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At least 433 records · Page 24

Constraints on the composition of the Venus atmosphere from microwave measurements near 1.35 cm wavelength

The determination of the brightness temperature of Venus near 1.35 cm wavelength is reviewed. The observed brightness temperature is compared with models for the microwave emission based on the physical and chemical structure of the atmosphere as obtained from spacecraft. Upper limits are set on the concentrations of microwave-absorbing minor constituents. In particular, upper limits are determined for SO2 (180 ppm) and H2O (0.3%) for a mixing-ratio profile that is uniformly mixed up to the cloud bottom at 50 km and is rapidly depleted (scale height, approximately 1 km) at higher altitudes. The total optical depth of the cloud region at or above 50 km is less than 0.17 at 1.35 cm wavelength. The SO2 upper limit is only in marginal agreement with the spacecraft results, and it may be that the latter have been overestimated, or that the distribution of SO2 is more complex than given by the uniform mixing model.

Janssen, M. A.↗

Research on planetary samples

Sputtering yields of solid SO2 by high energy ions were measured in order to study the mechanism for sputtering dielectrics with ions in the electronic stopping power region. The incident ions were helium and fluorine with energies ranging from 1.5 MeV to 25 MeV. Yields as high as 7000 SO2 molecules/incident F ion were measured; the 1.5 MeV He4 beam had a sputtering yield of 50. The data are compared to yield measurements made on UF4 and H2O targets. There is a striking similarity in the yield as a function of the Energy for all three targets. The data compare favorably with theoretical curves based on a model for the sputtering which considers the electronic excitations induced the target by the incident beam. Measurements and calculations of the sort are also useful in understanding processes which occur on the surface of Jupiter's satellite Io, which is covered with SO2 frost and bombarded by energetic ions trapped in the Jovian magnetosphere.

Tombrello, T. A.↗

Photochemistry of the stratosphere of Venus - Implications for atmospheric evolution

The photochemistry of the Venus stratosphere is modeled using an updated and expanded chemical scheme along with the results of recent observations and laboratory studies. Three models, with H2 mixing ratio equal to 2 x 10 to the -5th, 5 x 10 to the -7th, and 1 x 10 to the -13th, respectively, are examined. All three models are found to satisfactorily account for the observations of CO, O2, O2(1Delta), and SO2 in the stratosphere, but only the last one may be able to account for the diurnal behavior of mesospheric CO and the UV albedo. Oxygen, derived from CO2 photolysis, is mainly consumed by CO2 recombination and oxidation of SO2 to H2SO4. The photolysis of HCl in the upper stratosphere provides a major source of odd hydrogen and free chlorine radicals, essential for the catalytic oxidation of CO. Oxidation of SO2 by O occurs in the lower stratosphere. The modeling reveals a number of interesting similarities, previously unsuspected between the chemistry of the stratosphere of Venus and that of the earth; photochemistry may have played a major role in the evolution of the atmosphere.

Yung, Y. L.↗

Mechanism of the atmospheric oxidation of sulfur dioxide - Catalysis by hydroxyl radicals

A flash photolysis/resonance fluorescence technique was used to investigate the decay of OH due to the reaction OH + SO2 (+M) to HOSO2 (+M). In the presence of small amounts of NO (10 to the 14th per cu cm), the decays deviated from the normal semilogarithmic linearity due to reformation of OH. On the basis of computer simulations of the decay curves, it is suggested that the reactions HOSO2 + O2 to HO2 + SO3 (k3), and HO2 + HO to OH + NO2 are the likely subsequent steps in SO2 oxidation. The upper limit for the binding energy of HOSO2 relative to OH + SO2 is estimated to be 32 kcal/mol. The atmospheric implications of a catalytic oxidation mechanism are briefly discussed.

