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At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
NASA NTRS1998

Global Studies of the Sulfur Cycle Including the Influence of DMS and Fossil Fuel Sulfur on Climate and Climate Change

The indirect effect of anthropogenic aerosols, wherein aerosol particles are thought to increase cloud droplet concentrations and cloud lifetime, is the most uncertain component of climate forcing over the past 100 years. Here, for the first time, we use a mechanistic treatment of droplet nucleation and a prognostic treatment of the number of cloud droplets to study the indirect aerosol effect from changes in carbonaceous and sulfate aerosols. Cloud droplet nucleation is parameterized as a function of total aerosol number concentration, updraft velocity and a shape parameter, which takes into account the mechanism, of sulfate aerosol formation, while cloud droplet number depends on the nucleation as well as on droplet sinks. Whereas previous treatments have predicted annual average indirect effects between -1 and -2 W/sq m, we obtain an indirect aerosol effect between -0.14 W/sq m and -0.42 W/sq m in the global mean.

Penner, Joyce E.↗
NASA NTRS1999

Sulfuric Acid on Europa's Surface and the Radiolytic Sulfur Cycle

Galileo infrared spectra of Europa's surface show distorted water bands that have been attributed to hydrated evaporite salts (McCord et al., J. Geophys. Res. 104, 11827, 1999) or to the scattering properties of ice (Dalton and Clark, Bull. Am. Astron. Soc. 30, 1081, 1998).

Jupiter satellites composition infrared↗
NASA NTRS2008

Sulfur Dioxide and the Production of Sulfuric Acid on Present-Day and Early Mars: Implications for the Lack of Detected Carbonates on the Surface

In the early history of Mars, volcanic activity associated with the formation of the Tharsis ridge produced a very large amount of atmospheric SO2--on the order of a bar of atmospheric SO2. In the present-day atmosphere of Mars, the lifetime of SO2 is relatively short with a lifetime of less than a day. The short lifetime of SO2 in the present Mars atmosphere makes the production of significant levels of H2SO4 very difficult since the SO2 may be destroyed by various chemical and photochemical processes before the SO2 can be converted to H2SO4. However, photochemical calculations performed and described here, indicate that enhanced atmospheric levels of CO2 in the early atmosphere of Mars resulted in a significantly enhanced atmospheric lifetime for SO2 up to several years. With a significantly enhanced atmospheric lifetime, SO2 could readily form large amounts of H2SO4, which precipitated out of the atmosphere in the form of droplets. The precipitated H2SO4 then reacted with potential surface carbonates, destroying the carbonates and resulting in the abundant and widespread distribution of sulfates on the surface of Mars as detected by recent Mars missions.

Levine, Joel S.↗
NASA NTRS2025

Sulfur outgassing and in-gassing in lunar orange glass beads and implications for 33S “Anomaly” in the Moon

Our recent investigations have discovered inward diffusion (in-gassing) of moderately volatile elements (MVEs; e.g., Na, K and Cu) from volcanic gas into volcanic beads/droplets. In this work, we examine the distribution of sulfur in lunar orange glass beads. Our analyses reveal that sulfur exhibits a non-uniform distribution across the beads, forming “U” or “W” shaped profiles typical of in-gassing. A model developed to assess sulfur contributions from different sources (original magmatic sulfur versus atmospheric in-gassed sulfur) in the orange beads indicates that atmospheric sulfur in-gassed during eruption contributes approximately 9–24 % to the total sulfur content of an orange bead, averaging around 16 %. This in-gassed sulfur is derived from the eruption plume, where atmospheric sulfur could undergo photochemical reactions induced by UV light, leading to mass independent fractionation and a distinct sulfur isotope signature. Interestingly, a recent study discovered a small mass independent isotope fractionation of sulfur in lunar orange glass beads in drive tube 74002/1 and a lack of such mass independent isotope fractionation in black glass beads in the same lunar sample. This finding contrasts with sulfur in lunar basalts, which typically exhibit mass dependent fractionation. With our work, the observed mass independent fractionation signal in sulfur isotopes of orange beads can be attributed to the in-gassing of photolytic sulfur in the optically thin part of the eruption plume where UV light can penetrate. Using the sulfur isotope data of lunar orange beads, we estimate that the Δ33S value of atmospheric sulfur is approximately −0.18 ‰. Our study provides new insights into the complex dynamics of volatile elements in lunar volcanic processes, highlighting the role of in-gassing in shaping sulfur isotope signatures in volcanic glass beads.

