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All sourcesNASA NTRSDOE OSTI
NASA NTRS1993

Carbon Isotope Biogeochemistry of Methane from Anoxic Sediments

The isotopic composition of naturally occurring methane was used to constrain the tropospheric budget of that radiatively active gas. Numerous studies have shown that the isotopic composition is not constant, even for a specific source, and may vary temporally and spatially. The objective was to develop a process-level model that reproduced the seasonal variations in the C-13/C-12 composition of methane observed at the coastal site, Cape Lookout Bight, NC. Details of the mass balance are provided. Experiments and models designed to determine what factors incluence C-13/C-12 ratio of dissolved CO2 are reported. All the factors described were combined in a model that faithfully reproduces the seasonal C-13/C-12 variations observed at Cape Lookout. The model is described.

Blair, Neal E.↗
NASA NTRS1999

Air Force F-16 Aircraft Engine Aerosol Emissions Under Cruise Altitude Conditions

Selected results from the June 1997 Third Subsonic Assessment Near-Field Interactions Flight (SNIF-III) Experiment are documented. The primary objectives of the SNIF-III experiment were to determine the partitioning and abundance of sulfur species and to examine the formation and growth of aerosol particles in the exhaust of F-16 aircraft as a function of atmospheric and aircraft operating conditions and fuel sulfur concentration. This information is, in turn, being used to address questions regarding the fate of aircraft fuel sulfur impurities and to evaluate the potential of their oxidation products to perturb aerosol concentrations and surface areas in the upper troposphere. SNIF-III included participation of the Vermont and New Jersey Air National Guard F-16's as source aircraft and the Wallops Flight Facility T-39 Sabreliner as the sampling platform. F-16's were chosen as a source aircraft because they are powered by the modern F-100 Series 220 engine which is projected to be representative of future commercial aircraft engine technology. The T-39 instrument suite included sensors for measuring volatile and non-volatile condensation nuclei (CN), aerosol size distributions over the range from 0.1 to 3.0 (micro)m, 3-D winds, temperature, dewpoint, carbon dioxide (CO2), sulfur dioxide (SO2), sulfuric acid (H2SO4), and nitric acid (HNO3).

Anderson, Bruce E.↗
NASA NTRS2011

Radiolytic Cryovolcanism Revisited

Location of Enceladus within the inner magnetosphere of Saturn makes it likely that energetic electron irradiation, ion-neutral chemistry of the emergent cryovolcanic plume gas, and resultant radiolytic modification of surface ice composition could impact long-term evolution of molecular composition in the global ice crust. Thermally-driven convection of ice in the south polar terrain would bring radiolytic oxidant products into contact with subsurface reservoirs of primordial organics on million-year time scales. The chemical reactions leading to CO2 gas production as a primary gas-piston driver of cryovolcanic activity would be exponentially elevated in the warm-ice margins of a heated fluid. The fluid temperature is typically assumed to be below 273 K but could be much higher in a gas-pressurized deep subsurface environment. The Perrier Ocean model has demonstrated how a CO2-loaded fluid could account for the observed jets, while the heat content of the fluid arising from the moon's deeper interior could support high levels of chemical reactivity in the thermal margins. Since mass loss and tidal dissipation arguments do not support continuous activity over billions of years, the activity is likely very episodic so that even low-level energy sources including irradiation-driven radiolysis of surface ices could substantially contribute to the chemical dynamics of the activity apparently now in high phase. A multi-phase thermochemical model, and supporting laboratory measurements of temperature-dependent reaction rates, are needed to investigate these potentially complex processes.

Cooper, John F.↗
NASA NTRS1974

Astronomical Fourier spectropolarimetry

Spectra of the Stokes polarization parameters of Venus (resolution 0.5 per cm) are presented. They were obtained at the Cassegrain focus of the 154-cm telescope of the National Mexican Observatory, Baja California, Mexico, July 12 and 13, 1972, with the Fourier Interferometer Polarimeter (FIP). A preliminary, limited analysis of four spectral features and of the CO2 rotational band structures at 6080 and 6200 per cm has demonstrated that spectral polarization is indeed present. These experimental results, confirmed by two series of observations, provide substantiation for this theoretically predicted phenomenon. They also tend to show that the FIP represents a novel astronomical tool for variable spectral resolution studies of both the intensity and the state of polarization of astronomical light sources.

