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At least 415 records · Page 23

C-13/C-12 ratio in methane from the flooded Amazon forest

The C1-C4 hydrocarbon concentrations and the C-13/C-12 ratio in CH4 detected in air samples collected in the Amazon region (3.5 deg S latitude and 5.9 deg W longitude) are analyzed. It is observed that the CH4 concentrations of each sample are enhanced over the background concentration for remote locations, and the C-13/C-12 ratio in this biogenic methane is depleted in C-13 relative to atmospheric CH4. It is concluded, from the C2-C4 hydrocarbon data, that minor yields of C2-C4 hyrocarbons are released coincident with CH4; however, the minor yields do not contribute to the regionally enhanced concentrations of hydrocarbons found in Amazonia and the global atmosphere release of C2-C4 compounds.

Tyler, Stanley C.↗

Oxidation and reduction rates for organic carbon in the Amazon mainstream tributary and floodplain, inferred from distributions of dissolved gases

Concentrations of CO2, O2, CH4, and N2O in the Amazon River system reflect an oxidation-reduction sequence in combination with physical mixing between the floodplain and the mainstem. Concentrations of CO2 ranged from 150 microM in the Amazon mainstem to 200 to 300 microM in aerobic waters of the floodplain, and up to 1000 microM in oxygen-depleted environments. Apparent oxygen utilization (AOU) ranged from 80 to 250 microM. Methane was highly supersaturated, with concentrations ranging from 0.06 microM in the mainstem to 100 microM on the floodplain. Concentrations of N2O were slightly supersaturated in the mainstem, but were undersaturated on the floodplain. Fluxes calculated from these concentrations indicated decomposition of 1600 g C sq m y(-1) of organic carbon in Amazon floodplain waters. Analysis of relationships between CH4, O2, and CO2 concentrations indicated that approximately 50 percent of carbon mineralization on the floodplain is anaerobic, with 20 percent lost to the atmoshphere as CH4. The predominance of anaerobic metabolism leads to consumption of N2O on the flood plane. Elevated concentrations of CH4 in the mainstem probably reflect imput from the floodplain, while high levels of CO2 in the mainstem are derived from a combination of varzea drainage and in situ respiration.

Richey, Jeffrey E.↗

Liquid-Vapor Equilibrium of Multicomponent Cryogenic Systems

Liquid-vapor and solid-vapor equilibria at low to moderate pressures and low temperatures are important in many solar system environments, including the surface and clouds of Titan, the clouds of Uranus and Neptune, and the surfaces of Mars and Triton. The familiar cases of ideal behavior are limiting cases of a general thermodynamic representation for the vapor pressure of each component in a homogeneous multicomponent system. The fundamental connections of laboratory measurements to thermodynamic models are through the Gibbs-Duhem relation and the Gibbs-Helmholtz relation. Using laboratory measurements of the total pressure, temperature, and compositions of the liquid and vapor phases at equilibrium, the values of these parameters can be determined. The resulting model for vapor-liquid equilibrium can then conveniently and accurately be used to calculate pressures, compositions, condensation altitudes, and their dependencies on changing climatic conditions. A specific system being investigated is CH4-C2H6-N2, at conditions relevant to Titan's surface and atmosphere. Discussed are: the modeling of existing data on CH4-N2, with applications to the composition of Titan's condensate clouds; some new measurements on the CH4-C2H6 binary, using a high-precision static/volumetric system, and on the C2H6-N2 binary, using the volumetric system and a sensitive cryogenic flow calorimeter; and describe a new cryogenic phase-equilibrium vessel with which we are beginning a detailed, systematic study of the three constituent binaries and the ternary CH4-C2H6-N2 system at temperatures ranging from 80 to 105 K and pressures from 0.1 to 7 bar.

