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At least 19 records

Radiolysis of Sulfuric Acid, Sulfuric Acid Monohydrate, and Sulfuric Acid Tetrahydrate and Its Relevance to Europa

We report laboratory studies on the 0.8 MeV proton irradiation of ices composed of sulfuric acid (H2SO4), sulfuric acid monohydrate (H2SO4 H2O), and sulfuric acid tetrahydrate (H2SO4 4H2O) between 10 and 180 K. Using infrared spectroscopy, we identify the main radiation products as H2O, SO2, (S2O3)x, H3O+, HSO4(exp -), and SO4(exp 2-). At high radiation doses, we find that H2SO4 molecules are destroyed completely and that H2SO4 H2O is formed on subsequent warming. This hydrate is significantly more stable to radiolytic destruction than pure H2SO4, falling to an equilibrium relative abundance of 50% of its original value on prolonged irradiation. Unlike either pure H2SO4 or H2SO4 H2O, the loss of H2SO4 4H2O exhibits a strong temperature dependence, as the tetrahydrate is essentially unchanged at the highest irradiation temperatures and completely destroyed at the lowest ones, which we speculate is due to a combination of radiolytic destruction and amorphization. Furthermore, at the lower temperatures it is clear that irradiation causes the tetrahydrate spectrum to transition to one that closely resembles the monohydrate spectrum. Extrapolating our results to Europa s surface, we speculate that the variations in SO2 concentrations observed in the chaotic terrains are a result of radiation processing of lower hydration states of sulfuric acid and that the monohydrate will remain stable on the surface over geological times, while the tetrahydrate will remain stable in the warmer regions but be destroyed in the colder regions, unless it can be reformed by other processes, such as thermal reactions induced by diurnal cycling.

Loeffler, M. J.

Sulfuric acid on Europa and the radiolytic sulfur cycle

A comparison of laboratory spectra with Galileo data indicates that hydrated sulfuric acid is present and is a major component of Europa's surface. In addition, this moon's visually dark surface material, which spatially correlates with the sulfuric acid concentration, is identified as radiolytically altered sulfur polymers. Radiolysis of the surface by magnetospheric plasma bombardment continuously cycles sulfur between three forms: sulfuric acid, sulfur dioxide, and sulfur polymers, with sulfuric acid being about 50 times as abundant as the other forms. Enhanced sulfuric acid concentrations are found in Europa's geologically young terrains, suggesting that low-temperature, liquid sulfuric acid may influence geological processes.

unmanned

Cytochromes and iron sulfur proteins in sulfur metabolism of phototrophic bacteria

Dissimilatory sulfur metabolism in phototrophic sulfur bacteria provides the bacteria with electrons for photosynthetic electron transport chain and, with energy. Assimilatory sulfate reduction is necessary for the biosynthesis of sulfur-containing cell components. Sulfide, thiosulfate, and elemental sulfur are the sulfur compounds most commonly used by phototrophic bacteria as electron donors for anoxygenic photosynthesis. Cytochromes or other electron transfer proteins, like high-potential-iron-sulfur protein (HIPIP) function as electron acceptors or donors for most enzymatic steps during the oxidation pathways of sulfide or thiosulfate. Yet, heme- or siroheme-containing proteins themselves undergo enzymatic activities in sulfur metabolism. Sirohemes comprise a porphyrin-like prosthetic group of sulfate reductase. eenzymatic reactions involve electron transfer. Electron donors or acceptors are necessary for each reaction. Cytochromes and iron sulfur problems, are able to transfer electrons.

Fischer, U.

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.

The Mauna Loa sulfur flow as an analog to secondary sulfur flows on Io

Independent evidence suggests that both sulfur and silicate materials exist on the surface of Io. Spectral data indicate the presence of sulfur compounds, some of which are suggested to be of fumarolic origin. Morphological evidence and inferences of the physical properties of some land-forms suggest that silicate volcanism has occurred, which would involve temperatures 650 C or greater. Because the liquidus of sulfur is only about 115 C, it is likely that sulfur in close proximity to 'hot spots' or to active silicate volcanic areas on Io would be melted and mobilized as flows. The Mauna Loa sulfur flow may serve as an analog for such flows, as it consists of fumarolic sulfur that was melted as a consequence of a basaltic eruption and produced a small flow superimposed on silicate lavas.

Greeley, R.