Forbes, F. F.↗
NASA NTRS1971

Structure of the plasma fireball produced by a CO2 laser.

Study of the space and time resolved structure of a helium plasma produced with a repetitive CO2 laser during the first 15 microsec of the afterglow period. The spectra of several neutral and ionized helium lines are used in the determination of the density and temperature profiles of the luminous fireball. It is found that the plasma is comprised of a dense hot core, which emits primarily ionic lines, and a well-defined tenuous outer shell, which is primarily the source of neutral emission lines. This ?two-component' plasma structure develops at about 0.4 microsec after breakdown, at about the time when the luminous fireball dissipates its expansion energy and comes to a virtual standstill.

George, E. V.↗
NASA NTRS1987

Analysis of intrapulse chirp in CO2 oscillators

Pulsed single-frequency CO2 laser oscillators are often used as transmitters for coherent lidar applications. These oscillators suffer from intrapulse chirp, or dynamic frequency shifting. If excessive, such chirp can limit the signal-to-noise ratio of the lidar (by generating excess bandwidth), or limit the velocity resolution if the lidar is of the Doppler type. This paper describes a detailed numerical model that considers all known sources of intrapulse chirp. Some typical predictions of the model are shown, and simple design rules to minimize chirp are proposed.

Moody, Stephen E.↗
NASA NTRS1988

Calculation of space station infrared irradiance from atmosphere-induced emissions

The excitation mechanisms and radiance estimates over the 1 to 10 micron region for CO2(v), H2O(v), CO(v), OH(v), NO2(2B-2A) and N2(B3 pi - A3 sigma) are discussed. The infrared irradiance of the Space Station at an altitude of 460 km was estimated. The surface material was presumed to be non-carbonaceous and inert. The determined number densities of the various gases relevant to the Space Station from both ambient and outgassing sources are presented. A model for the production of and emission from the infrared active molecules was constructed that considers two classes of production processes: (1) gas phase excitation of molecules in the near Station environment by collision with ambient flux; and (2) surface processes that lead to molecular excitation. A composite spectrum of all major emitting species shows that the observed irradiance is non-uniform over the 1 to 8 micron region. The comparison of predicted irradiance with the zodiacal background indicates that the Space Station infrared background from atmosphere-induced emissions may be a problem of consequence.

