The sub-millimeterwave rotational spectrum of sulfaric acid
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Spacecraft radio occultation measurements imply the presence of a nonuniformly mixed gaseous absorber within, but mostly below, the main cloud layer of sulfuric acid-water droplets measured by Pioneer-Venus. Preliminary considerations of the amount, distribution, and effects of sulfur dioxide and other gases, which apparently are associated with and produce the cloud, indicate that they constitute an important, and probably the predominant, source of the observed microwave opacity of the middle atmosphere of Venus.
Global climatic effects brought about by volcanism are related to the impact of volcanic gases and their derivative aerosols on the atmosphere, rather than the effects of volcanic ash. Evidence from both historic eruptions and polar ice cores indicate that volcanic sulfur gases are the dominant aerosol-forming component, resulting in produciton of a sulfuric acid-rich stratosphere aerosol that can have profound effects on the earth radiation budget over periods of a few years. Due to highly variable sulfur content of different magma types, the climatic effects do not relate simply to total erupted mass. There is a close relationship between volcanic sulfur yield to the atmospheric and hemispheric surface temperature decrease following an eruption, with up to 1 C surface temperature decrease indicated following a major volcanic event such as the 1815 Tambora eruption. While the erupted mass of HCl and HF is equal to or greater than that of sulfur gases in some volcanic events, the halogens do not form known aerosols nor are they abundant in ice core acidity layers. The early removal of halogens from eruption columns occurs by rain flushing and adsorption onto tephra particles, but the fate of halogens in the atmosphere following very large explosive eruptions is unknown. The CO2 flux to the atmosphere from volcanic eruptions is volumetrically one of the most important of the gas species, but owing to the huge size of the atmospheric reservoir of this gas, the volcanic contribution is likely to have negligible effects.
Electrochemical reduction of ozone in sulfuric and perchloric acid media at Pt electrode, investigating stoichiometry and measuring diffusion coefficients
Archived samples from a previously unreported 1958 Stanley Miller electric discharge experiment containing hydrogen sulfide (H2S) were recently discovered and analyzed using high-performance liquid chromatography and time-of-flight mass spectrometry. We report here the detection and quantification of primary amine-containing compounds in the original sample residues, which were produced via spark discharge using a gaseous mixture of H2S, CH4, NH3, and CO2. A total of 23 amino acids and 4 amines, including 7 organosulfur compounds, were detected in these samples. The major amino acids with chiral centers are racemic within the accuracy of the measurements, indicating that they are not contaminants introduced during sample storage. This experiment marks the first synthesis of sulfur amino acids from spark discharge experiments designed to imitate primordia! environments. The relative yield of some amino acids, in particular the isomers of aminobutyric acid, are the highest ever found in a spark discharge experiment. The simulated primordial conditions used by Miller may serve as a model for early volcanic plume chemistry and provide insight to the possible roles such plumes may have played in abiotic organic synthesis. Additionally, the overall abundances of the synthesized amino acids in the presence of H2S are very similar to the abundances found in some carbonaceous meteorites, suggesting that H2S may have played an important role in prebiotic reactions in early solar system environments.
