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At least 73 records · Page 4

Thermoelectric properties of non-stoichiometric lanthanum sulfides

The lanthanum sulfides are promising candidate materials for high-efficiency thermoelectric applications at temperatures up to 1300 C. The non-stoichiometric lanthanum sulfides (LaS(x), where x is in the range 1.33-1.50) appear to possess the most favorable thermoelectric properties. The Seebeck coefficient and resistivity vary significantly with composition, so that an optimum value of alpha sq/rho (where alpha is the Seebeck coefficient and rho is the resistivity) can be chosen. The thermal conductivity remains approximately constant with stoichiometry, so a material with an optimum value of alpha sq/rho should possess the optimum figure-of-merit. Data for the Seebeck coefficient and electrical resistivity of non-stoichiometric lanthanum sulfides will be pressed, together with structural properties of these materials.

Shapiro, E.↗

Microbial communities and microprofiles of sulfide and oxygen of alum rock sulfur springs

The microbial community of Alum Rock sulfur spring Site 3 was studied along one branch of the main stream and between the two branches, 150 cm distant from the source. The community at the source was dominated by green sulfur photosynthetic bacteria of the genus Chlorobium. At 15 cm to 35 cm from the source dominance in the community shifted to the genus Flexibacter at the surface of the mat and purple bacteria of the genus Chromatium underneath. At 50 cm to 80 cm colorless sulfur oxidizing bacteria of the genus Thiothrix began to appear. At 100 cm to 150 cm, the surface of the mat was still dominated by Flexibacter, but underneath dominance shifted to purple sulfur bacteria as above, as well as cyanobacteria of the genus Oscillatoria and Pseudonabaena. The measurements of temperature along the stream showed no significant gradient. Community variations appear to be controlled more by sulfide than temperature. Ten ml of the overlying water were taken and fixed immediately to determine the sulfide concentration by the methylene blue method. A sulfide concentration of 106 micro-m was calculated for the overlying water.

Fischer, U.↗

Sulfides and oxides in comets

Metal abundances associated with Sun-grazing P/comet Ikeya-Seki 1965f, the mineralogy of chrondritic interplanetary dust particles and cosmochemical affinities of Co, V, Cr, and Ni in extraterrestrial materials and probable vaporization data for nonsilicate minerals are used to evaluate the putative dearth of nonsilicates in short-period comets. It is concluded that sulfides and oxides are common, albeit minor, constituents of these comets. Sulfides and oxides can form in situ during perihelion passage in the nucleus of active short-period comets by sulfidation of Mg, Fe-silicates.

Rietmeijer, Frans J. M.↗

Micrometeorite dynamic pyrometamorphism: Observation of a thermal gradient in iron-nickel sulfide

Dynamic pyrometamorphism describes the mineralogical changes in a micrometeorite that occur in response to flash-heating during atmospheric entry. Mineral reactions during this event will be endothermic and act as local sinks for thermal energy which delays a uniform temperature distribution in decelerating micrometeorites. The most common pyrometamorphic reaction is formation of magnetite nanocrystal decorations on Mg,Fe-silicate grains and magnetite or (partial) maghemite rims. Constituent silicates also respond to this thermal event and show formation of olivine-maghemite symplectites and growth of garnet and partial laihunitisation. In continued effort to constrain dynamic pyrometamorphism of unmelted interplanetary dust particles (IDP's), I determined the mineralogical composition, and Fe,Ni-sulfide chemistry, in the sulfide-rich particles L2005C39, L2005E40, and L2006A28 using a JEOL 2000FX analytical electron microscope equipped with a TN5500 energy dispersive spectrometer for in situ microanalysis. Sulfide compositions in these three IDP's are distinctly different from those in silicate-rich particle L2005T13 which might suggest a delicate balance of the fO2/fS2 ratios during dynamic pyrometamorphism.

