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NASA NTRS2021

Extreme Ozone Loss Following Nuclear War Results in Enhanced Surface Ultraviolet Radiation

For the first time, we use a modern climate model with interactive chemistry including the effects of aerosols on photolysis rates to simulate the consequences of regional and global scale nuclear wars (injecting 5 and 150 Tg of soot respectively) for the ozone layer and surface ultraviolet (UV) light. For a global nuclear war, heating in the stratosphere, reduced photolysis, and an increase in catalytic loss from the Hox cycle cause a 15 year-long reduction in the ozone column, with a peak loss of 75% globally and 65% in the tropics. This is larger than predictions from the 1980s, which assumed large injections of nitrogen oxides (NOx),but did not include the effects of smoke. NOx from the fireball and the fires provide a small (5%) Increase to the global average ozone loss for the first few years. Initially, soot would shield the surface from UV-B, but UV Index values would become extreme: greater than 35in the tropics for 4years, and greater than 45during the summer in the southern polar regions for 3 years. For a regional war, global column ozone would be reduced by 25% with recovery taking 12 years. This is similar to previous simulations, but with a faster recovery time due to a shorter lifetime for soot in our simulations. In-line photolysis provides process specific action spectra enabling future integration with biogeochemistry models and allows output that quantifies the potential health impacts from changes in surface UV for this and other larger aerosol injections.

nuclear war↗

NASA NTRS2005

Bifunctional catalytic electrode

The present invention relates to an oxygen electrode for a unitized regenerative hydrogen-oxygen fuel cell and the unitized regenerative fuel cell having the oxygen electrode. The oxygen electrode contains components electrocatalytically active for the evolution of oxygen from water and the reduction of oxygen to water, and has a structure that supports the flow of both water and gases between the catalytically active surface and a flow field or electrode chamber for bulk flow of the fluids. The electrode has an electrocatalyst layer and a diffusion backing layer interspersed with hydrophilic and hydrophobic regions. The diffusion backing layer consists of a metal core having gas diffusion structures bonded to the metal core.

Cisar, Alan↗

NASA NTRS1972

Bosch CO2 reduction unit research and development.

Development of Bosch CO2 reduction units for manned spacecraft application has been in progress for a decade. The Bosch process catalytically reacts CO2 with H2 to produce water and carbon. The water may then be electrolyzed to close the biological oxygen and process hydrogen loops. A critical problem has been to confine the reaction so that carbon does not block flow and stop the process. Reaction isolation within a replaceable catalyst cartridge has been successfully demonstrated. Objectives of the current development program are a 25% reduction in operating power, an 80% reduction in expendable weight, and minimized resupply volume.

Holmes, R. F.↗

NASA NTRS2014

CO2 Reduction Assembly Prototype Using Microlith-Based Sabatier Reactor for Ground Demonstration

The utilization of CO2 to produce life support consumables, such as O2 and H2O, via the Sabatier reaction is an important aspect of NASA's cabin Atmosphere Revitalization System (ARS) and In-Situ Resource Utilization (ISRU) architectures for both low-earth orbit and long-term manned space missions. Carbon dioxide can be reacted with H2, obtained from the electrolysis of water, via Sabatier reaction to produce methane and H2O. Methane can be stored and utilized as propellant while H2O can be either stored or electrolyzed to produce oxygen and regain the hydrogen atoms. Depending on the application, O2 can be used to replenish the atmosphere in human-crewed missions or as an oxidant for robotic and return missions. Precision Combustion, Inc. (PCI), with support from NASA, has previously developed an efficient and compact Sabatier reactor based on its Microlith® catalytic technology and demonstrated the capability to achieve high CO2 conversion and CH4 selectivity (i.e., ≥90% of the thermodynamic equilibrium values) at high space velocities and low operating temperatures. This was made possible through the use of high-heat-transfer and high-surface-area Microlith catalytic substrates. Using this Sabatier reactor, PCI designed, developed, and demonstrated a stand-alone CO2 Reduction Assembly (CRA) test system for ground demonstration and performance validation. The Sabatier reactor was integrated with the necessary balance-of-plant components and controls system, allowing an automated, single "push-button" start-up and shutdown. Additionally, the versatility of the test system prototype was demonstrated by operating it under H2-rich (H2/CO2 of >4), stoichiometric (ratio of 4), and CO2-rich conditions (ratio of <4) without affecting its performance and meeting the equilibrium-predicted water recovery rates. In this paper, the development of the CRA test system for ground demonstration will be discussed. Additionally, the performance results from testing the system at various operating conditions and the results from durability testing will be presented.