Following the discovery of an archived set of samples from Stanley Miller's early experiments, analyses were undertaken to better understand the diversity of compounds produced from electric discharges acting on reducing gas mixtures. The paper chromatography methods that Miller used in the 1950s were only capable of detecting a few amino acids and were unable to provide substantial quantitative data relative to today's techniques. Current analytical techniques are much more sensitive and selective, and are capable of precisely quantifying a much larger range of amino acids and their enantiomeric abundances. In one study, preserved dried samples produced by Miller using a lesser-known volcanic apparatus which differed from Miller's classic apparatus in that it utilized an aspirator that injected steam into the electric discharge chamber, simulating a volcanic eruption. The volcanic apparatus produced a wider variety of amino acids than the classic configuration. Prebiotic compounds synthesized in these environments may have locally accumulated where they could have undergone further processing. An additional preserved set of samples from an experiment conducted in 1958 were also found in Miller's archived collection. These samples which had been generated using a mixture of CH4, NH3, H2S and CO2 were collected, catalogued, and stored by Miller, but for unknown reasons were never studied. In our analyses a total of 23 amino acids and 4 amines, including 7 organosulfur compounds, were detected in these samples. The major amino acids with chiral centers are racemic within the accuracy of the measurements, indicating that they are not contaminants introduced during sample storage. This experiment marks the first synthesis of sulfur amino acids from spark discharge experiments designed to imitate primordial environments. The relative yield of some amino acids, in particular the isomers of amino butyric acid, are the highest ever found in a spark discharge experiment. The simulated primordial conditions used by Miller in these experiments may serve as a model for early volcanic plume chemistry and provide insight to the possible roles such plumes may have played in abiotic organic synthesis. Additionally, the overall abundances of the synthesized amino acids in the presence of H2S are very similar to the abundances found in some carbonaceous meteorites, suggesting that H2S may have played an important role in prebiotic reactions in early solar system environments. Although experiments using a variety of gases as components of the primordial Earth's atmospheric composition and a spark discharge apparatus configured according to Miller's original or volcanic design can be readily carried out, the unique opportunity to investigate samples prepared by the pioneer in abiotic synthesis using state of the art analytical methods is of considerable historic interest.
X-ray photoelectron spectroscopy analyses and hardness experiments were conducted with cleaved magnesium oxide /001/ surfaces. The magnesium oxide bulk crystals were cleaved into specimens along the /001/ surface, and indentations were made on the cleaved surface in laboratory air, in nitrogen gas, or in degassed mineral oil with and without an additive while not exposing specimen surface to any other environment. The various additives examined contained sulfur, phosphorus, chlorine, or oleic acid. The sulfur-containing additive exhibited the highest hardness and smallest dislocation patterns evidencing plastic deformation; the chlorine-containing additive exhibited the lowest hardness and largest dislocation patterns evidencing plastic deformation. Hydrocarbon and chloride (MgCl2) films formed on the magnesium oxide surface. A chloride film was responsible for the lowest measured hardness.
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.
Compared to terrestrial basalts, the Martian shergottite meteorites have an extraordinary range of Sr and Nd isotopic signatures. In addition, the S isotopic compositions of many shergottites show evidence of interaction with the Martian surface/ atmosphere through mass-independent isotopic fractionations (MIF, positive, non-zero delta(exp 33)S) that must have originated in the Martian atmosphere, yet ultimately were incorporated into igneous sulfides (AVS - acid-volatile sulfur). These positive delta(exp 33)S signatures are thought to be governed by solar UV photochemical processes. And to the extent that S is bound to Mars and not lost to space from the upper atmosphere, a positive delta(exp 33)S reservoir must be mass balanced by a complementary negative reservoir.
The recent suggestions that the target area for the K-T bolide may have been a sulfate-rich evaporite and that the resulting sulfuric acid-rich aerosol was responsible for the subsequent cooling of the Earth and the resulting biological extinctions has prompted us to experimentally examine the impact-induced devolatization of the sulfate minerals anhydrite (CaSO4) and gypsum (CaSO4(2H2O)). Preliminary results for anhydrite are reported. Up to 42 GPa peak shock pressure, little or no devolatilization occurs, consistent with chemical thermodynamic calculations. Calculation of the influence of the partial pressure of the gas species on impact-induced devolatilization suggests that an even greater amount of sulfur than that proposed by Brett could have been released to the atmosphere by an impact into a sulfate-rich layer. Solid recovery, impact-induced devolatilization experiments were performed on the Caltech 20mm gun using vented, stainless steel sample assemblies.
A gas chromatograph mounted in the Pioneer Venus sounder probe measured the chemical composition of the atmosphere of Venus at three altitudes. Ne, N2, O2, Ar, CO, H2O, SO2, and CO2 were measured, and upper limits set for H2, COS, H2S, CH4, Kr, N2O, C2H4, C2H6, and C3H8. Simulation studies have provided indirect evidence for sulfuric acid-like droplets and support the possibility of water vapor at altitudes of 42 and 24 km. The paper discusses the implications of these results for the origin, evolution, and present state of Venus' atmosphere.
