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Sample records for sulfur oxidation state

  1. Composition and oxidation state of sulfur in atmospheric particulate matter

    Directory of Open Access Journals (Sweden)

    A. F. Longo

    2016-10-01

    Full Text Available The chemical and physical speciation of atmospheric sulfur was investigated in ambient aerosol samples using a combination of sulfur near-edge x-ray fluorescence spectroscopy (S-NEXFS and X-ray fluorescence (XRF microscopy. These techniques were used to determine the composition and oxidation state of sulfur in common primary emission sources and ambient particulate matter collected from the greater Atlanta area. Ambient particulate matter samples contained two oxidation states: S0 and S+VI. Ninety-five percent of the individual aerosol particles (> 1 µm analyzed contain S0. Linear combination fitting revealed that S+VI in ambient aerosol was dominated by ammonium sulfate as well as metal sulfates. The finding of metal sulfates provides further evidence for acidic reactions that solubilize metals, such as iron, during atmospheric transport. Emission sources, including biomass burning, coal fly ash, gasoline, diesel, volcanic ash, and aerosolized Atlanta soil, and the commercially available bacterium Bacillus subtilis, contained only S+VI. A commercially available Azotobacter vinelandii sample contained approximately equal proportions of S0 and S+VI. S0 in individual aerosol particles most likely originates from primary emission sources, such as aerosolized bacteria or incomplete combustion.

  2. The oxidation state of sulfur in apatite: A new oxybarometer?

    Science.gov (United States)

    Fiege, A.; Konecke, B.; Kim, Y.; Simon, A. C.; Becker, U.; Parat, F.

    2016-12-01

    Oxygen fugacity (fO2) of magmatic and hydrothermal systems influences, for instance, crystallization and degassing processes as well as metal solubilities in melts and fluids. Apatite is a ubiquitous mineral in magmatic and hydrothermal environments that can record and preserve volatile zonation. It can contain several thousand μg/g of the redox sensitive element sulfur (S), making S-in-apatite a potential fO2 sensor. Despite the polyvalent properties of S (e.g., S2-, S4+, S6+), the oxidation state and incorporation mechanisms of S in the apatite structure are poorly understood. In this study, the oxidation state of S-in-apatite as a function of fO2 is investigated using X-ray absorption near-edge structures (XANES) spectroscopy at the S K-edge. Apatites crystallized from lamproitic melts at 1000°C, 300 MPa and over a broad range of fO2 and sulfur fugacities (fS2) were measured. Peaks corresponding to S6+ ( 2482 eV), S4+ ( 2478 eV) and S2- ( 2470 eV) were identified in apatite. The integrated S6+/STotal (STotal = S6+ + S4+ + S2-) peak area ratios show a distinct positive correlation with fO2, increasing from 0.17 at FMQ+0 to 0.96 at FMQ+3. Ab-initio calculations were performed to further understand the energetics and geometry of incorporation of S6+, S4+ and S2- into the apatite (F-, Cl-, OH-) end-members. The results confirm that apatite can contain three different oxidations states of S (S6+, S4+, S2-) as a function of fO2. This makes apatite probably the first geologically relevant mineral to incorporate reduced (S2-), intermediate (S4+), and oxidized (S6+) S in variable proportions. We emphasize that the strong dependence of the S oxidation state in apatite as a function of fO2 is also coupled with changing S content of apatite and co-existing melt (i.e., with changing fS2), resulting in a complex correlation between [1] apatite-melt (or fluid) partitioning, [2] redox conditions and [3] the melt and/or fluid composition, making the application of previously

  3. Oxidation state of sulfur, iron and tin at the surface of float glasses

    International Nuclear Information System (INIS)

    Lagarde, P; Flank, A-M; Jupille, J; Montigaud, H

    2009-01-01

    Sulfur is an important element of glasses, not because of its amount, always very low (less than 0.4 % in weight of SO 3 ), but because of its role since it actively participates to the refinement process and, combined to other elements, it can be responsible for the coloration of the glass. Iron is also of a major importance in most of the glasses. In the case of the float glass, the two faces, because of the fabrication process, are different in terms of composition (presence of Sn for one face) and also in terms of oxidation state of these minority elements (Fe, Sn, S). There should be a subtle interplay between the concentrations and the oxidation states of these different minority elements, and anyway these variations occur over a thickness of the order of few micrometers below the surface. Using the high intensity and the focusing properties (3 x 3 μm 2 ) of the x-ray beam from the Lucia beamline, we have therefore studied the speciation of iron and sulfur near the face of a float glass in relation with the behavior of tin. This has been obtained by combining elemental x-ray fluorescence cartography and x-ray micro-absorption at the different K-edges.

  4. Oxidation state of sulfur, iron and tin at the surface of float glasses

    Energy Technology Data Exchange (ETDEWEB)

    Lagarde, P; Flank, A-M [Synchrotron SOLEIL, l' Orme des Merisiers, BP 48 91192 Gif/Yvette cedex (France); Jupille, J [IMPMC, Universite P. and M. Curie, Campus de Boucicaut, 140 rue de Lourmel 75015 Paris (France); Montigaud, H [Saint-Gobain Recherche 39, quai Lucien Lefranc, BP 135 93303 Aubervilliers Cedex (France)

    2009-11-15

    Sulfur is an important element of glasses, not because of its amount, always very low (less than 0.4 % in weight of SO{sub 3}), but because of its role since it actively participates to the refinement process and, combined to other elements, it can be responsible for the coloration of the glass. Iron is also of a major importance in most of the glasses. In the case of the float glass, the two faces, because of the fabrication process, are different in terms of composition (presence of Sn for one face) and also in terms of oxidation state of these minority elements (Fe, Sn, S). There should be a subtle interplay between the concentrations and the oxidation states of these different minority elements, and anyway these variations occur over a thickness of the order of few micrometers below the surface. Using the high intensity and the focusing properties (3 x 3 {mu}m{sup 2}) of the x-ray beam from the Lucia beamline, we have therefore studied the speciation of iron and sulfur near the face of a float glass in relation with the behavior of tin. This has been obtained by combining elemental x-ray fluorescence cartography and x-ray micro-absorption at the different K-edges.

  5. The changing face of lower tropospheric sulfur oxides in the United States

    Directory of Open Access Journals (Sweden)

    G. M. Hidy

    2016-12-01

    Full Text Available Abstract Sulfur oxides, sulfur dioxide and airborne sulfate, SOx, are short-lived species in the troposphere whose concentrations in air and precipitation have changed dramatically in association with fossil fuel combustion. The historic rise in concentration is coincident with the era of the so-called “Anthropocene.” Unlike concentrations of long-lived species such as carbon dioxide, atmospheric SOx in the United States (US peaked between 1970 and 2005 then declined. The rise and fall of SOx is traced by comparing national data on emission changes, ambient concentrations, and precipitation sulfate from prior to World War II to the present. Surface SOx concentrations and precipitation sulfate have decreased with emissions in most parts of the US after the late 1970s. Continued reduction toward a natural “background” condition has depended on aggressive management of anthropogenic emission sources. Annual average ambient concentrations of SO2 and SO4 have become more uniform across the US at levels of 1–3 ppbv and 0.3–3 µg/m3, respectively. Precipitation SO4 has a nominal concentration generally less than 0.5 mg/L. The effective lifetime of SOx in the troposphere is a few days. This duration limits the spatial extent of emission source influence of SOx to regional scales, wherein spatial gradients in species concentrations lead to variations in human exposure and impacts on vulnerable terrestrial and aquatic ecosystems. The effects of domestic emission reductions on SOx levels are moderated by intra- and intercontinental transport of SOx from Canada, Mexico, Asia and elsewhere. The trends in tropospheric SOx concentrations illustrate the results of more than a century of rising public awareness and action to progressively reduce a US environmental risk, accomplished with advances in energy production technology that have maintained economic well-being.

  6. Sulfur diffusion in dacitic melt at various oxidation states: Implications for volcanic degassing

    Science.gov (United States)

    Lierenfeld, Matthias Bernhard; Zajacz, Zoltán; Bachmann, Olivier; Ulmer, Peter

    2018-04-01

    The diffusivity of S in a hydrous dacitic melt (4.5-6.0 wt.% H2O) has been investigated in the temperature (T) and pressure (P) range of 950 °C to 1100 °C and 200 to 250 MPa, respectively. Three series of experiments were conducted at relatively low oxygen fugacity (fO2) conditions [0.8 log units below fayalite-magnetite-quartz equilibrium (FMQ -0.8); referred to as "low fO2"] and high fO2 conditions (FMQ +2.5; referred to as "high fO2") to determine if the diffusivity of S is affected by its oxidation state and speciation. Sulfur concentration profiles were measured by electron microprobe and the diffusion coefficient (D) was calculated by fitting these profiles. Sulfur diffusion is approximately one order of magnitude faster when S is dominantly present as sulfide species (low fO2) in comparison to the sulfate dominated experiments (high fO2). The following Arrhenian equations were obtained for high and low fO2 conditions at 200 MPa: high fO2: D = 10-5.92±0.86 * exp ({-137.3±21.5 kJ/mol}/{RT}) low fO2: D = 10-5.18±1.39 * exp ({-125.7±34.4 kJ/mol}/{RT}) where D is the average diffusion coefficient in m2 s-1, R is the gas constant in 8.3144 J mol-1 K-1 and T is the temperature in K. Our results demonstrate for the first time in natural melts that S diffusion is strongly sensitive to fO2. Our S diffusivities under low fO2 conditions are only slightly slower of those found for H2O, suggesting that S can be rather efficiently purged from reduced dacitic melts during volcanic eruptions. However, for more oxidized systems (e.g. subduction zones), S diffusion will be much slower and will hinder equilibrium syn-eruptive degassing during rapid decompression. Therefore, we conclude that the "excess" measured during many explosive volcanic eruptions in arcs is dominantly derived from S-rich bubble accumulation in the eruptible portion of the magma reservoir.

  7. Current emission trends for nitrogen oxides, sulfur dioxide, and volatile organic compounds by month and state: Methodology and results

    International Nuclear Information System (INIS)

    Kohout, E.J.; Miller, D.J.; Nieves, L.A.; Rothman, D.S.; Saricks, C.L.; Stodolsky, F.; Hanson, D.A.

    1990-08-01

    This report presents estimates of monthly sulfur dioxide (SO 2 ), nitrogen oxides (NO x ), and nonmethane voltatile organic compound (VOC) emissions by sector, region, and state in the contiguous United States for the years 1975 through 1988. This work has been funded as part of the National Acid Precipitation Assessment Program's Emissions and Controls Task Group by the US Department of Energy (DOE) Office of Fossil Energy (FE). The DOE project officer is Edward C. Trexler, DOE/FE Office of Planning and Environment

  8. Air Quality Criteria for Sulfur Oxides.

    Science.gov (United States)

    National Air Pollution Control Administration (DHEW), Washington, DC.

    Included is a literature review which comprehensively discusses knowledge of the sulfur oxides commonly found in the atmosphere. The subject content is represented by the 10 chapter titles: Physical and Chemical Properties and the Atmospheric Reactions of the Oxides of Sulfur; Sources and Methods of Measurements of Sulfur Oxides in the Atmosphere;…

  9. X-ray spectral determination of chemical state of phosphorus and sulfur in anodic oxide films on niobium

    International Nuclear Information System (INIS)

    Bokij, L.P.; Kostikov, Yu.P.

    1989-01-01

    Chemical forms of phosphorus and sulfur in niobium oxide anodic film, obtained by electrochemical technique using niobium in H 2 SO 4 and H 3 PO 4 aqueous solutions, are determined using data on chemical shifts of X-ray emission lines. Films represent Nb 2 O 5(1-γ) (SO 4 ) 5γ and Nb 2 O 5(1-γ) (PO 4 ) 10γ/3 (γ -share of oxygen substituted by acid anion) composition oxosalts. Electrolyte role in formation of niobium anodic oxide structure and effect of phosphorus and sulfur compounds on anodic film conductivity are determined

  10. Halophilic and haloalkaliphilic sulfur-oxidizing bacteria

    NARCIS (Netherlands)

    Sorokin, D.Y.; Banciu, H.; Robertson, L.A.; Kuenen, J.G.; Muntyan, M.S.; Muyzer, G.; Rosenberg, E.; DeLong, F.; Delong, E.; Lory, S.; Stackebrandt, E.; Thompson, F.

    2013-01-01

    Chemotrophic sulfur-oxidizing bacteria (SOB) represent an important functional group of microorganisms responsible for the dark oxidation of reduced sulfur compounds generated by sulfidogens. Until recently, only a single genus of halophilic SOB (Halothiobacillus) has been described, and nothing was

  11. Sulfur-centered reactive intermediates derived from the oxidation of sulfur compounds of biological interest

    Energy Technology Data Exchange (ETDEWEB)

    Abedinzadeh, Z. [Lab. de Chimie Physique, UMR, Univ. Rene Descartes, Paris (France)

    2001-02-01

    Sulphur compounds play a central role in the structure and activity of many vital systems. In the living cell, sulfur constitutes an essential part of the defense against oxidative damage and is transformed into a variety of sulfur free radical species. Many studies of the chemistry of sulfur-centered radicals using pulse radiolysis and photolysis techniques to detect and measure the kinetics of these radicals have been published and reviewed. This paper discusses the present state of research on the formation and reactivity of certain sulfur-centered radicals [RS{sup .}, RSS{sup .}, RS{sup .+}, (RSSR){sup .+}] and their implications for biological systems. (author)

  12. Sulfur-centered reactive intermediates derived from the oxidation of sulfur compounds of biological interest

    International Nuclear Information System (INIS)

    Abedinzadeh, Z.

    2001-01-01

    Sulphur compounds play a central role in the structure and activity of many vital systems. In the living cell, sulfur constitutes an essential part of the defense against oxidative damage and is transformed into a variety of sulfur free radical species. Many studies of the chemistry of sulfur-centered radicals using pulse radiolysis and photolysis techniques to detect and measure the kinetics of these radicals have been published and reviewed. This paper discusses the present state of research on the formation and reactivity of certain sulfur-centered radicals [RS . , RSS . , RS .+ , (RSSR) .+ ] and their implications for biological systems. (author)

  13. Influence of sulfurous oxide on plants

    Energy Technology Data Exchange (ETDEWEB)

    Schroeder, J

    1872-01-01

    It has been determined that of the trees living in an atmosphere containing sulfurous oxide, the conifers suffer more injuries than ordinary foliaged trees. Experiments were conducted to find the causes of injuries and their relation in these two kinds of plants. Pine and alder were chosen as test plants. It was found that 1000 square centimeters of pine leaves had absorbed 1.6 c.c. of sulfurous oxide and the same surface area of alder leaves had accumulated 7.9 c.c. of sulfurous oxide. Experiments were also conducted to determine the effects of sulfurous oxide on transpiration in plants. Two similar twigs of a sycamore were arranged so that the water transpired could be weighed. Results indicate that the ratio between the total amount of water transpired by the leaves not acted on by the sulfurous oxide and those under its influence was 3.8:1. The author concludes that the amount of sulfurous oxide absorbed by pine leaves is smaller than that absorbed by trees with ordinary foliage for equal surfaces. Since its effect on transpiration is less in the case of pine, the cause of the greater injury to pine trees in nature must be due to the accumulation of sulfur. In trees annual leaves the damage to one year's foliage would have only an indirect influence on that of the following year.

  14. 40 CFR 52.1126 - Control strategy: Sulfur oxides.

    Science.gov (United States)

    2010-07-01

    ... Department of Environmental Quality Engineering.). Gardner State Hospital, Gardner. Grafton State Hospital... 40 Protection of Environment 4 2010-07-01 2010-07-01 false Control strategy: Sulfur oxides. 52... (CONTINUED) APPROVAL AND PROMULGATION OF IMPLEMENTATION PLANS (CONTINUED) Massachusetts § 52.1126 Control...

  15. Plutonium oxides analysis. Sulfur potentiometric analysis

    International Nuclear Information System (INIS)

    Anon.

    Total sulfur determination (sulfur, sulfates, sulfides ...) in plutonium oxides, suitable for sulfate ion content between 0.003 percent to 0.2 percent, by dissolution in nitric hydrofluoric acid, nitrates elimination, addition of hydrochloric acid and reduction in hydrogen sulfide which is carried by an inert gas and neutralized by sodium hydroxide. Sodium sulfide is titrated with mercuric acetate by constant intensity potentiometry [fr

  16. Effects of sulfur oxides on eicosanoids

    International Nuclear Information System (INIS)

    Chen, L.C.; Miller, P.D.; Amdur, M.O.

    1989-01-01

    Ultrafine metal oxides and SO2 react during coal combustion or smelting operations to form primary emissions coated with an acidic SOx layer. Ongoing work in this laboratory has examined the effects of sulfur oxides on pulmonary functions of guinea pigs. We have previously reported that 20 micrograms/m3 acidic sulfur oxide as a surface layer on ultrafine ZnO particles decreases lung volumes, decreases carbon monoxide diffusing capacity, and causes lung inflammation in guinea pigs after 4 daily 3-h exposures. It also produces bronchial hypersensitivity following a single 1-h exposure. The importance of this surface layer is demonstrated by our observation that 200 micrograms/m3 of sulfuric acid droplets of equivalent size are needed to produce the same degree of hypersensitivity. This study characterized the concentration-dependent effects of in vivo exposures to sulfur oxides on arachidonic acid metabolism in the guinea pig lung, and investigated the time course and the relation between eicosanoid composition and pulmonary functions. We focused specifically on four cyclooxygenase metabolites of arachidonic acid, that is, prostaglandins (PG) E1, F2 alpha, 6-keto prostaglandin F1 alpha, and thromboxane (Tx) B2, and two groups of sulfidopeptide leukotrienes (C4, D4, E4, and F4). Guinea pigs were exposed to ultrafine ZnO aerosol (count median diameter = 0.05 microns, sigma g = 1.80) with a layer of acidic sulfur oxide on the surface of the particles. Lung lavage was collected after exposures, and the levels of arachidonic acid metabolites were determined using radioimmunoassay (RIA). Concentration-dependent promotion of PGF2 alpha and concentration-dependent suppression of LtB4 were observed. The increased PGF2 alpha was associated with depressed vital capacity and diffusing capacity of the lungs measured in guinea pigs exposed to the same atmosphere described in a previous study

  17. Physiology of alkaliphilic sulfur-oxidizing bacteria from soda lakes

    NARCIS (Netherlands)

    Banciu, H.L.

    2004-01-01

    The inorganic sulfur oxidation by obligate haloalkaliphilic chemolithoautotrophs was only recently discovered and investigated. These autotrophic sulfur oxidizing bacteria (SOB), capable of oxidation of inorganic sulfur compounds at moderate to high salt concentration and at high pH, can be divided

  18. Integrated Science Assessment (ISA) for Sulfur Oxides ...

    Science.gov (United States)

    This draft document provides EPA’s evaluation and synthesis of the most policy-relevant science related to the health effects of sulfur oxides. When final, it will provide a critical part of the scientific foundation for EPA’s decision regarding the adequacy of the current primary (health-based) National Ambient Air Quality Standard (NAAQS) for sulfur dioxide. The references considered for inclusion in or cited in the external review draft ISA are available at https://hero.epa.gov/hero/sulfur-oxides. The intent of the ISA, according to the CAA, is to “accurately reflect the latest scientific knowledge expected from the presence of [a] pollutant in ambient air” (U.S. Code, 1970a, 1970b). It includes an assessment of scientific research from atmospheric sciences, exposure sciences, dosimetry, mode of action, animal and human toxicology, and epidemiology. Key information and judgments formerly found in the Air Quality Criteria Documents (AQCDs) for sulfur oxides (SOx) are included; Annexes provide additional details supporting the ISA. Together, the ISA and Annexes serve to update and revise the last SOx ISA which was published in 2008.

  19. Mapping critical levels of ozone, sulfur dioxide and nitrogen oxide for crops, forests and natural vegetation in the United States

    International Nuclear Information System (INIS)

    Rosenbaum, B.J.; Strickland, T.C.; McDowell, M.K.

    1994-01-01

    Air pollution abatement strategies for controlling nitrogen dioxide, sulfur dioxide, and ozone emissions in the United States focus on a 'standards-based' approach. This approach places limits on air pollution by maintaining a baseline value for air quality, no matter what the ecosystem can or cannot withstand. This paper, presents example critical levels maps for the conterminous U.S. developed using the 'effects-based' mapping approach as defined by the United Nations Economic Commission for Europe's Convention on Long-Range Transboundary Air Pollution, Task Force on Mapping. This approach emphasizes the pollution level or load capacity an ecosystem can accommodate before degradation occurs, and allows for analysis of cumulative effects. Presents the first stage of an analysis that reports the distribution of exceedances of critical levels for NO 2 , SO 2 , and O 3 in sensitive forest, crop, and natural vegetation ecosystems in the contiguous United States. It is concluded that extrapolation to surrounding geographic areas requires the analysis of diverse and compounding factors that preclude simple extrapolation methods. Pollutant data depicted in this analysis are limited to locationally specific data, and would be enhanced by utilizing spatial statistics, along with converging associated anthropogenic and climatological factors. Values used for critical levels were derived from current scientific knowledge. While not intended to be a definitive value, adjustments will occur as the scientific community gains new insight to pollutant/receptor relationships. We recommend future analysis to include a refinement of sensitive receptor data coverages and to report relative proportions of exceedances at varying grid scales. 27 refs., 4 figs., 1 tab

  20. Methane oxidation in presence of sulfur dioxide

    International Nuclear Information System (INIS)

    Mantashyan, A.A.; Avetisyan, A.M.; Makaryan, E.M.; Wang, H.

    2006-01-01

    The emission of sulfurous gases including SO 2 from stationary power generation remains to be a serious environmental and ecological problem. Sulfurous gases are almost entirely produced from the combustion of sulfur-containing fuels. While fuel desulfurization and flue gas scrubbing is a viable solution, in the developing countries it remains to be an economical challenge to implement these SO x reduction technologies. The oxidation of methane in presence of sulfurous gas (SO 2 ) addition was studied experimentally. Te experiments were conducted in a static reactor at temperature of 728-786 K, and for mixture of C 4 /O 2 ≡ 1/2 at a pressure of 117 Torr with varying amount of SO 2 addition. It was observed that SO 2 addition accelerated the oxidation process, reduced the induction period and increased the extent of methane consumption. At the relatively short resident time (less than 50 sec) SO 3 was detected, but at longer residence time SO 3 was reduced spontaneously to SO 2

  1. Durability of solid oxide fuel cells using sulfur containing fuels

    DEFF Research Database (Denmark)

    Hagen, Anke; Rasmussen, Jens Foldager Bregnballe; Thydén, Karl Tor Sune

    2011-01-01

    The usability of hydrogen and also carbon containing fuels is one of the important advantages of solid oxide fuel cells (SOFCs), which opens the possibility to use fuels derived from conventional sources such as natural gas and from renewable sources such as biogas. Impurities like sulfur compounds...... are critical in this respect. State-of-the-art Ni/YSZ SOFC anodes suffer from being rather sensitive towards sulfur impurities. In the current study, anode supported SOFCs with Ni/YSZ or Ni/ScYSZ anodes were exposed to H2S in the ppm range both for short periods of 24h and for a few hundred hours. In a fuel...