Margitan, J. J.↗

Laboratory studies on the reactions between chlorine, sulfur dioxide, and oxygen - Implications for the Venus stratosphere

Fourier transform IR spectrophotometry is used to monitor the reactants and products in a Venus stratosphere simulation study involving the photolysis of mixtures of Cl2 and SO2, with and without O2 present in an atmosphere of N2. When several speculative reactions inferred from these experiments are incorporated by the Yung and DeMore (1982) model of Venus stratospheric chemistry, it emerges that SO2Cl2 is a key reservoir species for chlorine, and that the reaction between Cl and SO2 furnishes an important cycle for the destruction of O2 and the conversion of SO2 to H2SO4, thereby providing a possible solution to the photochemistry of the Venus stratosphere.

Demore, W. B.↗

Vertical distribution of dimethylsulfide, sulfur dioxide, aerosol ions, and radon over the northeast Pacific Ocean

The vertical distributions, in temperate latitudes, of dimethylsulfide (DMS), SO2, radon, methanesulfonate (MSA), nonsea-salt sulfate (nss-sulfate), and aerosol Na(+), NH4(+), and NO(-) ions were determined in samples collected by an aircraft over the northeast Pacific Ocean during May 3-12, 1985. DMS was also determined in surface seawater. It was found that DMS concentrations, both in seawater and in the atmospheric boundary layer, were significantly lower than the values reported previously for subtropical and tropical regions, reflecting the seasonal variability in the temperate North Pacific. The vertical profiles of DMS, MSA, SO2, and nss-sulfate were found to be strongly dependent on the convective stability of the atmosphere and on air mass origin. Biogenic sulfur emissions could account for most of the sulfur budget in the boundary layer, while the long-range transport of continentally derived air masses was mainly responsible for the elevated levels of both SO2 and nss-sulfate in the free troposphere.

Andreae, M. O.↗

Variation in sulfur dioxide emissions related to earth tides, Halemaumau crater, Kilauea volcano, Hawaii

Variation in SO2 emissions from Halemaumau crater, Kilauea volcano, Hawaii is analyzed using a set of techniques known as exploratory data analysis. SO2 flux was monitored using a correlation spectrometer. A total of 302 measurements were made on 73 days over a 90-day period. The mean flux was 171 t/d with a standard deviation of 52 t/d. A significant increase in flux occurs during increased seismic activity beneath the caldera. SO2 flux prior to this change varies in a systematic way and may be related to variation in the tidal modulation envelope.

Connor, Charles B.↗

Io's tenuous atmosphere

An evaluation is made of observational evidence adduced to date for the various extant models of the Io atmosphere. SO2 and its various photochemical products have been noted to play a major role in the atmosphere; such atomic species as Na and K are present in smaller quantities, and play an important role in the atmosphere's ion chemistry. The vapor pressure equilibrium between condensed SO2 on the surface and the atmospheric gas is an important factor in the global control of SO2 gas distribution, but cannot account for the neutral densities at the terminator required for ionospheric models in view of realistic surface temperature distributions.

Johnson, T. V.↗

Laboratory evaluation and application of microwave absorption properties under simulated conditions for planetary atmospheres

Laboratory measurements of microwave and millimeter wave properties of the simulated atmosphere of the outer planets and their satellites has continued. One of the focuses is on the development of a radiative transfer model of the Jovian atmosphere at wavelengths from 1 mm to 10 cm. This modeling effort led to laboratory measurements of the millimeter wave opacity of hydrogen sulfide (H2S) under simulated Jovian conditions. Descriptions of the modeling effort, the Laboratory experiment, and the observations are presented. Correlative studies of measurements with Pioneer-Venus radio occultation measurements with longer wavelength emission measurements have provided new ways for characterizing temporal and spatial variations in the abundance of both gases H2SO4 and SO2, and for modeling their roles in the subcloud atmosphere. Laboratory measurements were conducted on 1.35 cm (and 13 cm) opacity of gaseous SO2 and absorptivity of gaseous SO2 at the 3.2 mm wavelength under simulated Venus conditions. Laboratory measurements were completed on millimeter wave dielectric properties of liquid H2SO4, in order to model the effects of the opacity of the clouds of Venus onto millimeter wave emission spectrum.

