperature and moisture. Here we investigate the impacts of anthropogenic legacy effects and moderate drought on root litter decomposition rates in five "Land Use History Types": crop fields, cow pastures, remnant tallgrass prairie, and prairie restored from crop fields and pastures. We measured root losses of mass, carbon, and nitrogen over 11 months. Further, soil bulk density was unimportant for decomposition, but soil moisture content and temperature were relevant for decomposition rates while time since disturbance predicted decomposition initiation times. Furthermore, soil moisture and temperature dynamics alone could not explain the responses of decomposition rates to drought, which were positively correlated to time since disturbance. Our findings suggest that anthropogenic legacy impacts decomposition rates in grasslands, especially when soil moisture and temperature dynamics are substantially altered, and mediates soil community responses to drought.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2024

Light-enhanced oxygen degradation of MAPbBr 3 single crystal

Organometal halide perovskites are promising materials for optoelectronic applications, whose commercial realization depends critically on their stability under multiple environmental factors. In this study, a methylammonium lead bromide (MAPbBr 3 ) single crystal was cleaved and exposed to simultaneous oxygen and light illumination under ultrahigh vacuum (UHV). The exposure process was monitored using X-ray photoelectron spectroscopy (XPS) with precise control of the exposure time and oxygen pressure. It was found that the combination of oxygen and light accelerated the degradation of MAPbBr 3 , which could not be viewed as a simple addition of that by oxygen-only and light-only exposures. The XPS spectra showed significant loss of carbon, bromine, and nitrogen at an oxygen exposure of 10 10 Langmuir with light illumination, approximately 17 times of the additive effects of oxygen-only and light-only exposures. It was also found that the photoluminescence (PL) emission was much weakened by oxygen and light co-exposure, while previous reports had shown that PL was substantially enhanced by oxygen-only exposure. Measurements using a scanning electron microscope (SEM) and focused ion beam (FIB) demonstrated that the crystal surface was much roughened by the co-exposure. Furthermore, Density functional theory (DFT) calculations revealed the formation of superoxide and oxygen induced gap state, suggesting the creation of oxygen radicals by light illumination as a possible microscopic driving force for enhanced degradation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Biochar-compost-based controlled-release nitrogen fertilizer intended for an active microbial community

Nitrogen (N) fertilizers in agriculture suffer losses by volatilization of N to the air, surface runoff and leaching into the soil, resulting in low N use efficiency (NUE) (< 50%) and raising severe environmental pollutions. Controlled- release nitrogen fertilizers (CRNFs) can control the release of N nutrients to NUE in crop production. Different methods were used to develop new CRNFs. However, different CRNF technologies are still underdeveloped due to inadequate controlling on N releasing time and/or unsustainable diffusion. The study on the influences of CRNF processing parameters on microbial conditions are lacking when the CRNFs composed of various bio-ingredients such as biochar, composts, and biowaste. The complexity of processing methods, material biodegradability, and other physical properties make current CRNFs of questionable value in agricultural production. This research aims to develop a novel biochar-compost-based controlled-release urea fertilizer (BCRUF) to preserve microbial properties carried by the compost. The BCRUF was synthesized by pelletizing the 50:50 (dry, wt/wt) mixture of biochar and compost. BCRUF was loaded with urea and then spray-coated with polylactic acid (PLA). The releasing time of two types of BCRUFs, coated and uncoated with PLA, for 80% of N release in water was up to 6 h at three different temperatures (4, 23, and 40 °C), compared to conventional urea fertilizer and commercial environmentally smart N (ESN) fertilizer. The releasing time of coated BCRUF for 80% N release in soil was up to 192 h (8 days). Fourier-transform infrared spectroscopy (FTIR) analysis revealed that no new functional groups were found in the release solution, indicating no new chemical hazards generated. The differential scanning calorimetry (DSC) tests also verified that its thermal stability could be up to 160 °C. The microbe populations in the BCRUF pellets were reduced after the pelleting and drying processes in BCRUF fabrication, but a few bacteria can endure in the air-drying process. BCRUF pellets soaked in water for 4 days retained some bacteria. The BCRUF showed very promising characteristics to improve NUE and sustainability in agricultural production.

