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NASA NTRS1990

Methane flux from the Amazon River floodplain - Emissions during rising water

Methane flux data obtained during a period of high and falling water level in the course of the dry season of 1985 (the Amazon Boundary Layer Experiment, ABLE 2A) and a period of moderate and rising water during the wet season of 1987 (ABLE 2B) were used to characterize the influence of seasonal variations in the vegetation, water column depth, and chemistry, as well as atmospheric dynamics, on the methane flux from the Amazon River floodplain. It was found that the annual estimate of methane from wetlands is identical to the annual estimate made by Matthews and Fung (1987) (both at 111 Tg). However, it was found that peatlands between 50 and 70 N contribute 39 Tg, with the large areas of forested and nonforested bogs making up 37 Tg of this figure, while the figures of Matthews and Fung were 63 and 62 Tg, respectively.

Bartlett, Karen B.↗

NASA NTRS1990

Rheology of solid methane and nitrogen - Applications of Triton

The existing information about the rheological properties of solid methane and nitrogen is reviewed. The main limitation is the absence of creep data for solid nitrogen, but estimated properties are derived on the basis of simple scaling arguments for van der Waals bonded materials. On Triton solid methane and most likely nitrogen are too soft to support any topography over billions of years. Topographic support by water ice-rich materials seems almost certain. Nitrogen and methane do not intermix by solid-state diffusion. The weakness (absence?) of the opposition effect on Triton can be explained by annealing of nitrogen grains, provided the latter have sizes characteristic of freshly deposited frost.

Eluszkiewicz, Janusz↗

NASA NTRS1992

Voyager 2 ultraviolet spectrometer solar occultations at Neptune - Constraints on the abundance of methane in the stratosphere

The study compares Voyager 2 ultraviolet spectrometer (UVS) solar occultation lightcurves at wavelengths 125-138 nm acquired during the Neptune encounter with 1D methane photochemical transport models. For the p-T models under consideration, acceptable fits to the UVS lightcurves are obtained with eddy mixing coefficient values (K sub 1/2) near the half-light altitudes of 2-15 x 10 exp 6 sq cm/s (ingress) and 4-35 x 10 exp 6 sq cm/s (egress) and lower stratospheric methane mixing ratio values of 5-100 x 10 exp -5. For the nominal p-T models and a criterion based on replicating the spacing in altitude of the 125-138 nm UVS lightcurves, K sub 1/2 values of 10 exp 7 sq cm/s (ingress) and 1-2 x 10 exp 7 sq cm/s (egress) and methane mixing ratios of about 0.0004 (ingress and egress) are indicated.

Bishop, James↗

NASA NTRS1993

Atmospheric methane at Cape Meares - Analysis of a high-resolution data base and its environmental implications

Between 1979 and 1992 we took some 120,000 measurements of atmospheric methane at Cape Meares on the Oregon coast. The site is representative of methane concentrations in the northern latitudes (from 30 deg N to 90 deg N). The average concentration during the experiment was 1698 parts per billion by volume (ppbv). Methane concentration increased by 190 ppbv (or 11.9 percent) during the 13-year span of the experiment. The rate of increase was about 20 +/- 4 ppbv/yr in the first 2 yr and 10 +/- 2 ppbv/yr in the last 2 yr of the experiment, suggesting a substantial decline in the trend at northern middle and high latitudes. Prominent seasonal cycles were observed. During the year, the concentration stays more or less constant until May and then starts falling, reaching lowest levels in July and August, then rises rapidly to nearly maximum concentrations in October. Interannual variations with small amplitudes of 2-3 ppbv occur with periods of 1.4 and 6.5 yr.

Khalil, M. A. K.↗

NASA NTRS1952

Flame Speeds of Methane-Air, Propane-Air, and Ethylene-Air Mixtures at Low Initial Temperatures

Flame speeds were determined for methane-air, propane-air, and ethylene-air mixtures at -73 C and for methane-air mixtures at -132 C. The data extend the curves of maximum flame speed against initial mixture temperature previously established for the range from room temperature to 344 C. Empirical equations for maximum flame speed u(cm/ sec) as a function of initial mixture temperature T(sub O) were determined to be as follows: for methane, for T(sub O) from 141 to 615 K, u = 8 + 0.000160 T(sub O)(exp 2.11); for propane, for T(sub O) from 200 to 616 K, u = 10 + 0.000342 T(sub O)(exp 2.00); for ethylene, for T(sub O) from 200 to 617 K, u = 10 + 0.00259 T(sub O)(exp 1.74). Relative flame speeds at low initial temperatures were predicted within approximately 20 percent by either the thermal theory as presented by Semenov or by the diffusion theory of Tanford and Pease. The same order was found previously for high initial temperatures. The low-temperature data were also found to extend the linear correlations between maximum flame speed and calculated equilibrium active-radical concentrations, which were established by the previously reported high-temperature data.

