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NASA NTRS1976

Evaluation of a spacecraft nitrogen generator

A method is discussed of generating nitrogen for cabin leakage makeup aboard space vehicles having longer duration missions. The nitrogen generation concept is based on using liquid hydrazine as the stored form of nitrogen to reduce the higher tankage and expendables weight associated with high pressure gaseous or cryogenic liquid nitrogen storage. The hydrazine is catalytically dissociated to yield a mixture of nitrogen and hydrogen. The nitrogen/hydrogen mixture is then separated to yield the makeup nitrogen. The excess supply of hydrogen would be available for use in the reduction of metabolic carbon dioxide. A detailed comparison was completed of Palladium/Silver and Polymer Electrochemical-based Nitrogen Generation Systems. The palladium/silver-based system was judged better than the Polymer Electrochemical Nitrogen Generation System because of lower expendable weight and palladium/silver nitrogen/hydrogen separation represents 'off-the-shelf' technology.

Marshall, R. D.↗
NASA NTRS1978

Reduction of aircraft gas turbine engine pollutant emissions

To accomplish simultaneous reduction of unburned hydrocarbons, carbon monoxide, and oxides of nitrogen, required major modifications to the combustor. The modification most commonly used was a staged combustion technique. While these designs are more complicated than production combustors, no insurmountable operational difficulties were encountered in either high pressure rig or engine tests which could not be resolved with additional normal development. The emission reduction results indicate that reductions in unburned hydrocarbons were sufficient to satisfy both near and far-termed EPA requirements. Although substantial reductions were observed, the success in achieving the CO and NOx standards was mixed and depended heavily on the engine/engine cycle on which it was employed. Technology for near term CO reduction was satisfactory or marginally satisfactory. Considerable doubt exists if this technology will satisfy all far-term requirements.

Diehl, L. A.↗
NASA NTRS2022

Mineral-Catalysed Formation of Marine NO and N 2 O on the Anoxic Early Earth

Microbial denitrification converts fixed nitrogen species into gases in extant oceans. However, it is unclear how such transformations occurred within the early nitrogen cycle of the Archean. Here 5we present experimental anoxic surface-catalyzed reduction of nitrite and nitrate via green rust and magnetite combined with diffusion and photochemical modeling. We find that in a Fe 2+ -rich marine environment, Fe minerals could have catalyzed abiotic denitrification reactions leading to the formation of nitric oxide (NO) and nitrous oxide (N 2 O). Nitrate did not exhibit reactivity in the presence of either mineral or aqueous Fe2+, however, both minerals induced rapid nitrite reduction 10to NO and N 2 O. While N 2 O escaped into the atmosphere (63% of nitrite-nitrogen, with green rust as catalyst), NO remained associated with precipitates (7%) serving as a potential shuttle to the benthic ocean.The modeling suggests that marine N 2 O emissions would have sustained 0.8-6 ppb of atmospheric N 2 O without a protective ozone layer. Our findings add detail to the as yet incompletely documented Archean nitrogen cycle, implying a globally distributed process driven 15by chemical kinetics similar to those of modern enzymatically mediated conversions.

Steffen Buessecker↗
NASA NTRS1993

Destruction of problematic airborne contaminants by hydrogen reduction using a Catalytically Active, Regenerable Sorbent (CARS)

Thermally regenerable sorbent beds were demonstrated to be a highly efficient means for removal of toxic airborne trace organic contaminants aboard spacecraft. The utilization of the intrinsic weight savings available through this technology was not realized since many of the contaminants desorbed during thermal regeneration are poisons to the catalytic oxidizer or form highly toxic oxidation by-products in the Trace Contaminant Control System (TCCS). Included in this class of compounds are nitrogen, sulfur, silicon, and halogen containing organics. The catalytic reduction of these problematic contaminants using hydrogen at low temperatures (200-300 C) offers an attractive route for their destruction since the by-products of such reactions, hydrocarbons and inorganic gases, are easily removed by existing technology. In addition, the catalytic oxidizer can be operated more efficiently due to the absence of potential poisons, and any posttreatment beds can be reduced in size. The incorporation of the catalyst within the sorbent bed further improves the system's efficiency. The demonstration of this technology provides the basis for an efficient regenerable TCCS for future NASA missions and can be used in more conventional settings to efficiently remove environmental pollutants.

