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All sourcesNASA NTRSDOE OSTI
NASA NTRS1977

Possible variations in atmospheric methane

A model coupling photochemistry and vertical transport in the troposphere has been used to investigate the magnitude of possible future perturbations to atmospheric CH4. The response of atmospheric CH4 to an increase in the concentration of CO or to a variation in stratospheric O3 is studied. Both of the above mechanisms, which could be caused by man's activities, arise because a change in the concentration of tropospheric OH will lead to a change in the CH4 abundance. The calculations imply that a perturbation of about 30-40% in atmospheric CH4 could occur if stratospheric O3 were perturbed by 10% or if man-made CO continued to increase. The possible consequences of a CH4 perturbation may entail a perturbation in stratospheric photochemistry or in the thermal balance of the atmosphere.

Chameides, W. L.↗
NASA NTRS1989

Photochemistry of biogenic gases

The relationship between the biosphere and the atmosphere is examined, emphasizing the composition and photochemistry and chemistry of the troposphere and stratosphere. The reactions of oxygen, ozone, and hydroxyl are reviewed and the fate of the biogenic gases ammonia, methane, reduced sulfur species, reduced halogen species, carbon monoxide, nitric oxide, nitrous oxide, nitrogen, and carbon dioxide are described. A list is given of the concentration and sources of the various gases.

Levine, Joel S.↗
NASA NTRS2000

Hydrogen Biogeochemistry in Anaerobic and Photosynthetic Ecosystems

The simple biochemistry of molecular hydrogen is central to a large number of microbial processes, affecting the interaction of organisms with each other and with the environment. In anoxic sediments, a great majority of microbial redox processes involve hydrogen as a reactant, product or potential by-product. Accordingly, the energetics (thermodynamics) of each of these processes is affected by variations in local H2 concentrations. It has long been established that this effect is important in governing microbe-microbe interactions and there are multiple demonstrations that "interspecies hydrogen transfer" can alter the products of, inhibit/stimulate, or even reverse microbial metabolic reactions. In anoxic sediments, H2 concentrations themselves are thought to be controlled by the thermodynamics of the predominant H2-consuming microbial process. In sediments from Cape Lookout Bight, this relationship quantitatively describes the co-variation of H2 concentrations with temperature (for methanogens and sulfate reducers) and with sulfate concentration (for sulfate reducers). The quantitative aspect is import= for two reasons: 1) it permits the modeling of H2-sensitive biogeochemistry, such as anaerobic methane oxidation or pathways of organic matter remineralization, as a function of environmental controls; 2) for such a relationship to be observed requires that intracellular biochemistry and bioenergetics are being directly expressed in a component of the extracellular medium. H2 could therefore be utilized a non-invasive probe of cellular energetic function in intact microbial ecosystems. Based on the latter principle we have measured down-core profiles of H2 and other relevant physico-chemical parameters in order to calculate the metabolic energy yields (DG) that support microbial metabolism in Cape Lookout Bight sediments. Methanogens in this system apparently function with energy yields significantly smaller than the minimum requirements suggested by pure culture studies. Our recent work has extended the study of hydrogen to cyanobacterial mat communities. The large amounts of reducing power generated during photosynthetic activity carry the potential to contribute a swamping term to the H2 economy of the anaerobic microbial populations within the mat - and thereby to alter the population structure and biogeochemical function of the mat as a whole. In hypersaline microbial mats, we observe a distinct diel cycle in H2 production and a substantial corresponding flux. On an early Earth dominated by microbial mats, this transmission of photosynthetic reducing power may have carried important implications for both biospheric and atmospheric evolution.

