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At least 883 records · Page 49

New observations of interstellar organic molecules

Discussed here are new observations of 3-carbon-containing interstellar molecules which play an important role in the chemistry of dense molecular clouds: protonated carbon dioxide, formic acid, and propynal. In 1984 a new oxide of carbon, C3O, was discovered in the interstellar medium (Matthews et al. 1984; Brown et al. 1985). Theoretical models suggest that C3O is produced by dissociative electron recombination with the ion H3C3O+. Although no laboratory data for the branching ratios of such a recombination exist, it seemed to us likely that additional products would include H2C3O. This molecule has more than one isomeric form, but one stable species is propynal (HC2CHO), which had been suggested as a possible interstellar molecule by Winnewisser (1973). In observations at the National Radio Astronomy Observatory 43 m telescope in Green Bank earlier this year, researchers detected a line in the cold cloud TMC-1 which they assign to the 2(0,2)-1(0,1) transition of propynal. The observed line agrees with the laboratory frequency to well within the experimental uncertainty a few parts in 10 to the 7th power. Researchers sought and failed to detect the corresponding 2(1,1)-1(1,0) line, which is understandable given the presence of both a and b components of the electric dipole moment in propynal. The b type transitions will drain population from energy levels with K(sub p) does not equal 0 into the K(sub p) equal 0 stack. If the researchers' assignment is correct, this is the first interstellar detection of propynal. Assuming typical rotational temperatures for TMC-1 and that the line is optically thin, the column density determined is about 5 times 10 to the 12th power cm to the -2nd power, or about three times that for C3O. Formic acid (HCOOH) was the first organic acid to be observed in the interstellar medium, in the Galactic center source Sgr B2. The only other interstellar detection has been recently made in the giant molecular cloud in Orion. As part of the same project that led to the detection of propynal, researchers sought formic acid in the nearby, cold dark clouds TMC-1 and L134N. It is seen only in L134N. This difference between the two clouds appears to be consistent with a model in which the oxygen/carbon ratio is higher in L134N. This would be consistent with the higher abundances for SO and SO2, observed in that cloud, and the higher abundances of many carbon-rich species in TMC-1 (Irvine et al. 1985).

Irvine, W. M.↗

Io meteorology - How atmospheric pressure is controlled locally by volcanos and surface frosts

The present modification of the Ingersoll et al. (1985) hydrodynamic model of the SO2 gas sublimation-driven flow from the day to the night side of Io includes the effects of nonuniform surface properties noted in observational studies. Calculations are conducted for atmospheric pressures, horizontal winds, sublimation rates, and condensation rates for such surface conditions as patchy and continuous frost cover, volcanic venting, surface temperature discontinuities, subsurface cold trapping, and the propagation of insolation into the frost. While pressure is found to follow local vapor pressure away from the plumes, it becomes higher inside them.

Ingersoll, Andrew P.↗

Chemistry of a polluted cloudy boundary layer

A one-dimensional photochemical model for cloud-topped boundary layers has been developed to include descriptions of gas- and aqueous-phase chemistry and the radiation field in and below the cloud. The model is applied to the accumulation of pollutants during a wintertime episode with low stratus over Bakersfield, CA. The mechanisms of sulfate production and the balance between the concentrations of acids and bases are examined. It is shown that most of the sulfate production may be explained by the Fe(III)-catalyzed autoxidation of S(IV). Another source of sulfate is the oxidation of SO2 by OH in both the gas and the aqueous phase. It is shown that the sulfate production in the model is controlled by the availability of NH3. It is suggested that this explains the balance observed between total concentration of acids and bases.

Jacob, Daniel J.↗

The photochemistry of planetary atmospheres

Recent theoretical and observational investigations of photochemical processes in the atmospheres of the planets and their satellites are reviewed. Particular attention is given to the CO2-dominated atmospheres of Mars and Venus, the hydrogen-dominated atmospheres of the Jovian planets, the SO2 atmosphere of Io, and the massive atmospheres of Titan and Triton. The principal reaction paths involved are listed and briefly characterized, and numerical data on atmospheric compositions are given in tables.