58 GEOSCIENCES↗

NASA NTRS1975

Experimental investigations of argon and xenon ion sources

The multipole thruster was used to investigate the use of argon and xenon propellants as possible alternatives to the electric thruster propellants of mercury and cesium. The multipole approach was used because of its general high performance level. The design employed, using flat and cylindrical rolled sections of sheet metal, was selected for ease of fabrication, design, assembly, and modification. All testing was conducted in a vacuum facility and the pumping was accomplished by a 0.8 m diffusion pump together with liquid nitrogen cooled liner. Minimum discharge losses were in the 200-250 ev. ion range for both argon and xenon. Flatness parameters were typically in the 0.70-0.75 range.

Kaufman, H. R.↗

NASA NTRS1975

The N I /5200 A/ dayglow

The production and loss mechanisms of metastable (2D) nitrogen atoms are studied on the basis of Atmosphere Explorer satellite's measurements of 5200-A emission by the visible airglow experiment, complemented by simultaneous measurements of the ion and neutral composition of the atmosphere and the photoelectron flux. The relative yield of (2D) metastable and (4S) ground-state nitrogen atoms in the creation and destruction processes is examined. The results are used to calculate NO densities, making allowance for photochemical and vertical diffusion processes.

Rusch, D. W.↗

NASA NTRS1976

Biomedical results of the Skylab Program

Skylab, the fourth in a logical sequence of USA manned space flight projects following Mercury, Gemini and Apollo, presented life scientists with their first opportunity for an in-depth study of man's response to the space environment. Extensive medical investigations were undertaken to increase our understanding of man's adaptation to the space environment and his readaptation to gravity upon return to earth. The flight durations of the three Skylab missions were progressively increased from 28 days to 59 days and, finally, 84 days. The results of these investigations of the various body systems clearly denonstrated that man can adapt to zero gravity and perform useful work during long-duration space flight. However, definite changes (some unexpected) in the vestibular, cardiovascular, musculo-skeletal, renal and electrolyte areas were documented. The most significant were: the occurrence of space motion sickness early in the missions; diminished orthostatic tolerance, both in-flight and post-flight; moderate losses of calcium, phosphorus and nitrogen; and decreased tolerance for exercise post-flight. The mechanisms responsible for these physiological responses must be understood and, if necessary, effective countermeasures developed before man can endure unlimited exposure to space flight.

Michel, E. L.↗

NASA NTRS2017

How Hospitable are Space Weather Affected Habitable Zones? The Role of Ion Escape

Atmospheres of exoplanets in the habitable zones around active young G-K-M stars are subject to extreme X-ray and EUV (XUV) (Extreme Ultraviolet) fluxes from their host stars that can initiate atmospheric erosion. Atmospheric loss affects exoplanetary habitability in terms of surface water inventory, atmospheric pressure, the efficiency of greenhouse warming, and the dosage of the UV surface irradiation. Thermal escape models suggest that exoplanetary atmospheres around active K-M stars should undergo massive hydrogen escape, while heavier species including oxygen will accumulate forming an oxidizing atmosphere. Here, we show that non-thermal oxygen ion escape could be as important as thermal, hydrodynamic H escape in removing the constituents of water from exoplanetary atmospheres under supersolar XUV irradiation. Our models suggest that the atmospheres of a significant fraction of Earth-like exoplanets around M dwarfs and active K stars exposed to high XUV fluxes will incur a significant atmospheric loss rate of oxygen and nitrogen, which will make them uninhabitable within a few tens to hundreds million years, given a low replenishment rate from volcanism or cometary bombardment. Our non-thermal escape models have important implications for the habitability of the Proxima Centauri's terrestrial planet.

radiation mechanisms↗

NASA NTRS1973

New techniques for far-infrared filters.

The techniques considered make it possible to construct high performance low-pass wide-band, and medium-band filters at wavelengths in the range from 25 to 300 micrometers. Short wavelength rejection without appreciable loss at long wavelengths is achieved by means of small particle scattering. Spectral definition in the far infrared is obtained by cooling one or more crystalline materials to liquid-He or liquid-nitrogen temperatures. The problem of reflection losses at the various surfaces is solved by a new antireflection coating technique.