Thompson, John O.↗
NASA NTRS2023

Marsh Archive Reveals Human Population History and Future Implications for Estuarine Health in Long Island Sound

Coastal marshes are efficient ecosystems providing a multitude of benefits for invertebrates, birds, fish and humans alike. Yet despite these benefits, wetlands are threatened by anthropogenic inputs such as human wastewater which contain high levels of nitrogen (N). Increased nitrogen loads cause eutrophication and hypoxia in estuaries leading to further degradation of these valuable ecosystems that are already stressed by sea level rise and climate change. Policies to protect wetlands via wastewater treatments are reactive rather than proactive and a growing body of research shows that characteristics associated with population health and economic activity can be identified in wastewater. Analysis of a 2-m salt marsh sediment core reveals δN15 signatures indicative of human population rise and connects human impact to ecosystem health. Using key X-ray fluorescence (XRF), pollen, sediment and nitrogen signatures along the core, a robust chronology was produced dating back to 1700. This result was coupled with population data to observe the relationship between δN15 levels and population over three centuries. There is a statistically significant positive correlation between δN15 and population. Other external factors such as federal government policies (regulating clean water) show a clear reduction in this association but the use of synthetic nitrogen fertilizer masks the strength of this relationship. Further research to refine the relationship between population and δN15 could be beneficial in predicting nitrogen loads as human population grows, which in turn would create a proactive system to protect our coastal ecosystems.

Nitrogen↗
NASA NTRSDate not supplied

A Simulated High CO 2 Spaceflight Environment Increases Plant Preference for Ammonium as a Nitrogen Source.

Future long-duration missions will require a sustainable supply of food to support human crews. The spaceflight cabin environment often contains very high concentrations of CO 2 due to release of CO 2 by astronauts that is not completely scrubbed from the cabin, and it is therefore crucial to understand plant responses to elevated CO 2 (eCO 2 ) environments. Much focus has been given to changes in plant photosynthetic and performance parameters in response to eCO 2 , but the effects of eCO 2 on nitrogen (N) uptake are poorly understood. Shoot nitrate reduction may be reduced at eCO 2 , likely due to less reductant available for nitrate reduction because of reduced photorespiration and increased carbon fixation 1. Relative growth rate can be reduced at eCO 2 when N is provided only as nitrate and can be unaffected when N is supplied as ammonium 1. However, N uptake in response to eCO 2 has, to our knowledge, not yet been studied. An increased ‘preference’ for plants to take up N as ammonium at eCO 2 could have important implications for growth in the space environment, where N is currently only supplied as nitrate. In this study, novel stable isotope approaches were used in conjunction with hydroponics and isotope ratio mass spectrometry to determine the effect of eCO 2 on N preference for ammonium or nitrate in spring barley and lettuce when both N forms are provided equally. Several varieties of spring barley displayed increased ammonium preference at eCO 2 (720 ppm) compared to ambient CO 2 (410 ppm), though this was not true for all varieties 2. In most cases, increases in ammonium preference were driven by increases in ammonium uptake at eCO 2 and not decreases in nitrate uptake. Current research is assessing whether similar responses are observed in the candidate space crop lettuce, at levels of CO 2 like those observed on ISS (3000 ppm), and these results will also be presented. This work will enable the development of optimized nutrient regimes for candidate crops in space environments and the selection of crop varieties adapted to eCO 2 environments. Plants adapted to ammonium nutrition may play a role in future plant-based bioregenerative life support systems with higher ammonium concentrations due to waste recycling 3. Moreover, this research will further our understanding of plant responses to the eCO 2 environment brought about by climate change, allowing the development of future-proof crops that will help to maintain food security. References: 1. Bloom (2015). The increasing importance of distinguishing among plant nitrogen sources. Current Opinion in Plant Biology 25, 10-16. 2. Fountain (2023). Understanding interactions of barley (Hordeum vulgare) with soil nitrogen cycling activity and links to plant nitrogen preference. Ph.D. Thesis, The University of Sheffield. 3. Schiefloe et al. (2023). From urine to food and oxygen: effects of high and low NH4+:NO3- ratio on lettuce cultivated in a gas-tight hydroponic facility. Frontiers in Plant Science 14:1229476.

nitrogen↗
NASA NTRSDate not supplied

A Simulated High CO 2 Spaceflight Environment Increases Plant Preference for Ammonium as a Nitrogen Source.