Dalgarno, A.↗

Sulfur, ultraviolet radiation, and the early evolution of life

The present biosphere is shielded from harmful solar near ultraviolet (UV) radiation by atmospheric ozone. It is suggested that elemental sulfur vapor could have played a similar role in an anoxic, ozone-free, primitive atmosphere. Sulfur vapor would have been produced photochemically from volcanogenic SO2 and H2S. It is composed of ring molecules, primarily S8, that absorb strongly throughout the near UV, yet are expected to be relatively stable against photolysis and chemical attack. It is also insoluble in water and would thus have been immune to rainout or surface deposition over the oceans. Since the concentration of S8 in the primitive atmosphere would have been limited by its saturation vapor pressure, surface temperatures of 45 C or higher, corresponding to carbon dioxide partial pressures exceeding 2 bars, are required to sustain an effective UV screen. A warm, sulfur-rich, primitive atmosphere is consistent with inferences drawn from molecular phylogeny, which suggest that some of the earliest organisms were thermophilic bacteria that metabolized elemental sulfur.

Kasting, J. F.↗

New remote sensing techniques facilitate study of earth's far-flung volcanos

The study of volcanos using remote sensing is discussed. The dynamics of volcanic eruptions and the interactions between volcanos and the atmosphere and ecosphere are examined. Remote sensing equipment can effectively detect mud flows, pyroclastic falls, debris avalanches, lava flows, and hazards to aircraft from eruption plumes. Consideration is given to the use of thermal IR imaging, weather satellites, and polar-orbiting satellites to study such features as lava flow, silica content, and SO2 distribution.

Mouginis-Mark, Peter J.↗

Remote sensing of the troposphere by infrared emission spectroscopy

This paper describes the concept of a cryogenic IR imaging Fourier transform spectrometer, called the Tropospheric Emission Spectrometer (TES), designed for observations of the troposphere and lower stratosphere from a near-earth orbit, using natural thermal emission and reflected sunlight. The principal molecular species to be measured by TES are O3, CO, CO2, N2O, H2O, H2O2, NO, NO2, HNO3, NH3, CH4, C2H6, C2H2, SO2, COS, CFCl3, and CF2Cl2. The TES is scheduled for a launch on the second polar platform of the Earth Observing System in 1998.

Beer, Reinhard↗

The atmospheric sulfur cycle over the Amazon Basin. II - Wet season

The fluxes and concentrations of atmospheric sulfur species were determined at ground level and from aircraft over the Amazon Basin during the 1987 wet season, providing a comprehensive description of the sulfur cycle over a remote tropical region. The vertical profile of dimethylsulfide (DMS) during the wet season was found to be very similar to that measured during the dry season, suggesting little seasonal variation in DMS fluxes. The concentrations of H2S were almost an order of magnitude higher than those of DMS, which makes H2S the most important biogenic source species in the atmosheric sulfur cycle over the Amazon Basin. Using the gradient-flux approach, the flux of DMS at the top of the tree canopy was estimated. The canopy was a source of DMS during the day, and a weak sink during the night. Measurements of sulfur gas emissions from soils, using the chamber method, showed very small fluxes, consistent with the hypothesis that the forest canopy is the major source of sulfur gases. The observed soil and canopy emission fluxes are similar to those measured in temperate regions. The concentrations of SO2 and sulfate aerosol in the wet season atmosphere were similar to dry season values.

Andreae, M. O.↗

Procedure for generating global atmospheric engine emissions data from future supersonic transport aircraft. The 1990 high speed civil transport studies

The input for global atmospheric chemistry models was generated for baseline High Speed Civil Transport (HSCT) configurations at Mach 1.6, 2.2, and 3.2. The input is supplied in the form of number of molecules of specific exhaust constituents injected into the atmosphere per year by latitude and by altitude (for 2-D codes). Seven exhaust constituents are currently supplied: NO, NO2, CO, CO2, H2O, SO2, and THC (Trace Hydrocarbons). An eighth input is also supplied, NO(x), the sum of NO and NO2. The number of molecules of a given constituent emitted per year is a function of the total fuel burned by a supersonic fleet and the emission index (EI) of the aircraft engine for the constituent in question. The EIs for an engine are supplied directly by the engine manufacturers. The annual fuel burn of a supersonic fleet is calculated from aircraft performance and economic criteria, both of which are strongly dependent on basic design parameters such as speed and range. The altitude and latitude distribution of the emission is determined based on 10 Intern. Air Transport Assoc. (IATA) regions chosen to define the worldwide route structure for future HSCT operations and the mission flight profiles.