Thompson, W. Reid↗

Global mapping of minor atmospheric constituents with AIRS on EOS

The Atmospheric Infrared Sounder (AIRS) is a grating-array spectrometer on EOS. It covers the region from 650 to 3000/cm with spectral resolution of 1200. The prime objective of AIRS is the global retrieval of temperature and water vapor profiles and of surface temperatures. The wide spectral coverage of AIRS permits the measurement of a number of additional atmospheric and surface parameters. Of particular interest is the potential to produce daily global maps of the spatial distribution of the more abundant of the minor gases, e.g. ozone, CO, CH4, and N2O. This potential capability for CH4 and N2O is strongly affected by cloud residual. Using the CH4 band at 1306/cm as example, spatial averaging of AIRS data is required to measure a 10 percent change in the nominal CH4 column abundance. At 1300/cm, this requires cloud clearing at the 0.3 percent level. The mapping capability for ozone and CO in terms of rural/urban abundance patterns is not likely to be impacted with cloud-clearing residuals as high as 5 percent.

Aumann, H. H.↗

A new spectrum of Triton near the time of the Voyager encounter

A 5200-10,000 A spectrum of Triton that was telescopically obtained during the summer of 1989, just before the Voyager II encounter with the Neptune system, exhibits a measurable 8900 A CH4 ice absorption band. A combination of these data with those of Voyager indicates that the absorption is caused solely by Triton surface CH4 ice. A Hapke-type model for the Triton spectrum (1) sets a 20-micron lower limit on the CH4 ice's mean grain size (although it is suspected that actual grain size is closer to 100 microns), and (2) indicates that CH4 ice is widely distributed on the southern-hemisphere surface of Triton.

Grundy, William M.↗

Non-LTE models of Titan's upper atmosphere

Models for the thermal structure of Titan's upper atmosphere, between 0.1 mbar and 0.01 nbar are presented. The calculations include non-LTE heating/cooling in the rotation-vibration bands of CH4, C2H2, and C2H6, absorption of solar IR radiation in the near-IR bands of CH4 and subsequent cascading to the nu-4 band of CH4, absorption of solar EUV and UV radiation, thermal conduction and cooling by HCN rotational lines. Unlike earlier models, the calculated exospheric temperature agrees well with observations, because of the importance of HCN cooling. The calculations predict a well-developed mesopause with a temperature of 135-140 K at an altitude of approximately 600 km and pressure of about 0.1 microbar. The mesopause is at a higher pressure than predicted by earlier calculations because non-LTE radiative transfer in the rotation-vibration bands of CH4, C2H2, and C2H6 is treated in an accurate manner. The accuracy of the LTE approximation for source functions and heating rates is discussed.

Yelle, Roger V.↗

Methane measurement by the Pioneer Venus large probe neutral mass spectrometer

The Pioneer Venus Large Probe Mass Spectrometer detected a large quantity of methane as it descended below 20 km in the atmosphere of Venus. Terrestrial methane and Xe-136, both originating in the same container and flowing through the same plumbing, were deliberately released inside the mass spectrometer for instrumental reasons. However, the Xe-136 did not exhibit behavior similar to methane during Venus entry, nor did CH4 in laboratory simulations. The CH4 was deuterium poor compared to Venus water and hydrogen. While the inlet to the mass spectrometer was clogged with sulfuric acid droplets, significant deuteration of CH4 and its H2 progeny was observed. Since the only source of deuterium identifiable was water from sulfuric acid, we have concluded that we should correct the HDO/H2O ratio in Venus water from 3.2 x 10(exp -2) to (5 plus or minus 0.7) x 10(exp -2). When the probe was in the lower atmosphere, transfer of deuterium from Venus HDO and HD to CH4 can account quantitatively for the deficiencies recorded in HDO and HD below 10 km, and consequently, the mysterious gradients in water vapor and hydrogen mixing ratios we have reported. The revision in the D/H ratio reduces the mixing ratio of water vapor (and H2) reported previously by a factor of 3.2/5. We are not yet able to say whether the methane detected was atmospheric or an instrumental artifact. If it was atmospheric, its release must have been episodic and highly localized. Otherwise, the large D/H ratio in Venus water and hydrogen could not be maintained.

