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NASA NTRS1975

International Symposium on Combustion, 15th, Tokyo, Japan, August 25-31, 1974, Proceedings

Recent theoretical and experimental studies concerned with detonation and pressure wave combustion interaction, fire and explosion research and safety, heterogeneous combustion, flame-flow interactions, kinetics of elementary reactions, pollution control in and by combustion systems, and ignition are presented. Some of the topics covered include critical power density for direct initiation of unconfined gaseous detonations, extinction of laminar diffusion flames for liquid fuels, combustion of bulk titanium in oxygen, flame propagation in small spheres of unconfined and slightly confined flammable mixtures, kinetics of the reaction of nitric oxide with hydrogen, production of chemi-ions and formation of CH and CH2 radicals in methane-oxygen and ethylene-oxygen flames, NOx emission characteristics in two-stage combustion, and spherical ignition of oxyhydrogen behind a reflected shock wave. Individual items are announced in this issue.

Source record↗
NASA NTRS2013

Aerospace Fuels From Nonpetroleum Raw Materials

Recycling human metabolic and plastic wastes minimizes cost and increases efficiency by reducing the need to transport consumables and return trash, respectively, from orbit to support a space station crew. If the much larger costs of transporting consumables to the Moon and beyond are taken into account, developing waste recycling technologies becomes imperative and possibly mission enabling. Reduction of terrestrial waste streams while producing energy and/or valuable raw materials is an opportunity being realized by a new generation of visionary entrepreneurs; several relevant technologies are briefly compared, contrasted and assessed for space applications. A two-step approach to nonpetroleum raw materials utilization is presented; the first step involves production of supply or producer gas. This is akin to synthesis gas containing carbon oxides, hydrogen, and simple hydrocarbons. The second step involves production of fuel via the Sabatier process, a methanation reaction, or another gas-to-liquid technology, typically Fischer-Tropsch processing. Optimization to enhance the fraction of product stream relevant to transportation fuels via catalytic (process) development at NASA Glenn Research Center is described. Energy utilization is a concern for production of fuels whether for operation on the lunar or Martian surface, or beyond. The term green relates to not only mitigating excess carbon release but also to the efficiency of energy usage. For space, energy usage can be an essential concern. Another issue of great concern is minimizing impurities in the product stream(s), especially those that are potential health risks and/or could degrade operations through catalyst poisoning or equipment damage; technologies being developed to remove heteroatom impurities are discussed. Alternative technologies to utilize waste fluids, such as a propulsion option called the resistojet, are discussed. The resistojet is an electric propulsion technology with a powered thruster to vaporize and heat a propellant to high temperature, hot gases are subsequently passed through a converging-diverging nozzle expanding gases to supersonic velocities. A resistojet can accommodate many different fluids, including various reaction chamber (by-)products.

Palaszewski, Bryan A.↗
NASA NTRS2013

Aerospace Fuels from Nonpetroleum Raw Materials

Recycling human metabolic and plastic wastes minimizes cost and increases efficiency by reducing the need to transport consumables and return trash, respectively, from orbit to support a space station crew. If the much larger costs of transporting consumables to the Moon and beyond are taken into account, developing waste recycling technologies becomes imperative and possibly mission enabling. Reduction of terrestrial waste streams while producing energy and/or valuable raw materials is an opportunity being realized by a new generation of visionary entrepreneurs; several relevant technologies are briefly compared, contrasted and assessed for space applications. A two-step approach to nonpetroleum raw materials utilization is presented; the first step involves production of supply or producer gas. This is akin to synthesis gas containing carbon oxides, hydrogen, and simple hydrocarbons. The second step involves production of fuel via the Sabatier process, a methanation reaction, or another gas-to-liquid technology, typically Fischer- Tropsch processing. Optimization to enhance the fraction of product stream relevant to transportation fuels via catalytic (process) development at NASA GRC is described. Energy utilization is a concern for production of fuels whether for operation on the lunar or Martian surface, or beyond. The term "green" relates to not only mitigating excess carbon release but also to the efficiency of energy usage. For space, energy usage can be an essential concern. Other issues of great concern include minimizing impurities in the product stream(s), especially those that are potential health risks and/or could de-grade operations through catalyst poisoning or equipment damage; technologies being developed to remove heteroatom impurities are discussed. Alternative technologies to utilize waste fluids, such as a propulsion option called the resistojet, are discussed. The resistojet is an electric propulsion technology with a powered thruster to vaporize and heat a propellant to high temperature, hot gases are subsequently passed through a converging-diverging nozzle expanding gases to supersonic velocities. A resistojet can accommodate many different fluids, including various reaction chamber (by-)products.