Fraser, M. E.↗
NASA NTRS1997

Kinetics and Thermochemistry of the Br((sup 2)P3/2) + NO2 Association Reaction

A laser flash photolysis-resonance fluorescence technique has been employed to study the kinetics of the Br((sup 2)P3/2) + NO2 association reaction as a function of temperature (259-432 K) pressure (12.5 - 700 Torr), and buffer gas identity (He, Ar, H2, N2, CO2, CF4, SF6). The reaction is found to be in the falloff regime between third and second order over the entire range of conditions investigated. At temperatures below 350 K, the association reaction is found to be irreversible on the time scale of the experiment (approximately 30 ms). At higher temperatures reversible addition is observed, allowing equilibrium constants for BrNO2 formation and dissociation to be determined. Second- and third-law analyses of the equilibrium data are in only fair agreement and lead to the following thermochemical parameters for the association reaction: Delta-H(298) = 19.6 +/- 1.7 kcal/mol, Delta-H(0) = -18.6 +/- 2.0 kcal/mol, Delta-S(298) = 29.3 +/- 4.2 cal/mol/K, Delta-H(sub f)(sub 298)(BrNO2) = 17.0 +/-1.8 kcal/mol(uncertainties are 2 sigma estimates of absolute accuracy). The value for Delta-H(0) determined in this study has been employed to calculate k(sub 0)(sup SC), the low-pressure third-order rate coefficient in the strong collision limit, by using the method of Troe; calculated values of k(sub 0)(sup SC) are inconsistent with experimental results unless Delta-H(0) is assigned a value near the lower limit derived from analysis of the high-temperature approach to equilibrium data, i.e. delta-H(0) approximately equals -16.6 kcal/mol. A potential source of systematic error in the calculation of both k(sub 0)(sup SC) and the absolute entropy of BrNO2 results from the complete lack of knowledge of the energies and degeneracies of the electronic states of BrNO3. The procedure developed by Troe and co-workers has been employed to extrapolate experimental falloff curves to the low- and high-pressure limits. Derived values for k(sub 0)(M,298K) in units of 10(exp -31) cm(exp 6)/sq molecule/s range from 2.75 for M = He to 6.54 for M = CO2; 2 sigma uncertainties are estimated to be +/- 20%. Values for k(sub 0)(N2,T) in units of 10(exp -31) cm(exp 6)/sq molecule/s are 5.73 at 259 K, 4.61 at 298 K, and 3.21 at 346 K; the observed temperature dependence for k(sub 0)(N2,T) is consistent with the theoretical temperature dependence for Beta(sub c)k(sub 0)(sup SC). Values for k(sub infinity)(T) in units of 10(exp -11) cu cm/molecule/s are 2.86 at 259 K, 3.22 at 298 K, and 3.73 at 346 K; 2 sigma uncertainties are estimated to be a factor of 2. Approximate falloff parameters in a convenient format for atmospheric modeling are also derived.

Kreutter, K. D.↗
NASA NTRS2026

Tracing the Source of Carbon Oxides on the Large Moons of Uranus

The Uranian moons Ariel, Umbriel, Titania, and Oberon are enriched in CO 2 mixed with CO, but the origin(s) of these carbon oxides, be they primarily native or radiolytic, remain(s) uncertain. Using data collected by NIRSpec on the James Webb Space Telescope (JWST), we measured the spectral signature of CO 2 and other carbon oxides to help disentangle these hypotheses. Through comparison to laboratory data, we find that many of the detected spectral features are consistent with CO 2 ice, including 12 CO2 scattering peaks (4.15–4.26 μm), multilobe 13 CO 2 bands (4.35–4.43 μm), and CO 2 biphonon and triphonon modes (4.80–5.25 μm). Our measurements show that CO 2 and CO are concentrated on the trailing hemispheres of the inner moons Ariel and Umbriel, potentially supporting a radiolytic production hypothesis, consistent with prior ground-based results. However, many of the identified spectral features are only observed in thick crystalline ice deposits measured in the laboratory, which may be difficult to form via radiolysis of carbon-bearing material mixed in icy regoliths. Similarly, the data exhibit weak 4.02 and 4.40 μm bands, hinting at the presence of carbonate minerals and 13 CO 2 clathrates, respectively, possibly formed in the interiors of these moons. Furthermore, JWST has revealed that CO 2 is widespread at Uranus, present in its system of rings, ring moons, and irregular satellites, consistent with its largest moons accreting CO 2 and other carbon oxides from the Uranian subnebula. We conclude that exposed carbon oxides are potentially native, with their surface distributions shaped by charged particle irradiation and seasonal sublimation–condensation cycles.

Ice spectroscopy↗
NASA NTRS1988

Efficient 30-W, 140-MHz rf amplifier for CW CO2 waveguide laser excitation

Details of a 30-W, 140-MHz rf amplifier for CW CO2 waveguide laser excitation are presented. The amplifier delivers 30 W into a 50-Ohm load while requiring only 40 W of dc power from a 28-V supply and 100 mW of rf drive power for an overall efficiency of 75 percent. A coupling-starting network design theory is given that provides the initiation over voltage for the discharge plasma from an rf power source of limited output voltage capability. The network then matches the drive circuit to the new input impedance of the operating discharge without any adjustments. This design theory applies to the whole class of networks whose losses can be approximated by a loss conductance in parallel with the gas discharge.