Xue Su↗
NASA NTRS1982

A primer on sulfur for the planetary geologist

Sulfur has been proposed as the dominant composition for the volcanic material on Io. Sulfur is a complex element which forms many intramolecular and intermolecular allotropes exhibiting a variety of physical properties. Cyclo-S8 sulfur is the most abundant and stable molecular form. The important molecular species within liquid sulfur change in concentration with temperature. Concentrations of the allotropes control the physical properties of the melt. Discontinuities in density, viscosity, and thermal properties reflect the polymerization process within liquid sulfur. Variations in the melting point are related to autodissociation of the liquid. Many solids forms of sulfur have been identified but only orthorhombic alpha and monoclinic beta sulfur, both composed of cyclo-S8 sulfur, are stable under terrestrial conditions. Physical properties of solid sulfur are dependent on the allotrope and, in some cases, the thermal history. Three natural terrestrial sulfur flows are described: (1) Siretoko-Iosan, Japan; (2) Volcan Azufre, Galapagos Islands; and (3) Mauna Loa, Hawaii. All of the flows are associated with fumarolic areas and are considered to have formed by the melting and mobilization of sulfur deposits. Surface textures of the flows indicate a behavior of molten sulfur similar to that of silicate lava. Channels, rivulets, and lobate edges were described for the flows. The solidification of man-made sulfur flows formed as part of the Frasch mining process by which sulfur is removed from the subsurface in a liquid state is described.

Theilig, E.↗
NASA NTRS1987

Sulfur-oxygen processes on Io

Laboratory studies of irradiated sulfur dioxide frost have found that sulfur trioxide should be formed as a consequence of the irradiation process. The spectral reflectance of solid sulfur trioxide was measured in the laboratory and it was found that the compound has strong absorption features at 3.37 and 3.70 microns. These features are not present in the spectral geometric albedo of Io. This is interpreted as an indication that sulfur trioxide may exist in such limited abundance that it is undetectable in disk averaged spectrophotometry. It is suggested that the Near-Infrared Mapping Spectrometer on the Galileo spacecraft should be able to identify condensed sulfur trioxide on Io particularly in regions bordering the sulfur dioxide deposits. The presence of elemental sulfur on Io's surface has been questioned on several grounds, most notably the suggested production process (quenched molten sulfur extrusions) and the effect of radiation (particularly X-rays) on some of the allotropes. Mixtures of sulfur allotropes were produced in the laboratory by quenching molten sulfur and it was found that the spectra indicate the presence of certain red-colored allotropes which are preserved upon quenching. The color of the sulfur glass produced is redder when the temperature of the original melt is higher. This is consistent with the suggestion that Io's spectral geometric albedo can be partly explained by the presence of quenched sulfur glasses.

Nelson, Robert M.↗
NASA NTRS1987

Solid sulfur in vacuum: Sublimation effects on surface microtexture, color and spectral reflectance, and applications to planetary surfaces