Dugger, Gordon L↗

NASA NTRS1994

Direct numerical simulations of turbulent non-premixed methane-air flames modeled with reduced kinetics

Turbulent non-premixed stoichiometric methane-air flames modeled with reduced kinetics have been studied using the direct numerical simulation approach. The simulations include realistic chemical kinetics, and the molecular transport is modeled with constant Lewis numbers for individual species. The effect of turbulence on the internal flame structure and extinction characteristics of methane-air flames is evaluated. Consistent with earlier DNS with simple one-step chemistry, the flame is wrinkled and in some regions extinguished by the turbulence, while the turbulence is weakened in the vicinity of the flame due to a combination of dilatation and an increase in kinematic viscosity. Unlike previous results, reignition is observed in the present simulations. Lewis number effects are important in determining the local stoichiometry of the flame. The results presented in this work are preliminary but demonstrate the feasibility of incorporating reduced kinetics for the oxidation of methane with direct numerical simulations of homogeneous turbulence to evaluate the limitations of various levels of reduction in the kinetics and to address the formation of thermal and prompt NO(x).

Card, J. M.↗

NASA NTRS1994

Measurement of pressure-broadening and lineshift coefficients at 77 and 296 K of methane lines in the 727 nm band using intracavity laser spectroscopy

Pressure-broadening coefficients and pressure-induced lineshifts of several rotational-vibrational lines have been measured in the 727 nm absorption band of methane at temperatures of 77 and 296 K, using nitrogen, hydrogen, and helium as the foreign-gas collision partners. A technique involving intracavity laser spectroscopy is used to record the methane spectra. Average values of the broadening coefficients (/cm/atm) at 77 K are: 0.199, 0.139, 0.055, and 0.29 for collision partners N2, H2, He, and CH4, respectively. Typical average values of the pressure-induced lineshifts (/cm/atm) at 77 K and for the range of foreign gas pressures between 10 and 200 torr are -0.052 for N2, -0.063 for H2, and +0.031 for He. All the values obtained at 296 K are considerably different from the corresponding values at 77 K. This represents the first report of pressure-broadening and shifting coefficients for the methane transitions in a region where the delta nu(sub C-H) = 5 band occurs.

Singh, Kuldip↗

NASA NTRS1995

The abundances of methane and ortho/para hydrogen on Uranus and Neptune: Implications of New Laboratory 4-0 H2 quadrupole line parameters

The tropospheric methane molar fraction (f(sub CH4, t) and the ortho/para hydrogen ratio are derived for Uranus and Neptune based on new determinations of spectroscopic parameters for key hydrogen features as reported by D. W./ Ferguson et al. (1993). For each planet, the relatively weak laboratory linestrengths (approximately 30 and 15% less than the theoretical 4-0 S(0) and S(1) linestrengths, respectively) results, when compared to analyses adopting theroetical values, in a approximately 30% decrease in the tropospheric methane ratio and a comparable increase in the pressure level of the optically thick cloudtop marking the bottom of the visible atmosphere (P(sub c/d)). The increase in the ratio of S(1)/S(0) linestrengths from 4.4 (theoretical) to approximately 5.9 (measured) results in a decrease in the range of viable ortho/para ratios; an equilibrium hydrogen distribution is now the best fit for both planets. The methane mixing ratios reported here are in agreement with the value of 0.023 derived by the Voyager Radio Occultation Experiment (G. F. Lindal, 1992) for Neptune, but slightly lower than the Voyager Uranus measurement of 0.023 reported by G. F. LIndel et al. (1987). The relative carbon-to-hydrogen abundances for Uranus and Neptune support planetary formation mechanisms involving the dissolution of carbon-bearing planetesimals in the atmospheres of both planets during their early stages of formation (e.g., J. B. Pollack et al., 1986).