The term aerosols, as used here, refers to the haze, smoke, and dust that appear in the troposphere. The term does not refer to the hydrometeors in cumulus and stratus clouds but does include the sulfuric acid-water droplets which are assumed to predominate in the stratospheric aerosol layer. The aerosol properties that were measured from satellites and those which can be made in the near term (up to 1992) will be reviewed. The capabilities that will exist in the years 1992 to 2000, with implementation of EOS, are then discussed. Finally, a few words will be said concerning the potential for aerosol measurements for the decade after 2000.
A method for inferring stratospheric aerosol composition and size distribution from the water vapor concentration and aerosol extinction measurements obtained in the Stratospheric Aerosol and Gas Experiment (SAGE) II and the associated temperature from the NMC. The aerosols are assumed to be sulfuric acid-water droplets. A modified Levenberg-Marquardt algorithm is used to determine model size distribution parameters based on the SAGE II multiwavelength aerosol extinctions. It is found that the best aerosol size information is contained in the aerosol radius range between about 0.25 and 0.80 micron.
This data set was collected by TE-1 to provide a set of soil properties for BOREAS investigators in the SSA. The soil samples were collected at sets of soil pits in 1993 and 1994. Each set of soil pits was in the vicinity of one of the five flux towers in the BOREAS SSA. The collected soil samples were sent to a lab, where the major soil properties were determined. These properties include, but are not limited to, soil horizon; dry soil color; pH; bulk density; total, organic, and inorganic carbon; electric conductivity; cation exchange capacity; exchangeable sodium, potassium, calcium, magnesium, and hydrogen; water content at 0.01, 0.033, and 1.5 MPascals; nitrogen; phosphorus; particle size distribution; texture; pH of the mineral soil and of the organic soil; extractable acid; and sulfur. The data are stored in tabular ASCII text files. The data files are available on a CD-ROM (see document number 20010000884), or from the Oak Ridge National Laboratory (ORNL) Distributed Active Archive Center (DAAC).
This data set contains the major soil properties of soil samples collected in 1994 at the tower flux sites in the Northern Study Area (NSA). The soil samples were collected by Hugo Veldhuis and his staff from the University of Manitoba. The mineral soil samples were largely analyzed by Barry Goetz, under the supervision of Dr. Harold Rostad at the University of Saskatchewan. The organic soil samples were largely analyzed by Peter Haluschak, under the supervision of Hugo Veldhuis at the Centre for Land and Biological Resources Research in Winnipeg, Manitoba. During the course of field investigation and mapping, selected surface and subsurface soil samples were collected for laboratory analysis. These samples were used as benchmark references for specific soil attributes in general soil characterization. Detailed soil sampling, description, and laboratory analysis were performed on selected modal soils to provide examples of common soil physical and chemical characteristics in the study area. The soil properties that were determined include soil horizon; dry soil color; pH; bulk density; total, organic, and inorganic carbon; electric conductivity; cation exchange capacity; exchangeable sodium, potassium, calcium, magnesium, and hydrogen; water content at 0.01, 0.033, and 1.5 MPascals; nitrogen; phosphorus: particle size distribution; texture; pH of the mineral soil and of the organic soil; extractable acid; and sulfur. These data are stored in ASCII text files. The data files are available on a CD-ROM (see document number 20010000884), or from the Oak Ridge National Laboratory (ORNL) Distributed Active Archive Center (DAAC).
The wavelength-dependent aerosol extinction in the 800-1250-cm(-1) region has been derived from ATMOS (atmospheric trace molecule spectroscopy) high-spectral-resolution IR transmission measurements.
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Spatially resolved NIR images and spectra of Venus obtained in 1983 revealed high-contrast emission features on the night side of the planet at wavelengths near 1.74 and 2.3 (micro)m. Subsequent observational and modeling studies confirmed that this radiation originates as thermal emission from the hot lower atmosphere (25-40 km).