Rietmeijer, Frans J. M.↗

Redetermination of piperidinium hydrogen sulfide structure

The presence of adventitious water in a reaction between dicyclopentamethylene thiuram-disulfide (C5H10NCS2)(sub 2) and a picoline solution of tricyclopentadienyl indium(III) (C5H5)(sub 3). It resulted in the formation of piperidinium hydrogen sulfide (C5H13NS). The piperidinium hydrogen sulfide produced in this way was unambiguously characterized by X-ray crystallography. The structure determination showed that the piperidinium hydrogen sulfide crystal (MW = 119.23 g/mol) has an orthorhombic (Pbcm) unit cell whose parameters are: a = 9.818(2), b = 7.3720(1), c = 9.754(1) A, V = 706.0(3) A(exp 3), Z=4. D(sub chi) = 1.122 g cm(exp -3), Mo K(alpha) (lamda = 0.71073), mu= 3.36 cm(exp -1), F(000) = 264.0, T =293 K, R = 0.036 for 343 reflections with F(sub O)(sup 2) greater than 3 sigma (F(sub O)(sup 2)) and 65 variables. The compound consists of (C5H10NH2)(+) cations and (SH)(-) anions with both species residing on crystallographic mirror planes. N-H -- S hydrogen bonding contributes to the interconnection of neighboring piperidinium components of the compound.

Andras, Maria T.↗

Melt Growth of a Nonlinear Optical Crystal Triethylphosphine Sulfide using Modified Bridgman-Stockbarger Technique

Bulk single crystals of triethylphosphine sulfide (C2H5)3P(S), a potential nonlinear optical organic material has been grown from melt using Bridgman- Stockbarger method. Commercially available material triethylphosphine sulfide procured from Johnson Matthey was purified by physical vapor transport using low pressure sublimaton (about 30 mTorr). Modified Bridgman-Stockbarger technique is characterized by the smallest possible quantity of product in the melt for a short period of time. The temperature gradient was chosen to be about 10 C/cm and the ampoule was lowering rate was chosen to be 0.2-0.3 mm/h. For various growth conditions, several single crystal of triethylphosphine sulfide have been grown with sizes 10X10X15mm(exp 3). The second harmonic generation (SHG) efficiency was measured and has been found to be comparable to phase matched potassium dihydrogen phosphate crystals. Further characterization of the grown single crystals is in progress and the results will be presented at the symposium.

Curry, K.↗

Theoretical Study of the First Transition Row Oxides and Sulfides

The first transition row oxides and sulfides are studied using several different levels of theory. The calculations show the bonding mechanism in the sulfides and oxides to be very similar. For the oxides, accurate experimental data allow the theoretical methods to be calibrated. The same level of theory is used to study the sulfides where there is far less experimental information. For ScO through MnO and CuO the coupled cluster singles and doubles technique including a perturbational estimate of the unliked triple excitations [CCSD(T)] yields spectroscopic constants ((tau)e, (omega)e, and D0) in good agreement with experiment. The triple excitations are found to be very important in achieving this accuracy. For FeO to NiO, the single determinant self-consistent-field (SCF) approach yields pi orbitals that are localized on the metal or oxygen. This appears to cause problems for the single reference techniques; this is discussed in detail for NiO. The complete-active-space SCF/internally contracted averaged coupled pair functional approach (CASSCF/ICACPF) works well for FeO to NiO. The calculation of accurate dipole moments is found to be very difficult.

Bauschlicher, Charles W., Jt.↗

Sulfide Stability of Planetary Basalts

The isotopic system, 187Re 187Os, can be used to determine the role of crust and mantle in magma genesis. In order to apply the system to natural samples, we must understand variations in Re/Os concentrations. It is thought that low [Os] and [Re] in basalts can be attributed to sulfide (FeS) saturation, as Re behaves incompatibly to high degrees of evolution until sulfide saturation occurs [1]. Previous work has shown that lunar basalts are sulfide under-saturated, and mid-ocean ridge, ocean-island and Martian (shergottites) basalts are saturated [2,3]. However, little is known about arc basalts. In this study, basaltic rocks were analyzed across the Trans-Mexican Volcanic Belt.

