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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.↗

Millimetre observations of comets P/Brorsen-Metcalf (1989o) and Austin (1989c1) with the IRAM 30-m radio telescope

Millimeter observations with the IRAM 30 m telescope were conducted in comet P/Brorsen-Metcalf (1989o) on September 1989 and Austin (1989c1) on April and May 1990. The HCN J(1-0) and J(3-2) lines were detected in both comets. The HCN production rate relative to water in P/Brorsen-Metcalf is comparable to that previously measured in comet P/Halley, while that inferred in comet Austin might be smaller by a factor of two. The H2CO(3 sub 12 - 2 sub 11) transition, marginally observed in comet P/Brorsen-Metcalf, was firmly detected in May 1990 in comet Austin. Observations performed at offset positions suggest that the source of H2CO might be distributed. The H2CO abundance is on the order of 0.5 percent that of water for both comets, assuming a scalelength of 10(exp 4) km at 1 AU from the Sun for the distributed source. During the May observing period of comet Austin, two new species were detected for the first time in a comet: hydrogen sulfide (H2S) through its 1(sub 10) - 1(sub 01) ortho line at 169 GHz, and methanol (CH3OH) through J(3-2) delta K = 0 transitions at 145 GHz. Preliminary estimates of their abundances are 1.5 x 10(exp -3) for H2S and 8 x 10(exp -3) for CH3OH.

Colom, P.↗

Millimeter-wave spectra of the Jovian planets

The millimeter wave portion of the electromagnetic spectrum is critical for understanding the subcloud atmospheric structure of the Jovian planets (Jupiter, Saturn, Uranus, and Neptune). This research utilizes a combination of laboratory measurements, computer modeling, and radio astronomical observation in order to obtain a better understanding of the millimeter-wave spectra of the Jovian planets. The pressure broadened absorption from gaseous ammonia (NH3) and hydrogen sulfide (H2S) was measured in the laboratory under simulated conditions for the Jovian atmospheres. Researchers developed new formalisms for computing the absorptivity of gaseous NH3 and H2S based on their laboratory measurements. They developed a radiative transfer and thermochemical model to predict the abundance and distribution of absorbing constituents in the Jovian atmospheres. They used the model to compute the millimeter wave emission from the Jovian planets.

Joiner, Joanna↗

The chemistry of dense interstellar clouds

The basic theme of this program is the study of molecular complexity and evolution in interstellar and circumstellar clouds incorporating the biogenic elements. Recent results include the identification of a new astronomical carbon-chain molecule, C4Si. This species was detected in the envelope expelled from the evolved star IRC+10216 in observations at the Nobeyama Radio Observatory in Japan. C4Si is the carrier of six unidentified lines which had previously been observed. This detection reveals the existence of a new series of carbon-chain molecules, C sub n Si (n equals 1, 2, 4). Such molecules may well be formed from the reaction of Si(+) with acetylene and acetylene derivatives. Other recent research has concentrated on the chemical composition of the cold, dark interstellar clouds, the nearest dense molecular clouds to the solar system. Such regions have very low kinetic temperatures, on the order of 10 K, and are known to be formation sites for solar-type stars. We have recently identified for the first time in such regions the species of H2S, NO, HCOOH (formic acid). The H2S abundance appears to exceed that predicted by gas-phase models of ion-molecule chemistry, perhaps suggesting the importance of synthesis on grain surfaces. Additional observations in dark clouds have studied the ratio of ortho- to para-thioformaldehyde. Since this ratio is expected to be unaffected by both radiative and ordinary collisional processes in the cloud, it may well reflect the formation conditions for this molecule. The ratio is observed to depart from that expected under conditions of chemical equilibrium at formation, perhaps reflecting efficient interchange between cold dust grains in the gas phase.

Irvine, W. M.↗

g-factors of the SH (0-0) band and SH upper limit in Comet P/Brorsen-Metcalf (1989o)

A search for SH, the prime dissociative product of H2S, has been prompted by the microwave-band detection of H2S in Comets Austin and Levy. Attention is accordingly given here to g-factors for the A-X (0-0) band of SH as a function of heliocentric velocity at a heliocentric distance of 1 AU. An upper-limit production rate for SH relative to water of 0.017 is derived for the case of Comet P/Brorsen-Metcalf. A dissociative lifetime of 105 sec, at 1 AU heliocentric distance, and a heliocentric velocity of -28.5 km/sec, are also obtained.