Future long-duration missions will require a sustainable supply of food to support human crews. The spaceflight cabin environment often contains very high concentrations of CO 2 due to release of CO 2 by astronauts that is not completely scrubbed from the cabin, and it is therefore crucial to understand plant responses to elevated CO 2 (eCO 2 ) environments. Much focus has been given to changes in plant photosynthetic and performance parameters in response to eCO 2 , but the effects of eCO 2 on nitrogen (N) uptake are poorly understood. Shoot nitrate reduction may be reduced at eCO 2 , likely due to less reductant available for nitrate reduction because of reduced photorespiration and increased carbon fixation 1. Relative growth rate can be reduced at eCO 2 when N is provided only as nitrate and can be unaffected when N is supplied as ammonium. However, N uptake in response to eCO 2 has, to our knowledge, not yet been studied. An increased ‘preference’ for plants to take up N as ammonium at eCO 2 could have important implications for growth in the space environment, where N is currently only supplied as nitrate. In this study, novel stable isotope approaches were used in conjunction with hydroponics and isotope ratio mass spectrometry to determine the effect of eCO 2 on N preference for ammonium or nitrate in spring barley and lettuce when both N forms are provided equally. Several varieties of spring barley displayed increased ammonium preference at eCO 2 (720 ppm) compared to ambient CO 2 (410 ppm), though this was not true for all varieties. In most cases, increases in ammonium preference were driven by increases in ammonium uptake at eCO 2 and not decreases in nitrate uptake. Current research is assessing whether similar responses are observed in the candidate space crop lettuce, at levels of CO 2 like those observed on ISS (3000 ppm), and these results will also be presented. This work will enable the development of optimized nutrient regimes for candidate crops in space environments and the selection of crop varieties adapted to eCO 2 environments. Plants adapted to ammonium nutrition may play a role in future plant-based bioregenerative life support systems with higher ammonium concentrations due to waste recycling. Moreover, this research will further our understanding of plant responses to the eCO 2 environment brought about by climate change, allowing the development of future-proof crops that will help to maintain food security.

nitrogen↗
NASA NTRSDate not supplied

Plant Nitrogen Uptake Responses to Elevated Carbon Dioxide

Future long-duration missions will require a sustainable supply of food to support human crews. The spaceflight cabin environment often contains very high concentrations of CO 2 due to release of CO 2 by astronauts that is not completely scrubbed from the cabin, and it is therefore crucial to understand plant responses to elevated CO 2 (eCO 2 ) environments. Much focus has been given to changes in plant photosynthetic and performance parameters in response to eCO 2 , but the effects of eCO 2 on nitrogen (N) uptake are poorly understood. Shoot nitrate reduction may be reduced at eCO 2 , likely due to less reductant available for nitrate reduction because of reduced photorespiration and increased carbon fixation 1. Relative growth rate can be reduced at eCO 2 when N is provided only as nitrate and can be unaffected when N is supplied as ammonium. However, N uptake in response to eCO 2 has, to our knowledge, not yet been studied. An increased ‘preference’ for plants to take up N as ammonium at eCO 2 could have important implications for growth in the space environment, where N is currently only supplied as nitrate. In this study, novel stable isotope approaches were used in conjunction with hydroponics and isotope ratio mass spectrometry to determine the effect of eCO 2 on N preference for ammonium or nitrate in spring barley and lettuce when both N forms are provided equally. Several varieties of spring barley displayed increased ammonium preference at eCO 2 (720 ppm) compared to ambient CO 2 (410 ppm), though this was not true for all varieties. In most cases, increases in ammonium preference were driven by increases in ammonium uptake at eCO 2 and not decreases in nitrate uptake. Current research is assessing whether similar responses are observed in the candidate space crop lettuce, at levels of CO 2 like those observed on ISS (3000 ppm), and these results will also be presented. This work will enable the development of optimized nutrient regimes for candidate crops in space environments and the selection of crop varieties adapted to eCO 2 environments. Plants adapted to ammonium nutrition may play a role in future plant-based bioregenerative life support systems with higher ammonium concentrations due to waste recycling. Moreover, this research will further our understanding of plant responses to the eCO 2 environment brought about by climate change, allowing the development of future-proof crops that will help to maintain food security.