Donahue, T. M.↗

Carbon monoxide and methane in the North American Arctic and Subarctic troposphere - July-August 1988

Enhanced concentrations of CH4 in the unpolluted atmospheric mixed layer over both Arctic and subarctic tundra landscapes are documented here using data from the NASA Arctic Boundary Layer Expedition (ABLE 3A). The CH4 concentration gradients were determined mainly by interactions of biogenic emission from wet tundra and turbulent mixing proceses. The gradient were most frequently associated with intrusion of upper tropospheric or stratospheric air into the midtroposphere, emissions from forest and tundra fires, and long-range transport of enhanced concentration of these gases from unidentified sources. Summertime haze layers exhibited midtropospheric enhancements of CH4 similar to those measured in winter Arctic events. The observations confirm the importance of Arctic and Subarctic wetland environments as a regional source of global atmospheric CH4.

Harriss, Robert C.↗

The distribution of hydrocarbons in Neptune's upper atmosphere

The distribution of hydrocarbons in the upper atmosphere of Neptune is determined on the basis of data from the Voyager UVS solar occultation experiment. Densities are inferred from the transmission properties of the atmosphere measured by the UVS. The CH4 mole fraction in the lower stratosphere is between 0.0006 and 0.005. It is inferred that CH4 in Neptune's lower stratosphere is oversaturated by at least a factor of 10, and possibly by as much as a factor of 100. The density of C2H6 reaches values of 3 x 10 exp 9/cu cm near 100 microbar; a C2H6 production efficiency of 35 +15/-5 percent is derived. The eddy diffusion coefficient is approximately constant at a value of 10,000 sq cm/s at altitudes below 300 km and increases at higher altitudes as the pressure to the 0.75 power. A mole fraction of 0.001 is found to be consistent with the CH4 vapor pressure at 3.4 mbar; consequently, CH4 ice particles must reach this level to produce the inferred oversaturation.

Yelle, Roger V.↗

Carbon cycling in high-latitude ecosystems

The carbon-rich soils and peatlands of high-latitude ecosystems could substantially influence atmospheric concentrations of CO2 and CH4 in a changing climate. Currently, cold, often waterlogged conditions retard decomposition, and release of carbon back to the atmosphere may be further slowed by physical protection of organic matter in permafrost. As a result, many northern ecosystems accumulate carbon over time (Billings et al., 1982; Poole and Miller, 1982), and although such rates of accumulation are low, thousands of years of development have left Arctic ecosystems with an extremely high soil carbon content; Schlesinger's (1984) average value of 20.4 kg C/m(sup 2) leads to a global estimate of 163 x 10(exp 15) g C. All GCM simulations of a doubled CO2 climate predict the greatest warming to occur in the polar regions (Dickinson, 1986; Mitchell, 1989). Given the extensive northern carbon pools and the strong sensitivity of decomposition processes to temperature, even a slight warming of the soil could dramatically alter the carbon balance of Arctic ecosystems. If warming accelerates rates of decomposition more than rates of primary production, a sizeable additional accumulation of CO2 in the atmosphere could occur. Furthermore, CH4 produced in anaerobic soils and peatlands of the Arctic already composes a good percentage of the global efflux (Cicerone and Oremlund, 1988); if northern soils become warmer and wetter as a whole, CH4 emissions could dramatically rise. A robust understanding of the primary controls of carbon fluxes in Arctic ecosystems is critical. As a framework for a systematic examination of these controls, we discussed a conceptual model of regional-scale Arctic carbon turnover, including CH4 production, and based upon the Century soil organic matter model.

Townsend, Alan↗

Lifetimes and eigenstates in atmospheric chemistry

The time scales and mode of the atmosphere's response to chemical perturbations are defined by the eigenvalues and eigenvectors of the system. The eigenstates of a simplified one-box CH4-CO-OH system are analyzed. The longest time constant (smallest eigenvalue) always exceeds the lifetime defined by the steady-state loss frequency for CH4, the longest lived gas. Thus, the extent of a CH4 perturbation -- the methane response time -- is always longer than predicted by the steady-state lifetime and is independent of size of the perturbation in the linear limit. This lengthening of the atmospheric recovery time can be diagnosed by how close we are to a chemically unstable troposphere, i.e., how much OH production exceeds that minimum needed to oxidize just the global emissions of CH4, CO, and other hydrocarbons and species.