Kim, Sang J.↗

Albedo patterns and gypsum generation in the central Namib Desert - Land, sea and air interactions on an arid West Coast

In the central Namib Desert, dune-free surfaces are separated abruptly from a sea of yellow and red sand dunes at the Kuiseb River canyon. The off-white hues of the dune-free area result from anomalously high surficial gypsum enrichment. Satellite imagery indicates that the gypsum surfaces are associated with lower surface maximum temperatures than those of the darker dune surfaces to the south. One of various sources of sulfate for the gypsum bodies is oceanic H2S, supplied to desert land-surfaces by regular fog incursions. Since fog events are widespread along the coast, the question of anomalous gypsum accumulations north of the dune sea arises. Satellite imagery, in conjunction with more detailed handheld photography from the space shuttle, indicates that the penetration of fog inland is significantly greater over the gypsum surfaces than it is over the dunes. It is postulated that the thermal gradient between these surfaces generates a heat low centered over the northern part of dune sea and that this enhances fog and H2S advection on its north side onto the nearby dune-free zone. In such a system, gypsum/caliche surfaces reinforce advection of fog over themselves in a positive feedback mode.

Wilkinson, M. J.↗

Emissions of sulfur gases from wetlands

Data on the emissions of sulfur gases from marine and freshwater wetlands are summarized with respect to wetland vegetation type and possible formation mechanisms. The current data base is largest for salt marshes inhabited by Spartina alterniflora. Both dimethyl sulfide (DMS) and hydrogen sulfide (H2S) dominate emissions from salt marshes, with lesser quantities of methyl mercaptan (MeSH), carbonyl sulfide (COS), carbon disulfide (CS2) and dimethyl disulfide (DMDS) being emitted. High emission rates of DMS are associated with vegetation that produces the DMS precursor dimethylsulfonionpropionate (DMSP). Although large quantities of H2S are produced in marshes, only a small percentage escapes to the atmosphere. High latitude marshes emit less sulfur gases than temperate ones, but DMS still dominates. Mangrove-inhabited wetlands also emit less sulfur than temperate S. alterniflora marshes. Few data are available on sulfur gas emissions from freshwater wetlands. In most instances, sulfur emissions from temperate freshwater sites are low. However, some temperate and subtropical freshwater sites are similar in magnitude to those from marine wetlands which do not contain vegetation that produces DMSP. Emissions are low in Alaskan tundra but may be considerably higher in some bogs and fens.

Hines, Mark E.↗

Troilite formation kinetics and growth mechanism in the solar nebula

Troilite formation via the reaction Fe(s) + H2S(g) + H2(g) is the major mechanism for S retention in grains in the solar nebula. Thermodynamic calculations predict that troilite condenses from a solar composition gas. We present experimental results on the kinetics and growth of troilite crystals on Fe metal at temperature (450-650 C) and composition (50-1000 ppm H2S in H2) conditions similar to those in the solar nebula. The fraction of Fe reacted (based on gravimetric data) is plotted at 450, 505, 575, and 650 C. The thickness change of unreacted iron (measured by optical microscopy) is plotted at 575 and 650 C vs. time. the weight change per unit area varies as the square root of time at the lower temperatures and varies linearly with time at the highest temperature. The growth behavior along the lower isotherms is due to diffusion. This behavior suggests sulfide diffusion to the metal-sulfide interface and suggests Fe(2+) diffusion to the sulfide-gas interface. The reaction along the highest isotherm appears to be interface controlled. The formation of troilite crystals is a rapid process forming measurable layers in a few hours. The crystalgrowth is complicated. Initially there are intergrowths of troilite into the pure Fe metal. As the reaction progresses two distinct layers of troilite crystals form. One is in contact with the Fe metal and consists of small randomly oriented crystals with pore space between them. The outermost layer contains large crystals that are all oriented in the same direction. The intergrowth layer is much smaller at 650 C than at 575 C. This suggest that FeS nucleation is inhibited at the higher temperature, accounting for the initially slower reaction rate. Once nucleated, the reaction kinetics are apparently controlled by the growth of the crystals at the interface.