Baines, Kevin H.↗

NASA NTRS1994

Use of SAR in Regional Methane Exchange Studies

Significant sources of uncertainty in global trace gas budgets are due to lack of knowledge concerning the areal and temporal extent of source and sink areas. Synthetic aperture radar (SAR) is particularly suited to studies of northern ecosystems because of its all-weather operating capability which enables the acquisition of seasonal data. As key controls on methane exchange, the ability to differentiate major vegetation communities, inundation, and leaf area index (LAI) with satellite and airborne SAR data would increase the accuracy and precision of regional and seasonal estimates of methane exchange. The utility of SAR data for monitoring key controls on methane emissions from Arctic and boreal ecosystems is examined.

Morrissey, L. A.↗

NASA NTRS1996

Stratospheric Observations of CH3D and HDO from ATMOS Infrared Solar Spectra: Enrichments of Deuterium in Methane and Implications for HD

Stratospheric mixing ratios of CH3D from 100 mb to 17mb (approximately equals 15 to 28 km)and HDO from 100 mb to 10 mb (approximately equals 15 to 32 km) have been inferred from high resolution solar occultation infrared spectra from the Atmospheric Trace MOlecule Spectroscopy (ATMOS) Fourier-transform interferometer. The spectra, taken on board the Space Shuttle during the Spacelab 3 and ATLAS-1, -2, and -3 missions, extend in latitude from 70 deg S to 65 deg N. We find CH3D entering the stratosphere at an average mixing ratio of (9.9 +/- 0.8) x 10(exp -10) with a D/H ratio in methane (7.1 +/- 7.4)% less than that in Standard Mean Ocean Water (SMOW) (1 sigma combined precision and systematic error). In the mid to lower stratosphere, the average lifetime of CH3D is found to be (1.19 +/- 0.02) times that of CH4, resulting in an increasing D/H ratio in methane as air 'ages' and the methane mixing ratio decreases. We find an average of (1.0 +/- 0.1) molecules of stratospheric HDO are produced for each CH3D destroyed (1 sigma combined precision and systematic error), indicating that the rate of HDO production is approximately equal to the rate of CH3D destruction. Assuming negligible amounts of deuterium in species other than HDO, CH3D and HD, this limits the possible change in the stratospheric HD mixing ratio below about 10 mb to be +/- 0.1 molecules HD created per molecule CH3D destroyed.

Irion, F. W.↗

NASA NTRS1997

Control of Methane Production and Exchange in Northern Peatlands

This proposal has successfully supported studies that have developed unique long ten-n datasets of methane (CH4) emissions and carbon dioxide (CO2) exchange in order to quantify the controls on CH4 production and exchange especially the linkages to the carbon cycle in northern peatlands. The primary research site has been a small fen in southeastern New Hampshire where a unique multi-year data baseline of CH4 flux measurements was begun (with NASA funding) in 1989. The fen has also been instrumented for continuous hydrological and meteorological observations and year-round porewater sampling. Multiyear datasets of methane flux are very valuable and very rare. Datasets using the same sampling techniques at the same sites are the only way to assess the effect of the integrated ecosystem response to climatological variability. The research has had two basic objectives: 1. To quantify the effect of seasonal and interannual variability on CH4flux. 2. To examine process level controls on methane dynamics.

Crill, Patrick↗

NASA NTRS1993

Ecophysiological Characteristics of Obligate Methanotrophic Bacteria and Methane Oxidation In Situ

Most of the obligate methane-oxidizing bacteria (MOB) described to date are neutrophilic mesophiles that grow optimally in dilute media. Kinetic analyses generally indicate that bacterial methane uptake occurs by transport systems with a K(sub m) greater than l micronM. These and other properties of MOB are inconsistent with characteristics of methane oxidation in situ. The inconsistencies indicate a need for greater attention to the ecophysiological characteristics of isolates and the design of enrichment and isolation schemes which emphasize ecologically relevant parameters (e.g., low temperature, limited and diverse substrate availability, low water potential).