A form of sulfur that is white at room temperature and very fluffy in texture has been found in laboratory experiments on the effects of vacuum sublimation (evaporation) on solid sulfur. This work is an outgrowth of proton sputtering experiments on sulfur directed toward understanding Jovian magnetospheric effects on the surface of Io. Fluffy white sulfur is formed on the surface of solid yellow, tan, or brown sulfur melt freezes in vacuum by differential (fractional) evaporation of two or more sulfur molecular species present in the original sulfur; S(8) ring sulfur is thought to be the dominant sublimination phase lost to the vacuum sink, and polymeric chain sulfur S(u) the dominant residual phase that remains in place, forming the residual fluffy surface layer. The reflectance spectrum of the original sulfur surface is greaty modified by formation of the fluffy layer: the blue absorption band-edge and shoulder move 0.05 to 0.06 microns toward shorter wavelengths resulting in a permanent increase in reflectivity near 0.42 to 0.46 microns; the UV reflectivity below 0.40 microns is reduced. This form of sulfur should exist in large quantity on the surface of Io, especially in hotspot regions if there is solid free sulfur there that has solidified from a melt. Its color and spectra will indicate relative crystallization age on a scale of days to months and/or surface temperature distribution history.

Nash, D. B.↗
NASA NTRS2001

Sulfate- and Sulfur-Reducing Bacteria as Terrestrial Analogs for Microbial Life on Jupiter's Satellite Io

Observations from the Voyager and Galileo spacecraft have revealed Jupiter's moon Io to be the most volcanically active body of our Solar System. The Galileo Near Infrared Imaging Spectrometer (NIMS) detected extensive deposits of sulfur compounds, elemental sulfur and SO2 frost on the surface of Io. There are extreme temperature variations on Io's surface, ranging from -130 C to over 2000 C at the Pillan Patera volcanic vent. The active volcanoes, fumaroles, calderas, and lava lakes and vast sulfur deposits on this frozen moon indicate that analogs of sulfur- and sulfate-reducing bacteria might inhabit Io. Hence Io may have great significance to Astrobiology. Earth's life forms that depend on sulfur respiration are members of two domains: Bacteria and Archaea. Two basic links of the biogeochemical sulfur cycle of Earth have been studied: 1) the sulfur oxidizing process (occurring at aerobic conditions) and 2) the process of sulfur-reduction to hydrogen sulfide (anaerobic conditions). Sulfate-reducing bacteria (StRB) and sulfur-reducing bacteria (SrRB) are responsible for anaerobic reducing processes. At the present time the systematics of StRB include over 112 species distributed into 35 genera of Bacteria and Archaea. Moderately thermophilic and mesophilic SrRB belong to the Bacteria. The hyperthermophilic SrRB predominately belong to the domain Archaea and are included in the genera: Pyrodictium, Thermoproteus, Pyrobaculum, Thermophilum, Desulfurococcus, and Thermodiscus. The StRB and SrRB use a wide spectrum of substrates as electron donors for lithotrophic and heterotrophic type nutrition. The electron acceptors for the StRB include: sulfate, thiosulfate, sulfite, sulfur, arsenate, dithionite, tetrathionate, sulfur monoxide, iron, nitrite, selenite, fumarate, oxygen, carbon dioxide, and chlorine-containing phenol compounds. The Sulfate- and Sulfur-reducing bacteria are widely distributed in anaerobic ecosystems, including extreme environments like hot springs, deepsea hydrothermal vents, soda and high salinity lakes, and cryo-environments. Furthermore, the StRB and SrRB have Astrobiological significance as these anaerobic extremophiles may represent the dominant relic life forms that inhabited our planet during the extensive volcanic activity in the Earth's early evolutionary period.