Lauretta, D. S.↗

Geochemical constraints on chemolithoautotrophic reactions in hydrothermal systems

Thermodynamic calculations provide the means to quantify the chemical disequilibrium inherent in the mixing of reduced hydrothermal fluids with seawater. The chemical energy available for metabolic processes in these environments can be evaluated by taking into account the pressure and temperature dependence of the apparent standard Gibbs free energies of reactions in the S-H2-H2O system together with geochemical constraints on pH, activities of aqueous sulfur species and fugacities of H2 and/or O2. Using present-day mixing of hydrothermal fluids and seawater as a starting point, it is shown that each mole of H2S entering seawater from hydrothermal fluids represents about 200,000 calories of chemical energy for metabolic systems able to catalyze H2S oxidation. Extrapolating to the early Earth, which was likely to have had an atmosphere more reduced than at present, shows that this chemical energy may have been a factor of two or so less. Nevertheless, mixing of hydrothermal fluids with seawater would have been an abundant source of chemical energy, and an inevitable consequence of the presence of an ocean on an initially hot Earth. The amount of energy available was more than enough for organic synthesis from CO2 or CO, and/or polymer formation, indicating that the vicinity of hydrothermal systems at the sea floor was an ideal location for the emergence of the first chemolithoautotrophic metabolic systems.

Shock, Everett L.↗

g-Factors of the SH (0-0) Band and SH Upper Limit in Comet P/Brorsen-Metcalf (1980o)

Since H2S was detected in Comets Austin (1989cl) and Levy (1990c) in the microwave range, there has been increasing interest in searching for SH, which is the prime dissociative product of H2S. We present g-factors for the A-X (0-0) band of SH as a function of heliocentric velocity at r = 1.0 AU. We derive an upper limit production rate, Q(SH)/Q(H2O) less than 0.017, for Comet Brorsen-Metcalf (1989o) and calculate a dissociative lifetime of 105 sec at a heliocentric distance, r = 1.0 AU, and at a heliocentric velocity, v(r) = -28.5 km/sec.

Kim, Sang J.↗

Chemical Analyses

As a preliminary study on the effects of chemical aging of polymer materials MERL and TRI have examined two polymeric materials that are typically used for offshore umbilical applications. These two materials were Tefzel, a copolymer of ethylene and tetrafluoroethylene, and Coflon, polyvinylidene fluoride. The Coflon specimens were cut from pipe sections and exposed to H2S at various temperatures and pressures. One of these specimens was tested for methane permeation, and another for H2S permeation. The Tefzel specimens were cut from .05 mm sheet stock material and were exposed to methanol at elevated temperature and pressure. One of these specimens was exposed to methanol permeation for 2 days at 100 C and 2500 psi. An additional specimen was exposed to liquid methanol for 3 days at 150 C and 15 Bar. Virgin specimens of each material were similarly prepared and tested.

Bulluck, J. W.↗

Comet Shoemaker-Levy 9, Jupiter, and Impact Shock Chemistry

Four years ago this month, a hitherto unknown comet in loose orbit around Jupiter passed so near the giant planet that it was torn apart into 20 fragments by tides. One orbit later, two years ago this month, the fragments of doomed comet P/Shoemaker Levy (SL9) fell into Jupiter. The enormous energies of these impacts (the largest fragments were nearly 1 km across and, hitting at 60 km/s, released some 2-4 x 10(exp 27) ergs) produced enormous explosions. Several of the ejecta plumes were imaged towering 3000 km above Jupiter's limb. The heat released when the plumes fell was considerable and easily observed on Earth. The impacts produced strong shocks, both promptly at the impact site and again, later, and over thousands of kilometers, when the ejecta plume reentered the atmosphere. The focus of this talk will be to discuss what the SL9 impacts taught us about impact shock chemistry - the processes, the ingredients, the results - and what inferences we may draw for impacts on early Earth. Shock chemistry generates a suite of molecules not usually seen on Jupiter. The most surprising report was of a huge amount of diatomic sulfur S2 at the site of the G impact. Other unusual products include CS, CS2, OCS, H2S, SO2, HCN, CO, and H2O; although H2S and H2O are doubtless abundant below the visible clouds. Hot or enhanced CH4 and NH3 were also detected. A general rule of shock chemistry is that CO forms until either C or O is exhausted. If O greater than C, the other products are oxidized, and excess O goes to H2O. If C greater than O, the other products are reduced, and excess C goes to HCN, C2H2, and a wide variety of more complicated organics. Ultimately, given time, the carbon would react all the way to graphite, but in practice the reactions are incomplete. The dark ejecta debris were probably composed in part of carbonaceous particles generated by the shocks. In a sense, the SL9 impacts performed the famous Miller-Urey experiment on a grand scale, with one result being the production of a lot of complex brown organic solids (called "tholins"). We use, a straightforward chemical kinetics model for the H, N, C, O, S system to follow the nonequilibrium chemistry behind the shocks. The model traces the evolving chemical composition of a parcel of gas by directly integrating the web of chemical reactions. Pressure and temperature histories of the parcels are patterned after those calculated by numerical hydrodynamic simulations of the ejecta plume. A given plume parcel is generally shocked twice; t.e a parcel shocked near the impact site is ejected at high velocity and is shocked again when it reenters the atmosphere. The final state of the gas depends mostly on the second shock, provided that the latter is hot enough. The chemical evidence is ambiguous, but most indications are that C greater than O in the shocked, reacting gas. Telltale signatures of abundant oxygen - SO2, SO, CO2, O2 - were not seen, while signatures of abundant carbon - CS, CS2, and HCN - were. On the other hand, abundant H2O would appear to require O greater than C, and two other observed sulfur species, S2 and OCS, appear to form more easily in a somewhat oxidized gas, presumable vaporized from the comet itself. Since on general principles one expects the -comet to have had a more-or-less cosmic composition, i.e. O greater than C, the production of CS, CS2, and HCN probably requires C greater than O in the shocked jovian air. This in turn implies that even the largest fragments released the bulk of their energy above the jovian water table, in all likelihood above 5 bars . There is no evidence in favor of the proposition that a significant amount of wet jovian air was shocked strongly enough to coax water to react; i.e. wet jovian air saw only temperatures significantly below 2000 K.