Steffes, Paul G.↗

Performance characteristics of lithium primary cells after controlled storage

A program was initiated to investigate the effects of storage on the performance of lithium primary cells. Two types of liquid cathode cells were chosen to investigate these effects. The cell types included Li-SOCl2/BCX cells, Li-SO2 cells from two different manufacturers, and a small sample size of 8-year-old Li-SO2 cells. The following measurements are performed at each test interval: open circuit voltage, resistance and weight, microcalorimetry, ac impedance, capacity, and voltage delay. The authors examine the performance characteristics of these cells after one year of controlled storage at two temperatures (10 and 30 C). The Li-SO2 cells experienced little to no voltage and capacity degradation after one year storage. The Li-SOCl2/BCX cells exhibited significant voltage and capacity degradation after 30 C storage. Predischarging shortly prior to use appears to be an effective method of reducing the initial voltage drop. Studies are in progress to correlate ac impedance and microcalorimetry measurements with capacity losses and voltage delay.

Deligiannis, F.↗

The structure, stability, and global distribution of Io's atmosphere

The paper reports on high-resolution millimeter-wave spectroscopic observations of Io carried out in 1990 and 1991 which allowed the first unambiguous ground-based detection of SO2 in Io's atmosphere. A reassessment of the IRIS-Voyager observations of the nu3 band of SO2 is presented, and it is shown that non-LTE effects are important in the formation of this band. It is thus concluded that the global SO2 atmosphere observed from earth has characteristics (pressure, temperature) similar to those observed at Loki by Voyager. The paper concludes with a simple thermal model of Io's lower atmosphere and a discussion of new upper limits that can be placed on the presence of H2S, SO, and CO in Io's atmosphere.

Lellouch, Emmanuel↗

Structure and chemistry of Orion S

We present interferometric observations of the SiO J = 2-1, H13CO(+) J = 1-0, HC3N J = 11-10, CH3OH J(K) = 2(0)-1(0), and SO2 J(KpK0) = 8(17)-8(08) transitions along with the 3.1 mm continuum toward the young stellar object Orion S. The HC3N and H13CO(+) emission trace similar spatial and velocity distributions which are extended and follow the Orion molecular ridge. The SiO emission is more spatially confined, peaking to the west of the 3.1 mm continuum source, while the CH3OH emission peaks to the southwest. Weak SO2 emission was detected southeast of the continuum source position. Column densities and fractional abundances are derived for each species at different positions in the region. In general, the molecular abundances near the continuum source are similar to those in the quiescent material near IRc 2, but the abundances decrease toward the continuum source position indicating localized depletions of at least a factor of three. The presence of strong SiO emission with much weaker SO2 emission is interpreted as resulting from high-velocity shock interactions between the outflow from Orion S and the surrounding cloud.

Mcmullin, Joseph P.↗

Theoretical studies of the marine sulfur cycle

Several reduced sulfur compounds are produced by marine organisms and then enter the atmosphere, where they are oxidized and ultimately returned to the ocean or the land. The oceanic dimethyl sulfide (DMS) flux, in particular, represents a significant fraction of the annual global sulfur input to the atmosphere. In the atmosphere, this gas is converted to sulfur dioxide (SO2), methane sulfonic acid, and other organic acids which are relatively stable and about which little is known. SO2 is a short lived gas which, in turn, is converted to sulfuric acid and other sulfate compounds which contribute significantly to acid rain. Because of the complexity of the sulfur system, it is not well understood even in the unperturbed atmosphere. However, a number of new observations and experiments have led to a significant increase in the understanding of this system. A number of one dimensional model experiments were conducted on the gas phase part of the marine sulfur cycle. The results indicate the measured concentration of DMS and the amplitude of its diurnal cycle are in agreement with estimates of its global flux. It was also found that DMS can make a large contribution to the background SO2 concentration in the free troposphere. Estimates of CS2 concentrations in the atmosphere are inconsistent with estimated fluxes; however, measured reaction rates are consistent with the observed steep tropospheric gradient in CS2. Observations of CS2 are extremely sparse. Further study is planned.