Palaszewski, B. A.↗
NASA NTRS2017

Quantifying the Causes of Differences in Tropospheric OH Within Global Models

The hydroxyl radical (OH) is the primary daytime oxidant in the troposphere and provides the main loss mechanism for many pollutants and greenhouse gases, including methane (CH4). Global mean tropospheric OH differs by as much as 80% among various global models, for reasons that are not well understood. We use neural networks (NNs), trained using archived output from eight chemical transport models (CTMs) that participated in the Polar Study using Aircraft, Remote Sensing, Surface Measurements and Models, of Climate, Chemistry, Aerosols and Transport Model Intercomparison Project (POLMIP), to quantify the factors responsible for differences in tropospheric OH and resulting CH4 lifetime (Tau CH4) between these models. Annual average Tau CH4, for loss by OH only, ranges from 8.0 to 11.6 years for the eight POLMIP CTMs. The factors driving these differences were quantified by inputting 3-D chemical fields from one CTM into the trained NN of another CTM. Across all CTMs, the largest mean differences in Tau CH4 (Delta Tau CH4) result from variations in chemical mechanisms (Delta Tau CH4 = 0.46 years), the photolysis frequency (J) of O3 yields O(D-1) (0.31 years), local O3 (0.30 years), and CO (0.23 years). The Delta Tau CH4 due to CTM differences in NO(x) (NO + NO2) is relatively low (0.17 years), although large regional variation in OH between the CTMs is attributed to NO(x). Differences in isoprene and J(NO2) have negligible overall effect on globally averaged tropospheric OH, although the extent of OH variations due to each factor depends on the model being examined. This study demonstrates that NNs can serve as a useful tool for quantifying why tropospheric OH varies between global models, provided that essential chemical fields are archived.

Surface Measurements and Models↗
NASA NTRS2015

Uncertainties in Isoprene Photochemistry and Emissions: Implications for the Oxidative Capacity of Past and Present Atmospheres and for Climate Forcing Agents

Current understanding of the factors controlling biogenic isoprene emissions and of the fate of isoprene oxidation products in the atmosphere has been evolving rapidly. We use a climate-biosphere-chemistry modeling framework to evaluate the sensitivity of estimates of the tropospheric oxidative capacity to uncertainties in isoprene emissions and photochemistry. Our work focuses on trends across two time horizons: from the Last Glacial Maximum (LGM, 21 000 years BP) to the preindustrial (1770s); and from the preindustrial to the present day (1990s). We find that different oxidants have different sensitivities to the uncertainties tested in this study, with OH being the most sensitive: changes in the global mean OH levels for the LGM-to-preindustrial transition range between -29 and +7, and those for the preindustrial-to-present day transition range between -8 and +17, across our simulations. Our results suggest that the observed glacial-interglacial variability in atmospheric methane concentrations is predominantly driven by changes in methane sources as opposed to changes in OH, the primary methane sink. However, the magnitudes of change are subject to uncertainties in the past isoprene global burdens, as are estimates of the change in the global burden of secondary organic aerosol (SOA) relative to the preindustrial. We show that the linear relationship between tropospheric mean OH and tropospheric mean ozone photolysis rates, water vapor, and total emissions of NOx and reactive carbon first reported in Murray et al. (2014) does not hold across all periods with the new isoprene photochemistry mechanism. Our results demonstrate that inadequacies in our understanding of present-day OH and its controlling factors must be addressed in order to improve model estimates of the oxidative capacity of past and present atmospheres.