Hoehler, Tori M.↗
NASA NTRS2003

Quantitative Species Measurements In Microgravity Combustion Flames

The capability of models and theories to accurately predict and describe the behavior of low gravity flames can only be verified by quantitative measurements. Although video imaging, simple temperature measurements, and velocimetry methods have provided useful information in many cases, there is still a need for quantitative species measurements. Over the past decade, we have been developing high sensitivity optical absorption techniques to permit in situ, non-intrusive, absolute concentration measurements for both major and minor flames species using diode lasers. This work has helped to establish wavelength modulation spectroscopy (WMS) as an important method for species detection within the restrictions of microgravity-based measurements. More recently, in collaboration with Prof. Dahm at the University of Michigan, a new methodology combining computed flame libraries with a single experimental measurement has allowed us to determine the concentration profiles for all species in a flame. This method, termed ITAC (Iterative Temperature with Assumed Chemistry) was demonstrated for a simple laminar nonpremixed methane-air flame at both 1-g and at 0-g in a vortex ring flame. In this paper, we report additional normal and microgravity experiments which further confirm the usefulness of this approach. We also present the development of a new type of laser. This is an external cavity diode laser (ECDL) which has the unique capability of high frequency modulation as well as a very wide tuning range. This will permit the detection of multiple species with one laser while using WMS detection.

Chen, Shin-Juh↗
NASA NTRS2012

Laboratory IR Studies and Astrophysical Implications of C2H2-Containing Binary Ices

Studies of molecular hot cores and protostellar environments have shown that the observed abundance of gas-phase acetylene (C2H2) cannot be matched by chemical models without the inclusion of C2H2 molecules subliming from icy grain mantles. Searches for infrared (IR) spectral features of solid-phase acetylene are under way, but few laboratory reference spectra of C2H2 in icy mixtures, which are needed for spectral fits to observational data, have been published. Here, we report a systematic study of the IR spectra of condensed-phase pure acetylene and acetylene in ices dominated by carbon monoxide (CO), carbon dioxide (CO2), methane (CH4), and water (H2O). We present new spectral data for these ices, including band positions and intrinsic band strengths. For each ice mixture and concentration, we also explore the dependence of acetylene's nu5-band position (743 cm-1, 13.46 micrometers) and FWHM on temperature. Our results show that the nu5 feature is much more cleanly resolved in ices dominated by non-polar and low-polarity molecules, specifically CO, CO2, and CH4, than in mixtures dominated by H2O-ice. We compare our laboratory ice spectra with observations of a quiescent region in Serpens.

Knez, C.↗
NASA NTRS1980

Response of the global climate to changes in atmospheric chemical composition due to fossil fuel burning

Recent modeling of atmospheric chemical processes (Logan et al, 1978; Hameed et al, 1979) suggests that tropospheric ozone and methane might significantly increase in the future as the result of increasing anthropogenic emissions of CO, NO(x), and CH4 due to fossil fuel burning. Since O3 and CH4 are both greenhouse gases, increases in their concentrations could augment global warming due to larger future amounts of atmospheric CO2. To test the possible climatic impact of changes in tropospheric chemical composition, a zonal energy-balance climate model has been combined with a vertically averaged tropospheric chemical model. The latter model includes all relevant chemical reactions which affect species derived from H2O, O2, CH4, and NO(x). The climate model correspondingly incorporates changes in the infrared heating of the surface-troposphere system resulting from chemically induced changes in tropospheric ozone and methane. This coupled climate-chemical model indicates that global climate is sensitive to changes in emissions of CO, NO(x) and CH4, and that future increases in these emissions could augment global warming due to increasing atmospheric CO2.

Hameed, S.↗
NASA NTRS2005

Simplified Two-Time Step Method for Calculating Combustion and Emission Rates of Jet-A and Methane Fuel With and Without Water Injection