Junaedi, Christian↗

NASA NTRS1974

Development of integrated, zero-G pneumatic transporter/rotating paddle incinerator/catalytic afterburner subsystem for processing human wastes on board spacecraft

A four component system was developed which consists of a particle size reduction mechanism, a pneumatic waste transport system, a rotating-paddle incinerator, and a catalytic afterburner to be integrated into a six-man, zero-g subsystem for processing human wastes on board spacecraft. The study included the development of different concepts or functions, the establishment of operational specifications, and a critical evaluation for each of the four components. A series of laboratory tests was run, and a baseline subsystem design was established. An operational specification was also written in preparation for detailed design and testing of this baseline subsystem.

Fields, S. F.↗

NASA NTRS1977

Nickel-copper-zirconium alloy for catalytic creactors

Catalytic and improved mechanical properties of alloy indicate its potential use as catalyst for reduction of nitrogen oxide from internal combustion engines.

Whittenberger, J. D.↗

NASA NTRS1981

Gasification of carbon fiber composites for the alleviation of electrical hazards

A mixture of calcium acetate and lithium acetate applied to the surface of carbon fibers caused the fibers to gasify in a simulated airplane-crash fire. Tests conducted with a JPL-developed electrical detector showed the catalyst-modified composites to release few fibers during burning, while state-of-the-art composites released several hundred. Mechanical property tests demonstrated nearly identical behavior of catalyst-modified and state-of-the-art composites. Aging tests also showed little difference in the composite strength except for a severe reduction when soaked in water. Several promising new concepts resulted from the project, including catalytic elimination of carbon particulates from diesel exhaust, catalytic improvement of coal combustion, and electrical destruction of carbon particulates in combustion systems.

Hull, G.↗

NASA NTRS2014

Visible-Light-Responsive Catalysts Using Quantum Dot-Modified TiO2 for Air and Water Purification

Photocatalysis, the oxidation or reduction of contaminants by light-activated catalysts, utilizing titanium dioxide (TiO2) as the catalytic substrate has been widely studied for trace contaminant control in both air and water applications. The interest in this process is due primarily to its low energy consumption and capacity for catalyst regeneration. Titanium dioxide requires ultraviolet light for activation due to its relatively large band gap energy of 3.2 eV. Traditionally, Hg-vapor fluorescent light sources are used in PCO reactors; however, the use of mercury precludes the use of this PCO technology in a spaceflight environment due to concerns over crew Hg exposure. The development of a visible-light responsive (VLR) TiO2-based catalyst would eliminate the concerns over mercury contamination. Further, VLR development would allow for the use of ambient visible solar radiation or highly efficient LEDs, both of which would make PCO approaches more efficient, flexible, economical, and safe. Though VLR catalyst development has been an active area of research for the past two decades, there are few commercially available VLR catalysts. Those VLR catalysts that are commercially available do not have adequate catalytic activity, in the visible region, to make them competitive with those operating under UV irradiation. This study was initiated to develop more effective VLR catalysts through a novel method in which quantum dots (QD) consisting of narrow band gap semiconductors (e.g., CdS, CdSe, PbS, ZnSe, etc.) are coupled to TiO2 via two preparation methods: 1) photodeposition and 2) mechanical alloying using a high-speed ball mill. A library of catalysts was developed and screened for gas and aqueous phase applications using ethanol and 4-chlorophenol as the target contaminants, respectively. Both target compounds are well studied in photocatalytic systems and served as model contaminants for this research. Synthesized catalysts were compared in terms of preparation method, nature of the quantum dots, and dosage of quantum dots.