Hochuli, U. E.↗
NASA NTRS1996

Surveying Dead Trees and CO2-Induced Stressed Trees Using AVIRIS in the Long Valley Caldera

Since 1980 the Long Valley Caldera in the eastern Sierra Nevada (California) has shown signs of renewed volcanic activity. Frequent earthquakes, a re-inflation of the caldera, hydrothermal activity and gas emissions are the outer symptoms of this renewed activity. In 1990 and 1991 several areas of dying trees were found around Mammoth Mountain. The cause of the die off of the trees was first sought in the persistent drought in the preceding years. However, the trees died regardless of age and species. Farrar et al. (1995) started a soil-gas survey in 1994 in the dead-tree areas and found carbon dioxide concentrations ranging from 30 to 96% at soil depths between 30 and 60 cm. CO2 concentrations in the atmosphere are usually around 0.03% and in the soil profile CO2 levels do commonly not exceed 4 to 5%. Although not much is known about the effect of high levels of carbon dioxide in the soil profile on roots, it is most likely that the trees are dying due to oxygen deprivation: the CO2 drives the oxygen out of the soil. So far, four sites of dead trees have been mapped around Mammoth Mountain. The two largest dying trees sites are located near Horseshoe Lake and near Mammoth Mountain Main Lodge covering approximately an area of 10 and 8 ha respectively. Analysis of the gas composition regarding the He-3/He-4 ratio and the percentage biogenic carbon reveals the source of the gas: the magma body beneath the Long Valley Caldera. Until recently it was not known that volcanoes release abundant carbon dioxide from their flanks as diffuse soil emanations. As a result of the magma gas emission around Mammoth Mountain there is an excellent sequence of dead trees, stressed trees, healthy trees and bare soil surfaces. This research site provides excellent opportunities to: (1) Study the capabilities of imaging spectrometry to map stressed (and dead) pine and fir species; (2) Study methods to separate the vivid vegetation, stressed vegetation and dead vegetation from the soil background of glacial deposits and crystalline rocks. The dead tree areas are located on the flanks of Mammoth Mountain (N:37 deg 37' 45" and W:119 deg 02' 05") at an elevation between 2600 and 3000 meters. The area is covered by an open type of Montane Forest. The dominant tree species are Lodgepole Pine (Pinus contorta), the Red Fir (Abies magnifica) and the Jeffrey Pine (Pinus jeffreyi). The soil surface near Horseshoe Lake is generally fairly bright. The surface is covered by glacial deposits (till) consisting mainly of weathered granitic rocks.

deJong, Steven M.↗
NASA NTRS1990

Receiving efficiency of monostatic pulsed coherent lidars. I - Theory. II - Applications

Pulsed coherent radars' receiving efficiency, eta, is presently investigated as a function of range z on the basis of a theory which relates eta(z) to both the transmitted laser intensity and the point-source receiving efficiency; this efficiency is calculated by a backward method employing the back-propagated local oscillator (BPLO) approach. The theory is applied to the ideal case, in order to study system optimization when both the transmitted and the BPLO fields at the antenna are Gaussian. In the second part of this work, eta(z) is calculated for various conditions of the NOAA/ERL Wave Propagation Laboratory CO2 Doppler lidar; the sensitivity of eta(z) to transmitted laser beam quality, telescope focal setting, telescope power, scanner astigmatism, and system misalignment.

Zhao, Yanzeng↗
NASA NTRS2019

Temporal Characterization of Dust Activity in the Central Patagonia Desert (years 1964-2017)

Like a peninsula into the Southern Ocean, the vast Patagonia desert in the southern tip of South America is exposed to extreme winds. Dust blown from this region has important impacts thousands of kilometers away, but these impacts are very difficult to assess. Questions such as the sources of dust found in snow in East Antarctica as well as the provenance of nutrients in the Southern Ocean remain unanswered. While the Patagonia desert is the likely source of dust, there is a dearth of observational records of dust activity from this desert. This study fills the gap in observations by providing a record of 50 years of surface and satellite observations of the largest and most active dust source in Patagonia: lake Colhu Huapi. The seasonality, frequency and periods of major dust activity are identified from meteorological records at a station located 100km downwind from the lake. Collocated satellite observations confirmed the major periods of dust activity in the last 30 years. This dataset provides information on how to interpret records of recent dust found in East Antarctica snow as well as help to understand the CO2 cycle in the Southern Ocean.