A simplified kinetic scheme for Jet-A, and methane fuels with water injection was developed to be used in numerical combustion codes, such as the National Combustor Code (NCC) or even simple FORTRAN codes. The two time step method is either an initial time averaged value (step one) or an instantaneous value (step two). The switch is based on the water concentration in moles/cc of 1x10(exp -20). The results presented here results in a correlation that gives the chemical kinetic time as two separate functions. This two time step method is used as opposed to a one step time averaged method previously developed to determine the chemical kinetic time with increased accuracy. The first time averaged step is used at the initial times for smaller water concentrations. This gives the average chemical kinetic time as a function of initial overall fuel air ratio, initial water to fuel mass ratio, temperature, and pressure. The second instantaneous step, to be used with higher water concentrations, gives the chemical kinetic time as a function of instantaneous fuel and water mole concentration, pressure and temperature (T4). The simple correlations would then be compared to the turbulent mixing times to determine the limiting rates of the reaction. The NASA Glenn GLSENS kinetics code calculates the reaction rates and rate constants for each species in a kinetic scheme for finite kinetic rates. These reaction rates are used to calculate the necessary chemical kinetic times. Chemical kinetic time equations for fuel, carbon monoxide and NOx are obtained for Jet-A fuel and methane with and without water injection to water mass loadings of 2/1 water to fuel. A similar correlation was also developed using data from NASA's Chemical Equilibrium Applications (CEA) code to determine the equilibrium concentrations of carbon monoxide and nitrogen oxide as functions of overall equivalence ratio, water to fuel mass ratio, pressure and temperature (T3). The temperature of the gas entering the turbine (T4) was also correlated as a function of the initial combustor temperature (T3), equivalence ratio, water to fuel mass ratio, and pressure.

Molnar, Melissa↗
NASA NTRS1996

Spacecraft Maximum Allowable Concentrations for Selected Airborne Contaminants

The National Aeronautics and Space Administration (NASA) has developed spacecraft maximum allowable concentrations (SMACs) for contaminants that might be found in the atmosphere within spacecraft during space missions to ensure the health and well-being of astronauts traveling and working in this unique environment. In volume 1 of this series, NASA developed SMACs for 11 compounds: acetaldehyde, ammonia, carbon monoxide, formaldehyde, Freon 113, hydrogen, methane, methanol, octamethyltrisiloxane, trimethylsilanol, and vinyl chloride. Volume 2 includes SMACs for 12 more airborne contaminants: acrolein, benzene, carbon dioxide, 2-ethoxyethanol, hydrazine, indole, mercury, methylene chloride, methyl ethyl ketone, nitromethane, 2-propoanol, and toluene. In developing SMACs from the toxicological literature, NASA followed the Guidelines for Developing Spacecraft Maximum Allowable Concentrations for Space Station Contaminants published in 1992 by the National Research Council.

Spacecraft contamination↗
NASA NTRS1988

The effects of biomass burning on the concentration of trace gases in the atmosphere

Over the past several years, there has been considerable interest concerning the global effects of biomass burning on concentrations of trace gases in the atmosphere. The paucity of reported studies and investigations into the effects of the Greenhouse Gases such as carbon dioxide (CO2), methane (CH4) and nitrous oxide (N2O), up until about a decade ago, would suggest that the topic was not then one of universal concern. Efforts are now being made to understand the biogenic, anthropogenic and photochemical sources of atmospheric trace gases. Biomass burning which includes the burning of forests for clearing, the burning of vegetative stubble after harvesting, and lightning and human-induced wildfires is but one consideration under the general paradigm of atmospheric perturbations. A team of researchers from the Langley Research Center, along with the Canadian Forest Ministry, Ontario, Canada collaborated in an experiment in a deforestration effort through a prescribed burn. Through a specially designed experimental modeling and instrumentation, a substantial pre-burn data set was collected. The primary focus of the pre-burn experimental activities was the emission of nitrous oxide (N2O) gas from selected sites.

Donaldson, Leon M.↗
NASA NTRS1989

Ozone depletion, greenhouse gases, and climate change

This symposium was organized to study the unusual convergence of a number of observations, both short and long term that defy an integrated explanation. Of particular importance are surface temperature observations and observations of upper atmospheric temperatures, which have declined significantly in parts of the stratosphere. There has also been a dramatic decline in ozone concentration over Antarctica that was not predicted. Significant changes in precipitation that seem to be latitude dependent have occurred. There has been a threefold increase in methane in the last 100 years; this is a problem because a source does not appear to exist for methane of the right isotopic composition to explain the increase. These and other meteorological global climate changes are examined in detail.