Pikuta, Elena V.↗
NASA NTRS2001

The Biogeochemistry of Sulfur in Hydrothermal Systems

The incorporation of sulfur into many biomolecules likely dates back to the development of the earliest metabolic strategies. Sulfur is common in enzymes and co-enzymes and is an indispensable structural component in many peptides and proteins. Early metabolism may have been heavily influenced by the abundance of sulfide minerals in hydrothermal systems. The incorporation of sulfur into many biomolecules likely dates back to the development of the earliest metabolic strategies. Sulfur is common in enzymes and co-enzymes and is an indispensable structural component in many peptides and proteins. Early metabolism may have been heavily influenced by the abundance of sulfide minerals in hydrothermal systems. Understanding how sulfur became prevalent in biochemical processes and many biomolecules requires knowledge of the reaction properties of sulfur-bearing compounds. We have previously estimated thermodynamic data for thiols, the simplest organic sulfur compounds, at elevated temperatures and pressures. If life began in hydrothermal environments, it is especially important to understand reactions at elevated temperatures among sulfur-bearing compounds and other organic molecules essential for the origin and persistence of life. Here we examine reactions that may have formed amino acids with thiols as reaction intermediates in hypothetical early Earth hydrothermal environments. (There are two amino acids, cysteine and methionine, that contain sulfur.) Our calculations suggest that significant amounts of some amino acids were produced in early Earth hydrothermal fluids, given reasonable concentrations H2, NH3, H2S and CO. For example, preliminary results indicate that glycine activities as high as 1 mmol can be reached in these systems at 100 C. Alanine formation from propanethiol is also a favorable reaction. On the other hand, the calculated equilibrium log activities of cysteine and serine from propanethiol are -21 and -19, respectively, at 100 C. These results indicate that while amino acid formation with thiols as intermediates is favored in some cases, other mechanisms may have been necessary to produce significant amounts of other amino acids. Coupled with our previous results for thiols, these studies imply that sulfur may have been easily incorporated into the organic geochemistry of early Earth hydrothermal systems, leading to its widespread use in biomolecules. Formation of more complex biomolecules in hydrothermal systems may have required sulfur-bearing organic compounds as reaction intermediates.

Schulte, Mitchell↗
NASA NTRS1996

Sulfur and Hydrogen Isotope Anomalies in Organic Compounds from the Murchison Meteorite

Isotopic measurements have been made on organic sulfur and phosphorus compounds recently discovered in the Murchison meteorite. Carbon, hydrogen and sulfur measurements were performed on individual members of the organic sulfur compounds, alkyl sulfonates; and carbon and hydrogen measurements were made on bulk alkyl phosphonates. Cooper and Chang reported the first carbon isotopic measurements of Murchison organic sulfonates, providing insight into the potential synthetic mechanisms of these and, possibly, other organic species. Hydrogen isotopic measurements of the sulforiates now reveal deuterium excesses ranging from +660 to +2730 %. The deuterium enrichments indicate formation of the hydrocarbon portion of these compounds in a low temperature astrophysical environment consistent with that of dense molecular clouds. Measurements of the sulfur isotopes provide further constraints on the origin and mechanism of formation of these organic molecules. Recently, there has been growing documentation of sulfur isotopic anomalies in meteoritic material. Thiemens and Jackson have shown that some bulk ureilites possess excess S-33 and Thiemens et al. have reported excess S-33 in an oldhamite separate from the Norton County meteorite. Rees and Thode reported a large S-33 excess in an Allende acid residue, however, attempts to verify this measurements have been unsuccessful, possibly due to the heterogeneous nature of the carrier phase. With the recognition that sulfur isotopes may reflect chemistry in the protosolar nebula or the precursor molecular cloud, identification of potential carriers is of considerable interest. In the present study, the stable isotopes of sulfur were measured in methane sulfonic acid extracted from the Murchison meteorite. The isotopic composition was found to be: (delta)S-33 = 2.48 %, (delta)S-34 = 2.49 % and (delta)S-36 = 6.76 %. Based upon analysis of more than 60 meteoritic and numerous terrestrial samples, the mass fractionation lines are defined by Delta-33 = (delta)S-33 -0.50(delta)S-34 and Delta-36 = (delta)s-36 - 1.97 (delta)S-34. From these relationships Delta-33 = 1.24 % and Delta-36 = 0.89 % are observed. These anomalies, particularly the Delta-33, lie well outside the range of analytical uncertainty. They are the largest observed in any meteoritic component and the first found in an organosulfur compound. As discussed by Thiemens and Jackson, due to it's position on the periodic chart, sulfur undergoes chemically induced mass independent isotopic fractionations as does oxygen. Experiments by Mauersberger et. al. show that in such processes, the magnitude of fractionation for the different isotopically substituted species varies with mass and angular momentum; thus, anomalies are expected for both S-33 and S-36, but not necessarily of the same magnitude. Laboratory experiments have also confirmed that chemically produced, mass independent fractionations are mediated by molecular symmetry factors. A chemical source of fractionation requires that the sulfur isotopic anomaly was established in the gas phase, probably in reactions involving symmetric CS2. The discovery of an anomalous sulfur isotopic composition in a specific molecule containing excess deuterium is an important advance in the understanding of the cosmochemistry of sulfur. This evidence suggests that methanesulfonic acid was synthesized by interstellar processes. Further measurements and details of possible synthesis and fractionation mechanisms will be presented.