Caiazza, C. M.↗

Sulfur isotope effects associated with oxidation of sulfide by O2 in aqueous solution

Normal sulfur isotope effects averaging epsilon = -5.2 +/- 1.4% (s.d.) were consistently observed for the oxidation of sulfide in aqueous solution. Reaction products were sulfate, thiosulfate and sulfite at pH 10.8-11 in distilled water; S0 was formed in two experiments with synthetic seawater at pH 8-9.5. Because the -5.2% normal isotope effect differs significantly from the previously measured +2% inverse effect associated with anaerobic oxidation of sulfide by photosynthetic bacteria, stable sulfur isotopic measurements are potentially useful for distinguishing aerobic vs. anaerobic sulfide oxidation in marine and freshwater sulfureta.

NASA Program Exobiology↗

Method of epitaxially depositing cadmium sulfide

A single crystal layer of either cadmium sulfide or an alloy of cadmium sulfide and indium phosphide is epitaxially deposited on a substrate of cadmium sulfide by liquid phase epitaxy using indium as the solvent.

Hawrylo, Frank Z.↗

Formation of "Chemically Pure" Magnetite from Mg-Fe-Carbonates Implications for the Exclusively Inorganic Origin of Magnetite and Sulfides in Martian Meteorite ALH84001

Magnetite and sulfides in the black rims of carbonate globules in Martian meteorite ALH84001 have been studied extensively because of the claim by McKay et al. that they are biogenic in origin. However, exclusively inorganic (abiotic) processes are able to account for the occurrence of carbonate-sulfide-magnetite assemblages in the meteorite. We have previously precipitated chemically zoned and sulfide-bearing carbonate globules analogous to those in ALH84001 (at less than or equal to 150 C) from multiple fluxes of variable-composition Ca-Mg-Fe-CO2-S-H2O solutions. Brief heating of precipitated globules to approx. 470 C produced magnetite and pyrrhotite within the globules by thermal decomposition of siderite and pyrite, respectively. We have also shown that morphology of magnetite formed by inorganic thermal decomposition of Fe-rich carbonate is similar to the morphology of so-called biogenic magnetite in the carbonate globules of ALH84001. Magnetite crystals in the rims of carbonate globules in ALH84001 are chemically pure [Note: "Chemically pure" is defined here as magnetite with Mg at levels comparable or lower than Mg detected by [8] in ALH84001 magnetite]. A debate continues on whether or not chemically pure magnetite can form by the thermal decomposition of mixed Mg-Fe-carbonates that have formed under abiotic conditions. Thomas-Keprta et al. argue that it is not possible to form Mg-free magnetite from Mg-Fe-carbonate based on thermodynamic data. We previously suggested that chemically pure magnetite could form by the thermal decomposition of relatively pure siderite in the outer rims of the globules. Mg-Fe-carbonates may also thermally decompose under conditions conducive for formation of chemically pure magnetite. In this paper we show through laboratory experiments that chemically pure magnetite can form by an inorganic process from mixed Mg-Fe-carbonates.

Golden, D. C.↗

Temperature Effect on Silicate Melt-Sulfide-Metal Trace Element Partitioning in the Presence of Sulfur Under Reduced Conditions