  2. Action of sulfurous oxide on plants

    Energy Technology Data Exchange (ETDEWEB)

    Schroeder, J

    1873-01-01

    In order to ascertain which trees best withstand the action of sulfurous oxide, and are, therefore, best suited for planting in neighborhoods where this gas is given off, young trees of various kinds growing in the open ground, were exposed under glass shades to air containing quantities of sulfurous oxide, varying from 1/10,000 to 1/70,000, under circumstances most favorable to its action, viz., in direct sunlight and after having been watered. The sensitiveness of the leaves was carefully noticed, and also the power which the trees possessed of compensating for injury by the reproduction of leaves; this was found to vary considerably in different trees, as did also the resisting power in the first case. Alder, sycamore, ash, and especially maple, are recommended for growth where exposed to smoke containing sulfurous oxide; next follow birch, hornbeam, and oak, and last, beech. The pines did not give constant results, but in nature they suffer more than other trees, and this is owing to the fact that, although their sensitiveness at first is less than that of other trees, their power of restoring lost leaves is much less.

  3. Anaerobic sulfide-oxidation in marine colorless sulfur-oxidizing bacteria

    Digital Repository Service at National Institute of Oceanography (India)

    LokaBharathi, P.A.; Nair, S.; Chandramohan, D.

    Colorless sulfur-oxidizing bacteria are ubiquitous in Indian waters and have the ability to oxidize sulfide under anaerobic conditions. These bacteria can not only mediate the sulfur cycle oxidatively but also the nitrogen cycle reductively without...

  4. Oxidation of inorganic sulfur compounds in acidophilic prokaryotes

    Energy Technology Data Exchange (ETDEWEB)

    Rohwerder, T.; Sand, W. [Universitaet Duisburg-Essen, Biofilm Centre, Aquatic Biotechnology, Duisburg (Germany)

    2007-07-15

    The oxidation of reduced inorganic sulfur compounds to sulfuric acid is of great importance for biohydrometallurgical technologies as well as the formation of acidic (below pH 3) and often heavy metal-contaminated environments. The use of elemental sulfur as an electron donor is the predominant energy-yielding process in acidic natural sulfur-rich biotopes but also at mining sites containing sulfidic ores. Contrary to its significant role in the global sulfur cycle and its biotechnological importance, the microbial fundamentals of acidophilic sulfur oxidation are only incompletely understood. Besides giving an overview of sulfur-oxidizing acidophiles, this review describes the so far known enzymatic reactions related to elemental sulfur oxidation in acidophilic bacteria and archaea. Although generally similar reactions are employed in both prokaryotic groups, the stoichiometry of the key enzymes is different. Bacteria oxidize elemental sulfur by a sulfur dioxygenase to sulfite whereas in archaea, a sulfur oxygenase reductase is used forming equal amounts of sulfide and sulfite. In both cases, the activation mechanism of elemental sulfur is not known but highly reactive linear sulfur forms are assumed to be the actual substrate. Inhibition as well as promotion of these biochemical steps is highly relevant in bioleaching operations. An efficient oxidation can prevent the formation of passivating sulfur layers. In other cases, a specific inhibition of sulfur biooxidation may be beneficial for reducing cooling and neutralization costs. In conclusion, the demand for a better knowledge of the biochemistry of sulfur-oxidizing acidophiles is underlined. (Abstract Copyright [2007], Wiley Periodicals, Inc.)

  5. Acidithiobacillus caldus sulfur oxidation model based on transcriptome analysis between the wild type and sulfur oxygenase reductase defective mutant.

    Directory of Open Access Journals (Sweden)

    Linxu Chen

    Full Text Available Acidithiobacillus caldus (A. caldus is widely used in bio-leaching. It gains energy and electrons from oxidation of elemental sulfur and reduced inorganic sulfur compounds (RISCs for carbon dioxide fixation and growth. Genomic analyses suggest that its sulfur oxidation system involves a truncated sulfur oxidation (Sox system (omitting SoxCD, non-Sox sulfur oxidation system similar to the sulfur oxidation in A. ferrooxidans, and sulfur oxygenase reductase (SOR. The complexity of the sulfur oxidation system of A. caldus generates a big obstacle on the research of its sulfur oxidation mechanism. However, the development of genetic manipulation method for A. caldus in recent years provides powerful tools for constructing genetic mutants to study the sulfur oxidation system.An A. caldus mutant lacking the sulfur oxygenase reductase gene (sor was created and its growth abilities were measured in media using elemental sulfur (S(0 and tetrathionate (K(2S(4O(6 as the substrates, respectively. Then, comparative transcriptome analysis (microarrays and real-time quantitative PCR of the wild type and the Δsor mutant in S(0 and K(2S(4O(6 media were employed to detect the differentially expressed genes involved in sulfur oxidation. SOR was concluded to oxidize the cytoplasmic elemental sulfur, but could not couple the sulfur oxidation with the electron transfer chain or substrate-level phosphorylation. Other elemental sulfur oxidation pathways including sulfur diooxygenase (SDO and heterodisulfide reductase (HDR, the truncated Sox pathway, and the S(4I pathway for hydrolysis of tetrathionate and oxidation of thiosulfate in A. caldus are proposed according to expression patterns of sulfur oxidation genes and growth abilities of the wild type and the mutant in different substrates media.An integrated sulfur oxidation model with various sulfur oxidation pathways of A. caldus is proposed and the features of this model are summarized.

  6. Graphene oxide as a sulfur immobilizer in high performance lithium/sulfur cells

    Science.gov (United States)

    Zhang, Yuegang; Cairns, Elton J.; Ji, Liwen; Rao, Mumin

    2017-06-06

    The loss of sulfur cathode material as a result of polysulfide dissolution causes significant capacity fading in rechargeable lithium/sulfur cells. Embodiments of the invention use a chemical approach to immobilize sulfur and lithium polysulfides via the reactive functional groups on graphene oxide. This approach obtains a uniform and thin (.about.tens of nanometers) sulfur coating on graphene oxide sheets by a chemical reaction-deposition strategy and a subsequent low temperature thermal treatment process. Strong interaction between graphene oxide and sulfur or polysulfides demonstrate lithium/sulfur cells with a high reversible capacity of 950-1400 mAh g.sup.-1, and stable cycling for more than 50 deep cycles at 0.1 C.

  7. Graphene oxide as a sulfur immobilizer in high performance lithium/sulfur cells

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yuegang; Cairns, Elton J.; Ji, Liwen; Rao, Mumin

    2017-12-26

    The loss of sulfur cathode material as a result of polysulfide dissolution causes significant capacity fading in rechargeable lithium/sulfur cells. Embodiments of the invention use a chemical approach to immobilize sulfur and lithium polysulfides via the reactive functional groups on graphene oxide. This approach obtains a uniform and thin (.about.tens of nanometers) sulfur coating on graphene oxide sheets by a chemical reaction-deposition strategy and a subsequent low temperature thermal treatment process. Strong interaction between graphene oxide and sulfur or polysulfides demonstrate lithium/sulfur cells with a high reversible capacity of 950-1400 mAh g.sup.-1, and stable cycling for more than 50 deep cycles at 0.1 C.

  8. Identification of major planktonic sulfur oxidizers in stratified freshwater lake.

    Directory of Open Access Journals (Sweden)

    Hisaya Kojima

    Full Text Available Planktonic sulfur oxidizers are important constituents of ecosystems in stratified water bodies, and contribute to sulfide detoxification. In contrast to marine environments, taxonomic identities of major planktonic sulfur oxidizers in freshwater lakes still remain largely unknown. Bacterioplankton community structure was analyzed in a stratified freshwater lake, Lake Mizugaki in Japan. In the clone libraries of 16S rRNA gene, clones very closely related to a sulfur oxidizer isolated from this lake, Sulfuritalea hydrogenivorans, were detected in deep anoxic water, and occupied up to 12.5% in each library of different water depth. Assemblages of planktonic sulfur oxidizers were specifically analyzed by constructing clone libraries of genes involved in sulfur oxidation, aprA, dsrA, soxB and sqr. In the libraries, clones related to betaproteobacteria were detected with high frequencies, including the close relatives of Sulfuritalea hydrogenivorans.

  9. Biogeochemistry of the sulfur oxidizer Thiomicrospira thermophila

    Science.gov (United States)

    Houghton, J.; Fike, D. A.; Wills, E.; Foustoukos, D.

    2013-12-01

    Near-seafloor hydrothermal environments such as diffuse flow venting or subsurface mixing are characterized by rapidly changing conditions and steep chemical and thermal gradients. Microorganisms living in these environments can take advantage of these changes by switching among metabolic pathways rather than specializing. We present reaction stoichiometry and rates for T. thermophila grown in a closed system both at ambient and elevated pressure (50 bars) that demonstrate substantial metabolic flexibility, shifting between up to 5 different sulfur cycling reactions over a 24 hour period. Based on the stoichiometry between S2O3 consumed and SO4 produced, three reactions are sulfur oxidation and two are disproportionation, which has not previously been demonstrated for Thiomicrospira strains. Reactants include S2O3, elemental S (both polymeric S chains and S8 rings), HS-, and O2, while products include polymeric elemental S, SO4, HS-, and polysulfides. The presence of μmolal concentrations of HS- has been confirmed during the time series only when stoichiometry predicts disproportionation. Production of HS- in the presence of elemental S results in abiotic conversion to polysulfides, keeping the sulfide concentrations low in solution. The transition from oxidation to disproportionation appears to be triggered by a depletion in dissolved oxygen and the rate of reaction is a second order function of S2O3 and O2 concentrations. Growth was tested at conditions spanning their pH tolerance (5.0 - 8.0) using a citrate buffer (pH 5.0), unbuffered media (initial pH 7.0), and Tris buffer (pH 8.0). The highest rates are observed at pH 8.0 with rates decreasing as a function of pH. The lowest rate occurs at pH 5.0 and exhibits pseudo-first order behavior over a 24 hour period, likely due to a long lag and very slow growth. Repeat injections after the culture is acclimated to the experimental conditions result in very high pseudo-first order rates due to rapid consumption of

  10. Quantification of Discrete Oxide and Sulfur Layers on Sulfur-Passivated InAs by XPS

    National Research Council Canada - National Science Library

    Petrovykh, D. Y; Sullivan, J. M; Whitman, L. J

    2005-01-01

    .... The S-passivated InAs(001) surface can be modeled as a sulfur-indium-arsenic layer-cake structure, such that characterization requires quantification of both arsenic oxide and sulfur layers that are at most a few monolayers thick...

  11. Sensing sulfur oxides and other sulfur bearing pollutants with solid electrolyte pellets. I. Gas concentration cells

    Energy Technology Data Exchange (ETDEWEB)

    Chamberland, A M; Gauthier, J M

    1977-01-01

    A new sensing technique using a solid electrolyte has been demonstrated for sulfur-bearing pollutants. Based on potentiometric measurements across a pellet of potassium sulfate, this sensor allows concentrations of sulfur dioxides, sulfur trioxide, hydrogen sulfide, methyl mercaptan and carbonyl sulfide in air to be measured with accuracy. Its operational concentration range at the present time is 0.1 ppM up to at least 10,000 ppM. The presence of other common pollutants such as carbon dioxide, methane, nitric oxide and nitrogen dioxide does not interfere with the measurement of air samples containing sulfur-bearing pollutants.

  12. Tuning the oxidative power of free iron-sulfur clusters.

    Science.gov (United States)

    Lang, Sandra M; Zhou, Shaodong; Schwarz, Helmut

    2017-03-15

    The gas-phase reactions between a series of di-iron sulfur clusters Fe 2 S x + (x = 1-3) and the small alkenes C 2 H 4 , C 3 H 6 , and C 4 H 8 have been investigated by means of Fourier-transform ion-cyclotron resonance mass spectrometry. For all studied alkenes, the reaction efficiency is found to increase in the order Fe 2 S + desulfurization of the cluster and formation of H 2 S. This indicates an increased propensity to induce oxidation reactions, i.e. oxidative power, of Fe 2 S 3 + that is attributed to an increased formal oxidation state of the iron atoms. Furthermore, the ability of Fe 2 S 3 + to activate and dissociate the C-H bonds of the alkenes is observed to increase with increasing size of the alkene and thus correlates with the alkene ionization energy.

  13. Process for removal of sulfur oxides from hot gases

    International Nuclear Information System (INIS)

    Bauerle, G. L.; Kohl, A. L.

    1984-01-01

    A process for the removal of sulfur oxides from two gas streams containing the same. One gas stream is introduced into a spray dryer zone and contacted with a finely dispersed spray of an aqueous medium containing an absorbent for sulfur oxides. The aqueous medium is introduced at a controlled rate so as to provide water to the gas in an amount to produce a cooled product gas having a temperature at least 7 0 C. above its adiabatic saturation temperature and from about 125-300% of the stoichiometric amount of absorbent required to react with the sulfur oxides to be removed from the gas stream. The effluent from the spray dryer zone comprises a gas stream of reduced sulfur oxide content and contains entrained dry particulate reaction products including unreacted absorbent. This gas stream is then introduced into a particulate removal zone from which is withdrawn a gas stream substantially free of particles and having a reduced sulfur oxide content. the dry particulate reaction products are collected and utilized as a source of absorbent for a second aqueous scrubbing medium containing unreacted absorbent for the sulfur oxides. An effluent gas stream is withdrawn from the aqueous scrubbing zone and comprises a water-saturated gas stream of reduced sulfur oxide content and substantially free of particles. The effluent gas streams from the particulate removal zone and the aqueous scrubbing zone are combined in such proportions that the combined gas stream has a temperature above its adiabatic saturation temperature

  14. Confine sulfur in mesoporous metal–organic framework @ reduced graphene oxide for lithium sulfur battery

    International Nuclear Information System (INIS)

    Bao, Weizhai; Zhang, Zhian; Qu, Yaohui; Zhou, Chengkun; Wang, Xiwen; Li, Jie

    2014-01-01

    Highlights: • Metal organic framework @ reduced graphene oxide was applied for sulfur cathode. • MIL-101(Cr)@rGO/S composites are synthesized by a facile two-step liquid method. • Cycling stability of MIL-101(Cr)@rGO/S sulfur cathode was improved. -- Abstract: Mesoporous metal organic framework @ reduced graphene oxide (MIL-101(Cr)@rGO) materials have been used as a host material to prepare the multi-composite sulfur cathode through a facile and effective two-step liquid phase method successfully, which is different from the simple MIL-101(Cr)/S mixed preparation method. The successful reduced graphene oxide coating in the MIL-101(Cr)@rGO improve the electronic conductivity of meso-MOFs effectively. The discharge capacity and capacity retention rate of MIL-101(Cr)@rGO/S composite sulfur cathode are as high as 650 mAh g −1 and 66.6% at the 50th cycle at the current density of 335 mA g −1 . While the discharge capacity and capacity retention rate of MIL-101(Cr)/S mixed sulfur cathode is 458 mAh g −1 and 37.3%. Test results indicate that the MIL-101(Cr)@rGO is a promising host material for the sulfur cathode in the lithium–sulfur battery applications

  15. In situ tribochemical sulfurization of molybdenum oxide nanotubes.

    Science.gov (United States)

    Rodríguez Ripoll, Manel; Tomala, Agnieszka; Gabler, Christoph; DraŽić, Goran; Pirker, Luka; Remškar, Maja

    2018-02-15

    MoS 2 nanoparticles are typically obtained by high temperature sulfurization of organic and inorganic precursors under a S rich atmosphere and have excellent friction reduction properties. We present a novel approach for making the sulfurization unnecessary for MoO 3 nanotubes during the synthesis process for friction and wear reduction applications while simultaneously achieving a superb tribological performance. To this end, we report the first in situ sulfurization of MoO 3 nanotubes during sliding contact in the presence of sulfur-containing lubricant additives. The sulfurization leads to the tribo-chemical formation of a MoS 2 -rich low-friction tribofilm as verified using Raman spectroscopy and can be achieved both during sliding contact and under extreme pressure conditions. Under sliding contact conditions, MoO 3 nanotubes in synergy with sulfurized olefin polysulfide and pre-formed zinc dialkyl dithiophosphate tribofilms achieve an excellent friction performance. Under these conditions, the tribochemical sulfurization of MoO 3 nanotubes leads to a similar coefficient of friction to the one obtained using a model nanolubricant containing MoS 2 nanotubes. Under extreme pressure conditions, the in situ sulfurization of MoO 3 nanotubes using sulfurized olefin polysulfide results in a superb load carrying capacity capable of outperforming MoS 2 nanotubes. The reason is that while MoO 3 nanotubes are able to continuously sulfurize during sliding contact conditions, MoS 2 nanotubes progressively degrade by oxidation thus losing lubricity.

  16. Dissimilatory oxidation and reduction of elemental sulfur in thermophilic archaea.

    Science.gov (United States)

    Kletzin, Arnulf; Urich, Tim; Müller, Fabian; Bandeiras, Tiago M; Gomes, Cláudio M

    2004-02-01

    The oxidation and reduction of elemental sulfur and reduced inorganic sulfur species are some of the most important energy-yielding reactions for microorganisms living in volcanic hot springs, solfataras, and submarine hydrothermal vents, including both heterotrophic, mixotrophic, and chemolithoautotrophic, carbon dioxide-fixing species. Elemental sulfur is the electron donor in aerobic archaea like Acidianus and Sulfolobus. It is oxidized via sulfite and thiosulfate in a pathway involving both soluble and membrane-bound enzymes. This pathway was recently found to be coupled to the aerobic respiratory chain, eliciting a link between sulfur oxidation and oxygen reduction at the level of the respiratory heme copper oxidase. In contrast, elemental sulfur is the electron acceptor in a short electron transport chain consisting of a membrane-bound hydrogenase and a sulfur reductase in (facultatively) anaerobic chemolithotrophic archaea Acidianus and Pyrodictium species. It is also the electron acceptor in organoheterotrophic anaerobic species like Pyrococcus and Thermococcus, however, an electron transport chain has not been described as yet. The current knowledge on the composition and properties of the aerobic and anaerobic pathways of dissimilatory elemental sulfur metabolism in thermophilic archaea is summarized in this contribution.

  17. Simultaneous removal of nitrogen oxides and sulfur oxides from combustion gases

    Science.gov (United States)

    Clay, David T.; Lynn, Scott

    1976-10-19

    A process for the simultaneous removal of sulfur oxides and nitrogen oxides from power plant stack gases comprising contacting the stack gases with a supported iron oxide catalyst/absorbent in the presence of sufficient reducing agent selected from the group consisting of carbon monoxide, hydrogen, and mixtures thereof, to provide a net reducing atmosphere in the SO.sub.x /NO.sub.x removal zone. The sulfur oxides are removed by absorption substantially as iron sulfide, and nitrogen oxides are removed by catalytic reduction to nitrogen and ammonia. The spent iron oxide catalyst/absorbent is regenerated by oxidation and is recycled to the contacting zone. Sulfur dioxide is also produced during regeneration and can be utilized in the production of sulfuric acid and/or sulfur.

  18. Physiology and genetics of sulfur-oxidizing bacteria.

    Science.gov (United States)

    Friedrich, C G

    1998-01-01

    Reduced inorganic sulfur compounds are oxidized by members of the domains Archaea and Bacteria. These compounds are used as electron donors for anaerobic phototrophic and aerobic chemotrophic growth, and are mostly oxidized to sulfate. Different enzymes mediate the conversion of various reduced sulfur compounds. Their physiological function in sulfur oxidation is considered (i) mostly from the biochemical characterization of the enzymatic reaction, (ii) rarely from the regulation of their formation, and (iii) only in a few cases from the mutational gene inactivation and characterization of the resulting mutant phenotype. In this review the sulfur-metabolizing reactions of selected phototrophic and of chemotrophic prokaryotes are discussed. These comprise an archaeon, a cyanobacterium, green sulfur bacteria, and selected phototrophic and chemotrophic proteobacteria. The genetic systems are summarized which are presently available for these organisms, and which can be used to study the molecular basis of their dissimilatory sulfur metabolism. Two groups of thiobacteria can be distinguished: those able to grow with tetrathionate and other reduced sulfur compounds, and those unable to do so. This distinction can be made irrespective of their phototrophic or chemotrophic metabolism, neutrophilic or acidophilic nature, and may indicate a mechanism different from that of thiosulfate oxidation. However, the core enzyme for tetrathionate oxidation has not been identified so far. Several phototrophic bacteria utilize hydrogen sulfide, which is considered to be oxidized by flavocytochrome c owing to its in vitro activity. However, the function of flavocytochrome c in vivo may be different, because it is missing in other hydrogen sulfide-oxidizing bacteria, but is present in most thiosulfate-oxidizing bacteria. A possible function of flavocytochrome c is discussed based on biophysical studies, and the identification of a flavocytochrome in the operon encoding enzymes involved

  19. Mechanisms and evolution of oxidative sulfur metabolism in green sulfur bacteria

    DEFF Research Database (Denmark)

    Gregersen, Lea Haarup; Bryant, Donald A.; Frigaard, Niels-Ulrik

    2011-01-01

    Green sulfur bacteria (GSB) constitute a closely related group of photoautotrophic and thiotrophic bacteria with limited phenotypic variation. They typically oxidize sulfide and thiosulfate to sulfate with sulfur globules as an intermediate. Based on genome sequence information from 15 strains...... product is further oxidized to sulfite by the dissimilatory sulfite reductase (DSR) system. This system consists of components horizontally acquired partly from sulfide-oxidizing and partly from sulfate-reducing bacteria. Depending on the strain, the sulfite is probably oxidized to sulfate by one of two...... in sulfate formation in other bacteria has been replaced by the DSR system in GSB. Sequence analyses suggested that the conserved soxJXYZAKBW gene cluster was horizontally acquired by Chlorobium phaeovibrioides DSM 265 from the Chlorobaculum lineage and that this acquisition was mediated by a mobile genetic...

  20. Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium?sulfur battery design

    OpenAIRE

    Tao, Xinyong; Wang, Jianguo; Liu, Chong; Wang, Haotian; Yao, Hongbin; Zheng, Guangyuan; Seh, Zhi Wei; Cai, Qiuxia; Li, Weiyang; Zhou, Guangmin; Zu, Chenxi; Cui, Yi

    2016-01-01

    Lithium?sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understandin...

  1. Comparative analysis of the mechanisms of sulfur anion oxidation and reduction by dsr operon to maintain environmental sulfur balance.