Mooney, Harold A.↗
NASA NTRSDate not supplied

The membrane bioreactor (MBR): A hybrid technology for bioregenerative wastewater treatment and resource recovery in space

Extraplanetary surface habitat life support systems (LSS) on the Moon and Mars, as well as long-duration space travel, will require novel capabilities to withstand anticipated unique, harsh conditions. In order to provide safe, habitable environments for the crew, water purification and waste processing systems will be required to treat all sources of water (condensate, Sabatier, urine, hygiene, fecal, food waste) in order to achieve the necessary levels of recovery needed to sustain life over the long-duration missions. The ability to recycle organic wastes creates an opportunity to recover critical elements (e.g., C, H, O, N, P) for subsequent food production, water purification, and atmospheric regeneration. Bioregenerative systems mimic functions of nature in engineered systems, or bioreactors, utilizing combination of prokaryotes, eukaryotes and archaea. While these systems are commonly used on Earth for wastewater treatment, bioreactors for space travel face additional challenges. Terrestrial bioreactors often rely on gravitational settling of dense flocs and granules for cell retention. For micro- or partial-gravity environments, density differential alone will not be adequate for cell retention; a gravity-independent means for cell retention is crucial. The membrane bioreactor represents the state of the art in wastewater treatment. This hybrid system combines biological processes with membrane filtration to achieve performance beyond what each can accomplish individually. The complete cell retention in an MBR allows for the decoupling of hydraulic retention time (HRT) and solids retention time (SRT), which result in a high-thruput, compact, treatment system. The Bioregenerative Water Technology Team at NASA Kennedy Space Center and the University of South Florida has developed a bioregenerative platform based on the hybrid MBR technology. The overall architecture is compact, modular, flexible, and adaptable to mission evolutions. The main subsystems of the bioregenerative architecture include: 1) Anaerobic membrane bioreactor (AnMBR): Also termed the Organic processor assembly (OPA), the function of the AnMBR is to treat organic wastes such as fecal and food wastes. These wastes are characterized by a concentration of suspended solids comprised of carbohydrates, proteins and lipids. The assigned function of the AnMBR is to break down and covert suspended solids to biogas (methane, hydrogen and carbon dioxide), reduce effluent chemical oxygen demand (COD), liberate organically-bound nutrients, and remove pathogenic organisms. 2) Phototrophic membrane bioreactor (PMBR): The PMBR is comprised of a co-culture of microalgae and bacteria. The assigned function of the PMBR is to polish the permeate of the AnMBR to further remove dissolved organic carbon, manage nutrients (nitrogen transformation, load dampening), and perform air revitalization. 3) Food processor assembly (FPA): The FPA is a food production platform (prokaryotic or eukaryotic), fueled by outputs from the AnMBR, or PMBR. For the presentation, we will describe each step of the bioregenerative architecture, and present performance data from extended trials treating analog and real metabolic wastes.

Bioreactor↗
NASA NTRS2004

OVOC (Oxygenated Volatile Organic Chemicals) in the Global Atmosphere: Atmospheric Budgets, Oceanic Concentrations, and Uncertainties