methane↗
NASA NTRS2016

The Description and Validation of a Computationally-Efficient CH4-CO-OH (ECCOH) Module for 3D Model Applications

We present the Efficient CH4-CO-OH Module (ECCOH) that allows for the simulation of the methane, carbon monoxide and hydroxyl radical (CH4-CO-OH cycle, within a chemistry climate model, carbon cycle model, or earth system model. The computational efficiency of the module allows many multi-decadal, sensitivity simulations of the CH4-CO-OH cycle, which primarily determines the global tropospheric oxidizing capacity. This capability is important for capturing the nonlinear feedbacks of the CH4-CO-OH system and understanding the perturbations to relatively long-lived methane and the concomitant impacts on climate. We implemented the ECCOH module into the NASA GEOS-5 Atmospheric Global Circulation Model (AGCM), performed multiple sensitivity simulations of the CH4-CO-OH system over two decades, and evaluated the model output with surface and satellite datasets of methane and CO. The favorable comparison of output from the ECCOH module (as configured in the GEOS-5 AGCM) with observations demonstrates the fidelity of the module for use in scientific research.

Remote Sensing↗
NASA NTRS2009

Determination of Chemical Kinetic Rate Constants of a Model for Carbothermal Processing of Lunar Regolith Simulant Using Methane

We have previously developed a chemical conversion model of the carbothermal processing of lunar regolith using methane to predict the rate of production of carbon monoxide. In this carbothermal process, gaseous methane is pyrolyzed as it flows over the hot surface of a molten zone of lunar regolith and is converted to carbon and hydrogen. Hydrogen is carried away by the exiting stream of gases and carbon is deposited on the melt surface. The deposited carbon mixes with the melt and reacts with the metal oxides in it to produce carbon monoxide that bubbles out of the melt. In our model, we assume that the flux of carbon deposited is equal to the product of the surface reaction rate constant gamma and the concentration of methane adjacent to the melt surface. Similarly, the rate of consumption of carbon per unit volume in the melt is equal to the product of the melt reaction rate constant k and the concentrations of carbon and metal oxide in the melt. In this paper, we describe our effort to determine gamma and k by comparison of the predictions from our model with test data obtained by ORBITEC (Orbital Technologies Corporation). The concentration of methane adjacent to the melt surface is a necessary input to the model. It is inferred from the test data by a mass balance of methane, adopting the usual assumptions of the continuously-stirred-tank-reactor model, whereby the average concentration of a given gaseous species equals its exit concentration. The reaction rates gamma and k have been determined by a non-linear least-squares fit to the test data for the production of carbon monoxide and the fraction of the incoming methane that is converted. The comparison of test data with our model predictions using the determined chemical kinetic rate constants provides a consistent interpretation of the process over the full range of temperatures, pressures, and methane flow rates used in the tests, thereby increasing our confidence to use the model for scale-up purposes.

Balasubramaniam, R↗
NASA NTRS1996

Effect of chemistry and turbulence on NO formation in oxygen-natural gas flames

The effects of chemistry and turbulence on NO formation in oxygen-natural turbulent diffusion flames gas flames have been investigated. The chemistry of nitric oxides has been studied numerically in the counterflow configuration. Systematic calculations with the GRI 2.11 mechanism for combustion of methane and NO chemistry were conducted to provide a base case. It was shown that the 'simple' Zeldovich mechanism accounts for more than 75% of N2 consumption in the flame in a range of strain-rates varying between 10 and 1000 s-l. The main shortcomings of this mechanism are: 1) overestimation (15%) of the NO production rate at low strain-rates because it does not capture the reburn due to the hydrocarbon chemistry, and 2) underestimation (25%) of the NO production rate at high strainrates because it ignores NO production through the prompt mechanism. Reburn through the Zeldovich mechanism alone proves to be significant at low strain-rates. A one-step model based on the Zeldovich mechanism and including reburn has been developed. It shows good agreement with the GRI mechanism at low strain-rates but underestimates significantly N2 consumption (about 50%) at high strain-rates. The role of turbulence has been assessed by using an existing 3-D DNS data base of a diffusion flame in decaying turbulence. Two PDF closure models used in practical industrial codes for turbulent NO formation have been tested. A simpler version of the global one-step chemical scheme for NO compared to that developed in this study was used to test the closure assumptions of the PDF models, because the data base could not provide all the necessary ingredients. Despite this simplification, it was possible to demonstrate that the current PDF models for NO overestimate significantly the NO production rate due to the fact that they neglect the correlations between the fluctuations in oxygen concentration and temperature. A single scalar PDF model for temperature that accounts for such correlations based on laminar flame considerations has been developed and showed excellent agreement with the values given by the DNS.