King, Gary M.↗

NASA NTRS1997

Gaseous abundances and methane supersaturation in Titan's troposphere

Various properties of Titan's troposphere are inferred from an analysis of Voyager I infrared spectrometer (IRIS) data between 200 and 600/ cm. Two homogeneous spectral averages acquired at widely separated emission angles are chosen for the analysis. Both data sets are associated with northern low latitudes very close to that of the radio science ingress occultation point. Solutions require simultaneous nonlinear least-squares fits to the two IRIS data sets, coupled with iteration of the radio occultation refractivity data. Values and associated 1-sigma uncertainties of several parameters are inferred from our analysis. These include mole fractions for molecular hydrogen (approx. 0.0011), argon (small), and methane near the surface ( approx. 0.057). Solutions are also obtained for the hydrogen parafraction (close to equilibrium, with considerable uncertainty), air temperature near the surface ( approx. 93 K), surface surface temperature discontinuity (approx. 1 K), and maximum degree of methane supersaturation in the upper troposphere (approx. 1.5). Actual values for the above-mentioned parameters depend on the amount of ethane cloud near the tropopause. There is no evidence for methane clouds in the upper troposphere, nor is their presence compatible with large degrees of supersaturation. A wave number dependence for the stratospheric haze opacity is inferred similar to that found for a polymeric residue created in laboratory discharge experiments. This haze appears to be uniformly distributed with latitude between altitudes of 40 and 160 km, provided those nighttime data at southern high latitudes that are discounted.

Samuelson, Robert E.↗

NASA NTRS1999

Evidence for Methane Segregation at the Surface of Pluto

In May 1995, a set of spectrophotometric curves of the system Pluto-Charon was recorded with the UKIRT telescope equipped with the spectrometer CGS4. As for the previous observations, the spectra cover a part of the near infrared range, between 1.4 and 2.55 micrometers, but with a higher resolution of approximately 700. In both the 1992 and 1995 data, the existence of solid methane is confirmed by numerous absorption bands, and the carbon monoxide and the nitrogen ices are identified by their respective signatures at 2.35 and 2.15 um. The solid nitrogen seems to be the principal icy component and forms a matrix in which the CH4 and CO molecules are diluted. However a spectroscopic analysis of the 1995 observations indicates that pure methane may coexist with its diluted phase in N2. In order to derive the horizontal and vertical distribution of these different species and to obtain some quantitative information about their characteristics, we have modeled the spectrum of May 15 that corresponds to the maximum of Pluto's visible light curve. This was achieved by means of a radiative transfer algorithm dealing with compact and stratified media. Among the various representations we have tested to describe the surface of Pluto, only a geographical mixture of three distinct units explains all the significant structures of the analyzed spectrum. The first unit is a thin granular layer of pure CH4 covering a compact polycrystalline substratum of N2-CH4-CO, which are in a molecular mixture (concentrations of and CO of the order of 0.45%, 0.1-0.2% respectively). It covers about 70% of the observed area and corresponds to volatile deposits that are sublimating under solar illumination. The second unit is either (a) a single thick layer of pure granular methane or (b) a unit similar to the first unit but with the two components inverted (i.e. with CH4 forming a substratum and the N2-CH4-CO mixture a superficial layer of fine grains). Covering 20% of the surface, it represents some old surfaces that have been sublimated for a long time, and eventually recovered later by very small amounts of fresh deposits of the molecular mixture N2-CH4-CO. Finally, the third unit may result from the condensation of very fine grains of nearly pure N2. It covers the remainder of the surface (about 10%). All these results allow a better understanding of the processes of deposition, metamorphism, sublimation and transport affecting the different ices detected on Pluto during its climatic cycles.

Doute, S.↗

NASA NTRS2000

Contribution of Changing Sources and Sinks to the Growth Rate of Atmospheric Methane Concentrations for the Last Two Decades

In situ measurements of atmospheric methane concentrations begun in the early 1980s show decadal trends, as well as large interannual variations, in growth rate. Recent research indicates that while wetlands can explain several of the large growth anomalies for individual years, the decadal trend may be the combined effect of increasing sinks, due to increases in tropospheric OH, and stabilizing sources. We discuss new 20-year histories of annual, global source strengths for all major methane sources, i.e., natural wetlands, rice cultivation, ruminant animals, landfills, fossil fuels, and biomass burning, and present estimates of the temporal pattern of the sink required to reconcile these sources and atmospheric concentrations over the time period. Analysis of the individual emission sources, together with model-derived estimates of the OH sink strength, indicates that the growth rate of atmospheric methane observed over the last 20 years can only be explained by a combination of changes in source emissions and an increasing tropospheric sink.