visible light↗

NASA NTRS2014

Visible-Light Responsive Catalysts Using Quantum Dot-Modified TiO2 for Air and Water Purification

visible light↗

NASA NTRS2003

Structural Basis for Flip-Flop Action of Thiamin Pyrophosphate-dependent Enzymes Revealed by Human Pyruvate Dehydrogenase

The derivative of vitamin B1, thiamin pyrophosphate, is a cofactor of enzymes performing catalysis in pathways of energy production. In alpha (sub 2) beta (sub 2)-heterotetrameric human pyruvate dehydrogenase, this cofactor is used to cleave the C(sup alpha) -C(=O) bond of pyruvate followed by reductive acetyl transfer to lipoyl-dihydrolipoamide acetyltransferase. The dynamic nonequivalence of two, otherwise chemically equivalent, catalytic sites has not yet been understood. To understand the mechanism of action of this enzyme, we determined the crystal structure of the holo-form of human pyruvate dehydrogenase at 1.95-Angstrom resolution. We propose a model for the flip-flop action of this enzyme through a concerted approximately 2-Angstrom shuttle-like motion of its heterodimers. Similarity of thiamin pyrophosphate binding in human pyruvate dehydrogenase with functionally related enzymes suggests that this newly defined shuttle-like motion of domains is common to the family of thiamin pyrophosphate-dependent enzymes.

Ciszak, Ewa M.↗

NASA NTRS2016

Development of a Microwave Regenerative Sorbent-Based Hydrogen Purifier

This paper describes the design and fabrication of a Microwave Regenerative Sorbent-based Hydrogen Purifier (MRSHP). This unique microwave powered technology was developed for the purification of a hydrogen stream produced by the Plasma Pyrolysis Assembly (PPA). The PPA is a hydrogen recovery (from methane) post processor for NASA's Sabatier-based carbon dioxide reduction process. Embodied in the Carbon dioxide Reduction Assembly (CRA), currently aboard the International Space Station (ISS), the Sabatier reaction employs hydrogen to catalytically recover oxygen, in the form of water, from respiratory carbon dioxide produced by the crew. This same approach is base-lined for future service in the Air Revitalization system on extended missions into deep space where resupply is not practical. Accordingly, manned exploration to Mars may only become feasible with further closure of the air loop as afforded by the greater hydrogen recovery permitted by the PPA with subsequent hydrogen purification. By utilizing the well-known high sorbate loading capacity of molecular sieve 13x, coupled with microwave dielectric heating phenomenon, MRSHP technology is employed as a regenerative filter for a contaminated hydrogen gas stream. By design, freshly regenerated molecular sieve 13x contained in the MRSHP will remove contaminants from the effluent of a 1-CM scale PPA for several hours prior to breakthrough. By reversing flow and pulling a relative vacuum the MRSHP prototype then uses 2.45 GHz microwave power, applied through a novel coaxial antenna array, to rapidly heat the sorbent bed and drive off the contaminants in a short duration vacuum/thermal contaminant desorption step. Finally, following rapid cooling via room temperature cold plates, the MRSHP is again ready to serve as a hydrogen filter.