Zahnle, Kevin↗

CIGS2 Thin-Film Solar Cells on Flexible Foils for Space Power

CuIn(1-x)Ga(x)S2 (CIGS2) thin-film solar cells are of interest for space power applications because of the near optimum bandgap for AM0 solar radiation in space. CIGS2 thin film solar cells on flexible stainless steel (SS) may be able to increase the specific power by an order of magnitude from the current level of 65 Wkg(sup -1). CIGS solar cells are superior to the conventional silicon and gallium arsenide solar cells in the space radiation environment. This paper presents research efforts for the development of CIGS2 thin-film solar cells on 127 micrometers and 20 micrometers thick, bright-annealed flexible SS foil for space power. A large-area, dual-chamber, inline thin film deposition system has been fabricated. The system is expected to provide thickness uniformity of plus or minus 2% over the central 5" width and plus or minus 3% over the central 6" width. During the next phase, facilities for processing larger cells will be acquired for selenization and sulfurization of metallic precursors and for heterojunction CdS layer deposition both on large area. Small area CIGS2 thin film solar cells are being prepared routinely. Cu-rich Cu-Ga/In layers were sputter-deposited on unheated Mo-coated SS foils from CuGa (22%) and In targets. Well-adherent, large-grain Cu-rich CIGS2 films were obtained by sulfurization in a Ar: H2S 1:0.04 mixture and argon flow rate of 650 sccm, at the maximum temperature of 475 C for 60 minutes with intermediate 30 minutes annealing step at 120 C. Samples were annealed at 500 C for 10 minutes without H2S gas flow. The intermediate 30 minutes annealing step at 120 C was changed to 135 C. p-type CIGS2 thin films were obtained by etching the Cu-rich layer segregated at the surface using dilute KCN solution. Solar cells were completed by deposition of CdS heterojunction partner layer by chemical bath deposition, transparent-conducting ZnO/ZnO: Al window bilayer by RF sputtering, and vacuum deposition of Ni/Al contact fingers through metal mask. PV parameters of a CIGS2 solar cell on 127 micrometers thick SS flexible foil measured under AM 0 conditions at NASA GRC were: V(sub oc) = 802.9 mV, J(sub sc) = 25.07 mA per square centimeters, FF = 60.06%, and efficiency 0 = 8.84%. For this cell, AM 1.5 PV parameters measured at NREL were: V(sub oc) = 788 mV, J(sub sc) = 19.78 mA per square centimeter, FF = 59.44%, efficiency 0 = 9.26%. Quantum efficiency curve showed a sharp QE cutoff equivalent to CIGS2 bandgap of approximately 1.50 eV, fairly close to the optimum value for efficient AM0 PV conversion in the space.

