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At least 469 records · Page 26

The origin and evolution of sulfur in an Archean volcano-sedimentary basin, Deer Lake area, Minnesota

Rocks of the Deer Lake area, northcentral Minnesota, consist of Archean (age greater than 2.6 billion years) metasediments and metavolcanics intruded by mafic layered sills. Geologic and sulfur isotopic data suggest that sulfides in the sediments are bacteriogenic, having formed in response to the activity of sulfate reducing bacteria during diagenesis. Deposition of the sediments appears to have occurred in a deep marine basin with restricted circulation of sea water. The bulk of the sulfur in the igneous rocks is of deep seated origin, but basal contacts of the sills show evidence of assimilation of biogenic sulfur from the intruded sediments. This assimilation of biogenic sulfur is the primary geochemical control of local Cu-Ni sulfide mineralization.

Nicol, D. L.↗

Microbial Sulfate Reduction Measured by an Automated Electrical Impedance Technique

Electrical impedance measurements are used to investigate the rates of sulfate reduction by pure cultures of and sediments containing sulfur-reducing bacteria. Changes in the electrical impedance ratios of pure cultures of Desulfovibrio aestuarii and samples of reduced sediments from San Francisco Bay were measured by a Bactometer 32, and sulfate reduction was followed by measuring the incorporation of (S-35) sulfate into metal sulfides. The growth of the bacteria in pure culture is found to result in an increase of 0.2200 in the impedance ratio within 24 h, accompanied by increases in protein, ATP, sulfide and absorptance at 660 nm, all of which are inhibited by the addition of molybdate. Similar responses were observed in the sediments, although impedance ratio responses were not completely inhibited upon the addition of molybdate, due to the presence of nonsulfate-respiring microorganisms. Experiments conducted with sterile media and autoclaved sediments indicate that the presence of H2S together with iron is responsible for the impedance effect, and sulfate reduction rates ranging between 0.85 and 1.78 mmol/l per day are estimated for the sediments by the impedance technique.

Oremland, R. S.↗

A study of chondrule rims and chondrule irradiation records in unequilibrated ordinary chondrites

A study of the possibility that chondrules may have had an independent existence in space was made by searching for unusual track densities in chondrules and by an investigation of the compositions of chondrule rims from thirteen unequilibrated ordinary chondrites. No unusual radiation was found; observed track densities can be explained in terms of cosmic ray exposure ages of the respective meteorites. Fine-grained rims that surround chondrules in unequilibrated ordinary chondrites are heterogeneous in composition consisting of iron sulfide and a silicate phase; fine-grained rims of the kind observed in primitive type 3 ordinary chondrites are absent in higher petrographic grades, but more crystalline, coarse-grained, and lacy sulfide rims are observed. This can be explained by chondrules having had an independent existence in space during which they acquired rims by condensation on their surfaces or by accretion of fine particles.

Allen, J. S.↗

Hg and Pt-metals in meteorite carbon-rich residues - Suggestions for possible host phase for Hg

Carbon-rich and oxide residual phases have been isolated from Allende and Murchison by acid demineralization for the determination of their Hg, Pt-metal, Cr, Sc, Co, and Fe contents. Experimental procedures used eliminated the possibility of exogenous and endogenous contaminant trace elements from coprecipitating with the residues. Large enrichments of Hg and Pt-metals were found in Allende but not in Murchison residues. Hg-release profiles from stepwise heating experiments suggest a sulfide as the host for Hg. Diffusion calculations for Hg based on these experiments indicate an activation energy of 7-8 kcal/mol, the same as that for Hg in troilite from an iron meteorite. This is further support for a sulfide host phase for Hg. Equilibration of Hg with this phase at approximately 900 K is indicated. Reasons for the presence of Pt-metals in noncosmic relative abundances are explored.