Armstrong, K. R.↗

NASA NTRS1988

Chemistry of the Antarctic stratosphere

Interferometric measurements of HCl, ClNO3, HNO3, NO2, and NO obtained over the Antarctic in 1986 are used to model the chemistry of the atmosphere in the region of the Ozone Hole. The low abundance noted in stratospheric HCl is attributed to incorporation of HCl in polar stratospheric clouds and subsequent reaction of HCl with ClNO3. The results point to a net loss of HNO3 from the stratosphere and to the suppression of the abundance of odd nitrogen at high altitudes in the vortex. O3 loss is suggested to be due to the catalytic influence of halogen radicals.

Mcelroy, Michael B.↗

DOE OSTI2020

The impact of nitrogen oxides on electrochemical carbon dioxide reduction

The electroreduction of carbon dioxide offers a promising avenue to produce valuable fuels and chemicals using greenhouse gas carbon dioxide as the carbon feedstock. Because industrial carbon dioxide point sources often contain numerous contaminants, such as nitrogen oxides, understanding the potential impact of contaminants on carbon dioxide electrolysis is crucial for practical applications. Herein, we investigate the impact of various nitrogen oxides, including nitric oxide, nitrogen dioxide, and nitrous oxide, on carbon dioxide electroreduction on three model electrocatalysts (i.e., copper, silver, and tin). We demonstrate that the presence of nitrogen oxides (up to 0.83%) in the carbon dioxide feed leads to a considerable Faradaic efficiency loss in carbon dioxide electroreduction, which is caused by the preferential electroreduction of nitrogen oxides over carbon dioxide. The primary products of nitrogen oxides electroreduction include nitrous oxide, nitrogen, hydroxylamine, and ammonia. Despite the loss in Faradaic efficiency, the electrocatalysts exhibit similar carbon dioxide reduction performances once a pure carbon dioxide feed is restored, indicating a negligible long-term impact of nitrogen oxides on the catalytic properties of the model catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1976

On the reaction of N/+/ ions with O2

The reaction of atomic nitrogen ions with molecular oxygen is a major loss mechanism for N(+) ions in the ionosphere and is a source of NO(+) ions and atomic nitrogen at certain altitudes. Ion cyclotron resonance methods are used to measure the product distribution of thermal energy N(+) ions reacting with O2. Three product channels are identified with the following fractional distributions: O2(+) + N, 0.65 plus or minus 0.04; NO(+) + O, 0.31 plus or minus 0.04; O(+) + NO, 0.04 plus or minus 0.02.

Huntress, W. T., Jr.↗

NASA NTRS1991

Effects of high pressure nitrogen on the thermal stability of SiC fibers

Polymer-derived SiC fibers were exposed to nitrogen gas pressures of 7 and 50 atm at temperatures up to 1800 C. The fiber weight loss, chemical composition, and tensile strength were then measured at room temperature in order to understand the effects of nitrogen exposure on fiber stability. High pressure nitrogen treatments limited weight loss to 3 percent or less for temperatures up to 1800 C. The bulk Si-C-O chemical composition of the fiber remained relatively constant up to 1800 C with only a slight increase in nitrogen content after treatment at 50 atm; however, fiber strength retention was significantly improved. To further understand the effects of the nitrogen atmosphere on the fiber stability, the results of previous high pressure argon treatments were compared to those of the high pressure nitrogen treatments. High pressure inert gas can temporarily maintain fiber strength by physically inhibiting the evolution of gaseous species which result from internal reactions. In addition to this physical effect, it would appear that high pressure nitrogen further improved fiber temperature capability by chemically reacting with the fiber surface, thereby reducing the rate of gas evolution. Subsequent low pressure argon treatments following the initial nitrogen treatments resulted in stronger fibers than after argon treatment alone, further supporting the chemical reaction mechanism and its beneficial effects on fiber strength.