Wheeler, Richard R., Jr.↗

NASA NTRS2007

Oxygen Generation from Carbon Dioxide for Advanced Life Support

The partial electrochemical reduction of CO2 using ceramic oxygen generators (COGs) is well known and has been studied. Conventional COGs use yttria-stabilized zirconia (YSZ) electrolytes and operate at temperatures greater than 700 C (1, 2). Operating at a lower temperature has the advantage of reducing the mass of the ancillary components such as insulation. Moreover, complete reduction of metabolically produced CO2 (into carbon and oxygen) has the potential of reducing oxygen storage weight if the oxygen can be recovered. Recently, the University of Florida developed ceramic oxygen generators employing a bilayer electrolyte of gadolinia-doped ceria and erbia-stabilized bismuth oxide (ESB) for NASA s future exploration of Mars (3). The results showed that oxygen could be reliably produced from CO2 at temperatures as low as 400 C. These results indicate that this technology could be adapted to CO2 removal from a spacesuit and other applications in which CO2 removal is an issue. This strategy for CO2 removal in advanced life support systems employs a catalytic layer combined with a COG so that the CO2 is reduced completely to solid carbon and oxygen. First, to reduce the COG operating temperature, a thin, bilayer electrolyte was employed. Second, to promote full CO2 reduction while avoiding the problem of carbon deposition on the COG cathode, a catalytic carbon deposition layer was designed and the cathode utilized materials shown to be coke resistant. Third, a composite anode was used consisting of bismuth ruthenate (BRO) and ESB that has been shown to have high performance (4). The inset of figure 1 shows the conceptual design of the tubular COG and the rest of the figure shows schematically the test apparatus. Figure 2 shows the microstructure of a COG tube prior to testing. During testing, current is applied across the cell and initially CuO is reduced to copper metal by electrochemical pumping. Then the oxygen source becomes the CO/CO2. This presentation details the results of testing the COG.

Bishop, s. R.↗

NASA NTRS1984

Terrestrial nitrous oxide cycles and atmospheric effects

The basic processes that cause N2O emission from soils are briefly discussed, and the rate of the processes is shown to vary widely in space and time, depending on soil, climate, and agrotechnical conditions. Although significant amounts of N2O are indeed emitted from the land, the complexity of the soil processes involved and the wide variation of measured rates still prevents the quantitative evaluation, global budgeting, and reliable prediction of atmospheric N2O. Increased atmospheric N2O abundance increases the levels of odd-nitrogen in the stratosphere, which, in turn, decreases the stratospheric ozone density via a catalytic cycle. Using appropriate atmospheric models and current chemical kinetic data, it has been found that the dependence of ozone reduction on N2O increase is nearly linear; a simulated doubling of N2O leads to a predicted decrease of about 14 percent in total ozone column density. A 10 percent increase in N2O yields a predicted increase in nonmelanoma skin cancer of several percent, and a possible raising of surface temperature of 0.03 K.

Whitten, R. C.↗

NASA NTRS2005

Control of Effluent Gases from Solid Waste Processing Using Carbon Nanotubes

One of the major problems associated with solid waste processing technologies is the release of effluent gases and contaminants that are in gaseous formed from the processes. A number of other gases, in particular NO(x), SO2, NH3, Hydrocarbons (e.g. CH4) do present hazards to the crew in space habitats. Reduction of mass, power, volume and resupply can be achieved by using catalyst impregnated carbon nanotubes as compared to other catalytic systems. The development and characterization of an innovative approach for the control and elimination of gaseous toxins using single walled carbon nanotubes (SWNTs) promise superior performance over conventional approaches. This is due to the ability to direct the selective uptake of gaseous species based on their controllable pore size, high adsorptive capacity and the effectiveness of carbon nanotubes as catalyst supports for gaseous conversion. For example, SWNTs have high adsorptive capacity for NO and the adsorbed NO can be decomposed to N2 and O2 . Experimental results showing the decomposition of NO on metal impregnated carbon nanotubes is presented. Equivalent System Mass (ESM) comparisons are made of the existing TCCS systems with the carbon nanotube technology for removing NO(x). The potential for methane decomposition using carbon nanotubes catalysts is also discussed.

Fisher, John↗

NASA NTRS1976

A mature Bosch CO2 reduction technology

The reduction of CO2 is one of the steps in closing the oxygen loop for long-duration manned space missions. Several units utilizing the Bosch process, which catalytically reduces CO2 with hydrogen, have been built and operated during the past decade. Each contributed substantial information affecting subsequent designs. Early challenges were primarily concerned with carbon control, materials durability, and reliability of reaction initiation. These were followed by concern about power consumption, expendable weight, volume, and process rate control. Suitable materials and techniques for carbon containment and process reliability have been demonstrated. Power requirements have been reduced by almost an order of magnitude. Methods for significant reductions in expendable weight and volume have been developed. The technology is at a state of maturity directly applicable to designs for space missions.