Patagonia↗
NASA NTRS1989

Infrared aircraft measurements of stratospheric composition over Antarctica during September 1987

The Jet Propulsion Laboratory Mark IV interferometer recorded high-resolution, infrared solar spectra from the NASA DC-8 aircraft during flights over Antarctica in September 1987. The atmospheric absorption features in these spectra have been analyzed to determine the burdens of O3, NO, NO2, HNO3, ClNO3, HCl, HF, CO2, CH4, N2O, HCN, CO, H2O, CFCl3, and CF2Cl2. The results show a 'collar' of high HNO3 and ClNO3 surrounding a 'core' in which the burdens of these and of HCl and NO2 are very low. Clear increases in the burdens of HF and HNO3 were observed during the course of September in the vortex core. HCl and NO2 exhibited smaller, less significant increases. The burdens of the tropospheric source gases, N2O, CH4, HCN, CFCl3, CF2Cl2, CO, and H2O, were observed to be much smaller over Antarctica than at midlatitudes. This, together with the fact that HF over Antarctica was more than double its midlatidue value, suggests that downwelling had occurred.

Toon, G. C.↗
NASA NTRS2003

Distributions of Trace Gases and Aerosols during the Dry Biomass Burning Season in Southern Africa

Vertical profiles in the lower troposphere of temperature, relative humidity, sulfur dioxide (SO2), ozone (O3), condensation nuclei (CN), and carbon monoxide (CO), and horizontal distributions of twenty gaseous and particulate species, are presented for five regions of southern Africa during the dry biomass burning season of 2000. The regions are the semiarid savannas of northeast South Africa and northern Botswana, the savanna-forest mosaic of coastal Mozambique, the humid savanna of southern Zambia, and the desert of western Namibia. The highest average concentrations of carbon dioxide (CO2), CO, methane (CH4), O3, black particulate carbon, and total particulate carbon were in the Botswana and Zambia sectors (388 and 392 ppmv, 369 and 453 ppbv, 1753 and 1758 ppbv, 79 and 88 ppbv, 2.6 and 5.5 micrograms /cubic meter and 13.2 and 14.3 micrograms/cubic meter). This was due to intense biomass burning in Zambia and surrounding regions. The South Africa sector had the highest average concentrations of SO2, sulfate particles, and CN (5.1 ppbv, 8.3 micrograms/cubic meter, and per 6400 cubic meter , respectively), which derived from biomass burning and electric generation plants and mining operations within this sector. Air quality in the Mozambique sector was similar to the neighboring South Africa sector. Over the arid Namibia sector there were polluted layers aloft, in which average SO2, O3, and CO mixing ratios (1.2 ppbv, 76 ppbv, and 3 10 ppbv, respectively) were similar to those measured over the other more polluted sectors. This was due to transport of biomass smoke from regions of widespread savanna burning in southern Angola. Average concentrations over all sectors of CO2 (386 +/- 8 ppmv), CO (261 +/- 81 ppbv), SO2 (2.5 +/- 1.6 ppbv), O3 (64 +/- 13 ppbv), black particulate carbon (2.3 +/- 1.9 microgram/cubic meter), organic particulate carbon (6.2 +/- 5.2 microgram/cubic meter), total particle mass (26.0 +/- 4.7 microgram/cubic meter), and potassium particles (0.4 +- 0.1 microgram/cubic meter) were comparable to those in polluted, urban air. Since the majority of the measurements in this study were obtained in locations well removed from industrial sources of pollution, the high average concentrations of pollutants reflect the effects of widespread biomass burning. On occasions, relatively thin (-0.5 km) layers of remarkably clean air were located at -3 km above mean sea level, sandwiched between heavily polluted air. The data presented here can be used for inputs to and validation of regional and global atmospheric chemical models.