Samaniego, J. -M.↗
NASA NTRS2000

Reduced Gas Cycling in Microbial Mats: Implications for Early Earth

For more than half the history of life on Earth, biological productivity was dominated by photosynthetic microbial mats. During this time, mats served as the preeminent biological influence on earth's surface and atmospheric chemistry and also as the primary crucible for microbial evolution. We find that modern analogs of these ancient mat communities generate substantial quantities of hydrogen, carbon monoxide, and methane. Escape of these gases from the biosphere would contribute strongly to atmospheric evolution and potentially to the net oxidation of earth's surface; sequestration within the biosphere carries equally important implications for the structure, function, and evolution of anaerobic microbial communities within the context of mat biology.

Hoehler, Tori M.↗
NASA NTRS1999

Portable fiber-coupled diode-laser-based sensor for multiple trace gas detection

Tunable narrowband mid-infrared radiation from 3.25 to 4.4 micrometers is generated by a compact fiber-coupled, difference-frequency-based spectroscopic source. A 20-mW external cavity diode laser (with a tuning range from 814 to 870 nm) and a 50-mW distributed-Bragg-reflector diode-laser-seeded ytterbium-doped fiber amplifier operating at 1083 nm are difference-frequency mixed in a multi-grating, temperature-controlled periodically poled LiNbO3 crystal. A conversion efficiency of 0.44 mW/(W2cm) (corresponding to a power of approximately equal to 3 microW at 3.3 micrometers) represents the highest conversion efficiency reported for a portable device. Performance characteristics of such a sensor and its application to spectroscopic detection of CO2, N2O, H2CO, HCl, NO2, and CH4 will be reported in this work.

Non-NASA Center↗
NASA NTRS2007

Methylhopane Biomarker and Carbon Isotopic Evidence for Late Archean Aerobic Ecosystems

Molecular fossils are particularly valuable in early Earth studies because they provide information about microbial sources and ecology. Here we report on the distribution of 2- methyl and 3-methylhopanes preserved in a 2.72-2.56 billion-year-old section of shallow and deepwater sediments of the Hamersley Province [Eigenbrode et aI., submitted]. These biomarkers are mostly from cyanobacteria and oxygen-respiring methanotrophs, respectively. The relative abundance of 2-methylhopanes increases with carbonate abundance in shallow-water facies indicating cyanobacteria were key microbes in shallow ecosystems and suggesting they supplied both molecular oxygen and fixed carbon. The relative abundance of 3-methylhopane strongly correlates with kerogen-carbon isotopic values, and is more abundant in the samples with 13C-enriched signatures. Thus, molecular data provides evidence for cycling of methane in shallow settings, even though the anoxic deeper environments bear stronger 13C-depletion, which together suggests a more complex methane cycle than previously envisioned. Detailed facies analysis of the Hamersley carbon-isotope record reveals temporal changes suggesting continued oxidation of shallow settings favoring the expansion of aerobic ecosystems and respiring organisms [Eigenbrode et aI., 2006, PNAS, 103: 15759]. Similar analysis of published carbon-isotopic records suggests similar, but diachronous, expansion of oxygenated habitats in shallow then deep waters as anaerobic microbial communities gave way to respiring communities fueled by oxygenic photosynthesis before the post 2.45-Ga atmospheric oxygenation event [Eigenbrode et aI., 2006]. The robust relationships observed provide geochemical support for methanogenesis, aerobic methanotrophy, and oxygenic photosynthesis in the late Archean, as well as major ecological shifts linked to biogeochemical reorganization.