Sohn, R. A.↗

Historical evidence for a connection between volcanic eruptions and climate change

The times of historical volcanic aerosol clouds were compared with changes in atmospheric temperatures on regional, hemispheric, and global scales. These involve either a direct comparison of individual significant eruption years with temperature records, or a comparison of eruption years with composited temperature records for several years before and after chosen sets of eruptions. Some studies have challenged the connection between individual eruptions and climate change. Mass and Portman (1989) recently suggested that the volcanic signal was present, but smaller than previously thought. In a study designed to test the idea that eruptions could cause small changes in climate, Hansen and other (1978) chose one of the best monitored eruptions at the time, the 1963 eruption of Agung volcano on the island of Bali. Using a simple radiation-balance model, in which an aerosol cloud in the tropics was simulated, this basic pattern of temperature change in the tropics and subtropics was reproduced. There may be natural limits to the atmospheric effects of any volcanic eruption. Self-limiting physical and chemical effects in eruption clouds were proposed. Model results suggest that aerosol microphysical processes of condensation and coagulation produce larger aerosols as the SO2 injection rate is increased. The key to discovering the greatest effects of volcanoes on short-term climate may be to concentrate on regional temperatures where the effects of volcanic aerosol clouds can be amplified by perturbed atmospheric circulation patterns, especially changes in mid-latitudes where meridional circulation patterns may develop. Such climatic perturbations can be detected in proxy evidence such as decreases in tree-ring widths and frost damage rings in climatically sensitive parts of the world, changes in treelines, weather anomalies such as unusually cold summers, severity of sea-ice in polar and subpolar regions, and poor grain yields and crop failures.

Rampino, Michael R.↗

Airborne sulfur trace species intercomparison campaign: Sulfur dioxide, dimethylsulfide, hydrogen sulfide, carbon disulfide, and carbonyl sulfide

Results from an airborne intercomparison of techniques to measure tropospheric levels of sulfur trace gases are presented. The intercomparison was part of the NASA Global Tropospheric Experiment (GTE) and was conducted during the summer of 1989. The intercomparisons were conducted on the Wallops Electra aircraft during flights from Wallops Island, Virginia, and Natal, Brazil. Sulfur measurements intercompared included sulfur dioxide (SO2), dimethylsulfide (DMS), hydrogen sulfide (H2S), carbon disulfide (CS2), and carbonyl sulfide (OCS). Measurement techniques ranged from filter collection systems with post-flight analyses to mass spectrometer and gas chromatograph systems employing various methods for measuring and identifying the sulfur gases during flight. Sampling schedules for the techniques ranged from integrated collections over periods as long as 50 minutes to one- to three-minute samples every ten or fifteen minutes. Several of the techniques provided measurements of more than one sulfur gas. Instruments employing different detection principles were involved in each of the sulfur intercomparisons. Also included in the intercomparison measurement scenario were a host of supporting measurements (i.e., ozone, nitrogen oxides, carbon monoxide, total sulfur, aerosols, etc.) for purposes of: (1) interpreting results (i.e., correlation of any noted instrument disagreement with the chemical composition of the measurement environment); and (2) providing supporting chemical data to meet CITE-3 science objectives of studying ozone/sulfur photochemistry, diurnal cycles, etc. The results of the intercomparison study are briefly discussed.

Gregory, Gerald L.↗

Laboratory studies of the newly discovered infrared band at 4705.2/cm (2.1253 microns) in the spectrum of Io - The tentative identification of CO2

The present evaluation of results from over 120 laboratory experiments relevant to the Trafton et al. (1991) discovery of a 2.1253-micron line in the spectrum of Io demonstrates that this band is produced by neither overtones nor combinations of the fundamental bands of molecules already noted on Io. Since the band's frequency is close to the first overtone of the nu(3) asymmetric stretching mode of CO2, attention is given this molecule's behavior under Io conditions. While pure solid CO2, and CO2 intimately mixed in a matrix of solid SO2 and H2S, generate bands of similar widths, these fall at frequencies lower than the Io band. Attention is given to the possible identification of the Io band with CO2 multimers of 'clusters' on Io.