    Science.gov (United States)

    Ghosh, Semanti; Bagchi, Angshuman

    2015-12-01

    Sulfur metabolism is one of the oldest known redox geochemical cycles in our atmosphere. These redox processes utilize different sulfur anions and the reactions are performed by the gene products of dsr operon from phylogenetically diverse sets of microorganisms. The operon is involved in the maintenance of environmental sulfur balance. Interestingly, the dsr operon is found to be present in both sulfur anion oxidizing and reducing microorganisms and in both types of organisms DsrAB protein complex plays a vital role. Though there are various reports regarding the genetics of dsr operon there are practically no reports dealing with the structural aspects of sulfur metabolism by dsr operon. In our present study, we tried to compare the mechanisms of sulfur anion oxidation and reduction by Allochromatium vinosum and Desulfovibrio vulgaris respectively through DsrAB protein complex. We analyzed the modes of bindings of sulfur anions to the DsrAB protein complex and observed that for sulfur anion oxidizers, sulfide and thiosulfate are the best substrates whereas for reducers sulfate and sulfite have the best binding abilities. We analyzed the binding interaction pattern of the DsrA and DsrB proteins while forming the DsrAB protein complexes in Desulfovibrio vulgaris and Allochromatium vinosum. To our knowledge this is the first report that analyzes the differences in binding patterns of sulfur substrates with DsrAB protein from these two microorganisms. This study would therefore be essential to predict the biochemical mechanism of sulfur anion oxidation and reduction by these two microorganisms i.e., Desulfovibrio vulgaris (sulfur anion reducer) and Allochromatium vinosum (sulfur anion oxidizer). Our observations also highlight the mechanism of sulfur geochemical cycle which has important implications in future study of sulfur metabolism as it has a huge application in waste remediation and production of industrial bio-products viz. vitamins, bio-polyesters and bio

  2. Oxidation of phosphine by sulfur or selenium involving a catalytic ...

    Indian Academy of Sciences (India)

    Administrator

    P NMR spec- troscopy. Such interconversion with the participation of breaking of bridging copper-µ3-sulfur bond with the formation of new copper–phosphorous bond led to the development of a catalytic cycle using excess. PPh3 and S or Se as the reacting substrates. The turnover number for the oxidation of PPh3 by S ...

  3. Reduced graphene oxide encapsulated sulfur spheres for the lithium-sulfur battery cathode

    Directory of Open Access Journals (Sweden)

    Feiyan Liu

    Full Text Available Reduced graphene oxide (rGO encapsulated sulfur spheres for the Li-S batteries were prepared via the redox reaction between sodium polysulfide. XRD spectra showed that the diffraction peak of graphite oxide (GO at 10° disappeared, while the relatively weak diffraction peak at 27° belongs to graphene emerged. FT-IR spectra showed that the vibrations of the functional groups of GO, such as 3603 cm−1, 1723 cm−1and 1619 cm−1 which contributed from OH, COC and CO respectively, disappeared when compared to the spectra of GSC. SEM observations indicated that the optimum experimental condition followed as: mass ratio of GO and S was 1:1, 10% NaOH was used to adjust the pH. EDX analysis showed that the sulfur content reached at 68.8% of the composite material. The resultant electric resistance was nearly less than GO’s resistance in three orders of magnitude under same condition. Further electrochemical performance tests showed a coulombic efficiency was 96% from the first cycle capacity was 827 mAh g−1, to 388 mAh g−1 in the 100 cycles. This study carries substantial significance to the development of Li-S battery cathode materials. Keywords: Lithium-sulfur battery, Graphene, Sulfur spheres, Cathode material

  4. Sulfur Cycling in an Iron Oxide-Dominated, Dynamic Marine Depositional System: The Argentine Continental Margin

    Directory of Open Access Journals (Sweden)

    Natascha Riedinger

    2017-05-01

    Full Text Available The interplay between sediment deposition patterns, organic matter type and the quantity and quality of reactive mineral phases determines the accumulation, speciation, and isotope composition of pore water and solid phase sulfur constituents in marine sediments. Here, we present the sulfur geochemistry of siliciclastic sediments from two sites along the Argentine continental slope—a system characterized by dynamic deposition and reworking, which result in non-steady state conditions. The two investigated sites have different depositional histories but have in common that reactive iron phases are abundant and that organic matter is refractory—conditions that result in low organoclastic sulfate reduction rates (SRR. Deposition of reworked, isotopically light pyrite and sulfurized organic matter appear to be important contributors to the sulfur inventory, with only minor addition of pyrite from organoclastic sulfate reduction above the sulfate-methane transition (SMT. Pore-water sulfide is limited to a narrow zone at the SMT. The core of that zone is dominated by pyrite accumulation. Iron monosulfide and elemental sulfur accumulate above and below this zone. Iron monosulfide precipitation is driven by the reaction of low amounts of hydrogen sulfide with ferrous iron and is in competition with the oxidation of sulfide by iron (oxyhydroxides to form elemental sulfur. The intervals marked by precipitation of intermediate sulfur phases at the margin of the zone with free sulfide are bordered by two distinct peaks in total organic sulfur (TOS. Organic matter sulfurization appears to precede pyrite formation in the iron-dominated margins of the sulfide zone, potentially linked to the presence of polysulfides formed by reaction between dissolved sulfide and elemental sulfur. Thus, SMTs can be hotspots for organic matter sulfurization in sulfide-limited, reactive iron-rich marine sedimentary systems. Furthermore, existence of elemental sulfur and iron

  5. Oxidation of Reduced Sulfur Species: Carbonyl Sulfide

    DEFF Research Database (Denmark)

    Glarborg, Peter; Marshall, Paul

    2013-01-01

    satisfactorily oxidation of OCS over a wide range of stoichiometric air–fuel ratios (0.5 ≤λ≤7.3), temperatures (450–1700 K), and pressures (0.02–3.0 atm) under dry conditions. The governing reaction mechanisms are outlined based on calculations with the kinetic model. The oxidation rate of OCS is controlled...... by the competition between chain‐branching and ‐propagating steps; modeling predictions are particularly sensitive to the branching fraction for the OCS + O reaction to form CO + SO or CO2 + S....

  6. Selective oxidation of refractory sulfur compounds for the production of low sulfur transportation fuel

    Energy Technology Data Exchange (ETDEWEB)

    Jeong, Kwang-Eun; Kim, Tae-Wan; Kim, Joo-Wan; Chae, Ho-Jeong; Kim, Chul-Ung; Jeong, Soon-Yong [Korea Research Institute of Chemical Technology, Daejeon (Korea, Republic of); Park, Young-Kwon [University of Seoul, Seoul (Korea, Republic of)

    2013-03-15

    The current technologies for achieving low sulfur in diesel fuel are based on hydrotreating, which requires high temperature, high pressure and excessive supply of hydrogen. Oxidative desulfurization (ODS) is considered one of the promising new methods for super deep desulfurization, which could be carried out under very mild conditions (atmospheric pressure, <100 .deg.. C) without consumption of hydrogen. In this paper, development status of ODS process by major licensors are described as well as general concepts of ODS reaction. In addition, the ODS process has been categorized into single phasic and biphasic system according to the oxidants involved. Recent trends in both systems are reviewed in detail and future work is also proposed.

  7. Selective oxidation of refractory sulfur compounds for the production of low sulfur transportation fuel

    International Nuclear Information System (INIS)

    Jeong, Kwang-Eun; Kim, Tae-Wan; Kim, Joo-Wan; Chae, Ho-Jeong; Kim, Chul-Ung; Jeong, Soon-Yong; Park, Young-Kwon

    2013-01-01

    The current technologies for achieving low sulfur in diesel fuel are based on hydrotreating, which requires high temperature, high pressure and excessive supply of hydrogen. Oxidative desulfurization (ODS) is considered one of the promising new methods for super deep desulfurization, which could be carried out under very mild conditions (atmospheric pressure, <100 .deg.. C) without consumption of hydrogen. In this paper, development status of ODS process by major licensors are described as well as general concepts of ODS reaction. In addition, the ODS process has been categorized into single phasic and biphasic system according to the oxidants involved. Recent trends in both systems are reviewed in detail and future work is also proposed

  8. Characterization and uranium bioleaching performance of mixed iron- and sulfur-oxidizers versus iron-oxidizers

    International Nuclear Information System (INIS)

    Qian Li; Jing Sun; Dexin Ding; Qingliang Wang; Wenge Shi; Eming Hu; Xiaoyu Jiang; University of South China, Hengyang; Xingxing Wang

    2017-01-01

    In order to develop and apply mixed iron- and sulfur-oxidizers in uranium bioleaching, the characteristics of a mixed iron- and sulfur-oxidizing consortium (Consortium ISO) were comparatively investigated versus an iron-oxidizing consortium (Consortium IO). The results showed, the Consortium ISO exerted stronger oxidative ability and acid-producing ability than Consortium IO did. The synergy of sulfur-oxidizers and iron-oxidizers could change the structure and properties of the passivation substance, and work positively for eliminating the accumulation of passivation substance. In the bioleaching process, the uranium bioleaching experiments showed the recovery percentage of uranium reached 99.5% with Consortium ISO, 6.3% more than that of Consortium IO. (author)

  9. Method of removing oxides of sulfur and oxides of nitrogen from exhaust gases

    Science.gov (United States)

    Walker, Richard J.

    1986-01-01

    A continuous method is presented for removing both oxides of sulfur and oxides of nitrogen from combustion or exhaust gases with the regeneration of the absorbent. Exhaust gas is cleaned of particulates and HCl by a water scrub prior to contact with a liquid absorbent that includes an aqueous solution of bisulfite and sulfite ions along with a metal chelate, such as, an iron or zinc aminopolycarboxylic acid. Following contact with the combustion gases the spent absorbent is subjected to electrodialysis to transfer bisulfite ions into a sulfuric acid solution while splitting water with hydroxide and hydrogen ion migration to equalize electrical charge. The electrodialysis stack includes alternate layers of anion selective and bipolar membranes. Oxides of nitrogen are removed from the liquid absorbent by air stripping at an elevated temperature and the regenerated liquid absorbent is returned to contact with exhaust gases for removal of sulfur oxides and nitrogen oxides.

  10. Thermal stress analysis of sulfur deactivated solid oxide fuel cells

    Science.gov (United States)

    Zeng, Shumao; Parbey, Joseph; Yu, Guangsen; Xu, Min; Li, Tingshuai; Andersson, Martin

    2018-03-01

    Hydrogen sulfide in fuels can deactivate catalyst for solid oxide fuel cells, which has become one of the most critical challenges to stability. The reactions between sulfur and catalyst will cause phase changes, leading to increase in cell polarization and mechanical mismatch. A three-dimensional computational fluid dynamics (CFD) approach based on the finite element method (FEM) is thus used to investigate the polarization, temperature and thermal stress in a sulfur deactivated SOFC by coupling equations for gas-phase species, heat, momentum, ion and electron transport. The results indicate that sulfur in fuels can strongly affect the cell polarization and thermal stresses, which shows a sharp decrease in the vicinity of electrolyte when 10% nickel in the functional layer is poisoned, but they remain almost unchanged even when the poisoned Ni content was increased to 90%. This investigation is helpful to deeply understand the sulfur poisoning effects and also benefit the material design and optimization of electrode structure to enhance cell performance and lifetimes in various hydrocarbon fuels containing impurities.

  11. Electrochemical promotion of sulfur dioxide catalytic oxidation

    DEFF Research Database (Denmark)

    Petrushina, Irina; Bandur, Viktor; Cappeln, Frederik Vilhelm

    2000-01-01

    investigation was to study a possible non-Faradaic electrochemical promotion of the liquid-phase catalytic reaction. It has been shown that there are two negative potential promotion areas with maximum effects at approximately -0.1 and -0.2 V, and one positive potential promotion area with the maximum effect...... between 0.1 and 0.3 V. There were no Faradaic reactions in the negative polarization region, and there was an anodic current which was less than 16% of the theoretical value for an exclusively Faradaic SO2 oxidation. Therefore the promotion effects at negative polarization are completely non-Faradaic. All...... the promotion effects have been explained as mainly due to charging of the electric double layer at the gold electrode. The effect at -0.2 V also depends on the V2O5 concentration and is more pronounced at higher V2O5 concentrations. This has been ascribed to a destruction of the vanadium polymeric chains...

  12. Process for the removal of sulfur oxides and nitrogen oxides from flue gas

    International Nuclear Information System (INIS)

    Elshout, R.V.

    1992-01-01

    This patent describes a continuous process for removing sulfur oxide and nitrogen oxide contaminants from the flue gas generated by industrial power plants and boiler systems burning sulfur containing fossil fuels and for converting these contaminants, respectively, into recovered elemental liquid sulfur and nitrogen ammonia and mixtures thereof. It comprises removing at least a portion of the flue gas generated by a power plant or boiler system upstream of the stack thereof; passing the cooled and scrubbed flue gas through an adsorption system; combining a first portion of the reducing gas stream leaving the adsorbers of the adsorption system during regeneration thereof and containing sulfur oxide and nitrogen oxide contaminants with a hydrogen sulfide rich gas stream at a temperature of about 400 degrees F to about 600 degrees F and passing the combined gas streams through a Claus reactor-condenser system over a catalyst in the reactor section thereof which is suitable for promoting the equilibrium reaction between the hydrogen sulfide and the sulfur dioxide of the combined streams to form elemental sulfur

  13. Extractive de-sulfurization and de-ashing of high sulfur coals by oxidation with ionic liquids

    International Nuclear Information System (INIS)

    Saikia, Binoy K.; Khound, Kakoli; Baruah, Bimala P.

    2014-01-01

    Highlights: • Extractive de-sulfurization and de-ashing process for cleaning high sulfur coals. • The process removes inorganic as well as organic sulfur components from high sulfur coals. • The process has less risk to chemists and other surroundings. - Abstract: The environmental consequences of energy production from coals are well known, and are driving the development of desulfurization technologies. In this investigation, ionic liquids were examined for extractive desulfurization and de-ashing in industrially important high sulfur sub-bituminous Indian coals. The ionic liquids, namely, 1-n-butyl-3-methylimidazolium tetrafluoroborate (IL1) and 1-n-butyl 3-methylimidazolium chloride (IL2) were employed for desulfurization of a few Indian coal samples in presence of HCOOH/H 2 O 2 and V 2 O 5 . Results show the maximum removal of 50.20% of the total sulfur, 48.00% of the organic sulfur, and 70.37 wt% of the ash in this process. The ionic liquids were recovered and subsequently used for further desulfurization. FT-IR spectra reveal the transformation of organic sulfur functionalities into the sulfoxides (S=O) and sulfones (-SO 2 ) due to the oxidative reactions. The sulfate, pyrite and sulfides (aryls) signals in the near edge X-ray absorption fine structure (NEXAFS) of the oxidized coal samples showed sulfur transformation during the desulfurization process. The study demonstrates the removal of significant amount of inorganic as well as organic sulfur (aryls) components from the original high sulfur coal samples to make them cleaner

  14. Measurement of sulfur dioxide oxidation rates in wintertime orographic clouds

    International Nuclear Information System (INIS)

    Snider, J.R.

    1990-01-01

    SO2-reaction studies in the clouds are examined and summarized to experimentally confirm model predictions and previous field studies regarding dominant SO2-reaction pathways. Controlled amounts of SO2 were released into nonprecipitating orographic clouds, and sulfate yields are compared to oxidant depletions. The sulfate yields were taken from cloud-water samples and liquid-water-concentration measurements, and oxidant-depletion data were generated from continuous gas-phase measurements. Comparisons of Y sub SO4 and D sub H2O2 suggest that H2O2 is the dominant oxidant, and the in-cloud reaction between H2O2 and the bisulfite ion can be expressed by a simple rate that agrees with predictions and laboratory results. The rate measurements are found to be inconsistent with the rate law proposed by Hegg and Hobbs (1982) and with some observational data. The present conclusions are of interest to evaluating the effects of sulfur dioxide emissions on sulfuric acid deposition. 30 refs

  15. Hysteresis Phenomena in Sulfur Dioxide Oxidation over Supported Vanadium Catalysts

    DEFF Research Database (Denmark)

    Masters, Stephen G.; Eriksen, Kim Michael; Fehrmann, Rasmus

    1997-01-01

    Catalyst deactivation and hysteresis behavior in industrial SO2-oxidation catalysts have been studied in the temperature region 350-480 C by combined in situ EPR spectroscopy and catalytic activity measurements. The feed gas composition simulated sulfuric acid synthesis gas and wet/dry de......NOx'ed flue gas. The vanadium (IV) compound K4(VO)3(SO4)5 precipitated during all the investigated conditions hence causing catalyst deactivation. Hysteresis behavior of both the catalytic activity and the V(IV) content was observed during reheating....

  16. Photoactive thin film semiconducting iron pyrite prepared by sulfurization of iron oxides

    Energy Technology Data Exchange (ETDEWEB)

    Smestad, G.; Ennaoui, A.; Fiechter, S.; Tributsch, H.; Hofmann, W.K.; Birkholz, M. (Hahn-Meitner-Institut Berlin GmbH (Germany, F.R.). Abt. Solare Energetik Hahn-Meitner-Institut Berlin GmbH (Germany, F.R.). Abt. Materialforschung); Kautek, W. (Bundesanstalt fuer Materialforschung und -pruefung, Berlin (Germany, F.R.))

    1990-03-01

    Photoactive iron pyrite (FeS{sub 2}) thin film layers have been synthesized by a simple method involving the reaction of Fe{sub 3}O{sub 4} or Fe{sub 2}O{sub 3} with elemental sulfur. The films were formed on a variety of different substrate materials by converting or sulfurizing iron oxide layers. The subsequent sulfur treatment of the oxide layers consisted of exposure of the films to gaseous sulfur in open or closed ampules at 350degC for 0.5-2 h. The morphology, composition and photoactivity of the films produced were checked using X-ray diffraction, X-ray photoelectron spectroscopy (ESCA), optical absorption, steady state and transient photoconductivity. The best films showed good crystallinity and purity with concurrent photoconductivity and photoelectrochemical response. The ability of this technique to produce photoactive material can be explained by interpretation of the Gibbs ternary phase diagram for the Fe-O-S system, and may be related to the production of photoactive pyrite in nature. A discussion is made as to the future improvement of the solar cell response by proper optimization of geometric and configurational properties. (orig.).

  17. A novel hydrogen oxidizer amidst the sulfur-oxidizing Thiomicrospira lineage

    Science.gov (United States)

    Hansen, Moritz; Perner, Mirjam

    2015-01-01

    Thiomicrospira species are ubiquitously found in various marine environments and appear particularly common in hydrothermal vent systems. Members of this lineage are commonly classified as sulfur-oxidizing chemolithoautotrophs. Although sequencing of Thiomicrospira crunogena's genome has revealed genes that encode enzymes for hydrogen uptake activity and for hydrogenase maturation and assembly, hydrogen uptake ability has so far not been reported for any Thiomicrospira species. We isolated a Thiomicrospira species (SP-41) from a deep sea hydrothermal vent and demonstrated that it can oxidize hydrogen. We show in vivo hydrogen consumption, hydrogen uptake activity in partially purified protein extracts and transcript abundance of hydrogenases during different growth stages. The ability of this strain to oxidize hydrogen opens up new perspectives with respect to the physiology of Thiomicrospira species that have been detected in hydrothermal vents and that have so far been exclusively associated with sulfur oxidation. PMID:25226028

  18. Effects of reactive element additions and sulfur removal on the oxidation behavior of FECRAL alloys

    International Nuclear Information System (INIS)

    Stasik, M.C.; Pettit, F.S.; Meier, G.H.; Smialek, J.L.

    1994-01-01

    The results of this study have shown that desulfurization of FeCrAl alloys by hydrogen annealing can result in improvements in cyclic oxidation comparable to that achieved by doping with reactive elements. Moreover, specimens of substantial thicknesses can be effectively desulfurized because of the high diffusivity of sulfur in bcc iron alloys. The results have also shown that there is less stress generation during the cyclic oxidation of Y-doped FeCrAl compared to Ti-doped or desulfurized FeCrAl. This indicates that the growth mechanism, as well as the strength of the oxide/alloy interface, influences the ultimate oxidation morphology and stress state which will certainly affect the length of time the alumina remains protective

  19. A binder-free sulfur/reduced graphene oxide aerogel as high performance electrode materials for lithium sulfur batteries

    Science.gov (United States)

    Nitze, Florian; Agostini, Marco; Lundin, Filippa; Palmqvist, Anders E. C.; Matic, Aleksandar

    2016-12-01

    Societies’ increasing need for energy storage makes it necessary to explore new concepts beyond the traditional lithium ion battery. A promising candidate is the lithium-sulfur technology with the potential to increase the energy density of the battery by a factor of 3-5. However, so far the many problems with the lithium-sulfur system have not been solved satisfactory. Here we report on a new approach utilizing a self-standing reduced graphene oxide based aerogel directly as electrodes, i.e. without further processing and without the addition of binder or conducting agents. We can thereby disrupt the common paradigm of “no battery without binder” and can pave the way to a lithium-sulfur battery with a high practical energy density. The aerogels are synthesized via a one-pot method and consist of more than 2/3 sulfur, contained inside a porous few-layered reduced graphene oxide matrix. By combining the graphene-based aerogel cathode with an electrolyte and a lithium metal anode, we demonstrate a lithium-sulfur cell with high areal capacity (more than 3 mAh/cm2 after 75 cycles), excellent capacity retention over 200 cycles and good sulfur utilization. Based on this performance we estimate that the energy density of this concept-cell can significantly exceed the Department of Energy (DEO) 2020-target set for transport applications.

  20. Micro-Spherical Sulfur/Graphene Oxide Composite via Spray Drying for High Performance Lithium Sulfur Batteries

    Science.gov (United States)

    Tian, Yuan; Sun, Zhenghao; Zhang, Yongguang; Yin, Fuxing

    2018-01-01

    An efficient, industry-accepted spray drying method was used to synthesize micro-spherical sulfur/graphene oxide (S/GO) composites as cathode materials within lithium sulfur batteries. The as-designed wrapping of the sulfur-nanoparticles, with wrinkled GO composites, was characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The unique morphological design of this material enabled superior discharge capacity and cycling performance, demonstrating a high initial discharge capacity of 1400 mAh g−1 at 0.1 C. The discharge capacity remained at 828 mAh g−1 after 150 cycles. The superior electrochemical performance indicates that the S/GO composite improves electrical conductivity and alleviates the shuttle effect. This study represents the first time such a facile spray drying method has been adopted for lithium sulfur batteries and used in the fabrication of S/GO composites. PMID:29346303

  1. Oxidation of sulfur and nitrogen oxides by pulse corona discharge

    International Nuclear Information System (INIS)

    Amirov, R.H.; Desiaterik, Yu.N.; Filimonova, E.A.; Zhelezniak, M.B.; Chae, J.O.

    1996-01-01

    The NO x and SO 2 removal efficiency of the corona reactor has been measured both with and without ammonia addition to the gas stream. Experimental conditions are described. The dependence of NO and SO 2 removal efficiency from flow rate and initial pollutant concentrations were measured. One test with fixed amount of the inputted energy per the unit of SO 2 but with different initial concentration have been made. It is found that increasing of the initial concentration from 200 ppm to 700 ppm can enlarge the removal efficiency by factor 2.5. Some tests were carried out with both pollutant gases SO 2 and NO simultaneously. An efficiency on the SO 2 removal of 96% and on the NO removal 70% in pulse corona have been achieved with ammonia addition when SO 2 initial concentration was 480 ppm and the NO initial concentration was 230 ppm. A numerical model for NO and SO 2 oxidation in homogeneous gas flow has been developed. The flow contains cold (T = 300-400 K) background components N 2 , CO 2 , H 2 O, O 2 and impurities SO 2 , NO x , CO. A source of chemically active species is an electrical streamer discharge of corona type. (authors)

  2. Conversion of sulfur and nitrogen oxides in air under exposure to microsecond electron beams

    International Nuclear Information System (INIS)

    Denisov, G.V.; Kuznetsov, D.L.; Novoselov, Yu.N.; Tkachenko, R.M.