Jovanovic, S.↗

Interplanetary dust in the transmission electron microscope - Diverse materials from the early solar system

An analytical electron microscope study of dispersed interplanetary dust aggregates collected in the earth's stratosphere shows that, in spite of their similarities, the aggregates exhibit significant differences in composition, internal morphology, and mineralogy. Of 11 chondritic particles examined, two consist mostly of a noncrystalline chondritic material with an atomic S/Fe ratio equal to or greater than 2 in places, one consists of submicron metal and reduced silicate 'microchondrules' and sulfide grains embedded in a carbonaceous matrix, and another consists of submicron magnetic-decorated unequilibrated silicate and sulfide grains with thick low-Z coatings. Although the particles are unmetamorphosed by criteria commonly applied for chondritic meteorites, the presence of reduced chemistries and the ubiquity of mafic, instead of hydrated, silicates confirm that they are not simply C1 or C2 chondrite matrix material. The observations indicate that portions of some particles have not been significantly altered by thermal or radiation processes since their assembly, and that the particles probably contain fine debris from diverse processes in the early solar system.

Fraundorf, P.↗

Advanced high temperature thermoelectrics for space power

Preliminary results from a spacecraft system study show that an optimum hot junction temperature is in the range of 1500 K for advanced nuclear reactor technology combined with thermoelectric conversion. Advanced silicon germanium thermoelectric conversion is feasible if hot junction temperatures can be raised roughly 100 C or if gallium phosphide can be used to improve the figure of merit, but the performance is marginal. Two new classes of refractory materials, rare earth sulfides and boron-carbon alloys, are being investigated to improve the specific weight of the generator system. Preliminary data on the sulfides have shown very high figures of merit over short temperature ranges. Both n- and p-type doping have been obtained. Pure boron-carbide may extrapolate to high figure of merit at temperatures well above 1500 K but not lower temperature; n-type conduction has been reported by others, but not yet observed in the JPL program. Inadvertant impurity doping may explain the divergence of results reported.

Lockwood, A.↗

Thermodynamics of the potassium-sulfur-oxygen and related systems

The chemical reactions which occur when potassium sulfide, K2S, and potassium sulfite, K2SO3, are heated at temperatures where their vapor pressures are significant, were studied and the vapor pressures and the partial pressures of the chemical products were measured. Mass spectrometry of the vapor of potassium sulfide revealed only K(g). X-ray studies of the solid residues from vaporization experiments revealed K2S2(s) and chemical analyses of the same solid residues showed that the residues approached a composition K2Sx with x in the range 3-4. Vapor pressure of K2S was measured by simultaneous Knudsen-effusion and torsion-effusion (SKETE) in crucibles of aluminum oxide and of graphite. In each such experiment, the vapor pressures agreed initially, but then the apparent pressure by Knudsen-effusion increased suddenly and remained much greater than that by torsion-effusion for the remainder of the experiment. Results of third-law analysis of the torsion pressures imply a delta H (298K) of formation of K2S(s) of -364 + or - 12 kJ/mol. Vapor pressures over K2SO3(s) were measured by simultaneous Knudsen and torsion-effusion and by mass spectrometry. The vapor pressures of both K2S2O5(s) and K2SO3(s) were nonreproducible at a given temperature due to the vaporization reactions of the materials being irreversible under conditions in effusion cells.

Edwards, J. G.↗

Evidence for primitive nebular components in chondrules from the Chainpur chondrite

In view of the fact that the least equilibrated ordinary chondrites contain chondrules that have changed little since the time of their formation in the early solar system, and are therefore excellent indicators of the physical and chemical nature of the solar nebula, 36 chondrules were separated from the Chainpur chondrite and analyzed for 20 elements and petrographic properties. The dominant nebular components found are: (1) a mixture of metal and sulfide whose composition is similar to whole rock metal and sulfide, (2) Ir-rich metal, (3) olivine-rich silicates, (4) pyroxene-rich silicates, and possibly (5) a component containing the more volatile lithophiles. Although etching experiments confirm that chondrule rims are enriched in metal, troilite and moderately volatile elements relative to the bulk chondrules, a large fraction of the volatiles remains in the unetched interior.