Prather, Michael J.↗

An examination of the total hydrogen budget of the lower stratosphere

We analyze the hydrogen budget of the lower stratosphere using simultaneous in situ measurements of northern hemispheric water vapor (H2O) and methane (CH4) obtained during the spring Stratospheric Photochemistry, Aerosols, and Dynamics Expedition (SPADE), as well as previously published in situ H2 data. Based on this data, we conclude that approximately two H2O molecules are produced for each CH4 molecule destroyed. This implies that H2 production from CH4 oxidation is balanced by H2 oxidation. The uncertainty in this analysis is greatly reduced by the use of multiple data sets. Additionally, we infer that, on an annual and global average, H2O enters the stratosphere with a mixing ratio of 4.2 +/- 0.5 ppmv, and that the quasi-conserved quantity 2 x CH4 + H2O has a value of 7.6 +/- 0.6 ppmv in these northern hemishere air parcels (where xi denotes the mixing ratio of the constituent xi).

Dessler, A. E.↗

Infrared spectoscopy of Triton and Pluto ice analogs: The case for saturated hydrocarbons

The infrared transmission spectra and photochemical behavior of various organic compounds isolated in solid N2 ices, appropriate for applications to Triton ad Pluto, are presented. It is shown that excess absorption in the surface spectra of Triton and Pluto, i.e., absorption not explained by present models incorporating molecules already identified on these bodies (N2, CH4, CO, and CO2), that starts near 4450/cm (2.25 microns) and extends to lower frequencies, may be due to alkanes (C(n)H(2n+2)) and related molecules frozen in the nitrogen. Branched and linear alkanes may be responsible. Experiments in which the photochemstry of N2: CH4 and N2: CH4: CO ices was explored demonsrtrate that the surface ices of Triton and Pluto may contain a wide variety of additional species containing H, C, O, and N. Of these, the reactive molecule diazomethane, CH2N2, is particularly important since it may be largely responsible for the synthesis of larger alkanes from CH4 and other small alkanes. Diazomethane would also be expected to drive chemical reactions involving organics in the surface ices of Triton and Pluto toward saturation, i.e., to reduce multiple CC bonds. The positions and intrinsic strengths (A values) of many of the infrared absorption bands of N2 matrix-isolated molecules of relevance to Triton and Pluto have also been determined. These can be used to aid in their search and to place constraints on their abundances.

Bohn, Robert B.↗

The Spectrum of Titan near 3.4 Micron: Comparison of Spectral Features to Organic Molecules

In August 1993 we observed the spectrum of Titan from 2.9 to 4.1 micrometers at a resolving power of R=500-1000 (dw approx. 2-4 per cm). The spectrum shows, as expected, a strong absorption throughout this region from three strong bands Of CH4. However, comparison of the spectrum to simple radiative transfer models and to the spectrum of Jupiter reveal some interesting differences. A broad emission feature that we attribute to CH4 is centered at 3.3 micrometers. At 3.45 micrometers we see a distinct narrow absorption feature that is present in both the Jupiter and laboratory spectrum, but only when other features, absent in the Titan spectrum, are also present. In our attempt to understand the origin of this spectral feature we have compared the spectrum to CH4 and other organic molecules. Interesting similarities appear between the aliphatic hydrocarbons (CH2 and CH3 groups) seen in laboratory organics and the Titan spectrum, but only if we assume that the shorter wavelength feature (CH3) is masked by the broad CH4 emission. A second problem with the explanation is that like column abundance of organic haze (Toon et al. 1991) is insufficient to provide the required number of molecules to create a spectral feature with tau approx. 1. Laboratory organics produced through a variety of processes have been compared to the Titan spectrum and the results arc presented.