Sinha, Parikhit↗
NASA NTRS1990

Laboratory simulation of interstellar grain chemistry and the production of complex organic molecules

During the past 15 years considerable progress in observational techniques has been achieved in the middle infrared (5000 to 500 cm(-1), 2 to 20 microns m), the spectral region most diagnostic of molecular vibrations. Spectra of many different astronomical infrared sources, some deeply embedded in dark molecular clouds, are now available. These spectra provide a powerful probe, not only for the identification of interstellar molecules in both the gas solid phases, but also of the physical and chemical conditions which prevail in these two very different domains. By comparing these astronomical spectra with the spectra of laboratory ices one can determine the composition and abundance of the icy materials frozen on the cold (10K) dust grains present in the interior of molecular clouds. These grains and their ice mantles may well be the building blocks from which comets are made. As an illustration of the processes which can take place as an ice is irradiated and subsequently warmed, researchers present the infrared spectra of the mixture H2O:CH3OH:CO:NH3:C6H14 (100:50:10:10:10). Apart from the last species, the ratio of these compounds is representative of the simplest ices found in interstellar clouds. The last component was incorporated into this particular experiment as a tracer of the behavior of a non-aromatic hydrocarbon. The change in the composition that results from ultraviolet photolysis of this ice mixture using a UV lamp to simulate the interstellar radiation field is shown. Photolysis produces CO, CO2, CH4, HCO, H2CO, as well as a family of moderately volatile hydrocarbons. Less volatile carbonaceous materials are also produced. The evolution of the infrared spectrum of the ice as the sample is warmed up to room temperature is illustrated. Researchers believe that the changes are similar to those which occur as ice is ejected from a comet and warmed up by solar radiation. The warm-up sequence shows that the nitrile or iso-nitrile bearing compound produced during photolysis evaporates between 200 and 250K, suggesting that it is carried by a small molecular species. These molecules could be similar to the source material in Comet Halley that is ejected in grains into the coma, freed by sublimation, and photolyzed by solar radiation to produce the observed jets.

Allamandola, L. J.↗
NASA NTRS1988

Observations of stratospheric source gas profiles during the Arctic winter

An international campaign was performed at ESRANGE rocket base, near Kiruna, Sweden (68 N) from January 4 to February 15 in order to investigate the Chemistry of Ozone in the Polar Stratosphere (CHEOPS). Within the framework of this campaign two sets of large stratospheric air samples were collected by means of a balloon borne cryogenic air sampler. The two balloons were launched on February 1, and February 10, 1988. At present the samples are analyzed in our laboratory for their contents of several long lived trace gases such as CH4, N2O, H2, CO2, CO and the major halocarbons CH3Cl, CFCl3, CF2Cl2, CCl4, CH3CCl3, and C2F3Cl3. The vertical profiles derived from these samples will be presented and compared with previous observations made in February 1987. The data will be discussed in view of the dynamical evolution of the Arctic polar vortex during this winter.

Schmidt, U.↗
NASA NTRS1986

He-Ne and CW CO2 laser long-path systems for gas detection

This paper describes the design and testing of a laboratory prototype dual He-Ne laser system for the detection of methane leaks from underground pipelines and solid-waste landfill sites using differential absorption of radiation backscattered from topographic targets. A laboratory-prototype dual CW carbon dioxide laser system also using topographic backscatter is discussed, and measurement results for methanol are given. With both systems, it was observed that the time-varying differential absorption signal was useful in indicating the presence of a gas coming from a nearby source. Limitations to measurement sensitivity, especially the role of speckle and atmospheric turbulence, are described. The speckle results for hard targets are contrasted with those from atmospheric aerosols. The appendix gives appropriate laser lines and values of absorption coefficients for the hydrazine fuel gases.

Grant, W. B.↗