nitrogen↗
NASA NTRS1974

Feasibility demonstration of a road vehicle fueled with hydrogen-enriched gasoline

Evaluation of the concept of using hydrogen-enriched gasoline in a modified internal combustion engine in order to make possible the burning of ultralean mixtures. The use of such an engine in a road vehicle demonstrated that the addition of small quantities of gaseous hydrogen to gasoline resulted in significant reductions in exhaust emissions of carbon monoxide and nitrogen oxides as well as in thermal efficiency improvements of the engine performance.

Hoehn, F. W.↗
NASA NTRS1978

Evaluation of a spacecraft nitrogen generator

A research and development program was successfully completed towards the development of a method of generating nitrogen for cabin leakage makeup aboard space vehicles. The nitrogen generation concept used liquid hydrazine as the stored form of nitrogen. This reduced tankage and expendables weight associated with high pressure gaseous and cryogenic liquid nitrogen storage. The hydrazine was catalytically dissociated to yield a mixture of nitrogen and hydrogen. The latter was separated to provide the makeup nitrogen. The hydrogen will be used in the reduction of metabolic carbon dioxide.

Marshall, R. D.↗
NASA NTRS1987

The effects of gas mixtures on ion engine erosion and performance

Erosion measurements were performed on a modified J-series 30 cm ion engine operating on xenon propellant. Erosion data was obtained by measuring the trench depth etched into masked polished metal samples for test durations of up to 24 hours. The data indicates that erosion is greatest at the cathode side of the baffle, with tantalum being the material with the least erosion of all materials tested. There is a clear indication of a significant reduction in erosion of all materials tested when nitrogen is added to the propellant. The technique used in these experiments requires test samples which are extremely smooth and flat.

Garner, Charles E.↗
NASA NTRS2003

The Stable Isotope Fractionation of Abiotic Reactions: A Benchmark in the Detection of Life

One very important tool in the analysis of biogenic, and potentially biogenic, samples is the study of their stable isotope distributions. The isotope distribution of a sample depends on the process(es) that created it. One important application of the analysis of C & N stable isotope ratios has been in the determination of whether organic matter in a sample is of biological origin or was produced abiotically. For example, the delta C-13 of organic material found embedded in phosphate grains was cited as a critical part of the evidence for life in 3.8 billion year old samples. The importance of such analysis in establishing biogenicity was highlighted again by the role this issue played in the recent debate over the validity of what had been accepted as the Earth s earliest microfossils. These kinds of analysis imply a comparison with the fractionation that one would have seen if the organic material had been produced by alternative, abiotic, pathways. Could abiotic reactions account for the same level of fractionation? Additionally, since the fractionation can vary between different abiotic reactions, understanding their fractionations can be important in distinguishing what reactions may have been significant in the formation of different abiological samples (such as extraterrestrial samples). There is however, a scarcity of data on the fractionation of carbon and nitrogen by abiotic reactions. In order to interpret properly what the stable isotope ratios of samples tell us about their biotic or abiotic nature, more needs to be known about how abiotic reactions fractionate C and N. Carbon isotope fractionations have been studied for a few abiotic processes. These studies presumed the presence of a reducing atmosphere, focusing on reactions involving spark discharge, W photolysis of reducing gas mixtures, and cyanide polymerization in the presence of ammonia. They did find that the initial products showed a depletion in I3C with values in the range of a few per mil to as low as -60 % (potentially comparable to that which accompanies the biosynthesis of organic matter). We need to understand what kind of fractionations are observed with reactions under the non-reducing or mildly reducing conditions now thought to be present on the early Earth. While nitrogen is receiving increased attention as a tool for these kinds of analyses, almost nothing is known about the isotope fractionation that one would expect for abiotic sources of fixed/reduced nitrogen. This project will measure the fixation from a series of abiotic reactions that may have been present on the early Earth (and other terrestrial planets) and produced organic material that could have ended up in the rock record. The work will look at a number of reactions, under a non- reducing, or mildly reducing, atmosphere, covering sources of prebiotic organic C & N from shock heating, to photochemistry, to hydrothermal reactions. Some reactions that we plan to study are; Shock heating of a non-reducing atmosphere to produce CO and NO (in collaboration with Chris McKay), formation of formaldehyde (and related compounds) from COY the formation of ammonia from nitrogen oxides (ultimately from NO) by ferrous iron reduction, and the hydrothermal synthesis of compounds including the hydrocarboxylation/hydrocarbonylation reaction (in collaboration with George Cody), reactions of oxalate to form hydrocarbons and other oxygenated compounds and the formation of lipids from oxalic/formic acid (in collaboration with Tom McCollom), and reactions of carbon monoxide & carbon dioxide with N2, ammonia or nitritehitrate to form hydrogen cyanide, nitriles, ammonia/amines and nitrous