    2002-01-01

    Flue gases of power plants realizing sulfur and nitrogen oxides into the atmosphere represent one of the environmental pollution sources. Paper presents the results of experimental investigations of conversion of sulfur and nitrogen oxides in the ionized gas mixture simulating composition of off-gases of thermal power stations. Pulse beam of microsecond duration electrons was used as a source of ionization. Mutual influence of both types of oxides on process of their conversion is shown. One studied possible kinetic mechanisms to remove sulfur and nitrogen oxides from gaseous mixture [ru

  3. Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium-sulfur battery design.

    Science.gov (United States)

    Tao, Xinyong; Wang, Jianguo; Liu, Chong; Wang, Haotian; Yao, Hongbin; Zheng, Guangyuan; Seh, Zhi Wei; Cai, Qiuxia; Li, Weiyang; Zhou, Guangmin; Zu, Chenxi; Cui, Yi

    2016-04-05

    Lithium-sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understanding and corresponding selection criteria for the oxides are still lacking. Herein, various nonconductive metal-oxide nanoparticle-decorated carbon flakes are synthesized via a facile biotemplating method. The cathodes based on magnesium oxide, cerium oxide and lanthanum oxide show enhanced cycling performance. Adsorption experiments and theoretical calculations reveal that polysulfide capture by the oxides is via monolayered chemisorption. Moreover, we show that better surface diffusion leads to higher deposition efficiency of sulfide species on electrodes. Hence, oxide selection is proposed to balance optimization between sulfide-adsorption and diffusion on the oxides.

  4. Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium–sulfur battery design

    Science.gov (United States)

    Tao, Xinyong; Wang, Jianguo; Liu, Chong; Wang, Haotian; Yao, Hongbin; Zheng, Guangyuan; Seh, Zhi Wei; Cai, Qiuxia; Li, Weiyang; Zhou, Guangmin; Zu, Chenxi; Cui, Yi

    2016-01-01

    Lithium–sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understanding and corresponding selection criteria for the oxides are still lacking. Herein, various nonconductive metal-oxide nanoparticle-decorated carbon flakes are synthesized via a facile biotemplating method. The cathodes based on magnesium oxide, cerium oxide and lanthanum oxide show enhanced cycling performance. Adsorption experiments and theoretical calculations reveal that polysulfide capture by the oxides is via monolayered chemisorption. Moreover, we show that better surface diffusion leads to higher deposition efficiency of sulfide species on electrodes. Hence, oxide selection is proposed to balance optimization between sulfide-adsorption and diffusion on the oxides. PMID:27046216

  5. Production of petroleum bitumen by oxidation of heavy oil residue with sulfur

    Science.gov (United States)

    Tileuberdi, Ye.; Akkazyn, Ye. A.; Ongarbayev, Ye. K.; Imanbayev, Ye. I.; Mansurov, Z. A.

    2018-03-01

    In this paper production of bitumen adding elemental sulfur at oxidation of oil residue are investigated. The objects of research were distilled residue of Karazhanbas crude oil and elemental sulfur. These oil residue characterized by a low output of easy fractions and the high content of tar-asphaltene substances, therefore is the most comprehensible feedstock for producing bitumen. The sulfur is one of the oil product collected in oil extraction regions. Oxidation process of hydrocarbons carried out at temperatures from 180 up to 210 °С without addition of sulfur and with the addition of sulfur (5-10 wt. %) for 4 hours. At 200 °С oxidation of hydrocarbons with 5, 7 and 10 wt.% sulfur within 3-4 h allows receiving paving bitumen on the mark BND 200/300, BND 130/200, BN 90/130 and BN 70/30. Physical and mechanical characteristics of oxidation products with the addition of 5-7 wt. % sulfur corresponds to grade of paving bitumen BND 40/60. At the given temperature oxidized for 2.5-3 h, addition of 10 wt. % sulfur gave the products of oxidation describing on parameters of construction grades of bitumen (BN 90/10).

  6. Effect of antimony oxide on magnesium vanadates for the selective oxidation of hydrogen sulfide to sulfur

    Energy Technology Data Exchange (ETDEWEB)

    Li, K.T.; Chi, Z.H. [Department of Chemical Engineering, Tunghai University, ROC Taichung (Taiwan)

    2001-05-17

    The effect of antimony oxide addition to MgV{sub 2}O{sub 6} and Mg{sub 3}V{sub 2}O{sub 8} was studied in the selective oxidation of hydrogen sulfide to sulfur. Significant improvements in sulfur selectivity and yield were observed for the uncalcined mechanical mixtures of magnesium vanadates with {alpha}-Sb{sub 2}O{sub 4}. Calcination of the mechanical mixtures resulted in the much stronger synergy in catalytic activity and sulfur selectivity. For the uncalcined samples, XRD, TPR and XPS studies indicated that antimony reduction behaviors in the mechanical mixtures differed very much from those in {alpha}-Sb{sub 2}O{sub 4} alone, suggested that their selectivity improvements might be due to the interactions (probably oxygen transfer) between {alpha}-Sb{sub 2}O{sub 4} and magnesium vanadates. For the calcined samples, XRD results indicated that their better catalytic performances in H{sub 2}S oxidation were primarily attributed to the formation of VSbO{sub 4} compound from antimony oxide and magnesium vanadates.

  7. Garlic Sulfur Compounds Suppress Cancerogenesis and Oxidative Stress: a Review

    Directory of Open Access Journals (Sweden)

    Dvořáková M.

    2015-06-01

    Full Text Available Garlic has long been considered a food with many health benefits. Several studies have confirmed that sulfur compounds are responsible for the positive effects of garlic on organisms. Garlic acts as an antioxidant by increasing antioxidant enzyme activity, reducing reactive oxygen species generation, and protecting proteins and lipids from oxidation. Garlic suppresses carcinogenesis through several mechanisms: (1 it reduces oxidative stress, and therefore, prevents damage to DNA; (2 it induces apoptosis or cell cycle arrest in cancer cells; and (3 it modifies gene expression through histon acetylation. The positive effects of garlic could be mediated by several mechanisms. It influences signalling pathways of gasotransmitters such as hydrogen sulfide. Garlic enhances hydrogen sulfide production both through its direct release and through an increase in activity of enzymes which produce hydrogen sulfide. Hydrogen sulfide acts as a signalling molecule in various tissues and participates in the regulation of many physiological processes. We can presume that garlic, which is able to release hydrogen sulfide, exhibits effects similar to those of this gasotransmitter.

  8. Sulfur isotope fractionation during oxidation of sulfur dioxide: gas-phase oxidation by OH radicals and aqueous oxidation by H2O2, O3 and iron catalysis

    Directory of Open Access Journals (Sweden)

    J. N. Crowley

    2012-01-01

    Full Text Available The oxidation of SO2 to sulfate is a key reaction in determining the role of sulfate in the environment through its effect on aerosol size distribution and composition. Sulfur isotope analysis has been used to investigate sources and chemical processes of sulfur dioxide and sulfate in the atmosphere, however interpretation of measured sulfur isotope ratios is challenging due to a lack of reliable information on the isotopic fractionation involved in major transformation pathways. This paper presents laboratory measurements of the fractionation factors for the major atmospheric oxidation reactions for SO2: Gas-phase oxidation by OH radicals, and aqueous oxidation by H2O2, O3 and a radical chain reaction initiated by iron. The measured fractionation factor for 34S/32S during the gas-phase reaction is αOH = (1.0089±0.0007−((4±5×10−5 T(°C. The measured fractionation factor for 34S/32S during aqueous oxidation by H2O2 or O3 is αaq = (1.0167±0.0019−((8.7±3.5 ×10−5T(°C. The observed fractionation during oxidation by H2O2 and O3 appeared to be controlled primarily by protonation and acid-base equilibria of S(IV in solution, which is the reason that there is no significant difference between the fractionation produced by the two oxidants within the experimental error. The isotopic fractionation factor from a radical chain reaction in solution catalysed by iron is αFe = (0.9894±0.0043 at 19 °C for 34S/32S. Fractionation was mass-dependent with regards to 33S/32S for all the reactions investigated. The radical chain reaction mechanism was the only measured reaction that had a faster rate for the light isotopes. The results presented in this study will be particularly useful to determine the importance of the transition metal-catalysed oxidation pathway compared to other oxidation pathways, but other main oxidation pathways can not be distinguished based on stable sulfur isotope measurements alone.

  9. 40 CFR 52.1881 - Control strategy: Sulfur oxides (sulfur dioxide).

    Science.gov (United States)

    2010-07-01

    ....0 pounds of sulfur dioxide per million BTU actual heat input for the coal-fired boiler and 0.4... BTU actual heat input for coal-fired boiler C exiting through stack 5. (3) 2.24 pounds of sulfur dioxide per million BTU acutal heat input for coal-fired boiler D exiting through stack 6. (E) In lieu of...

  10. The influence of water vapor and sulfur dioxide on the catalytic decomposition of nitrous oxide

    Energy Technology Data Exchange (ETDEWEB)

    Yalamas, C.; Heinisch, R.; Barz, M. [Technische Univ. Berlin (Germany). Inst. fuer Energietechnik; Cournil, M. [Ecole Nationale Superieure des Mines, 42 - Saint-Etienne (France)

    2001-03-01

    For the nitrous oxide decomposition three groups of catalysts such as metals on support, hydrotalcites, and perovskites were studied relating to their activity in the presence of vapor or sulfur dioxide, in the temperature range from 200 to 500 C. It was found that the water vapor strongly inhibates the nitrous oxide decomposition at T=200-400 C. The sulfur dioxide poisons the catalysts, in particular the perovskites. (orig.)

  11. Ultrasound-assisted oxidative process for sulfur removal from petroleum product feedstock.

    Science.gov (United States)

    Mello, Paola de A; Duarte, Fábio A; Nunes, Matheus A G; Alencar, Mauricio S; Moreira, Elizabeth M; Korn, Mauro; Dressler, Valderi L; Flores, Erico M M

    2009-08-01

    A procedure using ultrasonic irradiation is proposed for sulfur removal of a petroleum product feedstock. The procedure involves the combination of a peroxyacid and ultrasound-assisted treatment in order to comply with the required sulfur content recommended by the current regulations for fuels. The ultrasound-assisted oxidative desulfurization (UAOD) process was applied to a petroleum product feedstock using dibenzothiophene as a model sulfur compound. The influence of ultrasonic irradiation time, oxidizing reagents amount, kind of solvent for the extraction step and kind of organic acid were investigated. The use of ultrasonic irradiation allowed higher efficiency for sulfur removal in comparison to experiments performed without its application, under the same reactional conditions. Using the optimized conditions for UAOD, the sulfur removal was about 95% after 9min of ultrasonic irradiation (20kHz, 750W, run at 40%), using hydrogen peroxide and acetic acid, followed by extraction with methanol.

  12. Regulation of dsr genes encoding proteins responsible for the oxidation of stored sulfur in Allochromatium vinosum.

    Science.gov (United States)

    Grimm, Frauke; Dobler, Nadine; Dahl, Christiane

    2010-03-01

    Sulfur globules are formed as obligatory intermediates during the oxidation of reduced sulfur compounds in many environmentally important photo- and chemolithoautotrophic bacteria. It is well established that the so-called Dsr proteins are essential for the oxidation of zero-valent sulfur accumulated in the globules; however, hardly anything is known about the regulation of dsr gene expression. Here, we present a closer look at the regulation of the dsr genes in the phototrophic sulfur bacterium Allochromatium vinosum. The dsr genes are expressed in a reduced sulfur compound-dependent manner and neither sulfite, the product of the reverse-acting dissimilatory sulfite reductase DsrAB, nor the alternative electron donor malate inhibit the gene expression. Moreover, we show the oxidation of sulfur to sulfite to be the rate-limiting step in the oxidation of sulfur to sulfate as sulfate production starts concomitantly with the upregulation of the expression of the dsr genes. Real-time RT-PCR experiments suggest that the genes dsrC and dsrS are additionally expressed from secondary internal promoters, pointing to a special function of the encoded proteins. Earlier structural analyses indicated the presence of a helix-turn-helix (HTH)-like motif in DsrC. We therefore assessed the DNA-binding capability of the protein and provide evidence for a possible regulatory function of DsrC.

  13. Removal and recovery of nitrogen and sulfur oxides from gaseous mixtures containing them

    International Nuclear Information System (INIS)

    Cooper, H.B.H.

    1984-01-01

    A cyclic process for removing lower valence nitrogen oxides from gaseous mixtures includes treating the mixtures with an aqueous media including alkali metal carbonate and alkali metal bicarbonate and a preoxygen oxidant to form higher valence nitrogen oxides and to capture these oxides as alkali metal salts, expecially nitrites and nitrates, in a carbonate/bicarbonate-containing product aqueous media. Highly selective recovery of nitrates in high purity and yield may then follow, as by crystallization, with the carbonate and bicarbonate alkali metal salts strongly increasing the selectivity and yield of nitrates. The product nitrites are converted to nitrates by oxidation after lowering the product aqueous media pH to below about 9. A cyclic process for removing sulfur oxides from gas mixtures includes treating these mixtures includes treating these mixtures with aqueous media including alkali metal carbonate and alkali metal bicarbonate where the ratio of alkali metal to sulfur dioxide is not less than 2. The sulfur values may be recovered from the resulting carbonate/bicarbonate/-sulfite containing product aqueous media as alkali metal sulfate or sulfite salts which are removed by crystallization from the carbonate-containing product aqueous media. As with the nitrates, the carbonate/bicarbonate system strongly increases yield of sulfate or sulfite during crystallization. Where the gas mixtures include both sulfur dioxide and lower valence nitrogen oxides, the processes for removing lower valence nitrogen oxides and sulfur dioxide may be combined into a single removal/recovery system, or may be effected in sequence

  14. Mesoporous binary metal oxide nanocomposites: Synthesis, characterization and decontamination of sulfur mustard

    Energy Technology Data Exchange (ETDEWEB)

    Praveen Kumar, J., E-mail: praveenjella10@gmail.com; Prasad, G.K.; Ramacharyulu, P.V.R.K.; Singh, Beer; Gopi, T.; Krishna, R.

    2016-04-15

    Mesoporous MnO{sub 2}–ZnO, Fe{sub 2}O{sub 3}–ZnO, NiO–ZnO, and CeO{sub 2}–ZnO binary metal oxide nanocomposites were studied as sorbent decontaminants against sulfur mustard. They were synthesized by precipitation pyrolysis method and characterized by means of transmission electron microscopy, scanning electron microscopy coupled with energy dispersive analysis of X rays, X ray diffraction, and nitrogen adsorption techniques. The transmission electron microscopy and nitrogen adsorption data indicated the presence of pores with diameter ranging from 10 to 70 nm in the binary metal oxide nanocomposites and these materials exhibited surface area values in the range of 76–134 m{sup 2}/g. These binary metal oxide nanocomposites demonstrated large decontamination efficiencies against sulfur mustard when compared to their single component metal oxide nanoparticles. The binary metal oxide nanocomposites effectively decontaminated sulfur mustard into relatively non toxic products such as chloro ethyl vinyl sulfide, divinyl sulfide, 1,4-oxathiane, etc. The promising decontamination properties of binary metal oxide nanocomposites against sulfur mustard were attributed to the basic sites, Lewis acid sites, and the presence of these sites was confirmed by CO{sub 2} and NH{sub 3} temperature programmed desorption. - Graphical abstract: Mesoporous MnO{sub 2}–ZnO, Fe{sub 2}O{sub 3}–ZnO, NiO–ZnO, and CeO{sub 2}–ZnO binary metal oxide nanocomposites were studied as sorbent decontaminants against sulfur mustard. - Highlights: • Binary metal oxide nanocomposites were synthesized by co-precipitation method. • They were studied as sorbent decontaminants against sulfur mustard. • They decontaminated sulfur mustard into non toxic products. • MnO{sub 2}–ZnO and CeO{sub 2}–ZnO nanocomposites showed greater decontamination efficiency.

  15. Interface polymerization synthesis of conductive polymer/graphite oxide@sulfur composites for high-rate lithium-sulfur batteries

    International Nuclear Information System (INIS)

    Wang, Xiwen; Zhang, Zhian; Yan, Xiaolin; Qu, Yaohui; Lai, Yanqing; Li, Jie

    2015-01-01

    Highlights: • A hybrid nanostructure that incorporate the merits of conductive polymer nanorods and graphite oxide sheets. • A novel approach based on interface polymerization for synthesizing CP/GO@S ternary composite. • CP/GO@S ternary composite cathode shows enhanced electrochemical properties compared with CP@S binary composite cathode. • PEDOT/GO@S composite is the material system that have best electrochemical performance in all CP/GO@S ternary composites. - Abstract: The novel ternary composites, conductive polymers (CPs)/graphene oxide (GO)@sulfur composites were successfully synthesized via a facile one-pot route and used as cathode materials for Li-S batteries The poly(3,4-ethylenedioxythiophene) (PEDOT)/GO and polyaniline (PANI)/GO composites were prepared by interface polymerization of monomers on the surface of GO sheets. Then sulfur was in-situ deposited on the CPs/GO composites in same solution. The component and structure of the composites were characterized by XPS, TGA, FTIR, SEM, TEM and electrochemical measurements. In this structure, the CPs nanostructures are believed to serve as a conductive matrix and an adsorbing agent, while the highly conductive GO will physically and chemically confine the sulfur and polysulfide within cathode. The PEDOT/GO@S composites with the sulfur content of 66.2 wt% exhibit a reversible discharge capacity of 800.2 mAh g −1 after 200 cycles at 0.5 C, which is much higher than that of PANI/GO@S composites (599.1 mAh g −1 ) and PANI@S (407.2 mAh g −1 ). Even at a high rate of 4 C, the PEDOT/GO@S composites still retain a high specific capacity of 632.4 mAh g −1

  16. Oxygen and sulfur isotope systematics of sulfate produced during abiotic and bacterial oxidation of sphalerite and elemental sulfur

    Science.gov (United States)

    Balci, N.; Mayer, B.; Shanks, Wayne C.; Mandernack, K.W.

    2012-01-01

    Studies of metal sulfide oxidation in acid mine drainage (AMD) systems have primarily focused on pyrite oxidation, although acid soluble sulfides (e.g., ZnS) are predominantly responsible for the release of toxic metals. We conducted a series of biological and abiotic laboratory oxidation experiments with pure and Fe-bearing sphalerite (ZnS & Zn 0.88Fe 0.12S), respectively, in order to better understand the effects of sulfide mineralogy and associated biogeochemical controls of oxidation on the resultant ?? 34S and ?? 18O values of the sulfate produced. The minerals were incubated in the presence and absence of Acidithiobacillus ferrooxidans at an initial solution pH of 3 and with water of varying ?? 18O values to determine the relative contributions of H 2O-derived and O 2-derived oxygen in the newly formed sulfate. Experiments were conducted under aerobic and anaerobic conditions using O 2 and Fe(III) aq as the oxidants, respectively. Aerobic incubations with A. ferrooxidans, and S o as the sole energy source were also conducted. The ??34SSO4 values from both the biological and abiotic oxidation of ZnS and ZnS Fe by Fe(III) aq produced sulfur isotope fractionations (??34SSO4-ZnS) of up to -2.6???, suggesting the accumulation of sulfur intermediates during incomplete oxidation of the sulfide. No significant sulfur isotope fractionation was observed from any of the aerobic experiments. Negative sulfur isotope enrichment factors (??34SSO4-ZnS) in AMD systems could reflect anaerobic, rather than aerobic pathways of oxidation. During the biological and abiotic oxidation of ZnS and ZnS Fe by Fe(III) aq all of the sulfate oxygen was derived from water, with measured ?? 18OSO 4-H 2O values of 8.2??0.2??? and 7.5??0.1???, respectively. Also, during the aerobic oxidation of ZnS Fe and S o by A. ferrooxidans, all of the sulfate oxygen was derived from water with similar measured ?? 18OSO 4-H 2O values of 8.1??0.1??? and 8.3??0.3???, respectively. During biological oxidation

  17. The mechanism of the catalytic oxidation of hydrogen sulfide: II. Kinetics and mechanism of hydrogen sulfide oxidation catalyzed by sulfur

    NARCIS (Netherlands)

    Steijns, M.; Derks, F.; Verloop, A.; Mars, P.

    1976-01-01

    The kinetics of the catalytic oxidation of hydrogen sulfide by molecular oxygen have been studied in the temperature range 20–250 °C. The primary reaction product is sulfur which may undergo further oxidation to SO2 at temperatures above 200 °C. From the kinetics of this autocatalytic reaction we

  18. Improvement of sulfur resistance of Pd/Ce-Zr-Al-O catalysts for CO oxidation

    Science.gov (United States)

    Shin, Haebin; Baek, Minsung; Ro, Youngsoo; Song, Changyeol; Lee, Kwan-Young; Song, In Kyu

    2018-01-01

    Two kinds of mesoporous ceria-zirconia-alumina supports were prepared by a single-step epoxide-driven sol-gel method (SGCZA) and by a co-precipitation method (PCZA). Palladium catalysts supported on these materials were then prepared by a wet impregnation method (Pd/SGCZA and Pd/PCZA). The prepared catalysts were applied to the CO oxidation reaction before and after sulfur aging. XRD and N2 adsorption-desorption analyses revealed that these two catalysts retained different physicochemical properties. Pd/SGCZA had higher surface area and larger pore volume than Pd/PCZA before and after sulfur aging. TPR (Temperature-programmed reduction), CO chemisorption, FT-IR, and XPS analyses showed that the catalysts were differently influenced by sulfur species. Pd/SGCZA formed less sulfate and retained higher palladium dispersion than Pd/PCZA after sulfur aging. In the CO oxidation, Pd/PCZA showed better activity than Pd/SGCZA before sulfur aging. However, Pd/SGCZA showed higher CO conversion than Pd/PCZA after sulfur aging. We concluded that Pd/SGCZA was less poisoned by sulfur species than Pd/PCZA.