Dhere, Neelkanth G.↗

Formation and Stability of Radiation Products in Europa's Icy Shell

Spectra of Europa reveal a surface dominated by water-ice along with hydrated materials and minor amounts of SO2, CO2, and H2O2. Jovian magnetospheric ions (protons, sulfur, and oxygen) and electrons produce significant chemical modifications of the surface on time scales of a few years at micrometer depths. Our laboratory studies examine the formation and stability of radiation products in H2O-rich ices relevant to Europa. Infrared (IR) spectra of ices before and after irradiation reveal the radiation destruction of molecules and the formation of products at 86 - 132 K. In addition, spectra of ices during warming track thermal evolution due to chemical changes and sublimation processes. IR-identified radiation products in 86 - 132 K irradiated H2O + SO2 ices are the bisulfate ion, HSO4(-), sulfate ion, SO4(2-) and the hydronium ion, H3O(+). Warming results in the formation of a residual spectrum similar to liquid sulfuric acid, H2SO4, for H2O:SO2 ratios of 30:1, whereas hydrated sulfuric acid, H2SO4 4 H2O, forms for ratios of 30:1. Radiation products identified for irradiated H2O + H2S ices at 86 K are H2S2 and SO2. When irradiated at 110 and 132 K, ices with H2O:H2S ratios if either 3:1 or 30:1 show the formation of H2SO4 4 H2O on warming to 175 K. We have also examined the radiation stability of H2SO4. Addition of CO2 to H2O + SO2 ices results in the formation of CO3 at 2046 cm (sup -1) (4.89 m). This is the strongest band from a carbon-containing product in the mid-IR spectral region, and it is also seen when either pure CO2 or H2O + CO2 ice is irradiated. Experiments with CH4 added to H2O + SO2 + CO2 ices addressed the question of methane's use as a marker of methanogens in an irradiated ice environment. New results on the near-IR spectrum of pure H2O2 will be included in this presentation. Interpretations of near-IR water bands, with H2O2 present, will be discussed. Irradiations of H2O2 and H2O + H2O2 mixtures, to examine the possibility of O2 and O3 formation, are currently under investigation and new results will be discussed.

Moore, M. H.↗

Competition for sulfide among colorless and purple sulfur bacteria in cyanobacterial mats

The vertical zonation of light, O2, H2S, pH, and sulfur bacteria was studied in two benthic cyanobacterial mats from hypersaline ponds at Guerrero Negro, Baja California, Mexico. The physical-chemical gradients were analyzed in the upper few mm at < or = 100 micrometers spatial resolution by microelectrodes and by a fiber optic microprobe. In mats, where oxygen produced by photosynthesis diffused far below the depth of the photic zone, colorless sulfur bacteria (Beggiatoa sp.) were the dominant sulfide oxidizing organisms. In a mat, where the O2-H2S interface was close to the photic zone, but yet received no significant visible light, purple sulfur bacteria (Chromatium sp.) were the dominant sulfide oxidizers. Analysis of the spectral light distribution here showed that the penetration of only 1% of the incident near-IR light (800-900 nm) into the sulfide zone was sufficient for the mass development of Chromatium in a narrow band of 300 micromoles thickness. The balance between O2 and light penetration down into the sulfide zone thus determined in micro-scale which type of sulfur bacteria became dominant.

NASA Center ARC↗

High-Temperature Desulfurization of Heavy Fuel-Derived Reformate Gas Streams for SOFC Applications

Desulfurization of the hot reformate gas produced by catalytic partial oxidation or autothermal reforming of heavy fuels, such as JP-8 and jet fuels, is required prior to using the gas in a solid oxide fuel cell (SOFC). Development of suitable sorbent materials involves the identification of sorbents with favorable sulfidation equilibria, good kinetics, and high structural stability and regenerability at the SOFC operating temperatures (650 to 800 C). Over the last two decades, a major barrier to the development of regenerable desulfurization sorbents has been the gradual loss of sorbent performance in cyclic sulfidation and regeneration at such high temperatures. Mixed oxide compositions based on ceria were examined in this work as regenerable sorbents in simulated reformate gas mixtures and temperatures greater than 650 C. Regeneration was carried out with dilute oxygen streams. We have shown that under oxidative regeneration conditions, high regeneration space velocities (greater than 80,000 h(sup -1)) can be used to suppress sulfate formation and shorten the total time required for sorbent regeneration. A major finding of this work is that the surface of ceria and lanthanan sorbents can be sulfided and regenerated completely, independent of the underlying bulk sorbent. This is due to reversible adsorption of H2S on the surface of these sorbents even at temperatures as high as 800 C. La-rich cerium oxide formulations are excellent for application to regenerative H2S removal from reformate gas streams at 650 to 800 C. These results create new opportunities for compact sorber/regenerator reactor designs to meet the requirements of solid oxide fuel cell systems at any scale.