Toon, Owen B.↗

Biospheric effects of a large extraterrestrial impact: Case study of the cretaceous/tertiary boundary crater

The Chicxulub impact crater, buried in the Yucatan carbonate platform in Mexico, is the site of the impact purported to have caused mass extinctions at the Cretaceous/Tertiary (K/T) boundary. A recently discovered Chicxulub ejecta deposit in Belize contains evidence of carbonate vaporization and precipitation from the vapor plume. Sulfate clasts are almost absent in the Belize ejecta, but are abundant in the coarse ejecta near the crater rim, hwich may reflect the greater abundance of sulfates deep in the target section. The absence of sulfate precipitates in Belize may indicate that most of the vaporized sulfur was deposited in the upper atmosphere. Hydrocode modeling of the impact indicates that between 0.4 to 7.0 x 10(exp 17) g of sulfur were vaporized by the impact in sulfates. Laser experiments indicate that SO2, SO3, and SO4 are produced, and that complex chemical reactions between plume constituents occur during condensation. The sulfur released as SO3 or SO4 converted rapidly into H2HO4 aerosol. A radiative transfer model coupled with a model of coagulation predicts that the aerosol prolonged the initial blackout period caused by impact dust only if it contained impurities. The sulfur released as SO2 converted to aerosol slowly due to the rate limiting oxidation of SO2. Radiative transfer calculations combined with rates of acid production, coagulation, and diffusion indicate that solar transmission was reduced to 10-20 percent of normal for a period of 8-13 years. This reduction produced a climate forcing (cooling) of -300 Wm(exp -2), which far exceeded the +8 Wm(exp -2) greenhouse warming caused by the CO2 released through the vaporization of carbonates, and therefore produced a decade of freezing and near-freezing temperatures. Several decades of moderate warming followed the decade of severe cooling due to the long residence time of CO2. The prolonged impact winter may have been a major cause of the K/T extinctions.

Pope, Kevin O.↗

On the vertical thermal structure of Io's atmosphere

A radiative-thermal conduction model for the vertical thermal structure of Io's atmosphere is developed with solar heating by SO2 absorption in UV and near-IR bands and non-local thermodynamic equilibrium (LTE) cooling by SO2 nu(sub 1), nu(sub 2), nu(sub 3), vibrational bands and rotational lines. The model predicts the existence of a mesopause in Io's atmosphere when the surface pressure exceeds approximately 10 nbar. The radiative time constant for establishing a mesosphere/mesopause on Io is only approximately 20 min, whereas the thermospheric radiative time constant is about 1 hr. These time constants are significantly shorter than the diurnal time scale and competitive with dynamic time scales. In the thermosphere when solar UV heating dominates, the asymptotic thermospheric temperature is approximately 270 K, only 140 K greater than the surface temperature because at high altiudes non-LTE cooling by SO2 rotation lines exceeds cooling in the nu(sub 2) virbrational band. Solar-heating-only modles are incapable of generating warm enough atmospheres to satisfy the observational inferences from UV and especially millimeter-wave meausrements. Joule heating driven by the penetration of Jupiter's corotational electric field into Io's conducting ionosphere is demonstrated to be the dominant heating mechanism in the subnanobar regions of Io's atmosphere with tempertures ranging from 150 to 1000 K as a function of decreasing pressure from 1 to 0.1 nbar, The asymoptotic thermospheric temperature can attain a value as high as 1800 K.