  19. Facile synthesis of graphene oxide @ mesoporous carbon hybrid nanocomposites for lithium sulfur battery

    International Nuclear Information System (INIS)

    Bao, Weizhai; Zhang, Zhian; Chen, Wei; Zhou, Chengkun; Lai, Yanqing; Li, Jie

    2014-01-01

    Graphical abstract: - Highlights: • A novel design and synthesis of GO@Meso-C using GO@MOF-5 as precursor. • GO@Meso-C hybrid material as a host material was applied for sulfur cathode. • Electrochemical performances were improved in sulfur cathode using Go@Meso-C. - Abstract: We present a design and synthesis of a hierarchical architecture of graphene oxide @ mesoporous carbon (GO@Meso-C) using graphene oxide @ metal-organic framework hybrid materials (GO@MOF-5) as both the template and precursor. Active sulfur is encapsulated into the GO@Meso-C matrix prepared via carbonize GO@MOF-5 polyhedrons for high performance lithium sulfur battery. The initial and 100th cycle discharge capacity of GO@Meso-C/S sulfur cathode are as high as 1122 mAh g −1 and 820 mAh g −1 at a current rate of 0.2 C. The remarkably high special capacity and capacity retention rate indicate that the GO@Meso-C is a promising host material for the sulfur cathode in the lithium sulfur battery applications

  20. Mathematical modelling of the kinetics of aerosol oxidation of sulfur dioxide upon electron-beam purification of power-plant flue gases from nitrogen and sulfur oxides

    International Nuclear Information System (INIS)

    Gerasimov, G.Ya.; Gerasimova, T.S.; Fadeev, S.A.

    1996-01-01

    A kinetic model of SO 2 oxidation in flue gases, irradiated with accelerated electron flux is proposed. The model comprises an optimized mechanism of gas phase radiation chemical oxidation of NO and SO 2 , kinetics circuit of SO 2 and NH 3 thermal interaction, kinetic models of volumetric condensation of water and sulfuric acid vapors and liquid-phase oxidation of SO 2 in aerosol drops, produced in the course of volumetric condensation. Calculation results are in a satisfactory agreement with experimental data. (author)

  1. Hydrogen sulfide oxidation by a microbial consortium in a recirculation reactor system: sulfur formation under oxygen limitation and removal of phenols.

    Science.gov (United States)

    Alcantara, Sergio; Velasco, Antonio; Muñoz, Ana; Cid, Juan; Revah, Sergio; Razo-Flores, Elías

    2004-02-01

    Wastewater from petroleum refining may contain a number of undesirable contaminants including sulfides, phenolic compounds, and ammonia. The concentrations of these compounds must be reduced to acceptable levels before discharge. Sulfur formation and the effect of selected phenolic compounds on the sulfide oxidation were studied in autotrophic aerobic cultures. A recirculation reactor system was implemented to improve the elemental sulfur recovery. The relation between oxygen and sulfide was determined calculating the O2/S2- loading rates (Q(O2)/Q(S)2- = Rmt), which adequately defined the operation conditions to control the sulfide oxidation. Sulfur-producing steady states were achieved at Rmt ranging from 0.5 to 1.5. The maximum sulfur formation occurred at Rmt of 0.5 where 85% of the total sulfur added to the reactor as sulfide was transformed to elemental sulfur and 90% of it was recovered from the bottom of the reactor. Sulfide was completely oxidized to sulfate (Rmt of 2) in a stirred tank reactor, even when a mixture of phenolic compounds was present in the medium. Microcosm experiments showed that carbon dioxide production increased in the presence of the phenols, suggesting that these compounds were oxidized and that they may have been used as carbon and energy source by heterotrophic microorganisms present in the consortium.

  2. Mesoporous CuO–ZnO binary metal oxide nanocomposite for decontamination of sulfur mustard

    International Nuclear Information System (INIS)

    Praveen Kumar, J.; Prasad, G.K.; Ramacharyulu, P.V.R.K.; Garg, P.; Ganesan, K.

    2013-01-01

    Mesoporous CuO–ZnO binary metal oxide nanocomposites were studied as sorbent decontaminants against sulfur mustard, a well known chemical warfare agent. They were prepared by precipitation pyrolysis method and characterized by means of X-ray diffraction, transmission electron microscopy, nitrogen adsorption, Fourier transform infrared spectroscopy techniques. Obtained data indicated the presence of mesopores with diameter ranging from 2 to 80 nm and the materials exhibited relatively high surface area 86 m 2 g −1 when compared to the individual metal oxide nanoparticles. Reactive sites of mesoporous CuO–ZnO binary metal oxide nanocomposites were studied by infrared spectroscopy technique using pyridine as a probe molecule. These materials demonstrated superior decontamination properties against sulfur mustard when compared to single component metal oxides and decontaminated it to divinyl sulfide, chloroethyl vinyl sulfide, hemisulfur mustard, etc. - Graphical abstract: Mesoporous CuO–ZnO binary metal oxide nanocomposites were studied as sorbent decontaminants against sulfur mustard, a well known chemical warfare agent. These materials demonstrated superior decontamination properties against sulfur mustard and decontaminated it to divinyl sulfide, chloroethyl vinyl sulfide, hemisulfur mustard, etc. - Highlights: • Preparation of mesoporous CuO–ZnO binary metal oxide nanocomposite. • CuO–ZnO with better surface area was synthesized by precipitation pyrolysis. • Decontamination of HD using mesoporous CuO–ZnO binary metal oxide nanocomposite. • HD decontaminated by elimination and hydrolysis reactions

  3. Mesoporous CuO–ZnO binary metal oxide nanocomposite for decontamination of sulfur mustard

    Energy Technology Data Exchange (ETDEWEB)

    Praveen Kumar, J.; Prasad, G.K., E-mail: gkprasad2001@yahoo.com; Ramacharyulu, P.V.R.K.; Garg, P.; Ganesan, K.

    2013-11-01

    Mesoporous CuO–ZnO binary metal oxide nanocomposites were studied as sorbent decontaminants against sulfur mustard, a well known chemical warfare agent. They were prepared by precipitation pyrolysis method and characterized by means of X-ray diffraction, transmission electron microscopy, nitrogen adsorption, Fourier transform infrared spectroscopy techniques. Obtained data indicated the presence of mesopores with diameter ranging from 2 to 80 nm and the materials exhibited relatively high surface area 86 m{sup 2} g{sup −1} when compared to the individual metal oxide nanoparticles. Reactive sites of mesoporous CuO–ZnO binary metal oxide nanocomposites were studied by infrared spectroscopy technique using pyridine as a probe molecule. These materials demonstrated superior decontamination properties against sulfur mustard when compared to single component metal oxides and decontaminated it to divinyl sulfide, chloroethyl vinyl sulfide, hemisulfur mustard, etc. - Graphical abstract: Mesoporous CuO–ZnO binary metal oxide nanocomposites were studied as sorbent decontaminants against sulfur mustard, a well known chemical warfare agent. These materials demonstrated superior decontamination properties against sulfur mustard and decontaminated it to divinyl sulfide, chloroethyl vinyl sulfide, hemisulfur mustard, etc. - Highlights: • Preparation of mesoporous CuO–ZnO binary metal oxide nanocomposite. • CuO–ZnO with better surface area was synthesized by precipitation pyrolysis. • Decontamination of HD using mesoporous CuO–ZnO binary metal oxide nanocomposite. • HD decontaminated by elimination and hydrolysis reactions.

  4. Synthesis of a Flexible Freestanding Sulfur/Polyacrylonitrile/Graphene Oxide as the Cathode for Lithium/Sulfur Batteries

    Directory of Open Access Journals (Sweden)

    Huifen Peng

    2018-04-01

    Full Text Available Rechargeable lithium/sulfur (Li/S batteries have received quite significant attention over the years because of their high theoretical specific capacity (1672 mAh·g−1 and energy density (2600 mAh·g−1 which has led to more efforts for improvement in their electrochemical performance. Herein, the synthesis of a flexible freestanding sulfur/polyacrylonitrile/graphene oxide (S/PAN/GO as the cathode for Li/S batteries by simple method via vacuum filtration is reported. The S/PAN/GO hybrid binder-free electrode is considered as one of the most promising cathodes for Li/S batteries. Graphene oxide (GO slice structure provides effective ion conductivity channels and increases structural stability of the ternary system, resulting in excellent electrochemical properties of the freestanding S/PAN/GO cathode. Additionally, graphene oxide (GO membrane was able to minimize the polysulfides’ dissolution and their shuttle, which was attributed to the electrostatic interactions between the negatively-charged species and the oxygen functional groups on GO. Furthermore, these oxygen-containing functional groups including carboxyl, epoxide and hydroxyl groups provide active sites for coordination with inorganic materials (such as sulfur. It exhibits the initial reversible specific capacity of 1379 mAh·g−1 at a constant current rate of 0.2 C and maintains 1205 mAh·g−1 over 100 cycles (~87% retention. In addition, the freestanding S/PAN/GO cathode displays excellent coulombic efficiency (~100% and rate capability, delivering up to 685 mAh·g−1 capacity at 2 C.

  5. Effects of sulfur dioxide and nitric oxide on mercury oxidation and reduction under homogeneous conditions

    Energy Technology Data Exchange (ETDEWEB)

    Yongxin Zhao; Michael D. Mann; Edwin S. Olson; John H. Pavlish; Grant E. Dunham [University of North Dakota, Grand Forks, ND (United States). Department of Chemical Engineering

    2006-05-15

    This paper is particularly related to elemental mercury (Hg{sup 0}) oxidation and divalent mercury (Hg{sup 2+} reduction under simulated flue gas conditions in the presence of nitric oxide (NO) and sulfur dioxide (SO{sub 2}). As a powerful oxidant and chlorinating reagent, Cl{sub 2} has the potential for Hg oxidation. However, the detailed mechanism for the interactions, especially among chlorine (Cl)-containing species, SO{sub 2}, NO, as well as H{sub 2}O, remains ambiguous. Research described in this paper therefore focused on the impacts of SO{sub 2} and NO on Hg{sup 0} oxidation and Hg{sup 2+} reduction with the intent of unraveling unrecognized interactions among Cl species, SO{sub 2}, and NO most importantly in the presence of H{sub 2}O. The experimental results demonstrated that SO{sub 2} and NO had pronounced inhibitory effects on Hg{sup 0} oxidation at high temperatures when H{sub 2}O was also present in the gas blend. Such a demonstration was further confirmed by the reduction of Hg{sup 2+} back into its elemental form. Data revealed that SO{sub 2} and NO were capable of promoting homogeneous reduction of Hg{sup 2+} to Hg{sup 0} with H{sub 2}O being present. However, the above inhibition or promotion disappeared under homogeneous conditions when H{sub 2}O was removed from the gas blend. 23 refs., 8 figs.

  6. Anthropogenic emissions of oxidized sulfur and nitrogen into the atmosphere of the former Soviet Union in 1985 and 1990

    Energy Technology Data Exchange (ETDEWEB)

    Ryaboshapko, A.G.; Brukhanov, P.A.; Gromov, S.A.; Proshina, Yu.V; Afinogenova, O.G. [Institute of Global Climate and Ecology, Moscow (Russian Federation)

    1996-09-01

    Anthropogenic emissions of oxidized sulfur and nitrogen over the former Soviet Union for 1985 and 1990 were calculated on the basis of a combination of `bottom-up` and `top-down` approaches. Sulfur dioxide emissions from combustion of hard coal, brown coal, oil products, natural gas, shale oil, peat, wood as well as from metallurgy, sulfuric acid production, and cement production were estimated. Nitrogen oxides emissions were considered separately for large power plants, small power plants, industrial boilers, residential combustion units, and for transport. The sulfur and nitrogen emissions were spatially distributed over the former Soviet Union with 1 x 1 degree resolution. Data on 721 point sources of sulfur dioxide emissions and on the 242 largest power stations as nitrogen oxides sources were used. The area sources of both sulfur dioxide and nitrogen oxides were distributed according to the population density separately for about 150 administrative units of the former Soviet Union. 63 refs., 19 tabs.

  7. Oxidation of refractory sulfur compounds over Ti-containing mesoporous molecular sieves prepared by using a fluorosilicon compound.

    Science.gov (United States)

    Jeong, Kwang-Eun; Cho, Chin-Soo; Chae, Ho-Jeong; Kim, Chul-Ung; Jeong, Soon-Yong

    2010-05-01

    Titanium containing mesoporous molecular sieve (Ti-MMS) catalysts were studied for the oxidative desulfurization of refractory sulfur compounds. Ti-MMS catalysts were synthesized from fluorosilicon compounds and Ti with the hydrolysis reaction of H2SiF6 in an ammonia-surfactant mixed solution. The solid products were characterized by XRD, XRF, nitrogen adsorption, and diffuse reflectance UV-vis spectroscopy. Effects of Ti loading and oxidant/sulfur mole ratio, and sulfur species on ODS activity were investigated.

  8. Mechanistic investigation of Fe(III) oxide reduction by low molecular weight organic sulfur species

    Science.gov (United States)

    Eitel, Eryn M.; Taillefert, Martial

    2017-10-01

    Low molecular weight organic sulfur species, often referred to as thiols, are known to be ubiquitous in aquatic environments and represent important chemical reductants of Fe(III) oxides. Thiols are excellent electron shuttles used during dissimilatory iron reduction, and in this capacity could indirectly affect the redox state of sediments, release adsorbed contaminants via reductive dissolution, and influence the carbon cycle through alteration of bacterial respiration processes. Interestingly, the reduction of Fe(III) oxides by thiols has not been previously investigated in environmentally relevant conditions, likely due to analytical limitations associated with the detection of thiols and their oxidized products. In this study, a novel electrochemical method was developed to simultaneously determine thiol/disulfide pair concentrations in situ during the reduction of ferrihydrite in batch reactors. First order rate laws with respect to initial thiol concentration were confirmed for Fe(III) oxyhydroxide reduction by four common thiols: cysteine, homocysteine, cysteamine, and glutathione. Zero order was determined for both Fe(III) oxyhydroxide and proton concentration at circumneutral pH. A kinetic model detailing the molecular mechanism of the reaction was optimized with proposed intermediate surface structures. Although metal oxide overall reduction rate constants were inversely proportional to the complexity of the thiol structure, the extent of metal reduction increased with structure complexity, indicating that surface complexes play a significant role in the ability of these thiols to reduce iron. Taken together, these results demonstrate the importance of considering the molecular reaction mechanism at the iron oxide surface when investigating the potential for thiols to act as electron shuttles during dissimilatory iron reduction in natural environments.

  9. The GC/AED studies on the reactions of sulfur mustard with oxidants

    International Nuclear Information System (INIS)

    Popiel, StanisIaw; Witkiewicz, Zygfryd; Szewczuk, Aleksander

    2005-01-01

    A gas chromatograph coupled with an atomic emission detector was used to identify and to determine the products formed on oxidation of sulfur mustard. The oxidation rate and the resulting oxidates were studied in relation to oxidant type and reaction medium parameters. Hydrogen peroxide, sodium hypochlorite, sodium perborate, potassium monopercarbonate, ammonium peroxydisulfate, potassium peroxymonosulfate (oxone), and tert-butyl peroxide were used as oxidants. Oxidations were run in aqueous media or in solvents of varying polarities. The oxidation rate was found to be strongly related to oxidant type: potassium peroxymonosulfate (oxone) and sodium hypochlorite were fast-acting oxidants; sodium perborate, hydrogen peroxide, ammonium peroxydisulfate, and sodium monopercarbonate were moderate oxidants; tert-butyl peroxide was the slowest-acting oxidant. In non-aqueous solvents, the oxidation rate was strongly related to solvent polarity. The higher the solvent polarity, the faster the oxidation rate. In the acid and neutral media, the mustard oxidation rates were comparable. In the alkaline medium, oxidation was evidently slower. A suitable choice of the initial oxidant-to-mustard concentration ratio allowed to control the type of the resulting mustard oxidates. As the pH of the reaction medium was increased, the reaction of elimination of hydrogen chloride from mustard oxidates becomes more and more intensive

  10. Molecular understanding of atmospheric particle formation from sulfuric acid and large oxidized organic molecules

    CERN Document Server

    Schobesberger, Siegfried; Bianchi, Federico; Lönn, Gustaf; Ehn, Mikael; Lehtipalo, Katrianne; Dommen, Josef; Ehrhart, Sebastian; Ortega, Ismael K; Franchin, Alessandro; Nieminen, Tuomo; Riccobono, Francesco; Hutterli, Manuel; Duplissy, Jonathan; Almeida, João; Amorim, Antonio; Breitenlechner, Martin; Downard, Andrew J; Dunne, Eimear M; Flagan, Richard C; Kajos, Maija; Keskinen, Helmi; Kirkby, Jasper; Kupc, Agnieszka; Kürten, Andreas; Kurtén, Theo; Laaksonen, Ari; Mathot, Serge; Onnela, Antti; Praplan, Arnaud P; Rondo, Linda; Santos, Filipe D; Schallhart, Simon; Schnitzhofer, Ralf; Sipilä, Mikko; Tomé, António; Tsagkogeorgas, Georgios; Vehkamäki, Hanna; Wimmer, Daniela; Baltensperger, Urs; Carslaw, Kenneth S; Curtius, Joachim; Hansel, Armin; Petäjä, Tuukka; Kulmala, Markku; Donahue, Neil M; Worsnop, Douglas R

    2013-01-01

    Atmospheric aerosols formed by nucleation of vapors affect radiative forcing and therefore climate. However, the underlying mechanisms of nucleation remain unclear, particularly the involvement of organic compounds. Here, we present high-resolution mass spectra of ion clusters observed during new particle formation experiments performed at the Cosmics Leaving Outdoor Droplets chamber at the European Organization for Nuclear Research. The experiments involved sulfuric acid vapor and different stabilizing species, including ammonia and dimethylamine, as well as oxidation products of pinanediol, a surrogate for organic vapors formed from monoterpenes. A striking resemblance is revealed between the mass spectra from the chamber experiments with oxidized organics and ambient data obtained during new particle formation events at the Hyytiälä boreal forest research station. We observe that large oxidized organic compounds, arising from the oxidation of monoterpenes, cluster directly with single sulfuric acid molec...

  11. Integrated Science Assessment (ISA) for Sulfur Oxides – Health Criteria (Final Report, Sep 2008)

    Science.gov (United States)

    EPA announced the availability of the final report, Integrated Science Assessment (ISA) for Sulfur Oxides – Health Criteria final assessment. This report represents a concise synthesis and evaluation of the most policy-relevant science and will ultimately provide the scien...

  12. Integrated Science Assessment (ISA) for Sulfur Oxides – Health Criteria (First External Review Draft, Sep 2007)

    Science.gov (United States)

    EPA has announced that the First External Review Draft of the Integrated Science Assessment (ISA) for Sulfur Oxides – Health Criteria has been made available for independent peer review and public review. This draft ISA document represents a concise synthesis and evaluatio...

  13. Characterization of sulfur-oxidizing bacteria isolated from acid mine drainage and black shale samples

    International Nuclear Information System (INIS)

    Sajjad, W.; Bhatti, T. M.; Hasan, F.; Khan, S.; Badshah, M.

    2016-01-01

    Acid mine drainage (AMD) and black shale (BS) are the main habitats of sulfur-oxidizing bacteria. The aim of this study was to isolate and characterize sulfur-oxidizing bacteria from extreme acidic habitats (AMD and BS). Concentration of metals in samples from AMD and BS varied significantly from the reference samples and exceeded the acceptable limits set by the Environmental Protection Agency (EPA) and the World Health Organization (WHO). A total of 24 bacteria were isolated from these samples that were characterized both morphologically as well as through biochemical tests. All the bacteria were gram-negative rods that could efficiently oxidize sulfur into sulfate ions (SO/sub 4/-2), resulted into decrease in pH up to 1.0 when grown in thiosulfate medium with initial pH 4.0. Out of 24, only 06 isolates were selected for phylogenetic analysis through 16S rRNA sequencing, on the basis of maximum sulfur-oxidizing efficiency. The isolates were identified as the species from different genera such as Alcaligenes, Pseudomonas, Bordetella, and Stenotrophomonas on the basis of maximum similarity index. The concentration of sulfate ions produced was estimated in the range of 179-272 mg/L. These acidophiles might have various potential applications such as biological leaching of metals from low-grade ores, alkali soil reclamation and to minimize the use of chemical S-fertilizers and minimize environmental pollution. (author)

  14. 40 CFR 52.125 - Control strategy and regulations: Sulfur oxides.

    Science.gov (United States)

    2010-07-01

    ... to existing fuel burning equipment producing electrical energy will provide for the attainment and...: Sulfur oxides. 52.125 Section 52.125 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... since the control strategy does not analyze the impact of smelter fugitive emissions on ambient air...

  15. Influence of zinc oxide during different stages of sulfur vulcanization. Elucidated by model compound studies

    NARCIS (Netherlands)

    Heideman, G.; Datta, Rabin; Noordermeer, Jacobus W.M.; van Baarle, B.

    2005-01-01

    The addition of zinc oxide (ZnO) as an activator for the sulfur vulcanization of rubbers enhances the vulcanization efficiency and vulcanizate properties and reduces the vulcanization time. The first part of this article deals with the reduction and optimization of the amount of ZnO. Two different

  16. Sulfur accumulation and atmospherically deposited sulfate in the Lake States.

    Science.gov (United States)

    Mark B. David; George Z. Gernter; David F. Grigal; Lewis F. Ohmann

    1989-01-01

    Characterizes the mass of soil sulfur (adjusted for nitrogen), and atmospherically deposited sulfate along an acid precipitation gradient from Minnesota to Michigan. The relationship of these variables, presented graphically through contour mapping, suggests that patterns of atmospheric wet sulfate deposition are reflected in soil sulfur pools.

  17. Dominance of sulfur-fueled iron oxide reduction in low-sulfate freshwater sediments.

    Science.gov (United States)

    Hansel, Colleen M; Lentini, Chris J; Tang, Yuanzhi; Johnston, David T; Wankel, Scott D; Jardine, Philip M

    2015-11-01

    A central tenant in microbial biogeochemistry is that microbial metabolisms follow a predictable sequence of terminal electron acceptors based on the energetic yield for the reaction. It is thereby oftentimes assumed that microbial respiration of ferric iron outcompetes sulfate in all but high-sulfate systems, and thus sulfide has little influence on freshwater or terrestrial iron cycling. Observations of sulfate reduction in low-sulfate environments have been attributed to the presumed presence of highly crystalline iron oxides allowing sulfate reduction to be more energetically favored. Here we identified the iron-reducing processes under low-sulfate conditions within columns containing freshwater sediments amended with structurally diverse iron oxides and fermentation products that fuel anaerobic respiration. We show that despite low sulfate concentrations and regardless of iron oxide substrate (ferrihydrite, Al-ferrihydrite, goethite, hematite), sulfidization was a dominant pathway in iron reduction. This process was mediated by (re)cycling of sulfur upon reaction of sulfide and iron oxides to support continued sulfur-based respiration--a cryptic sulfur cycle involving generation and consumption of sulfur intermediates. Although canonical iron respiration was not observed in the sediments amended with the more crystalline iron oxides, iron respiration did become dominant in the presence of ferrihydrite once sulfate was consumed. Thus, despite more favorable energetics, ferrihydrite reduction did not precede sulfate reduction and instead an inverse redox zonation was observed. These findings indicate that sulfur (re)cycling is a dominant force in iron cycling even in low-sulfate systems and in a manner difficult to predict using the classical thermodynamic ladder.