Airborne measurements of oxygenated volatile organic chemicals (OVOC), OH free radicals, and tracers of pollution were performed over the Pacific during Winter/Spring of 2001. Large concentrations of OVOC are present in the global troposphere and are expected to play an important role in atmospheric chemistry. Their total abundance (SIGMAOVOC) was nearly twice that of non-methane hydrocarbons (SIGMAC2-C8 NMHC). Throughout the troposphere, the OH reactivity of OVOC is comparable to that of methane and far exceeds that of NHMC. A comparison of these data with western Pacific observations collected some seven years earlier (Feb.-March, 1994) did not reveal significant differences. Analysis of the relative enhancement of selected OVOC with respect to CH3Cl and CO in twelve plumes originating from fires and sampled in the free troposphere (3-11 km) is used to assess their primary and secondary emissions from biomass combustion. The composition of these plumes also indicates a large shift of reactive nitrogen into the PAN reservoir thereby limiting ozone formation. These data are combined with other observations and interpreted with the help of a global 3-D model to assess OVOC global sources and sinks. We further interpret atmospheric observations with the help of an air-sea exchange model io show that oceans can be both net so~rces and sinks. An extremely large oceanic reservoir of OVOC, that exceeds the atmospheric reservoir by more than an order of magnitude, can be inferred to be present. We conclude that OVOC sources are extremely large (150-500 TgC y-1) but remain poorly quantified. In many cases, measured concentrations are uncertain and incompatible with our present knowledge of atmospheric chemistry. Results based on observations from several field studies and critical gaps will be discussed.

Singh, Hanwant B.↗
NASA NTRS1989

A search for biogenic trace gases in the atmosphere of Mars

The detection of certain trace gases in the atmosphere of Mars may serve as a possible indicator of microbial life on the surface of Mars. Candidate biogenic gases include methane CH4, ammonia NH3, nitrous oxide N2O, and several reduced sulfur species. Chemical thermodynamic equilibrium and photochemical calculations preclude the presence of these gases in any measurable concentrations in the atmosphere of Mars in the absence of biogenic production. A search for these gases utilizing either high resolution (spectral and spatial) spectroscopy from a Mars orbiter, such as the Observer, and or in situ measurements from a Mars lander or rover, is proposed.

Levine, Joel S.↗
NASA NTRS2000

BOREAS TF-11 SSA-Fen 1996 Water Surface Film Capping Data

The BOREAS TF-11 team gathered a variety of data to complement its tower flux measurements collected at the SSA-Fen site. The data described in this document were made by the TF-11 team at the SSA-Fen site to quantify the effect that the films observed to form on open water surfaces had on the transfer of carbon dioxide and methane from the water to the air. Measurements of fluxes of carbon dioxide and methane were made in 1994 and in 1996 using the chamber flux method. A gas chromatograph and a LI-COR LI-6200 were used to measure concentrations and to calculate the fluxes. The data are stored in tabular ASCII files.

Billesbach, David P.↗
NASA NTRS2004

New Reduced Two-Time Step Method for Calculating Combustion and Emission Rates of Jet-A and Methane Fuel With and Without Water Injection

A simplified kinetic scheme for Jet-A, and methane fuels with water injection was developed to be used in numerical combustion codes, such as the National Combustor Code (NCC) or even simple FORTRAN codes that are being developed at Glenn. The two time step method is either an initial time averaged value (step one) or an instantaneous value (step two). The switch is based on the water concentration in moles/cc of 1x10(exp -20). The results presented here results in a correlation that gives the chemical kinetic time as two separate functions. This two step method is used as opposed to a one step time averaged method previously developed to determine the chemical kinetic time with increased accuracy. The first time averaged step is used at the initial times for smaller water concentrations. This gives the average chemical kinetic time as a function of initial overall fuel air ratio, initial water to fuel mass ratio, temperature, and pressure. The second instantaneous step, to be used with higher water concentrations, gives the chemical kinetic time as a function of instantaneous fuel and water mole concentration, pressure and temperature (T4). The simple correlations would then be compared to the turbulent mixing times to determine the limiting properties of the reaction. The NASA Glenn GLSENS kinetics code calculates the reaction rates and rate constants for each species in a kinetic scheme for finite kinetic rates. These reaction rates were then used to calculate the necessary chemical kinetic times. Chemical kinetic time equations for fuel, carbon monoxide and NOx were obtained for Jet-A fuel and methane with and without water injection to water mass loadings of 2/1 water to fuel. A similar correlation was also developed using data from NASA's Chemical Equilibrium Applications (CEA) code to determine the equilibrium concentrations of carbon monoxide and nitrogen oxide as functions of overall equivalence ratio, water to fuel mass ratio, pressure and temperature (T3). The temperature of the gas entering the turbine (T4) was also correlated as a function of the initial combustor temperature (T3), equivalence ratio, water to fuel mass ratio, and pressure.