Grossman, J. N.↗

Mineralogy and petrology of the Abee enstatite chondrite breccia and its dark inclusions

A model is proposed for the petrogenesis of the Abee E4 enstatite chondrite breccia, which consists of clasts, dark inclusions and matrix, and whose dark inclusions are an unusual kind of enstatite chondritic material. When the maximum metamorphic temperature of the breccia parent material was greater than 840 C, euhedral enstatite crystals in metallic Fe, Ni, and sulfide-rich areas grew into pliable metal and sulfide. Breccia parent material was impact-excavated, admixed with dark inclusions, and rapidly cooled. During this cooling, the clast and matrix material acquired thermal remanent magnetization. A subsequent ambient magnetic field imparted a uniform net magnetic orientation to the matrix and caused the magnetic orientation of the clasts to be less random. The Abee breccia was later consolidated by shock or by shallow burial and long period, low temperature metamorphism.

Rubin, A. E.↗

Low temperature hot corrosion

The reaction of Co-Cr, Ni-Cr, Co-Cr-Al, and Ni-Cr-Al alloys with Na2SO4 in the presence of SO3 at temperatures between 700 and 750 C leads to the formation of liquid CoSO4-Na2SO4 or NiSO4-Na2SO4 deposits on the alloy surface. The formation of Cr2O3 and/or Al2O3 below this deposit results in a locally low P(O2) and a higher P(S2) and P(SO2). It is noted that these conditions can prevent protective oxide formation either by sulfide formation in the alloy, which localizes the Cr and/or Al in discrete particles, or by acid fluxing involving a reaction between Al2O3 or Cr2O3 and SO2 to form a salt-soluble species and subsequent reprecipitation as porous oxides in regions of higher P(O2). These processes may occur simultaneously, although a given alloy generally exhibits features of predominantly one type. Here, the Ni-Cr and Ni-Cr-Al alloys, and to some extent the Co-Cr alloys, exhibit features indicative of the sulfidation mechanism, whereas the morphology for the Co-Cr-Al alloy is more consistent with a predominant acid fluxing mechanism.

Chiang, K. T.↗

Effects of surface chemistry on hot corrosion life

Baseline burner rig hot corrosion with Udimet 700, Rene' 80; uncoated and with RT21, Codep, or NiCoCrAlY coatings were tested. Test conditions are: 900C, hourly thermal cycling, 0.5 ppm sodium as NaCl in the gas stream, velocity 0.3 Mach. The uncoated alloys exhibited substantial typical sulfidation in the range of 140 to 170 hours. The aluminide coatings show initial visual evidence of hot corrosion at about 400 hours, however, there is no such visual evidence for the NiCoCrAlY coatings. The turbine components show sulfidation. The extent of this distress appeared to be inversely related to the average length of mission which may, reflect greater percentage of operating time near ground level or greater percentage of operation time at takeoff conditions (higher temperatures). In some cases, however, the location of maximum distress did not exhibit the structural features of hot corrosion.

Fryxell, R. E.↗

Unexplained Fe, Ni and S anomalies in CV chondrite components

Large negative anomalies in Fe, Co, Ni, S and Se are present in Allende Type B Ca-Al-rich inclusions (CAI's). Based on compilations of all the known published analyses, Allende chondrules, aggregates and other types of CAI's also display anomalies. These observations show that: (1) since Fe, Co, Ni, S and Se are more depleted than elements bracketing them in volatility (such as Pt and Au, and Su and Cd), the anomalies were not produced during the volatility dependent, high temperature CAI forming processes; (2) since Pt, Au, Ge and other siderophiles are not as depleted as Fe, Co and Ni, the anomalies are not due to a metal/silicate fractionation; (3) the association of Fe, Co, and Ni anomalies with S and Se anomalies suggests that the anomalies are due to the removal of FeNi sulfide; and (4) since these anomalies occur in all types of Allende inclusions, aggregates and chondrules, the Allende parental material must have undergone sulfide loss before the formation of these components.