Cooper, G. W.↗
NASA NTRS2018

Chapter 6: Sulfur on Mars from the Atmosphere to the Core

Observations of the martian surface from orbiting spacecraft and in situ landers and rovers, as well as analyses of martian meteorites in terrestrial laboratories, have consistently indicated that Mars is a sulfur-rich planet. The global inventory of sulfur, from the atmosphere to the core, carries widespread implications of potential geophysical, geochemical, climatological, and astrobiological significance. For example, the sulfur content of the core carries implications for core density; the speciation of igneous sulfur minerals reflects the oxidation state of the magma from which they formed; sulfur-bearing gases may have exerted control on the temperatures at the surface of early Mars; and the widespread availability of sulfur on Mars would have provided an abundant source for energy and nutrients to fuel sulfur-metabolizing microbes, such as those that arose during the emergence of primitive life on Earth. Here we provide an overview of martian sulfur and its relevance to these areas of interest, including a discussion of analytical techniques and results acquired by space missions and meteorite analyses to date. We review current studies modeling the potential effects of sulfur-bearing gases on the past martian climate and possible constraints on atmospheric composition implied by sulfur isotopic data. We also explore the importance of sulfur to the search for extinct or extant life on Mars. Finally, we summarize a few areas of interest to future work, including advances in space exploration technology and preparation for Mars sample return.

Climate↗
NASA NTRS1996

Growth of the facultative anaerobe Shewanella putrefaciens by elemental sulfur reduction

The growth of bacteria by dissimilatory elemental sulfur reduction is generally associated with obligate anaerobes and thermophiles in particular. Here we describe the sulfur-dependent growth of the facultatively anaerobic mesophile Shewanella putrefaciens. Six of nine representative S. putrefaciens isolates from a variety of environments proved able to grow by sulfur reduction, and strain MR-1 was chosen for further study. Growth was monitored in a minimal medium (usually with 0.05% Casamino Acids added as a growth stimulant) containing 30 mM lactate and limiting concentrations of elemental sulfur. When mechanisms were provided for the removal of the metabolic end product, H2S, measurable growth was obtained at sulfur concentrations of from 2 to 30 mM. Initial doubling times were ca. 1.5 h and substrate independent over the range of sulfur concentrations tested. In the cultures with the highest sulfur concentrations, cell numbers increased by greater than 400-fold after 48 h, reaching a maximum density of 6.8 x 10(8) cells ml-1. Yields were determined as total cell carbon and ranged from 1.7 to 5.9 g of C mol of S(0) consumed-1 in the presence of the amino acid supplement and from 0.9 to 3.4 g of C mol of S(0-1) in its absence. Several lines of evidence indicate that cell-to-sulfur contact is not required for growth. Approaches for the culture of sulfur-metabolizing bacteria and potential ecological implications of sulfur reduction in Shewanella-like heterotrophs are discussed.