Solubility of Sulfur Dioxide in Sulfuric Acid

The solubility of sulfur dioxide in 50% (wt./wt.) sulfuric acid was evaluated by regular solution theory, and the results verified by experimental measurements in the temperature range of 25 C to 70 C at pressures of 60 to 200 PSIA. The percent (wt./wt.) of sulfur dioxide in 50% (wt./wt.) sulfuric acid is given by the equation %SO2 = 2.2350 + 0.0903P - 0.00026P 10 to the 2nd power with P in PSIA.

Chang, K. K.

Sulfur cycling and metabolism of phototrophic and filamentous sulfur bacteria

Phototrophic sulfur bacteria taken from different habitate (Alum Rock State Park, Palo Alto salt marsh, and Big Soda Lake) were grown on selective media, characterized by morphological and pigment analysis, and compared with bacteria maintained in pure culture. A study was made of the anaerobic reduction of intracellular sulfur globules by a phototrophic sulfur bacterium (Chromatium vinosum) and a filamentous aerobic sulfur bacterium (Beggiatoa alba). Buoyant densities of different bacteria were measured in Percoll gradients. This method was also used to separate different chlorobia in mixed cultures and to assess the relative homogeneity of cultures taken directly or enriched from natural samples (including the purple bacterial layer found at a depth of 20 meters at Big Soda Lake.) Interactions between sulfide oxidizing bacteria were studied.

Guerrero, R.

Phase transformations and the spectral reflectance of solid sulfur - Can metastable sulfur allotropes exist on Io?

Laboratory investigations have been conducted on the effects of variations in sulfur sample histories on their solid-state transformation rate and the corresponding spectral variation of freshly frozen sulfur. The temporal variations in question may be due to differences in the amount and type of metastable allotropes present in the sulfur after solidification, as well as to the physics of the phase-transformation process itself. The results obtained are pertinent to the physical behavior and spectral variation of such freshly solidified sulfur as may exist on the Jupiter moon Io; this would initially solidify into a glassy solid or monoclinic crystalline lattice, then approach ambient dayside temperatures. Laboratory results imply that the monoclinic or polymeric allotropes can in these circumstances be maintained, and will take years to convert to the stable orthorhombic crystalline form.

Moses, Julianne I.

Martian volatiles in shergottite EETA 79001 - New evidence from oxidized sulfur and sulfur-rich aluminosilicates

Two equivalent chips of lithology A (lith-A) and lithology C (lith-C) taken from the same interior portion of EETA 79001 shergottite have been analyzed for volatile species produced by high-vacuum pyrolysis. The lith-C was found to contain an oxidized sulfur component that does not occur in lith-A. The preterrestrial origin of this component in lith-C is supported by the occurrence in lith-C of sulfur- and chlorine-rich aluminosilicates that are not the same as Antarctic weathering products found in the control samples. The oxidation state and distribution of sulfur found in lith-C are consistent with the interpretation of EETA 79001 as a rock from Mars.

Gooding, J. L.

Sulfur speciation in hydrous experimental glasses of varying oxidation state - Results from measured wavelength shifts of sulfur X-rays

The focusing geometry of an electron microprobe has been used to measure the wavelength shifts of sulfur X-rays from hydrous experimental melts synthesized at oxygen fugacities that range from near the iron-wustite buffer to the magnetite-hermatite buffer. It is found that the proportion of dissolved sulfur which is present as sulfate increases with increasing oxygen fugacity. It is noted that in natural melts that have equilibrated at or below fayalite-magnetite-quartz values of +1, sulfur is probably present mainly as S(2-).

Carroll, Michael R.

Identification of Martian Regolith Sulfur Components in Shergottites Using Sulfur K Xanes and Fe/S Ratios

Based on isotopic anomalies in Kr and Sm, Sr-isotopes, S-isotopes, XANES results on S-speciation, Fe/S ratios in sulfide immiscible melts [5], and major element correlations with S determined in impact glasses in EET79001 Lith A & Lith B and Tissint, we have provided very strong evidence for the occurrence of a Martian regolith component in some impact melt glasses in shergottites. Using REE measurements by LA-ICP-MS in shergottite impact glasses, Barrat and co-workers have recently reported conflicting conclusions about the occurrence of Martian regolith components: (a) Positive evidence was reported for a Tissint impact melt, but (b) Negative evidence for impact melt in EET79001 and another impact melt in Tissint. Here, we address some specific issues related to sulfur speciation and their relevance to identifying Martian regolith components in impact glasses in EET79001 and Tissint using sulfur K XANES and Fe/S ratios in sulfide immiscible melts. XANES and FE-SEM measurements in approx. 5 micron size individual sulfur blebs in EET79001 and Tissint glasses are carried out by us using sub-micron size beams, whereas Barrat and coworkers used approx. 90 micron size laser spots for LA- ICP-MS to determine REE abundances in bulk samples of the impact melt glasses. We contend that Martian regolith components in some shergottite impact glasses are present locally, and that studying impact melts in various shergottites can give evidence both for and against regolith components because of sample heterogeneity.