  18. EFFECT OF SOLE AND ASSOCIATIVE ACTIONS OF ELEMENTAL SULFUR AND INOCULATION SULFUR OXIDIZING BACTERIA ON GROWTH AND NUTRIENTS CONTENTS OF PEPPER PLANTS AND THE USED SOILS

    Directory of Open Access Journals (Sweden)

    S. A. Ibrahim

    2011-12-01

    Full Text Available A pot experiment was conducted to study the effect of elemental sulfur (E.S rate (2.5 g/kg soil and sulfur oxidizing bacteria on pepper plant and some chemical properties of two representative soil samples varying in their texture and CaCO3 content. Pepper was grown in Shobrakheet clay loam and Nobaria sandy loam soils for 50 days. Each soil was treated with elemental sulfur (2.5 g kg-1 soil and inoculated with two sulfur oxidizing bacteria (S.O.B. No.8 and S.O.B. ATCC 8158. Elemental sulfur with or without sulfur oxidizing bacteria increased shoot dry weights of pepper plants as compared with control. The highest effect was observed with E.S + ATCC 8158 treatment which resulted in increasing the pepper shoot dry weights from 1.36 to 2.08 g pot-1 with the clay loam soil and from 0.77 to 1.37 g pot-1 with the sandy loam soil. The same treatment resulted in the highest plant content of S, N, P, K and micronutrients.

  19. Acquisition of a Novel Sulfur-Oxidizing Symbiont in the Gutless Marine Worm Inanidrilus exumae

    Science.gov (United States)

    2018-01-01

    ABSTRACT Gutless phallodrilines are marine annelid worms without a mouth or gut, which live in an obligate association with multiple bacterial endosymbionts that supply them with nutrition. In this study, we discovered an unusual symbiont community in the gutless phallodriline Inanidrilus exumae that differs markedly from the microbiomes of all 22 of the other host species examined. Comparative 16S rRNA gene sequence analysis and fluorescence in situ hybridization revealed that I. exumae harbors cooccurring gamma-, alpha-, and deltaproteobacterial symbionts, while all other known host species harbor gamma- and either alpha- or deltaproteobacterial symbionts. Surprisingly, the primary chemoautotrophic sulfur oxidizer “Candidatus Thiosymbion” that occurs in all other gutless phallodriline hosts does not appear to be present in I. exumae. Instead, I. exumae harbors a bacterial endosymbiont that resembles “Ca. Thiosymbion” morphologically and metabolically but originates from a novel lineage within the class Gammaproteobacteria. This endosymbiont, named Gamma 4 symbiont here, had a 16S rRNA gene sequence that differed by at least 7% from those of other free-living and symbiotic bacteria and by 10% from that of “Ca. Thiosymbion.” Sulfur globules in the Gamma 4 symbiont cells, as well as the presence of genes characteristic for autotrophy (cbbL) and sulfur oxidation (aprA), indicate that this symbiont is a chemoautotrophic sulfur oxidizer. Our results suggest that a novel lineage of free-living bacteria was able to establish a stable and specific association with I. exumae and appears to have displaced the “Ca. Thiosymbion” symbionts originally associated with these hosts. IMPORTANCE All 22 gutless marine phallodriline species examined to date live in a highly specific association with endosymbiotic, chemoautotrophic sulfur oxidizers called “Ca. Thiosymbion.” These symbionts evolved from a single common ancestor and represent the ancestral trait for

  20. Genomic analysis reveals versatile heterotrophic capacity of a potentially symbiotic sulfur-oxidizing bacterium in sponge

    KAUST Repository

    Tian, Renmao

    2014-08-29

    Sulfur-reducing bacteria (SRB) and sulfur-oxidizing bacteria (SOB) play essential roles in marine sponges. However, the detailed characteristics and physiology of the bacteria are largely unknown. Here, we present and analyse the first genome of sponge-associated SOB using a recently developed metagenomic binning strategy. The loss of transposase and virulence-associated genes and the maintenance of the ancient polyphosphate glucokinase gene suggested a stabilized SOB genome that might have coevolved with the ancient host during establishment of their association. Exclusive distribution in sponge, bacterial detoxification for the host (sulfide oxidation) and the enrichment for symbiotic characteristics (genes-encoding ankyrin) in the SOB genome supported the bacterial role as an intercellular symbiont. Despite possessing complete autotrophic sulfur oxidation pathways, the bacterium developed a much more versatile capacity for carbohydrate uptake and metabolism, in comparison with its closest relatives (Thioalkalivibrio) and to other representative autotrophs from the same order (Chromatiales). The ability to perform both autotrophic and heterotrophic metabolism likely results from the unstable supply of reduced sulfur in the sponge and is considered critical for the sponge-SOB consortium. Our study provides insights into SOB of sponge-specific clade with thioautotrophic and versatile heterotrophic metabolism relevant to its roles in the micro-environment of the sponge body. © 2014 Society for Applied Microbiology and John Wiley & Sons Ltd.

  1. The role of sulfur-oxidizing bacteria Thiobacillus thiooxidans in pyrite weathering

    International Nuclear Information System (INIS)

    Sasaki, K.; Tsunekawa, M.; Ohtsuka, T.; Konno, H.

    1998-01-01

    The paper investigates the role of the sulfur-oxidizing bacteria Thiobacillus thiooxidans in pyrite weathering in order to clarify the effects of the bacteria on the dissolution behavior of pyrite and the formation of secondary minerals using Raman spectroscopy and powder X-ray diffraction (XRD) in addition to solution analysis. It was found that T. thiooxidans, when present with the iron-oxidizing bacteria Thiobacillus ferrooxidans, enhanced the dissolution of Fe and S species for pyrite, whereas T. thiooxidans alone did not oxidize pyrite. Enhancement of the consumption of elemental sulfur and regeneration of Fe(II) ions were also observed with T. thiooxidans together with T. ferrooxidans, while this did not occur with T. ferrooxidans alone

  2. 78 FR 5303 - Approval and Promulgation of Implementation Plans; State of Missouri; Control of Sulfur Emissions...

    Science.gov (United States)

    2013-01-25

    ... stringency of the SIP. Missouri's revision adds 10 CSR 10- 5.570 Control of Sulfur Emissions from Stationary... approving the State's request to add 10 CSR 10-5.570 Control of Sulfur Emissions from Stationary Boilers to... Management and Budget under Executive Order 12866 (58 FR 51735, October 4, 1993); Does not impose an...

  3. Biologically produced sulfur

    NARCIS (Netherlands)

    Kleinjan, W.E.; Keizer, de A.; Janssen, A.J.H.

    2003-01-01

    Sulfur compound oxidizing bacteria produce sulfur as an intermediate in the oxidation of hydrogen sulfide to sulfate. Sulfur produced by these microorganisms can be stored in sulfur globules, located either inside or outside the cell. Excreted sulfur globules are colloidal particles which are

  4. Sulfur tolerant composite cermet electrodes for solid oxide electrochemical cells

    Science.gov (United States)

    Isenberg, Arnold O.

    1987-01-01

    An electrochemical apparatus is made containing an exterior electrode bonded to the exterior of a tubular, solid, oxygen ion conducting electrolyte where the electrolyte is also in contact with an interior electrode, said exterior electrode comprising particles of an electronic conductor contacting the electrolyte, where a ceramic metal oxide coating partially surrounds the particles and is bonded to the electrolyte, and where a coating of an ionic-electronic conductive material is attached to the ceramic metal oxide coating and to the exposed portions of the particles.

  5. Sulfur-doped graphene via thermal exfoliation of graphite oxide in H2S, SO2, or CS2 gas.

    Science.gov (United States)

    Poh, Hwee Ling; Šimek, Petr; Sofer, Zdeněk; Pumera, Martin

    2013-06-25

    Doping of graphene with heteroatoms is an effective way to tailor its properties. Here we describe a simple and scalable method of doping graphene lattice with sulfur atoms during the thermal exfoliation process of graphite oxides. The graphite oxides were first prepared by Staudenmaier, Hofmann, and Hummers methods followed by treatments in hydrogen sulfide, sulfur dioxide, or carbon disulfide. The doped materials were characterized by scanning electron microscopy, high-resolution X-ray photoelectron spectroscopy, combustible elemental analysis, and Raman spectroscopy. The ζ-potential and conductivity of sulfur-doped graphenes were also investigated in this paper. It was found that the level of doping is more dramatically influenced by the type of graphite oxide used rather than the type of sulfur-containing gas used during exfoliation. Resulting sulfur-doped graphenes act as metal-free electrocatalysts for an oxygen reduction reaction.

  6. Oxyhalogen-Sulfur Chemistry: Kinetics and Mechanism of Oxidation ...

    African Journals Online (AJOL)

    The oxidation of N-acetylthiourea (ACTU) by acidic bromate has been studied by observing formation of bromine in excess bromate conditions. The reaction displays an induction period before formation of bromine. The stoichiometry of the reaction was determined to be 4:3: 4BrO3 ...

  7. Oxyhalogen-Sulfur Chemistry: Kinetics and Mechanism of Oxidation ...

    African Journals Online (AJOL)

    NICOLAAS

    The oxidation of N-acetylthiourea (ACTU) by acidic bromate has been studied by observing formation of bromine in excess .... kinetics experiments were performed at 25.0 ± 0.1 °C and at an ..... thiourea compounds with potent anti-HIV activity.

  8. Synthesis and characterization of porous metal oxides and desulfurization studies of sulfur containing compounds

    Science.gov (United States)

    Garces Trujillo, Hector Fabian

    This thesis contains two parts: 1) synthesis and characterization of porous metal oxides that include zinc oxide and a porous mixed-valent manganese oxide with an amorphous structure (AMO) 2) the desulfurization studies for the removal of sulfur compounds. Zinc oxide with different nano-scale morphologies may result in various porosities with different adsorption capabilities. A tunable shape microwave synthesis of ZnO nano-spheres in a co-solvent mixture is presented. The ZnO nano-sphere material is investigated as a desulfurizing sorbent in a fixed bed reactor in the temperature range 200 to 400 °C and compared with ZnO nanorods and platelet-like morphologies. Fresh and sulfided materials were characterized by X-ray diffraction (XRD), BET specific surface area, pore volume, scanning electron microscopy (SEM), X-ray energy dispersive spectroscopy (SEM/EDX), Raman spectroscopy, and thermogravimetric analysis (TGA). The tunable shape microwave synthesis of ZnO presents a high sulfur sorption capacity at temperatures as low as 200 °C which accounts for a three and four fold enhancement over the other preparations presented in this work, and reached 76 % of the theoretical sulfur capacity (TSC) at 300 °C. Another ZnO material with a bimodal micro- and mesopore size distribution investigated as a desulfurizing sorbent presents a sorption capacity that reaches 87% of the theoretical value for desulfurization at 400 °C at breakthrough time. A deactivation model that considers the activity of the solid reactant was used to fit the experimental data. Good agreement between the experimental breakthrough curves and the model predictions are obtained. Manganese oxides are a type of metal oxide materials commonly used in catalytic applications. Little is known about the adsorption capabilities for the removal of sulfur compounds. One of these manganese oxides; amorphous manganese oxide (AMO) is highly promising material for low temperature sorption processes. Amorphous

  9. Isolation and characterization of a sulfur-oxidizing chemolithotroph growing on crude oil under anaerobic conditions.

    Science.gov (United States)

    Kodama, Yumiko; Watanabe, Kazuya

    2003-01-01

    Molecular approaches have shown that a group of bacteria (called cluster 1 bacteria) affiliated with the epsilon subclass of the class Proteobacteria constituted major populations in underground crude-oil storage cavities. In order to unveil their physiology and ecological niche, this study isolated bacterial strains (exemplified by strain YK-1) affiliated with the cluster 1 bacteria from an oil storage cavity at Kuji in Iwate, Japan. 16S rRNA gene sequence analysis indicated that its closest relative was Thiomicrospira denitrificans (90% identity). Growth experiments under anaerobic conditions showed that strain YK-1 was a sulfur-oxidizing obligate chemolithotroph utilizing sulfide, elemental sulfur, thiosulfate, and hydrogen as electron donors and nitrate as an electron acceptor. Oxygen also supported its growth only under microaerobic conditions. Strain YK-1 could not grow on nitrite, and nitrite was the final product of nitrate reduction. Neither sugars, organic acids (including acetate), nor hydrocarbons could serve as carbon and energy sources. A typical stoichiometry of its energy metabolism followed an equation: S(2-) + 4NO(3)(-) --> SO(4)(2-) + 4NO(2)(-) (Delta G(0) = -534 kJ mol(-1)). In a difference from other anaerobic sulfur-oxidizing bacteria, this bacterium was sensitive to NaCl; growth in medium containing more than 1% NaCl was negligible. When YK-1 was grown anaerobically in a sulfur-depleted inorganic medium overlaid with crude oil, sulfate was produced, corresponding to its growth. On the contrary, YK-1 could not utilize crude oil as a carbon source. These results suggest that the cluster 1 bacteria yielded energy for growth in oil storage cavities by oxidizing petroleum sulfur compounds. Based on its physiology, ecological interactions with other members of the groundwater community are discussed.

  10. Sulfur isotope fractionation during heterogeneous oxidation of SO2 on mineral dust

    Directory of Open Access Journals (Sweden)

    P. Hoppe

    2012-06-01

    Full Text Available Mineral dust is a major fraction of global atmospheric aerosol, and the oxidation of SO2 on mineral dust has implications for cloud formation, climate and the sulfur cycle. Stable sulfur isotopes can be used to understand the different oxidation processes occurring on mineral dust. This study presents measurements of the 34S/32S fractionation factor α34 for oxidation of SO2 on mineral dust surfaces and in the aqueous phase in mineral dust leachate. Sahara dust, which accounts for ~60% of global dust emissions and loading, was used for the experiments. The fractionation factor for aqueous oxidation in dust leachate is αleachate = 0.9917±0.0046, which is in agreement with previous measurements of aqueous SO2 oxidation by iron solutions. This fractionation factor is representative of a radical chain reaction oxidation pathway initiated by transition metal ions. Oxidation on the dust surface at subsaturated relative humidity (RH had an overall fractionation factor of αhet = 1.0096±0.0036 and was found to be almost an order of magnitude faster when the dust was simultaneously exposed to ozone, light and RH of ~40%. However, the presence of ozone, light and humidity did not influence isotope fractionation during oxidation on dust surfaces at subsaturated relative humidity. All the investigated reactions showed mass-dependent fractionation of 33S relative to 34S. A positive matrix factorization model was used to investigate surface oxidation on the different components of dust. Ilmenite, rutile and iron oxide were found to be the most reactive components, accounting for 85% of sulfate production with a fractionation factor of α34 = 1.012±0.010. This overlaps within the analytical uncertainty with the fractionation of other major atmospheric oxidation pathways such as the oxidation of SO2 by H2O2 and O3 in the aqueous phase and OH in the gas phase. Clay minerals accounted for roughly 12% of the sulfate production, and oxidation on clay minerals

  11. [Oxidation of sulfur-containing substrates by aboriginal and experimentally designed microbial communities].

    Science.gov (United States)

    Pivovarova, T A; Bulaev, A G; Roshchupko, P V; Belyĭ, A V; Kondrat'eva, T F

    2012-01-01

    Aboriginal and experimental (constructed of pure microbial cultures) communities of acidophilic chemolithotrophs have been studied. The oxidation of elemental sulfur, sodium thiosulfate, and potassium tetrathionate as sole sources of energy has been monitored. The oxidation rate of the experimental community is higher as compared to the aboriginal community isolated from a flotation concentrate of pyrrhotine-containing pyrite-arsenopyrite gold-arsenic sulfide ore. The degree of oxidation of the mentioned S substrates amounts to 17.91, 68.30, and 93.94% for the experimental microbial community and to 10.71, 56.03, and 79.50% for the aboriginal community, respectively. The degree of oxidation of sulfur sulfide forms in the ore flotation concentrate is 59.15% by the aboriginal microbial community and 49.40% by the experimental microbial community. Despite a higher rate of oxidation of S substrates as a sole source of energy by the experimental microbial community, the aboriginal community oxidizes S substrates at a higher rate in the flotation concentrate of pyrrhotine-containing pyrite-arsenopyrite gold-arsenic sulfide ore, from which it was isolated. Bacterial-chemical oxidation of the flotation concentrate by the aboriginal microbial community allows for the extraction of an additional 32.3% of gold from sulfide minerals, which is by 5.7% larger compared to the yield obtained by the experimental microbial community.

  12. Composite harm to plants by sulfurous acid gas and oxidant

    Energy Technology Data Exchange (ETDEWEB)

    Matsushima, J

    1971-01-01

    The composite effects on plants of sulfur dioxide and ozone, SO/sub 2/ and PAN, SO/sub 2/ and nitrogen dioxide, and NO/sub 2/ and ozone were studied. Pinto bean plants were exposed to SO/sub 2/ or O/sub 3/ only, to each gas alternately, and to a mixture of the two. The degree of injury by the gas or gases was indicated in percentage by area of the leaves damaged. In cases where no geometric effect occurred the damage to the plant by the individual gas had been great; damage from the individual gas had been slight in these cases where such an effect was observed. The geometric effect is produced when the density of SO/sub 2/ is rather low, generally 0.05-0.25 ppm. A mixture of SO/sub 2/ and O/sub 3/ was applied to a tabacco plant; it affected fully grown leaves. In experiments on the composite effects of SO/sub 2/ and PAN on bean, tomato and pepper plants, PAN affected mainly young leaves while SO/sub 2/ affected mature ones. These effects were arithmetric rather then geometric. The SO/sub 2/ and NO/sub 2/ were also studied in the same manner. When SO/sub 2/ and NO/sub 2/ were mixed, a geometric effect was conspicuous in damage to vegetables, the symptoms of damage by either of the two appeared about the same, younger leaves being affected less. When treated with the two gases alternately, the damage was greater if the plants were first treated with NO/sub 2/; possible causes for this effect are discussed. No significant composite effect of NO/sub 2/ and O/sub 3/ was observed.

  13. Additive for vanadium and sulfur oxide capture in catalytic cracking

    International Nuclear Information System (INIS)

    Chin, A.A.; Sapre, A.V.; Sarli, M.S.

    1991-01-01

    This patent describes a fluid catalytic cracking process in which a hydrocarbon feedstock. It comprises: a vanadium contaminant in an amount of a least 2 ppmw is cracked under fluid catalytic cracking conditions with a solid, particulate cracking catalyst to produce cracking products of lower molecular weight while depositing carbonaceous material on the particles of cracking catalyst, separating the particles of cracking catalyst from the cracking products in the disengaging zone and oxidatively regenerating the cracking catalyst by burning off the deposited carbonaceous material in a regeneration zone, the improvement comprising reducing the make-up rate of the cracking catalyst by contacting the cracking feed with a particulate additive composition for passivating the vanadium content of the feed, comprising an alkaline earth metal oxide and an alkaline earth metal spinel

  14. Ag@Ni core-shell nanowire network for robust transparent electrodes against oxidation and sulfurization.

    Science.gov (United States)

    Eom, Hyeonjin; Lee, Jaemin; Pichitpajongkit, Aekachan; Amjadi, Morteza; Jeong, Jun-Ho; Lee, Eungsug; Lee, Jung-Yong; Park, Inkyu

    2014-10-29

    Silver nanowire (Ag NW) based transparent electrodes are inherently unstable to moist and chemically reactive environment. A remarkable stability improvement of the Ag NW network film against oxidizing and sulfurizing environment by local electrodeposition of Ni along Ag NWs is reported. The optical transmittance and electrical resistance of the Ni deposited Ag NW network film can be easily controlled by adjusting the morphology and thickness of the Ni shell layer. The electrical conductivity of the Ag NW network film is increased by the Ni coating via welding between Ag NWs as well as additional conductive area for the electron transport by electrodeposited Ni layer. Moreover, the chemical resistance of Ag NWs against oxidation and sulfurization can be dramatically enhanced by the Ni shell layer electrodeposited along the Ag NWs, which provides the physical barrier against chemical reaction and diffusion as well as the cathodic protection from galvanic corrosion. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Sulfur cycle

    Digital Repository Service at National Institute of Oceanography (India)

    LokaBharathi, P.A.

    Microbes, especially bacteria, play an important role in oxidative and reductive cycle of sulfur. The oxidative part of the cycle is mediated by photosynthetic bacteria in the presence of light energy and chemosynthetic forms in the absence of light...

  16. Kinetic effects of sulfur oxidation on catalytic nitrile hydration: nitrile hydratase insights from bioinspired ruthenium(II) complexes.

    Science.gov (United States)

    Kumar, Davinder; Nguyen, Tho N; Grapperhaus, Craig A

    2014-12-01

    Kinetic investigations inspired by the metalloenzyme nitrile hydratase were performed on a series of ruthenium(II) complexes to determine the effect of sulfur oxidation on catalytic nitrile hydration. The rate of benzonitrile hydration was quantified as a function of catalyst, nitrile, and water concentrations. Precatalysts L(n)RuPPh3 (n = 1-3; L(1) = 4,7-bis(2'-methyl-2'-mercapto-propyl)-1-thia-4,7-diazacyclononane; L(2) = 4-(2'-methyl-2'-sulfinatopropyl)-7-(2'-methyl-2'-mercapto-propyl)-1-thia-4,7-diazacyclononane; L(3) = 4-(2'-methyl-2'-sulfinatopropyl)-7-(2'-methyl-2'-sulfenato-propyl)-1-thia-4,7-diazacyclononane) were activated by substitution of triphenylphosphine with substrate in hot dimethylformamide solution. Rate measurements are consistent with a dynamic equilibrium between inactive aqua (L(n)Ru-OH2) and active nitrile (L(n)Ru-NCR) derivatives with K = 21 ± 1, 9 ± 0.9, and 23 ± 3 for L(1) to L(3), respectively. Subsequent hydration of the L(n)Ru-NCR intermediate yields the amide product with measured hydration rate constants (k's) of 0.37 ± 0.01, 0.82 ± 0.07, and 1.59 ± 0.12 M(-1) h(-1) for L(1) to L(3), respectively. Temperature dependent studies reveal that sulfur oxidation lowers the enthalpic barrier by 27 kJ/mol, but increases the entropic barrier by 65 J/(mol K). Density functional theory (DFT) calculations (B3LYP/LanL2DZ (Ru); 6-31G(d) (all other atoms)) support a nitrile bound catalytic cycle with lowering of the reaction barrier as a consequence of sulfur oxidation through enhanced nitrile binding and attack of the water nucleophile through a highly organized transition state.

  17. Contribution of sulfuric acid and oxidized organic compounds to particle formation and growth

    Directory of Open Access Journals (Sweden)

    F. Riccobono

    2012-10-01

    Full Text Available Lack of knowledge about the mechanisms underlying new particle formation and their subsequent growth is one of the main causes for the large uncertainty in estimating the radiative forcing of atmospheric aerosols in global models. We performed chamber experiments designed to study the contributions of sulfuric acid and organic vapors to the formation and early growth of nucleated particles. Distinct experiments in the presence of two different organic precursors (1,3,5-trimethylbenzene and α-pinene showed the ability of these compounds to reproduce the formation rates observed in the low troposphere. These results were obtained measuring the sulfuric acid concentrations with two chemical ionization mass spectrometers confirming the results of a previous study which modeled the sulfuric acid concentrations in presence of 1,3,5-trimethylbenzene.