Eigenbrode, Jennifer L.↗
NASA NTRS2016

Lightning NOx and Impacts on Air Quality

Lightning generates relatively large but uncertain quantities of nitrogen oxides, critical precursors for ozone and hydroxyl radical (OH), the primary tropospheric oxidants. Lightning nitrogen oxide strongly influences background ozone and OH due to high ozone production efficiencies in the free troposphere, effecting small but non-negligible contributions to surface pollutant concentrations. Lightning globally contributes 3-4 ppbv of simulated annual-mean policy-relevant background (PRB) surface ozone, comprised of local, regional, and hemispheric components, and up to 18 ppbv during individual events. Feedbacks via methane may counter some of these effects on decadal time scales. Lightning contributes approximately 1 percent to annual-mean surface particulate matter, as a direct precursor and by promoting faster oxidation of other precursors. Lightning also ignites wildfires and contributes to nitrogen deposition. Urban pollution influences lightning itself, with implications for regional lightning-nitrogen oxide production and feedbacks on downwind surface pollution. How lightning emissions will change in a warming world remains uncertain.

Reactive nitrogen oxides↗
NASA NTRS1981

Io - Thermal models and chemical evolution

A combined thermal and chemical evolution model of Io is presented, outlining limits on the possible starting materials, heating history, chemical history, and present state of Io. Our best scenario starts with Io being accreted from material in a proto-Jovian nebula which condensed between 400-600 K. Radionuclides and tidal heating would lead to large-scale convection within Io and chemical reactions leading to the outgassing of water and methane. Reactions between Fe(0)-FeS and water, at least near the surface, go to completion, resulting in all Fe being oxidized with elemental sulfur producing a low-conductivity crust. In the deep interior, these reactions may not completely exhaust Fe metal, and an FeS-rich core may be formed.

Consolmagno, G. J.↗
NASA NTRS1987

On the sputter alteration of regoliths of outer solar system bodies

Several processes that are expected to occur when the porous regoliths of outer solar system bodies (without atmospheres) are subjected to energetic ion bombardment are discussed. The conclusions reached in much of the literature addressing sputtering are quantitatively or qualitatively incorrect because effects of soil porosity have been neglected. It is shown theoretically and experimentally that porosity reduces the effective sputtering yield of a soil by more than an order of magnitude. Between 90 and 97% of the sputtered atoms are trapped within the regolith, where they are factionated by differential desorption. Experiments indicate that more volatile species have higher desorption probabilities. This process is the most important way in which alteration of chemical and optical properties occurs when a regolith is sputtered. When a basic silicate soil is irradiated these effects lead to sputter-deposited films enriched in metallic iron, while O, Na and K are preferentially lost. The Na and K are present in the atmosphere above the sputtered silicate in quantities much greater than their abundances in the regolith. Icy regoliths of SO2 should be enriched in elemental S and/or S2O. This prediction is supported by the probable identification of S2O and polysulfur oxide bands in the IR spectra of H-sputtered SO2 reported by Moore. When porous mixtures of water, ammonia and methane frosts are sputtered, the loss of H and surface reactions of C, N and O in the deposits should produce complex hydrocarbons and carbohydrates, some of which may be quite dark. Such reactions may have played a role in the formation of the matrix material of carbonaceous chondrites prior to agglomeration.

Hapke, Bruce↗
NASA NTRS2005

Preliminary System Analysis of In Situ Resource Utilization for Mars Human Exploration

We carried out a system analysis of processes for utilization of Mars resources to support human exploration of Mars by production of propellants from indigenous resources. Seven ISRU processes were analyzed to determine mass. power and propellant storage volume requirements. The major elements of each process include C02 acquisition, chemical conversion, and storage of propellants. Based on a figure of merit (the ratio of the mass of propellants that must be brought from Earth in a non-ISRU mission to the mass of the ISRU system. tanks and feedstocks that must be brought from Earth for a ISRU mission) the most attractive process (by far); is one where indigenous Mars water is accessible and this is processed via Sabatier/Electrolysis to methane and oxygen. These processes are technically relatively mature. Other processes with positive leverage involve reverse water gas shift and solid oxide electrolysis.