Jaskowiak, Martha H.↗

DOE OSTI2021

Probing Heterogeneous Degradation of Catalyst in PEM Fuel Cells under Realistic Automotive Conditions with Multi-Modal Techniques

The heterogeneity of polymer electrolyte fuel cell catalyst degradation is studied under varied relative humidity and types of feed gas. Accelerated stress tests (ASTs) are performed on four membrane electrode assemblies (MEAs) under wet and dry conditions in an air or nitrogen environment for 30 000 square voltage cycles. The largest electrochemically active area loss is observed for MEA under wet conditions in a nitrogen gas environment AST due to constant upper potential limit of 0.95 V and significant water content. The mean Pt particle size is larger for the ASTs under wet conditions compared to dry conditions, and the Pt particle size under land is generally larger than under the channel. Observations from ASTs in both conditions and gas environments indicate that water content promotes Pt particle size growth. ASTs under wet conditions and an air environment show the largest difference in Pt particle size growth for inlet versus outlet and channel versus land, which can be attributed to larger water content at outlet and under land compared to inlet and under channel. From X-ray fluorescence experiments Pt particle size increase is a local phenomenon as Pt loading remains relatively uniform across the MEA.

25 ENERGY STORAGE↗

NASA NTRS1993

Nitrates in SNCs: Implications for the nitrogen cycle on Mars

Nitrogen is the second most abundant constituent of the Martian atmosphere, after CO2, present at a level of ca. 2.7 percent. Several authors have hypothesized that earlier in the planet's history, nitrogen was more abundant, but has been removed by processes such as exospheric loss from the atmosphere. However, an alternative sink for atmospheric nitrogen is the regolith; model calculations have predicted that, via the formation of NOx, HNO2 and HNO3 in the lower layers of the Martian atmosphere, the regolith might trap nitrite and nitrate anions, leading to the build-up of involatile nitrates. Integrated over 4.5 x 10(exp 9) yr, such a mechanism would contribute the equivalent of a layer of nitrates up to 0.3 cm thick distributed across the Martian surface. Features in thermal emission spectra of the surface of Mars have been interpreted tentatively as emanating from various anions (carbonates, bicarbonates, sulphates, etc.), and the presence of nitrates has also been addressed as a possibility. The identification of carbonates in SCN meteorites has allowed inferences to be drawn concerning the composition and evolution of the Martian atmosphere in terms of its carbon isotope systematics; if nitrites, nitrates, or other nitrogen-bearing salts could be isolated from SNC's, similar conclusions might be possible for an analogous nitrogen cycle. Nitrates are unstable, being readily soluble in water, and decomposed at temperatures between 50 C and 600 C, depending on composition. Any nitrates present in SNC's might be removed during ejection from the planet's surface, passage to Earth, or during the sample's terrestrial history, by weathering etc. The same might have been said for carbonates, but pockets of shock-produced glass (lithology C) from within the EET A79001 shergottite and bulk samples of other SNC contain this mineral, which did apparently survive. Nitrates occurring within the glassy melt pockets of lithology C in EET A79001 might likewise be protected. Lithology C glass was therefore selected for nitrate analysis, first by non-destructive infra red spectroscopy, and then by stepped combustion.

Grady, Monica M.↗

DOE OSTI2022

Nitrogen plasma passivated niobium resonators for superconducting quantum circuits

Microwave loss in niobium metallic structures used for superconducting quantum circuits is limited by a native surface oxide layer formed over a timescale of minutes when exposed to an ambient environment. Here, in this work, we show that nitrogen plasma treatment forms a niobium nitride layer at the metal–air interface, which prevents such oxidation. X-ray photoelectron spectroscopy confirms the doping of nitrogen more than 5 nm into the surface and a suppressed oxygen presence. This passivation remains stable after aging for 15 days in an ambient environment. Cryogenic microwave characterization shows an average filling-factor-adjusted two-level-system loss tangent Fδ TLS of (2.9±0.5)·10 –7 for resonators with a 3 μm center strip and (1.0±0.3)·10 –7 for a 20 μm center strip, exceeding the performance of unpassivated samples by a factor of four.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