Sutton, S. R.

Autothermal reforming of sulfur-free and sulfur-containing hydrocarbon liquids

The mechanisms by which various fuel component hydrocarbons related to both heavy petroleum and coal-derived liquids are converted to hydrogen without forming carbon were investigated. Reactive differences between paraffins and aromatics in autothermal reforming (ATR) were shown to be responsible for the observed fuel-specific carbon formation characteristics. The types of carbon formed in the reformer were identified by SEM and XRD analyses of catalyst samples and carbon deposits. From tests with both light and heavy paraffins and aromatics, it is concluded that high boiling point hydrocarbons and polynuclear aromatics enhance the propensity for carbon formation. The effects of propylene addition on the ATR performance of benzene are described. In ATR tests with mixtures of paraffins and aromatics, synergistic effects on conversion characteristics were identified. Indications that the sulfur content of the fuel may be the limiting factor for efficient ATR operation were found. The conversion and degradation effects of the sulfur additive (thiophene) were examined.

Source record

Effects of inorganic sulfur addition on fluxes of volatile sulfur compounds in Sphagnum peatlands

Short and long-term impacts of increased S deposition on fluxes of volatile S compounds (VSC's) from Sphagnum peatlands were investigated in an artificially acidified (sulfuric and nitric acids) poor fen (Mire 239) at the Experimental Lakes Area (ELA), Ontario, Canada. Additional experiments were conducted in a poor fen (Sallie's Fen) in Barrington, NH, USA. At Mire 239, emissions of VSC's were monitored, before and after acidification, at control (unacidified) and experimental sections within two major physiographic zones of the mire (oligotrophic and minerotrophic). The experimental segments of the mire received S amendments since 1983, in amounts equivalent to the annual S deposition in the highest polluted areas of Canada and U.S. Dimethyl sulfide (DMS) was the predominant VSC released from the mire and varied largely with time and space (i.e., from 2.5 to 127 nmol/m(sup -2)h(sup -1)). Sulfur addition did not affect DMS emissions in a period of hours to a few days, although it stimulated production of DMS and MSH in the anoxic surficial regions of the peat. DMS emissions in the experimental oligotrophic segment of the mire was approximately 3-fold greater than in the control oligotrophic segment, and approximately 10-fold greater than in the minerotrophic zones. These differences could be due to a combination of differences in types of vegetation, nutritional status, and S input. At Sallie's Fen, DMS fluxes were approximately 8 times higher from a Sphagnum site than from a bare peat site. Fluxes of VSC's were not significantly affected by sulfate amendments at both sites, while DMS and MSH concentrations increases greatly with time in the top 10 cm of the peat column. Our data indicated that although Sphagnum is not the direct source of DMS released from Sphagnum peatlands, it might play a role in regulating DMS emissions to the atmosphere.

Demello, William Zamboni

A study on the electrolysis of sulfur dioxide and water for the sulfur cycle hydrogen production process

Experimental electrolysis cells using various platinum catalyzed carbon electrodes were tested. When operated at 200 mA/sq cm current density using 50 w/o acid at 50 C and 1 atm, a reference cell required 1.22 volts and degraded rapidly. After several improvements were incorporated into electrodes and the test cell configuration, a later cell required only 0.77 volts under identical operating conditions. At a lower current density, 100 mA/sq cm, the cell required only 0.63 volts. Kinetic studies on metal electrodes, measurements of temperature effects on electrode kinetics, investigations of electrocatalytic activities of metal electrodes over a wide range of acid concentrations, cyclic voltametric studies and evaluation of alternate catalysts were also conducted. From diffusivity experiments, a cation exchange membrane material, P-4010, exhibited an excellent diffusion coefficient, more than two orders of magnitude lower than that of rubber. Ionic resistivity measurements of eight materials showed that microporous rubber had the lowest resistivity.

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