Wark, D. A.↗

Aerobic sulfur-oxidizing bacteria: Environmental selection and diversification

Sulfur-oxidizing bacteria oxidize reduced inorganic compounds to sulfuric acid. Lithotrophic sulfur oxidizer use the energy obtained from oxidation for microbial growth. Heterotrophic sulfur oxidizers obtain energy from the oxidation of organic compounds. In sulfur-oxidizing mixotrophs energy are derived either from the oxidation of inorganic or organic compounds. Sulfur-oxidizing bacteria are usually located within the sulfide/oxygen interfaces of springs, sediments, soil microenvironments, and the hypolimnion. Colonization of the interface is necessary since sulfide auto-oxidizes and because both oxygen and sulfide are needed for growth. The environmental stresses associated with the colonization of these interfaces resulted in the evolution of morphologically diverse and unique aerobic sulfur oxidizers.

Caldwell, D.↗

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.↗

Some thoughts on GAIA and the sulfur cycle

The data hypothesis states that the composition, oxidation reduction state, and temperature of the troposphere are actively regulated by the biota for the biota. One of the early predictions of the Gaia hypothesis was that there should be a sulfur compound made by the biota in the oceans. It would need to be stable enough against oxidation in water to allow its transfer to the air. Either the sulfur compound itself or its atmospheric oxidation product would have to return sulfur from the sea to the land surfaces. The most likely candidate for this role was dimethyl sulfide. Another sulfur compound of interest from a Gaian viewpoint CS2 (carbon disulfide) is discussed. Theories on the production of dimethyl sulfide and carbon disulfide related to the Gaian hypothesis are examined.

Lovelock, J. E.↗

Possible roles of manganese redox chemistry in the sulfur cycle

Sulfate reducing bacteria (SRB) are very potent MnO2 reducers by virtue of their sulfide production: H2S reacts rapidly with MnO2 to yield Mn(2), elemental sulfur, and water. In manganese rich zones, Mn cycles rapidly if sulfate is present to drive the reduction and the MnO2 precipitates and sinks into anaerobic zones. The production of sulfide (by organisms requiring organic carbon compounds) to reduce manganese oxides might act to couple the carbon and sulfur cycles in water bodies in which the two cycles are physically separated. Iron has been proposed for this provision of reducing power by (Jorgensen, 1983), but since MnS is soluble and FeS is very insoluble in water, it is equally likely that manganese rather than iron provides the electrons to the more oxidized surface layers.

Nealson, K. H.↗

Phototrophic bacteria and their role in the biogeochemical sulfur cycle

An essential step that cannot be bypassed in the biogeochemical cycle of sulfur today is dissimilatory sulfate reduction by anaerobic bacteria. The enormous amounts of sulfides produced by these are oxidized again either anaerobically by phototrophic bacteria or aerobically by thiobacilli and large chemotrophic bacteria (Beggiatoa, Thiovulum, etc.). Phototrophic bacteria use sulfide, sulfur, thiosulfate, and sulfite as electron donors for photosynthesis. The most obvious intermediate in their oxidative sulfur metabolism is a long chain polysulfide that appears as so called sulfur globules either inside (Chromatiaceae) or outside (Ectothiorhodospiraceae, Chlorobiaceae, and some of the Rhodospirillaceae) the cells. The assimilation of sulfur compounds in phototrophic bacteria is in principle identical with that of nonphototrophic bacteria. However, the Chlorobiaceae and some of the Chromatiaceae and Rhodospirillaceae, unable to reduce sulfate, rely upon reduced sulfur for biosynthetic purposes.

Trueper, H. G.↗

Anaerobic reduction of elemental sulfur by Chromatium vinosum and Beggiatoa alba

The effect of sulfur globules on the buoyant density of Chromatium vinosum and Beggiatoa alba was examined. The potential use of sulfur as a terminal electron acceptor in the anaerobic metabolism of Beggiatoa alba is also examined. The effect of the reduction of intracellular sulfur was investigated during dark metabolism on the buoyant density of C. vinosum. It is hypothesized from the results that the sulfur reduction to sulfide is part of an anaerobic energy operating system. Carbon stored as PHB can be oxidized with the concomitant reduction of sulfur to sulfide.

Schmidt, T. M.↗