Summers, David P.↗
NASA NTRS1981

Low NO/x/ combustion systems for burning heavy residual fuels and high-fuel-bound nitrogen fuels

Design concepts are presented for lean-lean and staged rich-lean combustors. The combustors are designed for the dry reduction of thermal NO(x), control of NO(x) from fuels containing high levels of organic nitrogen, and control of smoke from low hydrogen content fuels. The combustor concepts are tested with a wide variety of fuels including a middle distillate, a petroleum based heavy residual, a coal derived synthetic, and ratios of blends of these fuels. The configurations of the lean-lean and rich-lean combustion systems are provided along with a description of the test rig and test procedure.

White, D. J.↗
NASA NTRS2021

Global Impact of COVID-19 Restrictions on the Atmospheric Concentrations of Nitrogen Dioxide and Ozone

Social-distancing to combat the COVID-19 pandemic has led to widespread reductions in air pollutant emissions. Quantifying these changes requires a business-as-usual counterfactual that accounts for the synoptic and seasonal variability of air pollutants. We use a machine learning algorithm driven by information from the NASA GEOS-CF model to assess changes in nitrogen dioxide (NO2) and ozone (O3) at 5,756 observation sites in countries from January through June 2020. Reductions in NO2 coincide with timing and intensity of COVID-19 restrictions, ranging from 60% in severely affected cities (e.g., Wuhan, Milan) to little change (e.g., Rio de Janeiro, Taipei). On average, NO2 concentrations were (13-23) % lower than business as usual from February 2020 onward. China experienced the earliest and steepest decline, but concentrations since April have mostly recovered and remained within 5% to the business-as-usual estimate. NO2 reductions in Europe and the US have been more gradual with a halting recovery starting in late March. We estimate that the global NOx (NO+NO2) emission reduction during the first 6 months of 2020 amounted to 3.1 (2.6-3.6) TgN, equivalent to 5.5(4.7-6.4) % of the annual anthropogenic total. The response of surface O3 is complicated by competing influences of non-linear atmospheric chemistry. While surface O3 increased by up to 50% in some locations, we find the overall net impact on daily average O3 between February -June 2020 to be small. However, our analysis indicates a flattening of the O3 diurnal cycle with an increase in nighttime ozone due to reduced titration and a decrease in daytime ozone, reflecting a reduction in photochemical production.

Christoph A Keller↗
NASA NTRS1984

Reductions in ozone at high concentrations of stratospheric halogens

An increase in the concentration of inorganic chlorine to levels comparable to that of oxidized reactive nitrogen could cause a significant change in the chemistry of the lower stratosphere leading to a reduction potentially larger than 15 percent in the column density of ozone. This could occur, for example by the middle of the next century, if emissions of man-made chlorocarbons were to grow at a rate of 3 percent per year. Ozone could be further depressed by release of industrial bromocarbon.