Mars↗
NASA NTRS2001

Biogenic Methane and the Rise of Oxygen

Oxygenic photosynthesis does not make the rise of oxygen inevitable. What is required is that reductant and oxygen be separated and permanently segregated. The usual picture for Earth is that oxygenic photosynthesis split CO2 into carbon and oxygen, with the carbon buried in sediments and the oxygen mostly taken up by oxides of iron and sulfur. The relatively small atmospheric reservoir of O2 is regulated by the carbon burial rate, reaction with volcanic and metamorphic gases, and oxidation of reduced carbon released as old sediments weather. Absent from this picture is a distinction between the Archean and modern times: on average, carbon burial fluxes would have been matched by oxygen losses then as now. Separation of reductant from oxidant is only provisional. No net oxidation of the continents occurs, and so no change of diagenetic, metamorphic, or volcanic gases is expected. Nor would any change in oxidative weathering be expected. Something more than carbon burial is required to make the Archean different. The escape of hydrogen to space permanently separates the reductant from the oxidant. Hydrogen escape is widely believed to have led to the present highly oxidized states of Mars and Venus. Hydrogen escape has usually been thought small for Archaean Earth, because water vapor is cold-trapped at the troposphere and thus held to levels of a few ppmv in the stratosphere. This cold trapping renders hydrogen escape negligible. However, methane is not cold trapped, and its expected abundance in the Archaean, given low oxygen levels and a biogenic source, would have been high, probably more than 100 times present. At such levels methane would have driven geologically significant levels of hydrogen escape. Additional information is contained in the original extended abstract.

Catling, David↗
NASA NTRS2001

The Behavior of Methane-Air Partially Premixed Flames Under Normal- and Zero-G Conditions

Partially premixed flames (PPFs) represent a class of hybrid flames containing multiple reaction zones. These flames are established when less than stoichiometric quantity of oxidizer is molecularly mixed with the fuel stream before entering the reaction zone where additional oxidizer is available for complete combustion. This mode of combustion can be used to exploit the advantages of both nonpremixed and premixed flames regarding operational safety, lower pollutant emissions and flame stabilization. A double flame containing a fuel-rich premixed reaction zone, which is anchored by a nonpremixed reaction zone, is one example of a partially premixed flame. A triple flame is also a PPF that contains three reaction zones, namely, a fuel-rich premixed zone, a fuel-lean premixed zone, and a nonpremixed reaction zone. Herein we focus on two aspects of our investigation, one involving the development of optical diagnostics that can be used on a microgravity rig, which has been recently fabricated, and the other on the numerically predicted differences between normal- and zero-gravity PPFs. Both the measurements and simulations examine the detailed structure of methane-air PPFs stabilized on a Wolfhard-Parker slot burner.

Puri, Ishwar K.↗
NASA NTRS2014

Development of a Two-Stage Mars Ascent Vehicle Using In-Situ Propellant Production

Mars Sample Return (MSR) and Mars In-Situ Resource Utilization (ISRU) present two main challenges for the advancement of Mars science. MSR would demonstrate Mars lift-off capability, while ISRU would test the ability to produce fuel and oxidizer using Martian resources, a crucial step for future human missions. A two-stage Mars Ascent Vehicle (MAV) concept was developed to support sample return as well as in-situ propellant production. The MAV would be powered by a solid rocket first stage and a LOX-propane second stage. A liquid second-stage provides higher orbit insertion reliability than a solid second stage as well as a degree of complexity eventually required for manned missions. Propane in particular offers comparable performance to methane without requiring cryogenic storage. The total MAV mass would be 119.9 kg to carry an 11 kg payload to orbit. The feasibility of in-situ fuel and oxidizer production was also examined. Two potential schemes were evaluated for production capability, size and power requirements. The schemes examined utilize CO2 and water as starting blocks to produce LOX and a propane blend. The infrastructure required to fuel and launch the MAV was also explored.

Paxton, Laurel↗