    New analysis methods were applied to the data collected with a condensation particle counter battery and a scanning mobility particle sizer, allowing the assessment of the size resolved growth rates of freshly nucleated particles. The effect of organic vapors on particle growth was investigated by means of the growth rate enhancement factor (Γ, defined as the ratio between the measured growth rate in the presence of α-pinene and the kinetically limited growth rate of the sulfuric acid and water system. The observed Γ values indicate that the growth is already dominated by organic compounds at particle diameters of 2 nm. Both the absolute growth rates and Γ showed a strong dependence on particle size, supporting the nano-Köhler theory. Moreover, the separation of the contributions from sulfuric acid and organic compounds to particle growth reveals that the organic contribution seems to be enhanced by the sulfuric acid concentration. Finally, the size resolved growth analysis indicates that both condensation of oxidized organic compounds and reactive uptake contribute to particle growth.

  18. Isolation and characterization of ferrous- and sulfur-oxidizing bacteria from Tengchong solfataric region, China.

    Science.gov (United States)

    Jiang, Chengying; Liu, Ying; Liu, Yanyang; Guo, Xu; Liu, Shuang-Jiang

    2009-01-01

    Microbial oxidation and reduction of iron and sulfur are important parts of biogeochemical cycles in acidic environments such as geothermal solfataric regions. Species of Acidithiobacillus and Leptospirillum are the common ferrous-iron and sulfur oxidizers from such environments. This study focused on the Tengchong sofataric region, located in Yunnan Province, Southwest China. Based on cultivation, 9 strains that grow on ferrous-iron and sulfuric compounds were obtained. Analysis of 16S rRNA genes of the 9 strains indicated that they were affiliated to Acidithiobacillus, Alicyclobacillus, Sulfobacillus, Leptospirillum and Acidiphilium. Physiological and phylogenetic studies indicated that two strains (TC-34 and TC-71) might represent two novel members of Alicyclobacillus. Strain TC-34 and TC-71 showed 94.8%-97.1% 16S rRNA gene identities to other species of Alicyclobacillus. Different from the previously described Alicyclobacillus species, strains TC-34 and TC-71 were mesophilic and their cellular fatty acids do not contain omega-cyclic fatty acids. Strain TC-71 was obligately dependent on ferrous-iron for growth. It was concluded that the ferrous-iron oxidizers were diversified and Alicyclobacillus species were proposed to take part in biochemical geocycling of iron in the Tengchong solfataric region.

  19. KINETICS OF DIRECT OXIDATION OF H2S IN COAL GAS TO ELEMENTAL SULFUR; F

    International Nuclear Information System (INIS)

    K.C. Kwon

    2002-01-01

    Removal of hydrogen sulfide (H(sub 2)S) from coal gasifier gas and sulfur recovery are key steps in the development of Department of Energy's (DOE's) advanced Vision 21 plants that employ coal and natural gas and produce electric power and clean transportation fuels. These Vision 21 plants will require highly clean coal gas with H(sub 2)S below 1 ppm and negligible amounts of trace contaminants such as hydrogen chloride, ammonia, alkali, heavy metals, and particulate. The conventional method of sulfur removal and recovery employing amine, Claus, and tail-gas treatment is very expensive. A second generation approach developed under DOE's sponsorship employs hot-gas desulfurization (HGD) using regenerable metal oxide sorbents followed by Direct Sulfur Recovery Process (DSRP). However, this process sequence does not remove trace contaminants and is targeted primarily towards the development of advanced integrated gasification combined cycle (IGCC) plants that produce electricity (not both electricity and transportation fuels). There is an immediate as well as long-term need for the development of cleanup processes that produce highly clean coal gas for next generation Vision 21 plants. To this end, a novel process is now under development at Research Triangle Institute (RTI) in which the H(sub 2)S in coal gas is directly oxidized to elemental sulfur over a selective catalyst. Such a process is ideally suited for coal gas from commercial gasifiers with a quench system to remove essentially all the trace contaminants except H(sub 2)S. This direct oxidation process has the potential to produce a super clean coal gas more economically than both conventional amine-based processes and HGD/DSRP. The objective of this research is to support the near- and long-term DOE efforts to commercialize this direct oxidation technology. Specifically, we aim to: Measure the kinetics of direct oxidation of H(sub 2)S to elemental sulfur over selective catalysts in the presence of major

  20. Rhizosphere heterogeneity shapes abundance and activity of sulfur-oxidizing bacteria in vegetated salt marsh sediments

    Directory of Open Access Journals (Sweden)

    François eThomas

    2014-06-01

    Full Text Available Salt marshes are highly productive ecosystems hosting an intense sulfur (S cycle, yet little is known about S-oxidizing microorganisms in these ecosystems. Here, we studied the diversity and transcriptional activity of S-oxidizers in salt marsh sediments colonized by the plant Spartina alterniflora, and assessed variations with sediment depth and small-scale compartments within the rhizosphere. We combined next-generation amplicon sequencing of 16S rDNA and rRNA libraries with phylogenetic analyses of marker genes for two S-oxidation pathways (soxB and rdsrAB. Gene and transcript numbers of soxB and rdsrAB phylotypes were quantified simultaneously, using newly designed (RT-qPCR assays. We identified a diverse assemblage of S-oxidizers, with Chromatiales and Thiotrichales being dominant. The detection of transcripts from S-oxidizers was mostly confined to the upper 5 cm sediments, following the expected distribution of root biomass. A common pool of species dominated by Gammaproteobacteria transcribed S-oxidation genes across roots, rhizosphere, and surrounding sediment compartments, with rdsrAB transcripts prevailing over soxB. However, the root environment fine-tuned the abundance and transcriptional activity of the S-oxidizing community. In particular, the global transcription of soxB was higher on the roots compared to mix and rhizosphere samples. Furthermore, the contribution of Epsilonproteobacteria-related S-oxidizers tended to increase on Spartina roots compared to surrounding sediments. These data shed light on the under-studied oxidative part of the sulfur cycle in salt marsh sediments and indicate small-scale heterogeneities are important factors shaping abundance and potential activity of S-oxidizers in the rhizosphere.

  1. Kinetics of aerobic oxidation of volatile sulfur compounds in wastewater and biofilm from sewers

    DEFF Research Database (Denmark)

    Rudelle, Elise Alice; Vollertsen, Jes; Hvitved-Jacobsen, Thorkild

    2013-01-01

    Laboratory experiments were conducted to investigate the kinetics of aerobic chemical and biological oxidation of selected odorous volatile sulfur compounds (VSCs) by wastewater and biofilm from sewers. The VSCs included methyl mercaptan (MeSH), ethyl mercaptan (EtSH), dimethyl sulfide (DMS......-spot downstream of a force main and the other was a gravity sewer transporting young aerobic wastewater. The kinetics of VSC oxidation for both wastewater and suspended biofilm samples followed a first-order rate equation. The average values of the reaction rate constants demonstrated the following order...... in the aerobic wastewater....

  2. Diversity Profile of Microbes Associated with Anaerobic Sulfur Oxidation in an Upflow Anaerobic Sludge Blanket Reactor Treating Municipal Sewage

    Science.gov (United States)

    Aida, Azrina A.; Kuroda, Kyohei; Yamamoto, Masamitsu; Nakamura, Akinobu; Hatamoto, Masashi; Yamaguchi, Takashi

    2015-01-01

    We herein analyzed the diversity of microbes involved in anaerobic sulfur oxidation in an upflow anaerobic sludge blanket (UASB) reactor used for treating municipal sewage under low-temperature conditions. Anaerobic sulfur oxidation occurred in the absence of oxygen, with nitrite and nitrate as electron acceptors; however, reactor performance parameters demonstrated that anaerobic conditions were maintained. In order to gain insights into the underlying basis of anaerobic sulfur oxidation, the microbial diversity that exists in the UASB sludge was analyzed comprehensively to determine their identities and contribution to sulfur oxidation. Sludge samples were collected from the UASB reactor over a period of 2 years and used for bacterial 16S rRNA gene-based terminal restriction fragment length polymorphism (T-RFLP) and next-generation sequencing analyses. T-RFLP and sequencing results both showed that microbial community patterns changed markedly from day 537 onwards. Bacteria belonging to the genus Desulforhabdus within the phylum Proteobacteria and uncultured bacteria within the phylum Fusobacteria were the main groups observed during the period of anaerobic sulfur oxidation. Their abundance correlated with temperature, suggesting that these bacterial groups played roles in anaerobic sulfur oxidation in UASB reactors. PMID:25817585

  3. Fractionation of sulfur isotopes in the chemical and biochemical oxidation of sulfide to sulfate

    International Nuclear Information System (INIS)

    Maass, I.; Wetzel, K.; Weise, G.; Heyer, J.

    1983-01-01

    The behaviour of sulfur isotopes in the chemical and biochemical oxidation of marcasite (FeS 2 ) to sulfate has been investigated in rest and shaker cultures at 30 0 C. The microbiological oxidation was carried out using a mixed culture of Thiobacillus. The results show a considerably faster formation of sulfate in the biochemical oxidation in comparison with the chemical oxidation. Isotope analyses of the formed sulfates indicate no or only very small isotope fractionations depending on experimental conditions. The highest enrichment of 32 S in the sulfate is 1.7 per mille. In accordance with the results of other authors it is concluded that in both chemical and biochemical weathering of sedimentary sulfides resulting in the formation of sulfates isotope effects are not of importance. (author)

  4. Molecular characterization of anaerobic sulfur-oxidizing microbial communities in up-flow anaerobic sludge blanket reactor treating municipal sewage.

    Science.gov (United States)

    Aida, Azrina A; Hatamoto, Masashi; Yamamoto, Masamitsu; Ono, Shinya; Nakamura, Akinobu; Takahashi, Masanobu; Yamaguchi, Takashi

    2014-11-01

    A novel wastewater treatment system consisting of an up-flow anaerobic sludge blanket (UASB) reactor and a down-flow hanging sponge (DHS) reactor with sulfur-redox reaction was developed for treatment of municipal sewage under low-temperature conditions. In the UASB reactor, a novel phenomenon of anaerobic sulfur oxidation occurred in the absence of oxygen, nitrite and nitrate as electron acceptors. The microorganisms involved in anaerobic sulfur oxidation have not been elucidated. Therefore, in this study, we studied the microbial communities existing in the UASB reactor that probably enhanced anaerobic sulfur oxidation. Sludge samples collected from the UASB reactor before and after sulfur oxidation were used for cloning and terminal restriction fragment length polymorphism (T-RFLP) analysis of the 16S rRNA genes of the bacterial and archaeal domains. The microbial community structures of bacteria and archaea indicated that the genus Smithella and uncultured bacteria within the phylum Caldiserica were the dominant bacteria groups. Methanosaeta spp. was the dominant group of the domain archaea. The T-RFLP analysis, which was consistent with the cloning results, also yielded characteristic fingerprints for bacterial communities, whereas the archaeal community structure yielded stable microbial community. From these results, it can be presumed that these major bacteria groups, genus Smithella and uncultured bacteria within the phylum Caldiserica, probably play an important role in sulfur oxidation in UASB reactors. Copyright © 2014 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

  5. Sulfur isotopic and proteomic profiles of sulfate reducers grown under differential steady-states

    Science.gov (United States)

    Leavitt, W.; Venceslau, S.; Waldbauer, J.; Smith, D. A.; Boidi, F. J.; Bradley, A. S.

    2016-12-01

    Microbial sulfate reducers (MSR) drive the Earth's biogeochemical sulfur cycle. At the heart of this energy metabolism is a cascade of redox transformations coupling organic carbon and/or hydrogen oxidation to the dissimilatory reduction of sulfate to sulfide. The product sulfide is depleted in the heavier isotopes of sulfur, relative to the reactant sulfate, consistent with a normal kinetic isotope effect. However, the magnitude of the net fractionation during MSR can range over a range of 70 permil, consistent with a multi-step set of reactions. This range in MSR fractionation has been shown to mainly depend on: i) the cell-specific sulfate reduction rate (csSRR), and ii) the ambient sulfate concentration. However, the fractionation under identical conditions differs among strains (Bradley et al. 2016. Geobio), and so must also be mediated by strain-specific processes, such as the nature and quantity of individual proteins involved in sulfate reduction, electron transport, and growth. In recent work we have examined the influence of electron donor, electron acceptor, and co-limitation under controlled steady-state culture conditions in order better inform models of MSR isotope fractionation, and the physiological and isotopic response to differential environmental forcings (e.g. Leavitt et al. (2013) PNAS). Recent models of the fractionation response to MSR rate (c.f. Bradley 2016; Wing & Halevy, 2016) make specific predictions for the responses of the cellular metabolome and proteome. Here we compare the steady-state S-isotopic fractionation and proteome of `fast' versus `slow' grown D. vulgaris, using replicate chemostats under electron donor limitation. We observe clear and statistically robust changes in some key central MSR and C-metabolism enzymes, though a host of the critical energy-transfer enzymes show no statistically discernable change. We discuss these results in light of recent theoretical advances and their relevance to modern and ancient

  6. Use of liquid chromatography for measuring atmospheric sulfur dioxide and nitrogen oxide

    Energy Technology Data Exchange (ETDEWEB)

    Benova, E

    1973-02-01

    A literature search to ascertain the applicability of liquid chromatography to the analysis of atmospheric sulfur dioxide and various oxides of nitrogen is reported. Simple or enriched samples can be analyzed. Plastic bags are recommended for preparation of simple samples; and a table of 18 plastic materials, their manufacturers, and pollutants to which they are inert is provided. Enriched samples can be prepared in chromatographic columns by adsorption methods. Tables are provided listing carriers, stationary phase materials, temperatures, carrier liquids (helium or nitrogen), column dimensions, and other data recommended for chromatographic tests of SO/sub 2/ and NOx. Because of its reactivity and tendency to polymerize, sulfur trioxide should be reduced to SO/sub 2/ prior to analysis.

  7. Oxidation-sulfidation behavior of Ni aluminide in oxygen-sulfur mixed-gas atmospheres

    International Nuclear Information System (INIS)

    Natesan, K.

    1988-01-01

    Oxidation-sulfidation studies were conducted with sheet samples of nickel aluminide, containing 23.5 at. % Al, 0.5 at. % Hf, and 0.2 at. % B, in an annealed condition and after preoxidation treatments. Continuous weight-change measurements were made by a thermogravimetric technique in exposure atmospheres of air, a low-pO/sub 2/ gas mixture, and low-pO/sub 2/ gas mixtures with several levels of sulfur. The air-exposed specimens developed predominantly nickel oxide; the specimen exposed to a low-pO/sub 2/ environment developed an aluminum oxide scale. As the sulfur content of the gas mixture increased, the alumina scale exhibited spallation and the alloy tended to form nickel sulfide as the reaction phase. The results indicated that the sulfidation reaction of nickel aluminide specimens (both bare and preoxidized) was determined by the rate of transport of nickel from the substrate through the scale to the gas/alumina scale interface, the mechanical integrity of the oxide scale, and the H/sub 2/S concentration in the exposure environment

  8. Results of Study of Sulfur Oxide Reduction During Combustion of Coal-Water Slurry Fuel Through use of Sulfur Capturing Agents

    Directory of Open Access Journals (Sweden)

    Murko Vasiliy I.

    2016-01-01

    Full Text Available It is shown that an effective way of burning high sulfur coal is to burn coal-water slurry fuel (CWF prepared on its basis containing a sulfur capture agent (SCA entered in the slurry at the stage of preparation. The technique of thermodynamic analysis of chemical reactions during CWF burning has been developed including burning in the presence of SCA. Using the developed calculation program, the optimal temperature conditions have been determined as required for the effective reduction of sulfur oxides in flue gases when using different types of SCA. According to the results of calculating the composition of CWF combustion products when entering various substances in the burner space as SCA it has been determined that magnesite, calcite, and dolomite are the most effective natural minerals. The analysis of calculated and experimental data proves the efficiency of SCA addition as well as validity of the obtained results.

  9. A MnO2/Graphene Oxide/Multi-Walled Carbon Nanotubes-Sulfur Composite with Dual-Efficient Polysulfide Adsorption for Improving Lithium-Sulfur Batteries.

    Science.gov (United States)

    Li, Yong; Ye, Daixin; Liu, Wen; Shi, Bin; Guo, Rui; Zhao, Hongbin; Pei, Haijuan; Xu, Jiaqiang; Xie, Jingying

    2016-10-26

    Lithium-sulfur batteries can potentially be used as a chemical power source because of their high energy density. However, the sulfur cathode has several shortcomings, including fast capacity attenuation, poor electrochemical activity, and low Coulombic efficiency. Herein, multi-walled carbon nanotubes (CNTs), graphene oxide (GO), and manganese dioxide are introduced to the sulfur cathode. A MnO 2 /GO/CNTs-S composite with a unique three-dimensional (3D) architecture was synthesized by a one-pot chemical method and heat treatment approach. In this structure, the innermost CNTs work as a conducting additive and backbone to form a conducting network. The MnO 2 /GO nanosheets anchored on the sidewalls of CNTs have a dual-efficient absorption capability for polysulfide intermediates as well as afford adequate space for sulfur loading. The outmost nanosized sulfur particles are well-distributed on the surface of the MnO 2 /GO nanosheets and provide a short transmission path for Li + and the electrons. The sulfur content in the MnO 2 /GO/CNTs-S composite is as high as 80 wt %, and the as-designed MnO 2 /GO/CNTs-S cathode displays excellent comprehensive performance. The initial specific capacities are up to 1500, 1300, 1150, 1048, and 960 mAh g -1 at discharging rates of 0.05, 0.1, 0.2, 0.5, and 1 C, respectively. Moreover, the composite cathode shows a good cycle performance: the specific capacity remains at 963.5 mAh g -1 at 0.2 C after 100 cycles when the area density of sulfur is 2.8 mg cm -2 .

  10. Surface-initiated growth of thin oxide coatings for Li-sulfur battery cathodes

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Kyu Tae; Black, Robert; Yim, Taeeun; Ji, Xiulei; Nazar, Linda F. [University of Waterloo, Department of Chemistry, Waterloo, ON (Canada)

    2012-12-15

    The concept of surface-initiated growth of oxides on functionalized carbons is introduced as a method to inhibit the dissolution of polysulfide ions in Li-S battery cathode materials. MO{sub x} (M: Si, V) thin layers are homogeneously coated on nanostructured carbon-sulfur composites. The coating significantly inhibits the dissolution of polysulfides on cycling, resulting in enhanced cycle performance and coulombic efficiency of the Li-S battery. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  11. Degradation of solid oxide fuel cell metallic interconnects in fuels containing sulfur

    Energy Technology Data Exchange (ETDEWEB)

    Ziomek-Moroz, M.; Hawk, Jeffrey A.

    2005-01-01

    Hydrogen is the main fuel for all types of fuel cells except direct methanol fuel cells. Hydrogen can be generated from all manner of fossil fuels, including coal, natural gas, diesel, gasoline, other hydrocarbons, and oxygenates (e.g., methanol, ethanol, butanol, etc.). Impurities in the fuel can cause significant performance problems and sulfur, in particular, can decrease the cell performance of fuel cells, including solid oxide fuel cells (SOFC). In the SOFC, the high (800-1000°C) operating temperature yields advantages (e.g., internal fuel reforming) and disadvantages (e.g., material selection and degradation problems). Significant progress in reducing the operating temperature of the SOFC from ~1000 ºC to ~750 ºC may allow less expensive metallic materials to be used for interconnects and as balance of plant (BOP) materials. This paper provides insight on the material performance of nickel, ferritic steels, and nickel-based alloys in fuels containing sulfur, primarily in the form of H2S, and seeks to quantify the extent of possible degradation due to sulfur in the gas stream.

  12. Sulfur and nitrogen co-doped carbon dots sensors for nitric oxide fluorescence quantification

    Energy Technology Data Exchange (ETDEWEB)

    Simões, Eliana F.C. [Centro de Investigação em Química da Universidade do Porto (CIQ-UP), Faculdade de Farmácia da Universidade de Coimbra, Pólo das Ciências da Saúde, 3000-548 Coimbra (Portugal); Centro de Investigação em Química da Universidade do Porto (CIQ-UP), Departamento de Geociências, Ambiente e Ordenamento do Território, Faculdade de Ciências da Universidade do Porto, R. Campo Alegre 687, 4169-007 Porto (Portugal); Leitão, João M.M., E-mail: jleitao@ff.uc.pt [Centro de Investigação em Química da Universidade do Porto (CIQ-UP), Faculdade de Farmácia da Universidade de Coimbra, Pólo das Ciências da Saúde, 3000-548 Coimbra (Portugal); Esteves da Silva, Joaquim C.G. [Centro de Investigação em Química da Universidade do Porto (CIQ-UP), Departamento de Geociências, Ambiente e Ordenamento do Território, Faculdade de Ciências da Universidade do Porto, R. Campo Alegre 687, 4169-007 Porto (Portugal)

    2017-04-01

    Microwave synthetized sulfur and nitrogen co-doped carbon dots responded selectively to nitric oxide (NO) at pH 7. Citric acid, urea and sodium thiosulfate in the proportion of 1:1:3 were used respectively as carbon, nitrogen and sulfur sources in the carbon dots microwave synthesis. For this synthesis, the three compounds were diluted in 15 mL of water and exposed for 5 min to a microwave radiation of 700 W. It is observed that the main factor contributing to the increased sensitivity and selectivity response to NO at pH 7 is the sodium thiosulfate used as sulfur source. A linear response range from 1 to 25 μM with a sensitivity of 16 μM{sup −1} and a detection limit of 0.3 μM were obtained. The NO quantification capability was assessed in standard and in fortified serum solutions. - Highlights: • S,N co-doped CDs were microwave synthetized from citric acid, urea and sodium thiosulfate. • The NO fluorescence sensing was evaluated at pH 7. • The selective and sensitive detection of NO at pH 7 was achieved. • Good NO quantification results in serum samples were obtained.

  13. Sulfur and nitrogen co-doped carbon dots sensors for nitric oxide fluorescence quantification

    International Nuclear Information System (INIS)

    Simões, Eliana F.C.; Leitão, João M.M.; Esteves da Silva, Joaquim C.G.

    2017-01-01

    Microwave synthetized sulfur and nitrogen co-doped carbon dots responded selectively to nitric oxide (NO) at pH 7. Citric acid, urea and sodium thiosulfate in the proportion of 1:1:3 were used respectively as carbon, nitrogen and sulfur sources in the carbon dots microwave synthesis. For this synthesis, the three compounds were diluted in 15 mL of water and exposed for 5 min to a microwave radiation of 700 W. It is observed that the main factor contributing to the increased sensitivity and selectivity response to NO at pH 7 is the sodium thiosulfate used as sulfur source. A linear response range from 1 to 25 μM with a sensitivity of 16 μM"−"1 and a detection limit of 0.3 μM were obtained. The NO quantification capability was assessed in standard and in fortified serum solutions. - Highlights: • S,N co-doped CDs were microwave synthetized from citric acid, urea and sodium thiosulfate. • The NO fluorescence sensing was evaluated at pH 7. • The selective and sensitive detection of NO at pH 7 was achieved. • Good NO quantification results in serum samples were obtained.