Strobel, Darrell F.↗

The rate of pyrite decomposition on the surface of Venus

We report the results of a detailed experiment study of the kinetics and mechanism of pyrite (FeS2) chemical weathering under Venus surface conditions. Pyrite is thermodynamically unstable on the surface of Venus and will spontaneously decompose to pyrrhotite (Fe7S8) because the observed S2 partial pressure in the lower atmosphere of Venus is lower than the S2 vapor pressure over coexisting pyrite and pyrrhotite. Pyrite decomposition kinetics were studied in pure CO2 and CO2 gas mixtures along five isotherms in the temperature range 390-531 C. In all gas mixtures studied, pyrite thermally decomposes to pyrrhotite (Fe7S8), which on continued heating loses sulfur to form more Fe-rich pyrrhotites. During this process the pyrrhotites are also being oxidized to form magnetite (Fe3O4), which converts to maghemite (gamma-Fe2O3), and then to hematite (alpha-Fe2O3). The reaction rates for pyrite thermal decomposition to pyrrhotite were determined by measuring the weight loss. The thickness of the unreacted pyrite in the samples provided a second independent reaction rate measurement. Finally, Mossbauer spectra done on 42 of the 115 experimental samples provided a third set of independent reaction rate data. Pyrite decomposition follows zero-order kinetics and is independent of the amount of pyrite present. The rate of pyrite decomposition is apparently independent of the gas compositions used and of the CO2 number density over a range of a factor of 40. The derived activation energy of approximately 150 kJ/mole is the same in pure CO2, two different CO-CO2 mixtures, and a ternary CO-SO2-CO2 mixture. Based on data for a CO-CO2-SO2 gas mixture with a CO number density approximately 10 times higher than at the surface of Venus and a SO2 number density approximately equal to that at the surface of Venus, the rate of pyrite destruction on the surface of Venus varies from about 1225 +/- 238 days/cm at the top of Maxwell Montes (approximately 660 K) to about 233 +/- 133 days/cm in the plains of Venus (approximately 740 K). These lifetimes are very short on a geological time scale and show that pyrite cannot exist on the surface of Venus for any appreciable length of time.

Fegley, B., Jr.↗

Io's Sodium Corona and Spatially Extended Cloud: A Consistent Flux Speed Distribution

For Io neutral cloud calculations, an SO2 source strength of approximately 4x10(exp 27) molecules/sec was determined by successfully matching the SO2(+) density profile near the satellite deduced from magnetometer data acquired by the Galileo spacecraft during its close flyby on December 7, 1995. The incomplete collision source velocity distribution for SO2 is the same as recently determined for the trace species atomic sodium by Smyth and Combi (1997). Estimates for the total energy loss rate (i.e. power) of O and S atoms escaping Io were also determined and imply a significant pickup current and a significant reduction in the local planetary magnetic field near Io.

Smyth, William H.↗

Engine Gaseous, Aerosol Precursor and Particulated Flight Altitude Conditions

The overall objective of the NASA Atmospheric Effects of Aviation Project (AEAP) is to develop scientific bases for assessing atmospheric impacts of the exhaust emissions by both current and future fleets of subsonic and supersonic aircraft. Among the six primary elements of the AEAP is Emissions Characterization. The objective of the Emission Characterization effort is to determine the exhaust emission constituents and concentrations at the engine exit plane. The specific objective of this engine test is to obtain a database of gaseous and particulate emissions as a function of fuel sulfur and engine operating conditions. The database of the particulate emission properties is to be used as a comparative baseline with subsequent flight measurement. The engine used in this test was a Pratt & Whitney F1OO-200E turbofan engine. Aviation fuel (Jet A) with a range of fuel sulfur was used. Low and high sulfur values are limited by commercially available fuels and by fuel specification limits of O.3% by weight. Test matrix was set by parametrically varying the combustor inlet temperature (T(sub 3) between idle and maximum power setting at simulated SLS and up to five other altitudes for each fuel. Four diagnostic systems, extractive and non-intrusive, were assembled for the gaseous and particulate emissions characterization measurements study. NASA extractive system includes smoke meter and analyzers for measurement of CO, CO2, NO, NOx, O2, total unburnt hydrocarbons (THC), and SO2. Particulate emissions were characterized by University of Missouri-Rolla Mobile Aerosol Sampling System. A chemical ionization mass spectrometer from the Air Force Research Laboratory at Hanscom AFB was used to measure SO2 and HNO3. Aerodyne Research. Inc. used infrared tunable diode laser absorption to measure SO2, SO3, NO, H2O and CO2.

Wey, C. C.↗