Pendleton, Yvonne↗

Using Neural Networks to Describe Tracer Correlations

Neural networks are ideally suited to describe the spatial and temporal dependence of tracer-tracer correlations. The neural network performs well even in regions where the correlations are less compact and normally a family of correlation curves would be required. For example, the CH4-N2O correlation can be well described using a neural network trained with the latitude, pressure, time of year, and CH4 volume mixing ratio (v.m.r.). In this study a neural network using Quickprop learning and one hidden layer with eight nodes was able to reproduce the CH4-N2O correlation with a correlation co- efficient of 0.9995. Such an accurate representation of tracer-tracer correlations allows more use to be made of long-term datasets to constrain chemical models. Such as the dataset from the Halogen Occultation Experiment (HALOE) which has continuously observed CH4, (but not N2O) from 1991 till the present. The neural network Fortran code used is available for download.

Lary, D. J.↗

Tropospheric Methane Over the Pacific Basin During TRACE-P

We received funding for the acquisition, statistical analysis, interpretation, and publication of atmospheric methane data collected during the Transport and Chemical Evolution over the Pacific (TRACE-P) mission, flown February through April of 2001. These high precision measurements were made aboard the NASA DC-8 and P-3B aircraft using a fast response, tunable diode laser system, the DACOM instrument. Our analysis focused on the vertical and geographical distribution of this key trace gas, particularly in the context of other data available from the region such as those from the Pacific NOAA CMDL surface sites, and earlier NASA aircraft missions (such as PEM-West A and B). The paper reporting these results, "Large-Scale Distribution of CH4 in the Western Pacific: Sources and Transport from the Asian Continent" by authors K.B. Bartlett, G.W. Sachse, T. Slate, C. Harward, and D.R. Blake, is attached. The dataset of roughly 13,800 CH4 measurements ranged between 1602 ppb in stratospherically impacted air and 2149 ppb in highly polluted air. Overall, we found that CH4 concentrations were highly correlated with trace gases characteristic of a mix of anthropogenic industrial and combustion sources. They were strikingly correlated with ethane (C2H6) in particular, whose major sources are natural gas leakage and biomass burning. Correlation between the two hydrocarbons indicated that these sources may dominate for CH4 as well at this time.

Bartlett, Karen B.↗

Methane concentration and isotopic composition measurements with a mid-infrared quantum-cascade laser

A quantum-cascade laser operating at a wavelength of 8.1 micrometers was used for high-sensitivity absorption spectroscopy of methane (CH4). The laser frequency was continuously scanned with current over more than 3 cm-1, and absorption spectra of the CH4 nu 4 P branch were recorded. The measured laser linewidth was 50 MHz. A CH4 concentration of 15.6 parts in 10(6) ( ppm) in 50 Torr of air was measured in a 43-cm path length with +/- 0.5-ppm accuracy when the signal was averaged over 400 scans. The minimum detectable absorption in such direct absorption measurements is estimated to be 1.1 x 10(-4). The content of 13CH4 and CH3D species in a CH4 sample was determined.

Non-NASA Center↗

Detection of abundant ethane and methane, along with carbon monoxide and water, in comet C/1996 B2 Hyakutake: evidence for interstellar origin

The saturated hydrocarbons ethane (C2H6) and methane (CH4) along with carbon monoxide (CO) and water (H2O) were detected in comet C/1996 B2 Hyakutake with the use of high-resolution infrared spectroscopy at the NASA Infrared Telescope Facility on Mauna Kea, Hawaii. The inferred production rates of molecular gases from the icy, cometary nucleus (in molecules per second) are 6.4 X 10(26) for C2H6, 1.2 X 10(27) for CH4, 9.8 X 10(27) for CO, and 1.7 X 10(29) for H2O. An abundance of C2H6 comparable to that of CH4 implies that ices in C/1996 B2 Hyakutake did not originate in a thermochemically equilibrated region of the solar nebula. The abundances are consistent with a kinetically controlled production process, but production of C2H6 by gas-phase ion molecule reactions in the natal cloud core is energetically forbidden. The high C2H6/CH4 ratio is consistent with production of C2H6 in icy grain mantles in the natal cloud, either by photolysis of CH4-rich ice or by hydrogen-addition reactions to acetylene condensed from the gas phase.

Non-programmatic↗