Molnar, Melissa↗
NASA NTRS1993

The carbon isotope biogeochemistry of (epsilon)CO2 production in a methanogenic marine sediment

To investigate the relationship between sigma(CO2) delta(C-13) values and rates of the dominant remineralization processes at the organic-rich field site of Cape Lookout Bight, NC, the isotopic composition of porewater sigma(CO2) was measured on a seasonal basis. The sigma(CO2) delta(C-13) values varies seasonally in response to changes in rates of sulfate reduction and methanogenesis, the dominant remineralization processes at this site. A tube incubation experiment was also performed to determine the isotopic signature of the sigma(CO2) produced by sulfate reduction and methanogenesis. The delta(C-13) of the sigma(CO2) produced in the sulfate reduction zone determined from the tube incubation was -14.3 plus or minus 1.9, a value enriched in C-13 relative to the labile organic fraction. The C-13-enrichment may be caused by low rates of methanogenesis occurring in the sulfate reduction zone. The delta(C-13) of the sigma(CO2) produced in the methanogenic zone was estimated to be +44 per mil, whereas the co-produced methane was -65 per mil. The fractionation factor for CO2 reduction was calculated to be 1.055, a value in agreement with previous estimates at this site. The measured concentration and delta(C-13) of the sigma(CO2) at Cape Lookout was closely reproduced by a diagenetic model using the measured rates of sulfate reduction and sigma(CO2) production, and the isotopic signature of the sigma(CO2) production in the two biogeochemical zones.

Boehme, Susan E.↗
NASA NTRS2008

Mid-Infrared OPO for High Resolution Measurements of Trace Gases in the Mars Atmosphere

The Martian atmosphere is composed primarily (>95%) of CO2 and N2 gas, with CO, O2, CH4, and inert gases such as argon comprising most of the remainder. It is surprisingly dynamic with various processes driving changes in the distribution of CO2, dust, haze, clouds and water vapor on global scales in the meteorology of Mars atmosphere [I]. The trace gases and isotopic ratios in the atmosphere offer important but subtle clues as to the origins of the planet's atmosphere, hydrology, geology, and potential for biology. In the search for life on Mars, an important process is the ability of bacteria to metabolize inorganic substrates (H2, CO2 and rock) to derive energy and produce methane as a by-product of anaerobic metabolism. Trace gases have been measured in the Mars atmosphere from Earth, Mars orbit, and from the Mars surface. The concentration of water vapor and various carbon-based trace gases are observed in variable concentrations. Within the past decade multiple groups have reported detection of CH4, with concentrations in the 10's of ppb, using spectroscopic observations from Earth [2]. Passive spectrometers in the mid-infrared (MIR) are restricted to the sunlit side of the planet, generally in the mid latitudes, and have limited spectral and spatial resolution. To accurately map the global distribution and to locate areas of possibly higher concentrations of these gases such as plumes or vents requires an instrument with high sensitivity and fine spatial resolution that also has global coverage and can measure during both day and night. Our development goal is a new MIR lidar capable of measuring, on global scales, with sensitivity, resolution and precision needed to characterize the trace gases and isotopic ratios of the Martian atmosphere. An optical parametric oscillator operating in the MIR is well suited for this instrument. The sufficient wavelength tuning range of the OPO can extend the measurements to other organic molecules, CO2, atmospheric water vapor, clouds, temperature, dust, and aerosols, as well as possibly polar-cap properties. Our OPO-approach may allow a new capability for active remote sensing of the outer planets and moons, where the weaker sunlight further limit passive instruments. Here we report on the OPO development effort for this lidar instrument.

Yu, Anthony W.↗