Matthews, Elaine↗

NASA NTRS1983

Biomass measurement of methane forming bacteria in environmental samples

Methane-forming bacteria contain unusual phytanylglycerol ether phospholipids which can be extracted from the bacteria in sediments and assayed quantitatively by high performance liquid chromatography (HPLC). In this procedure the lipids were extracted, the phospholipids recovered, hydrolyzed, purified by thin layer chromatography, derivatized and assayed by HPLC. Ether lipids were recovered quantitatively from Methanobacterium thermoautotrophicum and sediments at levels as low as 8 x 10(-14) moles. In freshwater and marine sediments the flux of methane to the atmosphere and the methane levels in the pore water reflects the recovery of the phytanyl glycerol ether lipid 'signature'. The proportion of the ether phospholipid to the total recoverable phospholipid was highest in anaerobic digester sewage sludge and deeper subsurface freshwater sediment horizons.

Methanobacterium/metabolism/physiology↗

NASA NTRS2007

Hydrogen Migration and Vinylidene Pathway for Formation of Methane in the 193 nm Photodissociation of Propene: CH3CH=CH2 and CD3CD=CD2

Photodissociation channels and the final product yields from the 193 nm photolysis of propene-h6 (CH2=CHCH3) and propene-d6 (CD2=CDCD3) have been investigated, employing gas chromatography, mass spectroscopy, and flame ionization (GC/MS/FID) detection methods. The yields of methane as well as butadiene relative to ethane show considerable variations when propene-h6 or propene-d6 are photolyzed. This suggests significant variances in the relative importance of primary photolytic processes and/or secondary radical reactions, occurring subsequent to the photolysis. Theoretical calculations suggest the potential occurrence of an intramolecular dissociation through a mechanism involving vinylidene formation, accompanied by an ethylenic H-migration through the pi-orbitals. This process affects the final yields of methane-h4 versus methane-d4 with respect to other products. The product yields from previous studies of the 193 nm photolysis of methyl vinyl ketone-h6 and -d6 (CH2=CHCOCH3, CD2=CDCOCD3), alternative precursors for generating methyl and vinyl radicals, are compared with the current results for propene.

Zhao, Yi-Lei↗

NASA NTRS2008

Igniters for Liquid Oxygen/Liquid Methane Technology Development

As part of NASA's technology development of liquid methane / liquid oxygen engines for future exploration missions, two different igniters were recently studied at NASA Marshall Space Flight Center. The first igniter tested was an impinging injection, spark-initiated torch igniter, and the second was a microwave-generated plasma igniter. The purpose of the ignition tests was to define the ignition limits under vacuum conditions and characterize the transient start-up performance as a function of propellant mixture ratio (MR), mass flow rates, inlet temperatures, and pre-ignition chamber pressure. In addition, for the impinging igniter two different spark plugs were tested, and for the microwave igniter the magnetron filament warm-up time and the magnetron input power were both varied. The results gathered from these tests indicated that the impinging igniter is capable of operating over an MR range of 2 - 27, with methane and oxygen inlet temperatures as low as -161 F and -233 F, respectively. The microwave igniter was tested over an MR range of 2 - 9, with methane and oxygen inlet temperatures as low as -90 F and -200 F, respectively. The microwave igniter achieved ignition over this range, although an upper ignition limit was determined for the oxidizer mass flow rate. In general, the torch exhaust temperatures for the microwave igniter were not as high as those attained with the impinging igniter. The microwave igniter, however, was hot-fired 17 times and was still operational, whereas the impinging igniter spark plugs experienced thermal shock and erosion over nine hot-fire tests. It was concluded that for the microwave igniter better mixing of the propellants might be required in order to both raise the torch exhaust temperature and decrease the required magnetron input power, and for the impinging igniter the spark plug position within the igniter chamber should be varied in future tests to identify a more optimal location. All of the igniter tests were supported by the Propulsion & Cryogenics Advanced Development project, which is part of NASA's Exploration Technology Development Program.

Osborne, Robin J.↗