Sandford, Scott A.↗

Fossil fuel and biomass burning effect on climate - Heating or cooling?

The basic theory of the effect of pollution on cloud microphysics and its global implications is applied to compare the relative effect of a small increase in the consumption rate of oil, coal, or biomass burning on cooling and heating of the atmosphere. The characteristics of and evidence for the SO2 induced cooling effect are reviewed. This perturbation analysis approach permits linearization, therefore simplifying the analysis and reducing the number of uncertain parameters. For biomass burning the analysis is restricted to burning associated with deforestation. Predictions of the effect of an increase in oil or coal burning show that within the present conditions the cooling effect from oil and coal burning may range from 0.4 to 8 times the heating effect.

Kaufman, Yoram J.↗

Fluid dynamics of multiphase flow in volcanic environments on the Earth, Io, and other planets

Data was compiled on H2O, CO2, S, and SO2 and it was analyzed by various techniques to prepare phase diagrams relevant to conditions on the Earth, Io, Mars, and other planets. The use of Cray models for volcanic eruptions was examined. Attempts are being made to develop equations of state of the compounds listed above to be compatible with the Cray code so that they can be called as subroutines for the volcanic models. This is a major project, as the current code uses only the equation of state for a perfect gas, and requires that the atmosphere be the same composition as the volcanic gas. The analysis of the thermodynamic data is time consuming, and was complicated by changes from a VAX/VMS system to Macintosh's, Crays using CTSS, Crays using Unicos, and Sun workstations.

Kieffer, Susan Werner↗

Galileo-related ground-based observations of the Jovian System

The scientific objectives are to make millimeter observations of SO2 and other neutral molecules in Io's atmosphere and to conduct a program of observational and interpretive studies of the Jovian system in connection with the Galileo mission.

Belton, Michael J. S.↗

Io's atmosphere detected by ground-based microwave spectroscopy

Io's corona and extended atmosphere, i.e., the plasma torus and neutral Na and K clouds, were the subject of intensive ground-based studies. E. Lellouch et al. not only detected but also fully resolved the profiles of two pure rotational lines of SO2. The lines were found in emission showing that early theoretical predictions for a thermally inverted atmospheric structure were correct.

Belton, Michael J. S.↗

Carbonate and sulfate minerals in the Chassigny meteorite

SO2 and CO2 from pyrolysis and combustion of bulk Chassigny and infrared traces of sulfate and carbonate minerals have been previously reported. Using scanning electron microscopy (SEM) and energy-dispersive x ray spectrometry (EDS), portions of these samples are searched, and a Ca-sulfate/carbonate association is confirmed.

Wentworth, Susan J.↗

Possible atmospheric lifetimes and chemical reaction mechanisms for selected HCFCs, HFCs, CH3CCl3, and their degradation products against dissolution and/or degradation in seawater and cloudwater

For a wide variety of atmospheric species including CO2, HNO3, and SO2, dissolution in seawater or cloudwater followed by hydrolysis or chemical reaction represents a primary pathway for removal from the atmosphere. In order to determine if this mechanism can also remove significant amounts of atmospheric chlorofluorocarbons (HCFC's), fluorocarbons (HFC's), and their degradation products, an investigation was undertaken as part of the Alternative Fluorocarbons Environmental Acceptability Study (AFEAS). In this investigation, the rates at which CHCl2CF3 (HCFC-123), CCl2FCH3 (HCFC-141b), CClF2CH3 (HCFC-142b), CHClF2 (HCFC-22), CHClFCF3 (HCFC-124) CH2FCF3 (HFC-134a) CHF2CH3 (HFC-152a), CHF2CF3 (HFC-125), and CH3CCl3 can be dissolved in the oceans and in cloudwater were estimated from the species' thermodynamic and chemical properties using simple mathematical formulations to simulate the transfer of gases from the atmosphere to the ocean or cloudwater. The ability of cloudwater and rainwater to remove gas phase degradation products of these compounds was also considered as was the aqueous phase chemistry of the degradation products. The results of this investigation are described.

Wine, P. H.↗