King, C. D.↗

NASA NTRS2003

Structural Basis for Flip-Flop Action of Thiamin Pyrophosphate-Dependent Enzymes Revealed by Human Pyruvate Dehydrogenase

Thiamin pyrophosphate (TPP), the biologically active form of vitamin BI, is a cofactor of enzymes catalyzing reactions involving the cleavage of a carbon-carbon bond adjacent to an oxo group. TPP-dependent enzymes show a common mechanism of TPP activation by: (1) forming the ionic N-H...O(sup -) hydrogen bonding between the N1' atom of the aminopirymidine ring of the coenzyme and intrinsic gamma-carboxylate group of glutamate and (2) imposing an "active" V-conformation that brings the N4' atom of the aminopirymidine to the distance required for the intramolecular C-H.. .N hydrogen bonding with the thiazolium C2 atom. Within these two hydrogen bonds that rapidly exchange protons, protonation of the N1' atom is strictly coordinated with the deprotonation of the 4' -amino group and eventually abstraction of the proton from C2. The human pyruvate dehydrogenase Elp, component of human pyruvate dehydrogenase complex, catalyzes the irreversible decarboxylation of the pyruvate followed by the reductive acetylation of the lipoyl group of dihydrolipoyl acyltransferase. Elp is alpha(sub 2)beta(sub2)-heterotetrameric with a molecular mass of I54 kDa, which has two catalytic sites, each providing TPP and magnesium ion as cofactors and each formed on the interface between the PP and PYR domains. The dynamic nonequivalence of two otherwise chemically equivalent catalytic sites has been observed and the flip-flop mechanism was suggested, according to which two active sites affect each other and in which different steps of the catalytic reaction are performed in each of the sites at any given moment. Based on specific futures of human pyruvate dehydrogenase including rigid and flexible connections between domains that bind the cofactor we propose a mechanistic model for the flip-flop action of this enzyme. We postulate that the dynamic protein environment drives the exchange of tautomers in the 4' -aminopyrimidine ring of the cofactor through a concerted shuttl-like motion of tightly connected domains. The dynamic exchange of those tautomers, in turns, is required during the reactions of pyruvate decarboxylation and reductive acetylation of lipoamide. Thus the shuttle-like motion of the domains is coordinated with the reactions of decarboxylation and acetylation, which are carried out in each of the cofactor sites resulting in a flip-flop action of the enzyme. The structure-derived mechanism of action of human pyruvate dehydrogenase may be likely common for other TPP-dependent enzymes.

Dominiak, Paulina↗

NASA NTRSDate not supplied

Energetic Particles in Geospace: Origin, Dynamics, and Modeling

This presentation explores the origins and dynamics of energetic particles—specifically solar energetic particles (SEPs) and galactic cosmic rays (GCRs) - within the heliosphere and Earth's magnetosphere. We will discuss the fundamental physical processes governing their transport and acceleration in the heliosphere, including interactions with the solar wind and the interplanetary magnetic field. The penetration of these particles into Earth's magnetosphere is examined, emphasizing how the geomagnetic field influences their propagation across the magnetosphere. Key phenomena such as the temporal trapping of SEPs in geospace, reductions in rigidity cutoff during geomagnetic storms, and the enhancement of atmospheric NOx and HOx concentrations - which affect the ozone balance through catalytic reactions—are discussed. The presentation also outlines contemporary numerical modeling techniques used to simulate SEPs and GCRs, providing insights into their complex behaviors under varying geomagnetic conditions.

solar energetic particles↗

NASA NTRS1977

Solar proton event - Influence on stratospheric ozone

Large-scale reductions in the ozone content of the middle and upper stratosphere over the polar cap regions were associated with the major solar proton event of 4 August 1972. This reduction, which was determined from measurements with the backscattered ultraviolet experiment on the Nimbus 4 satellite, is interpreted as being due to the catalytic destruction of ozone by odd-nitrogen compounds (NOx) produced by the event.

Heath, D. F.↗