The reduced nature of Mercury, enstatite chondrites, and the aubrite parent bodies (APB) have raised many questions regarding the geochemical behavior of typically lithophile, heat-producing, and rare-earth elements (REE) in magmas at low oxygen fugacity (fO2). Due to decreasing O availability at these low fO2, and an abundance of S(sup 2(-)), sulfur (S) acts as an important anion that changes the partitioning behavior of many elements and modifies the physical properties of silicate melts. Preliminary observations suggest that major and minor elements exhibit different geochemical affinities in highly reduced, S-rich systems compared to terrestrial rocks. The speciation and bonding environment of S, dictated by P/T/fO2 conditions, may strongly influence the degree to which S affects partitioning behavior. Here we investigate the partitioning behavior of major, minor, and trace elements between silicate melt, sulfide melt, and metal as well as the coordination chemistry of S in highly reduced silicate melts. Our work is focused on investigating solely the entropy-dependent temperature effect on partitioning of elements for which we currently have MESSENGER data (K, Na, Th, U, Si, Mg, Fe, Ti, Ca, Al, Cr, Mn, S, Cl) as well as a host of geochemically relevant trace elements such as REEs (P, Co, Ni, Mo, Ce, Nd, Sm, Eu, Gd, Dy, Yb). Previous studies in which temperature, pressure, and fO2 were co-varied found that as fO2 decreases, heat-producing elements U and Th become more chalcophile, while K becomes less chalcophile. Concurrently, nominally lithophile elements Mg and Ca become more chalcophile and were observed as minor elements in exsolved sulfides and bonded with S species in silicate melt. These studies, however, could not disentangle entropic effects from changes in the fO2. New temperature-dependent partitioning data from our work will be used to determine which elements are most likely to retain their lithophile character and hence be incorporated into silicates, and which elements are likely contained within the sulfide (chalcophile) and metal core (siderophile), setting the stage for the thermal and magmatic evolution of reduced planetary bodies.

B A Anzures↗

Exposure Limits for Hydrogen Sulfide in Spaceflight

Hydrogen sulfide (H 2 S) has not historically been detected in spacecraft, but the possible evolution of volatile components from polar ice on the lunar surface is a potential concern for NASA’s planned Artemis missions. Numerous case reports and occupational epidemiological studies document that exposure to H 2 S at high concentrations has effects on the respiratory system, potentially leading to unconsciousness followed by debilitating neurological effects. Studies in rodents demonstrate sensitivity of the respiratory system to lower concentrations of H 2 S. Adverse respiratory effects have also been indicated in workers chronically exposed to H 2 S. The objective of the present publication is to develop Spacecraft Maximum Allowable Concentrations (SMACs) for H 2 S for all current standard durations of exposure for spaceflight (1-hour, 24-hours, 7-days, 30-days, 180-days, and 1000-days). Summary sources and literature review were used to identify relevant studies to inform SMAC development. Space flight mission specific activities and most probable exposure scenarios were used to determine the relevant toxicity endpoints and supporting studies. SMACs were established for hydrogen sulfide of 5 ppm for 1-hour, 1.3 ppm for 24-hours, 1.3 ppm for 7-days, 1.3 ppm for 30-days, and 0.3 ppm for 180-days. Data are not sufficient currently to establish a 1000-day SMAC value. SMACs for H 2 S will support development of handling protocols and proper containment for lunar sample collection.

hydrogen sulfide↗

Preparation of silver-activated zinc sulfide thin films

Silver improves luminescence and reduces contamination of zinc sulfide phosphors. The silver is added after the zinc sulfide phosphors are deposited in thin films by vapor evaporation, but before calcining, by immersion in a solution of silver salt.

Feldman, C.↗

Interstellar hydrogen sulfide.

Hydrogen sulfide has been detected in seven Galactic sources by observation of a single line corresponding to the rotational transition from the 1(sub 10) to the 1(sub 01) levels at 168.7 GHz. The observations show that hydrogen sulfide is only a moderately common interstellar molecule comparable in abundance to H2CO and CS, but somewhat less abundant than HCN and much less abundant than CO.

Thaddeus, P.↗

The hydrogen sulfide emissions abatement program at the Geysers Geothermal Power Plant

The scope of the hydrogen sulfide (H2S) abatement program at The Geysers Geothermal Power Plant and the measures currently under way to reduce these emissions are discussed. The Geysers steam averages 223 ppm H2S by weight and after passing through the turbines leaves the plant both through the gas ejector system and by air-stripping in the cooling towers. The sulfide dissolved in the cooling water is controlled by the use of an oxidation catalyst such as an iron salt. The H2S in the low Btu ejector off gases may be burned to sulfur dioxide and scrubbed directly into the circulating water and reinjected into the steam field with the excess condensate. Details are included concerning the disposal of the impure sulfur, design requirements for retrofitting existing plants and modified plant operating procedures. Discussion of future research aimed at improving the H2S abatement system is also included.

Allen, G. W.↗