NASA Discipline Exobiology↗
NASA NTRS1975

Evidence for an elemental sulfur component of the clouds from Venus spectrophotometry

The decrease in the reflectivity of Venus in the near-UV can be explained if the clouds contain particles of elemental sulfur in addition to sulfuric acid. The low-resolution McDonald-Pittsburgh spectrum can be fitted by two sulfur-containing, multiple-scattering cloud models: (1) a mixed cloud consisting of one particle of elemental sulfur of radius 10 microns for every 670 particles of sulfuric acid of radius 1 micron, and (2) a layered cloud of optical thickness tau = 1.0 consisting of one-micron particles of sulfuric acid overlying a thick cloud of elemental sulfur particles of radius 3.6 microns. Some of the sulfur is incompletely polymerized. The source of the sulfur is photo-dissociation of COS, although some may also be recycled from the lower atmosphere. The sulfur plays a crucial role in the planetary meteorology of Venus since it is responsible for the bulk of the absorption of solar energy.

Hapke, B.↗
NASA NTRS2018

Chain Formation as a Mechanism for Mass-Independent Fractionation of Sulfur Isotopes in the Archean Atmosphere

The anomalous abundances of sulfur isotopes in ancient sediments provide the strongest evidence for an anoxic atmosphere prior to ∼2.45 Ga, but the mechanism for producing this 'mass-independent' fractionation pattern remains in question. The prevailing hypothesis has been that it is created by differences in the UV photolysis rates of different SO2 isotopologues. We investigate here a recently proposed additional source of fractionation during gas-phase formation of elemental sulfur (S4 and S8). Because two minor S isotopes rarely occur in the same chain, the longer S4 and S8 chains should be strongly, and roughly equally, depleted in all minor isotopes. This gives rise to negative ∆(sup 33) S values and positive ∆(sub 36) S values in elemental sulfur-just the opposite of (and much larger than) what is predicted from SO2 photolysis itself. Back-reactions during chain formation, specifically photolysis of S2 and S3, pass sulfur having the opposite fractionation back to atomic S, and thence to other sulfur species, causing H2S, SO2, sulfate, and short-chain elemental sulfur to have positive ∆(sup 33) S and negative ∆(sup 36) S. Positive ∆(sup 33) S values in elemental sulfur produced in laboratory SO2 photolysis experiments could be caused by the initial fractionation during photolysis, combined with rapid condensation of short-chain sulfur species on the walls of the reaction chamber, along with a scarcity of back-reactions. The simulated fractionations produced by the chain formation mechanism do not directly match fractionations from the rock record. The mismatch might be explained if the isotopic signals leaving the atmosphere were significantly modulated by life, by uncertainties in the rates of reactions of both major and minor isotopic sulfur species, or by the relatively large potential range of atmospheric parameters. Further work is needed to better constrain these uncertainties, but this novel mechanism suggests new avenues to explore in our search for a explanation for the S-MIF record.

Great Oxidation Event↗
NASA NTRS1991

Lunar sulfur

Ideas introduced by Vaniman, Pettit and Heiken in their 1988 Uses of Lunar Sulfur are expanded. Particular attention is given to uses of SO2 as a mineral-dressing fluid. Also introduced is the concept of using sulfide-based concrete as an alternative to the sulfur-based concretes proposed by Leonard and Johnson. Sulfur is abundant in high-Ti mare basalts, which range from 0.16 to 0.27 pct. by weight. Terrestrial basalts with 0.15 pct. S are rare. For oxygen recovery, sulfur must be driven off with other volatiles from ilmenite concentrates, before reduction. Troilite (FeS) may be oxidized to magnetite (Fe3O4) and SO2 gas, by burning concentrates in oxygen within a magnetic field, to further oxidize ilmenite before regrinding the magnetic reconcentration. SO2 is liquid at -20 C, the mean temperature underground on the Moon, at a minimum of 0.6 atm pressure. By using liquid SO2 as a mineral dressing fluid, all the techniques of terrestrial mineral separation become available for lunar ores and concentrates. Combination of sulfur and iron in an exothermic reaction, to form iron sulfides, may be used to cement grains of other minerals into an anhydrous iron-sulfide concrete. A sulfur-iron-aggregate mixture may be heated to the ignition temperature of iron with sulfur to make a concrete shape. The best iron, sulfur, and aggregate ratios need to be experimentally established. The iron and sulfur will be by-products of oxygen production from lunar minerals.

Kuck, David L.↗