Prather, M. J.↗
NASA NTRS1992

Electric propulsion system technology

The work performed in fiscal year (FY) 1991 under the Propulsion Technology Program RTOP (Research and Technology Objectives and Plans) No. (55) 506-42-31 for Low-Thrust Primary and Auxiliary Propulsion technology development is described. The objectives of this work fall under two broad categories. The first of these deals with the development of ion engines for primary propulsion in support of solar system exploration. The second with the advancement of steady-state magnetoplasmadynamic (MPD) thruster technology at 100 kW to multimegawatt input power levels. The major technology issues for ion propulsion are demonstration of adequate engine life at the 5 to 10 kW power level and scaling ion engines to power levels of tens to hundreds of kilowatts. Tests of a new technique in which the decelerator grid of a three-grid ion accelerator system is biased negative of neutralizer common potential in order to collect facility induced charge-exchange ions are described. These tests indicate that this SAND (Screen, Accelerator, Negative Decelerator) configuration may enable long duration ion engine endurance tests to be performed at vacuum chamber pressures an order of magnitude higher than previously possible. The corresponding reduction in pumping speed requirements enables endurance tests of 10 kW class ion engines to be performed within the resources of existing technology programs. The results of a successful 5,000-hr endurance of a xenon hollow cathode operating at an emission current of 25 A are described, as well as the initial tests of hollow cathodes operating on a mixture of argon and 3 percent nitrogen. Work performed on the development of carbon/carbon grids, a multi-orifice hollow cathode, and discharge chamber erosion reduction through the addition of nitrogen are also described. Critical applied-field MPD thruster technical issues remain to be resolved, including demonstration of reliable steady-state operation at input powers of hundreds to thousands of kilowatts, achievement of thruster efficiency and specific impulse levels required for missions of interest, and demonstration of adequate engine life at these input power, efficiency, and specific impulse levels. To address these issues we have designed, built, and tested a 100 kW class, radiation-cooled applied-field MPD thruster and a unique dual-beam thrust stand that enables separate measurements of the applied- and self-field thrust components. We have also initiated the development of cathode thermal and plasma sheath models that will eventually be used to guide the experimental program. In conjunction with the cathode modeling, a new cathode test facility is being constructed. This facility will support the study of cathode thermal behavior and erosion mechanisms, the diagnosis of the near-cathode plasma and the development and endurance testing of new, high-current cathode designs. To facilitate understanding of electrode surface phenomenon, we have implemented a telephoto technique to obtain photographs of the electrodes during engine operation. In order to reduce the background vacuum tank pressure during steady-state engine operation in order to obtain high fidelity anode thermal data, we have developed and are evaluating a gas-dynamic diffuser. A review of experience with alkali metal propellants for MPD thrusters led to the conclusion that alkali metals, particularly lithium, offer the potential for significant engine performance and lifetime improvements. These propellants are also condensible at room temperature, substantially reducing test facility pumping requirements. The most significant systems-level issue is the potential for spacecraft contamination. Subsequent experimental and theoretical efforts should be directed toward verifying the performance and lifetime gains and characterizing the thruster flow field to assess its impact on spacecraft surfaces. Consequently, we have begun the design and development of a new facility to study engine operation with alkali metal propellants.

Brophy, John R.↗
NASA NTRS1972

Pollution measurements of a swirl-can combustor

Pollutant levels of oxides of nitrogen, unburned hydrocarbons, and carbon monoxide were measured for an experimental, annular, swirl can combustor. The combustor was 42 inches in diameter, incorporated 120 modules, and was specifically designed for elevated exit temperature performance. Test conditions included combustor inlet temperatures of 600, 900 and 1050 F, inlet pressures of 5 to 6 atmospheres, reference velocities of 69 to 120 feet per second and fuel-air ratios of 0.014 to 0.0695. Tests were also conducted at a simulated engine idle condition. Results demonstrated that swirl can combustors produce oxides of nitrogen levels substantially lower than conventional combustor designs. These reductions are attributed to reduced dwell times resulting from short combustor length, quick mixing of combustion gases with diluent air, and to uniform fuel distributions resulting from the swirl can approach. Radial staging of fuel at idle conditions resulted in increases in combustion efficiencies and corresponding reductions in pollutant levels.

Niedzwiecki, R. W.↗
NASA NTRS1980

Projected noise in submillimeter-wave mixers with InSb Schottky diodes

The reduction of the equivalent noise temperature in liquid-nitrogen-cooled submillimeter-wave mixers by the use of Schottky barriers on InSb instead of GaAs is evaluated by an analytical model that assumes limited local oscillator power and matched impedances. The calculations, executed at 1.0 and 1.8 THz, take plasma resonance and skin effect into account. For single and multiple contacts on homogeneous semiconductor materials of optimum doping, the noise of InSb diodes is smaller than that of GaAs diodes by a factor of 3 to 14. A simplified model is used to predict the performance of epitaxial structures as well as alternative materials.

Lieneweg, U.↗