Flytzani-Stephanopoulos, Maria↗

Prebiotic Synthesis of Methionine and Other Sulfur-Containing Organic Compounds on the Primitive Earth: A Contemporary Reassessment Based on an Unpublished 1958 Stanley Miller Experiment

Original extracts from an unpublished 1958 experiment conducted by the late Stanley L. Miller were recently found and analyzed using modern state-of-the-art analytical methods. The extracts were produced by the action of an electric discharge on a mixture of methane (CH4), hydrogen sulfide (H2S), ammonia (NH3), and carbon dioxide (CO2). Racemic methionine was farmed in significant yields, together with other sulfur-bearing organic compounds. The formation of methionine and other compounds from a model prebiotic atmosphere that contained H2S suggests that this type of synthesis is robust under reducing conditions, which may have existed either in the global primitive atmosphere or in localized volcanic environments on the early Earth. The presence of a wide array of sulfur-containing organic compounds produced by the decomposition of methionine and cysteine indicates that in addition to abiotic synthetic processes, degradation of organic compounds on the primordial Earth could have been important in diversifying the inventory of molecules of biochemical significance not readily formed from other abiotic reactions, or derived from extraterrestrial delivery.

Parker, Eric T.↗

Sources of Sulfate Found in Mounds and Lakes at the Lewis Cliffs Ice Tongue, Transantarctic

Massive but highly localized Na-sulfate mounds (mirabilite, Na2SO4.10H2O) have been found at the terminal moraine of the Lewis Cliffs Ice Tongue (LCIT), Antarctica. (Sigma)34S and (Sigma)18O values of LCIT mirabilite range from +48.8 to +49.3% (CDT), and -16.6 to -17.1% (V-SMOW), respectively, while (Delta)17O average -0.37% (V-SMOW). LCIT mirabilite mounds are isotopically different from other mirabilite mounds found in coastal regions of Antarctica, which have isotope values close to seawater compositions. (Sigma)18O and (Delta)17O values suggest the incorporation of isotopically light glacial water. Data point to initial sulfate formation in an anoxic water body, either as a stratified anoxic deep lake on the surface, a sub-glacial water reservoir, or a sub-glacial lake. Several surface lakes of varying size are also present within this region of the LCIT, and in some cases are adjacent to the mirabilite mounds. O and D isotope compositions of surface lakes confirm they are derived from a mixture of glacial ice and snow that underwent moderate evaporation. (Sigma)18O and (Sigma)D (V-SMOW) values of snow, ice, and lake water range from -64.2 to -29.7%, and -456.0 to -231.7%, respectively. However, the isotope chemistry of these surface lakes is extremely different from the mounds. Dissolved SO4-2 (Sigma)34S and (Sigma)18O values range from +12.0 to +20.0% and -12.8 to -22.2% (the most negative (Sigma)18O of terrestrial sulfate ever reported), respectively, with sulfate (Delta)17O ranging from +0.93 to 2.24%. Ion chromatography data show that lake water is fresh to brackish in origin, with TDS less than 1500 ppm, and sulfate concentration less than 431 ppm. Isotope and chemical data suggest that these lakes are unlikely the source of the mirabilite mounds. We suggest that lake water sulfate is potentially composed of a mixture of atmospheric sulfate and minor components of sulfate of weathering origin, much like the sulfate in the polar plateau soils of the McMurdo Dry Valleys. A simple model explains mirabilite mound formation at the LCIT. Sulfur redox processes could occur sub-glacially as a result of liquid-water-based glacial conditions (Alpine style glacier), most likely formed by pressure melting of overlying ice (Aharon, GCA, 52, 2321-2331). We suggest that the aqueous base of the LCIT contains dissolved SO42- and is anoxic where sulfate reduction to H2S, HS-, or native sulfur takes place. Sulfide is removed by either precipitation as sulfide minerals or by escape of H2S (neither of which have been observed). Mirabilite precipitation is likely the result of evaporation or freezing of sulfate-rich brines as they reach the surface where they manifest themselves as mounds. Pressure from the overlying ice contributing to a pressure-melting scenario that creates the sub-glacial aqueous environment also contributes to the mechanism of upward transport of the sulfate-rich fluids. Further evidence to support this upward transport model comes from the nature of ice motion at the LCIT. Cassidy et al (Meteoritics, 27, 490-525, 1992) pointed out that it is the vertical ice motion in this area that creates the meteorite-stranding surface that could also account for upward transport of sulfate-rich fluids. Alternatively, mirabilite was deposited in a similar condition as present-day coastal Antarctica when the LCIT was wetter and warmer

Socki, Richard↗