  14. Prevention of formation of acid drainage from high-sulfur coal refuse by inhibition of iron- and sulfur-oxidizing microorganisms. 1. Preliminary experiments in controlled shaken flasks

    Energy Technology Data Exchange (ETDEWEB)

    Dugan, P.R.

    1987-01-01

    Changes of pH and sulfate concentration in high-sulfur coal refuse slurries are used as measurements of microbial pyrite oxidation in the laboratory. Sodium lauryl sulfate (SLS), alkylbenzene sulfonate (ABS), benzoic acid (BZ) and combinations of SLS plus BZ and ABS plus BZ effectively inhibited formation of sulfate and acid when added in concentrations greater than 50 mg/l to inoculated 20 or 30% coal refuse slurries. Here 25 mg/l concentrations of SLS, ABS and ABS plus BZ stimulated acid production. Formic, hexanoic, oxalic, propionic, and pyruvic acids at 0.1% concentrations were also effective inhibitors. Four different lignin sulfonates were only slightly effective inhibitors at 0.1% concentrations. It was concluded that acid formation resulting from microbial oxidation in high-sulfur coal refuse can be inhibited. 22 references.

  15. The iron-sulfur cluster assembly network component NARFL is a key element in the cellular defense against oxidative stress.

    Science.gov (United States)

    Corbin, Monique V; Rockx, Davy A P; Oostra, Anneke B; Joenje, Hans; Dorsman, Josephine C

    2015-12-01

    Aim of this study was to explore cellular changes associated with increased resistance to atmospheric oxygen using high-resolution DNA and RNA profiling combined with functional studies. Two independently selected oxygen-resistant substrains of HeLa cells (capable of proliferating at >80% O2, i.e. hyperoxia) were compared with their parental cells (adapted to growth at 20% O2, but unable to grow at >80% O2). A striking consistent alteration found to be associated with the oxygen-resistant state appeared to be an amplified and overexpressed region on chromosome 16p13.3 harboring 21 genes. The driver gene of this amplification was identified by functional studies as NARFL, which encodes a component of the cytosolic iron-sulfur cluster assembly system. In line with this result we found the cytosolic c-aconitase activity as well as the nuclear protein RTEL1, both Fe-S dependent proteins, to be protected by NARFL overexpression under hyperoxia. In addition, we observed a protective effect of NARFL against hyperoxia-induced loss of sister-chromatid cohesion. NARFL thus appeared to be a key factor in the cellular defense against hyperoxia-induced oxidative stress in human cells. Our findings suggest that new insight into age-related degenerative processes may come from studies that specifically address the involvement of iron-sulfur proteins. Copyright © 2015 The Authors. Published by Elsevier Inc. All rights reserved.

  16. Forensic analysis of tire rubbers based on their sulfur chemical states.

    Science.gov (United States)

    Funatsuki, Atsushi; Shiota, Kenji; Takaoka, Masaki; Tamenori, Yusuke

    2015-05-01

    The chemical states of sulfur in 11 tires were analyzed using X-ray absorption near-edge structure (XANES) in order to discriminate between various tire rubbers. All tires had peaks around 2471.5 and 2480.5eV, and the shapes and heights of these peaks differed among tires, suggesting that the sulfur chemical state could be used for discrimination between tire rubbers. Based on t-tests on the results of XANES, 43 of 55 combinations were different at a significance level of 5%. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

  17. Block Copolymer Electrolytes: Thermodynamics, Ion Transport, and Use in Solid- State Lithium/Sulfur Cells

    Science.gov (United States)

    Teran, Alexander Andrew

    Nanostructured block copolymer electrolytes containing an ion-conducting block and a modulus-strengthening block are of interest for applications in solid-state lithium metal batteries. These materials can self-assemble into well-defined microstructures, creating conducting channels that facilitate ion transport. The overall objective of this dissertation is to gain a better understanding of the behavior of salt-containing block copolymers, and evaluate their potential for use in solid-state lithium/sulfur batteries. Anionically synthesized polystyrene-b-poly(ethylene oxide) (SEO) copolymers doped with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt were used as a model system. This thesis investigates the model system on several levels: from fundamental thermodynamic studies to bulk characterization and finally device assembly and testing. First, the thermodynamics of neat and salt-containing block copolymers was studied. The addition of salt to these materials is necessary to make them conductive, however even small amounts of salt can have significant effects on their phase behavior, and consequently their iontransport and mechanical properties. As a result, the effect of salt addition on block copolymer thermodynamics has been the subject of significant interest over the last decade. A comprehensive study of the thermodynamics of block copolymer/salt mixtures over a wide range of molecular weights, compositions, salt concentrations and temperatures was conducted. Next, the effect of molecular weight on ion transport in both homopolymer and copolymer electrolytes were studied over a wide range of chain lengths. Homopolymer electrolytes show an inverse relationship between conductivity and chain length, with a plateau in the infinite molecular weight limit. This is due to the presence of two mechanisms of ion conduction in homopolymers; the first mechanism is a result of the segmental motion of the chains surrounding the salt ions, 2 creating a liquid

  18. Isolation of Sulfur Reducing and Oxidizing Bacteria Found in Contaminated Drywall

    Directory of Open Access Journals (Sweden)

    Frederick T. Guilford

    2010-02-01

    Full Text Available Drywall from China has been reported to release sulfur producing products which are corrosive to metals, result in noxious odors, and represent a significant health risk. It has been reported that these emissions produce medical symptoms such as respiratory or asthma type problems, sinusitis, gastrointestinal disorders, and vision problems in home owners and their household pets. We report here a method of identifying a causative agent for these emissions by sampling affected gypsum wallboard and subjecting those samples to Real Time Polymerase Chain Reaction [RT-PCR] studies. Specific DNA probes and primers have been designed and patented that detect a specific iron and sulfur reducing bacterium (i.e., Thiobacillus ferrooxidans. One hundred percent of affected drywall samples obtained from homes located in the southeastern United States tested positive for the presence of T. ferrooxidans. All negative controls consisting of unaffected wallboard and internal controls, Geotrichum sp., tested negative within our limits of detection.

  19. Building better lithium-sulfur batteries: from LiNO3 to solid oxide catalyst

    Science.gov (United States)

    Ding, Ning; Zhou, Lan; Zhou, Changwei; Geng, Dongsheng; Yang, Jin; Chien, Sheau Wei; Liu, Zhaolin; Ng, Man-Fai; Yu, Aishui; Hor, T. S. Andy; Sullivan, Michael B.; Zong, Yun

    2016-09-01

    Lithium nitrate (LiNO3) is known as an important electrolyte additive in lithium-sulfur (Li-S) batteries. The prevailing understanding is that LiNO3 reacts with metallic lithium anode to form a passivation layer which suppresses redox shuttles of lithium polysulfides, enabling good rechargeability of Li-S batteries. However, this view is seeing more challenges in the recent studies, and above all, the inability of inhibiting polysulfide reduction on Li anode. A closely related issue is the progressive reduction of LiNO3 on Li anode which elevates internal resistance of the cell and compromises its cycling stability. Herein, we systematically investigated the function of LiNO3 in redox-shuttle suppression, and propose the suppression as a result of catalyzed oxidation of polysulfides to sulfur by nitrate anions on or in the proximity of the electrode surface upon cell charging. This hypothesis is supported by both density functional theory calculations and the nitrate anions-suppressed self-discharge rate in Li-S cells. The catalytic mechanism is further validated by the use of ruthenium oxide (RuO2, a good oxygen evolution catalyst) on cathode, which equips the LiNO3-free cell with higher capacity and improved capacity retention over 400 cycles.

  20. Properties of nanocellulose isolated from corncob residue using sulfuric acid, formic acid, oxidative and mechanical methods.

    Science.gov (United States)

    Liu, Chao; Li, Bin; Du, Haishun; Lv, Dong; Zhang, Yuedong; Yu, Guang; Mu, Xindong; Peng, Hui

    2016-10-20

    In this work, nanocellulose was extracted from bleached corncob residue (CCR), an underutilized lignocellulose waste from furfural industry, using four different methods (i.e. sulfuric acid hydrolysis, formic acid (FA) hydrolysis, 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-mediated oxidation, and pulp refining, respectively). The self-assembled structure, morphology, dimension, crystallinity, chemical structure and thermal stability of prepared nanocellulose were investigated. FA hydrolysis produced longer cellulose nanocrystals (CNCs) than the one obtained by sulfuric acid hydrolysis, and resulted in high crystallinity and thermal stability due to its preferential degradation of amorphous cellulose and lignin. The cellulose nanofibrils (CNFs) with fine and individualized structure could be isolated by TEMPO-mediated oxidation. In comparison with other nanocellulose products, the intensive pulp refining led to the CNFs with the longest length and the thickest diameter. This comparative study can help to provide an insight into the utilization of CCR as a potential source for nanocellulose production. Copyright © 2016 Elsevier Ltd. All rights reserved.

  1. Interfacial and electrical properties of HfAlO/GaSb metal-oxide-semiconductor capacitors with sulfur passivation

    International Nuclear Information System (INIS)

    Tan Zhen; Zhao Lian-Feng; Wang Jing; Xu Jun

    2014-01-01

    Interfacial and electrical properties of HfAlO/GaSb metal-oxide-semiconductor capacitors (MOSCAPs) with sulfur passivation were investigated and the chemical mechanisms of the sulfur passivation process were carefully studied. It was shown that the sulfur passivation treatment could reduce the interface trap density D it of the HfAlO/GaSb interface by 35% and reduce the equivalent oxide thickness (EOT) from 8 nm to 4 nm. The improved properties are due to the removal of the native oxide layer, as was proven by x-ray photoelectron spectroscopy measurements and high-resolution cross-sectional transmission electron microscopy (HRXTEM) results. It was also found that GaSb-based MOSCAPs with HfAlO gate dielectrics have interfacial properties superior to those using HfO 2 or Al 2 O 3 dielectric layers. (condensed matter: electronic structure, electrical, magnetic, and optical properties)

  2. Dynamic transition of chemolithotrophic sulfur-oxidizing bacteria in response to amendment with nitrate in deposited marine sediments

    Directory of Open Access Journals (Sweden)

    Tomo eAoyagi

    2015-05-01

    Full Text Available Although environmental stimuli are known to affect the structure and function of microbial communities, their impact on the metabolic network of microorganisms has not been well investigated. Here, geochemical analyses, high-throughput sequencing of 16S rRNA genes and transcripts, and isolation of potentially relevant bacteria were carried out to elucidate the anaerobic respiration processes stimulated by nitrate (20 mM amendment of marine sediments. Marine sediments deposited by the Great East Japan Earthquake in 2011 were incubated anaerobically in the dark at 25°C for 5 days. Nitrate in slurry water decreased gradually for 2 days, then more rapidly until its complete depletion at day 5; production of N2O followed the same pattern. From day 2 to 5, the sulfate concentration increased and the sulfur content in solid-phase sediments significantly decreased. These results indicated that denitrification and sulfur oxidation occurred simultaneously. Illumina sequencing revealed the proliferation of known sulfur oxidizers, i.e., Sulfurimonas spp. and Chromatiales bacteria, which accounted for approximately 43.5% and 14.8% of the total population at day 5, respectively. They also expressed 16S rRNA to a considerable extent, whereas the other microorganisms, e.g., iron(III reducers and methanogens, became metabolically active at the end of the incubation. Extinction dilution culture in a basal-salts medium supplemented with sulfur compounds and nitrate successfully isolated the predominant sulfur oxidizers: Sulfurimonas sp. strain HDS01 and Thioalkalispira sp. strain HDS22. Their 16S rRNA genes showed 95.2−96.7% sequence similarity to the closest cultured relatives and they grew chemolithotrophically on nitrate and sulfur. Novel sulfur-oxidizing bacteria were thus directly involved in carbon fixation under nitrate-reducing conditions, activating anaerobic respiration processes and the reorganization of microbial communities in the deposited marine

  3. Study on the Relation between the Mn/Al Mixed Oxides Composition and Performance of FCC Sulfur Transfer Agent

    Directory of Open Access Journals (Sweden)

    Ruiyu Jiang

    2016-01-01

    Full Text Available A sulfur transfer agent in catalysts can effectively reduce the emission of SO2 with minimum adverse effects on the catalytic cracking ability of the primary catalyst. In this paper, the composition and performance of sulfur transfer agents with different oxidative active components (such as Cu, Fe, Ni, Co, Ba, Zn and Cr were prepared by acid peptization technique and characterized by X-ray diffraction (XRD, Fourier transform infrared spectroscopy (FTIR and N2 adsorption-desorption technique. The relationship between the composition and performance of the new sulfur transfer agents was investigated and the regeneration and recycling of the agents were performed. The results indicates that copper is a very good desulfurization active component. Moreover, the presence of CO has no significant effect on the absorption ability of SO2 by the sulfur transfer agent.

  4. Kalman-variant estimators for state of charge in lithium-sulfur batteries

    DEFF Research Database (Denmark)

    Propp, Karsten; Auger, Daniel J.; Fotouhi, Abbas

    2017-01-01

    Lithium-sulfur batteries are now commercially available, offering high specific energy density, low production costs and high safety. However, there is no commercially-available battery management system for them, and there are no published methods for determining state of charge in situ...

  5. Effect of sulfur fertilization on the sanitary state of plants of the family Brassicaceae

    Directory of Open Access Journals (Sweden)

    Tomasz P. Kurowski

    2012-12-01

    Full Text Available The experiment was carried out in the years 2006-2008 in Bałcyny (N=53°35'49"; E=19°51'20". The aim of this study was to determine the effect of sulfur fertilization on the sanitary state of spring oilseed rape, winter oilseed rape, white mustard and Chinese mustard as well as on the species composition of fungi colonizing their seeds. Sulfur fertilization had a beneficial effect on the health of Brassicaceae plants infested by Alternaria blight, grey mould, Sclerotinia stem rot, Phoma stem canker and Verticillium wilt, but it had a varying effect on the occurrence of powdery mildew. Alternaria alternata and Penicillium spp. were isolated most frequently from Brassicaceae seeds. In general, more fungi (including pathogenic to Brassicaceae were isolated from the seeds of plants grown in non-sulfur fertilized plots. Pathogens occurred primarily on the seed surface, and their number decreased after surface disinfection of seeds.

  6. Bioleaching of heavy metal polluted sediment: kinetics of leaching and microbial sulfur oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Loeser, C. [Technische Universitaet Dresden, Institut fuer Lebenmitteltechnik und Bioverfahrenstechnik, D-01062 Dresden (Germany); Zehnsdorf, A. [UFZ-Umweltforschungszentrum Leipzig-Halle GmbH, Umwelt- und Biotechnologisches Zentrum (UBZ), Permoserstrasse 15, D-04318 Leipzig (Germany); Goersch, K.; Seidel, H. [UFZ-Umweltforschungszentrum Leipzig-Halle GmbH, Department Bioremediation, Permoserstrasse 15, D-04318 Leipzig (Germany)

    2005-12-01

    Remediation of heavy metal polluted sediment through bioleaching using elemental sulfur (S{sup 0}) as the leaching agent can be regarded as a two-step process: firstly, the microbial oxidation of the added S{sup 0} to sulfuric acid and, secondly, the reaction of the produced acid with the sediment. Here, both subprocesses were studied in detail independently: oxidized river sediment was either suspended in sulfuric acid of various strengths, or mixed with various amounts of finely ground S{sup 0} powder (diameter of the S{sup 0} particles between 1 and 175 {mu}m with a Rosin-Rammler-Sperling-Bennet (RRSB) distribution and an average diameter of 35 {mu}m) and suspended in water. The leaching process was observed by repeated analysis of the suspension concerning pH, soluble sulfate and metals, and remaining S{sup 0}. In the case of abiotic leaching with H{sub 2}SO{sub 4}, the reaction between the acid and the sediment resulted in a gradual increase in pH and a solubilization of sediment-borne heavy metals which required some time; 80 % of the finally solubilized heavy metals was dissolved after 1 h, 90 % after 10 h, and 100 % after 100 h. In the case of bioleaching, the rate of S{sup 0} oxidation was maximal at the beginning, gradually diminished with time, and was proportional to the initial amount of S{sup 0}. Due to its very low solubility in water, S{sup 0} is oxidized in a surface reaction catalyzed by attached bacteria. The oxidation let the particles shrink, their surface became smaller and, thus, the S{sup 0} oxidation rate gradually decreased. The shrinking rate was time-invariant and, at 30 C, amounted to 0.5 {mu}m/day (or 100 {mu}g/cm{sup 2}/day). Within 21 days, 90 % of the applied S{sup 0} was oxidized. Three models with a different degree of complexity have been developed that describe this S{sup 0} oxidation, assuming S{sup 0} particles of uniform size (I), using a measured particle size distribution (II), or applying an adapted RRSB distribution (III

  7. Removal of Sulfur from CaF2 Containing Desulfurization Slag Exhausted from Secondary Steelmaking Process by Oxidation

    Science.gov (United States)

    Hiraki, Takehito; Kobayashi, Junichi; Urushibata, Satomi; Matsubae, Kazuyo; Nagasaka, Tetsuya

    2012-08-01

    The oxidation behavior of sulfur in desulfurization slag generated from the secondary steelmaking process with air has been investigated in the temperature range of 973 K to 1373 K (700 °C to 1100 °C). Although a high removal rate of sulfur is not achieved at temperatures lower than 1273 K (1000 °C) because of the formation of CaSO4, most of the sulfur is rapidly removed from slag as SO2 gas in the 1273 K to 1373 K (700 °C to 1100 °C) range. This finding indicates that the desulfurization slag generated from the secondary steelmaking process can be reused as a desulfurized flux through air oxidation, making it possible to reduce significantly the amount of desulfurization slag for disposal.

  8. Performance evaluation of pilot scale sulfur-oxidizing denitrification for treatment of metal plating wastewater.

    Science.gov (United States)

    Flores, Angel S P; Gwon, Eun-Mi; Sim, Dong-Min; Nisola, Grace; Galera, Melvin M; Chon, Seung-Se; Chung, Wook-Jin; Pak, Dae-Won; Ahn, Zou Sam

    2006-01-01

    A full-scale and two pilot-scale upflow sulfur-oxidizing denitrification (SOD) columns were evaluated using metal plating wastewater as feed. The sludge was autotrophically enriched, and inoculated in the SOD columns attached to the effluent line of three metal plating wastewater treatment facilities. The effects of activated carbon and aeration were also studied, and found effective for the removal of suspended solids and ammonia, respectively. The results showed that the constituents, such as the total nitrogen, nitrates, nitrites, ammonia, chemical oxygen demand (COD), and heavy metals, were effectively removed. The pH was observed to be maintained at 7-8 due to the alkalinity supplied by the sulfur-calcium carbonate (SC) pellet. The denitrification efficiency and start-up period were observed to be affected by the influent quality. Chromium, iron, nickel, copper, and zinc--the major heavy metal components of the influent--were effectively reduced at certain concentrations. Other metal ions were also detected and reduced to undetectable concentrations, but no trends in the comparison with denitrification were observed. From the results it can be concluded that SOD is effective for the removal of nitrogen, particularly nitrates, without a drastic pH change, and can effectively remove minute concentrations of heavy metals and COD in metal plating wastewaters.

  9. Sulfur metabolism in phototrophic sulfur bacteria

    DEFF Research Database (Denmark)

    Frigaard, Niels-Ulrik; Dahl, Christiane

    2008-01-01

    Phototrophic sulfur bacteria are characterized by oxidizing various inorganic sulfur compounds for use as electron donors in carbon dioxide fixation during anoxygenic photosynthetic growth. These bacteria are divided into the purple sulfur bacteria (PSB) and the green sulfur bacteria (GSB......). They utilize various combinations of sulfide, elemental sulfur, and thiosulfate and sometimes also ferrous iron and hydrogen as electron donors. This review focuses on the dissimilatory and assimilatory metabolism of inorganic sulfur compounds in these bacteria and also briefly discusses these metabolisms...... in other types of anoxygenic phototrophic bacteria. The biochemistry and genetics of sulfur compound oxidation in PSB and GSB are described in detail. A variety of enzymes catalyzing sulfur oxidation reactions have been isolated from GSB and PSB (especially Allochromatium vinosum, a representative...

  10. Saline-water bioleaching of chalcopyrite with thermophilic, iron(II)- and sulfur-oxidizing microorganisms.

    Science.gov (United States)

    Watling, Helen R; Collinson, David M; Corbett, Melissa K; Shiers, Denis W; Kaksonen, Anna H; Watkin, Elizabeth L J

    2016-09-01

    The application of thermoacidophiles for chalcopyrite (CuFeS2) bioleaching in hot, acidic, saline solution was investigated as a possible process route for rapid Cu extraction. The study comprised a discussion of protective mechanisms employed for the survival and/or adaptation of thermoacidophiles to osmotic stress, a compilation of chloride tolerances for three genera of thermoacidophiles applied in bioleaching and an experimental study of the activities of three species in a saline bioleaching system. The data showed that the oxidation rates of iron(II) and reduced inorganic sulfur compounds (tetrathionate) were reduced in the presence of chloride levels well below chloride concentrations in seawater, limiting the applicability of these microorganisms in the bioleaching of CuFeS2 in saline water. Copyright © 2016. Published by Elsevier Masson SAS.

  11. Combined method for reducing emission of sulfur dioxide and nitrogen oxides from thermal power plants

    Energy Technology Data Exchange (ETDEWEB)

    Kotler, V.R.; Grachev, S.P.

    1991-11-01

    Discusses the method developed by the Fossil Energy Research Corp. in the USA for combined desulfurization and denitrification of flue gases from coal-fired power plants. The method combines two methods tested on a commercial scale: the dry additive method for suppression of sulfur dioxide and the selective noncatalytic reduction of nitrogen oxides using urea (the NOXOUT process). The following aspects of joint flue gas desulfurization and denitrification are analyzed: flowsheets of the system, chemical reactions and reaction products, laboratory tests of the method and its efficiency, temperature effects on desulfurization and denitrification of flue gases, effects of reagent consumption rates, operating cost, efficiency of the combined method compared to other conventional methods of separate flue gas desulfurization and denitrification, economic aspects of flue gas denitrification and desulfurization. 4 refs.

  12. 78 FR 27387 - Notice of Workshop and Call for Information on Integrated Science Assessment for Oxides of Sulfur

    Science.gov (United States)

    2013-05-10

    ... periodically, and, if appropriate, to revise existing air quality criteria to reflect advances in scientific... such as chemistry and physics, sources and emissions, analytical methodology, transport and... will update the scientific assessment presented in the Integrated Science Assessment for Sulfur Oxides...

  13. Adsorption/oxidation of sulfur-containing gases on nitrogen-doped activated carbon

    Directory of Open Access Journals (Sweden)

    Liu Qiang

    2016-01-01

    Full Text Available Coconut shell-based activated carbon (CAC was used for the removal of methyl mercaptan (MM. CAC was modified by urea impregnation and calcined at 450°C and 950°C. The desulfurization activity was determined in a fixed bed reactor under room temperature. The results showed that the methyl mercaptan adsorption/oxidation capacity of modified carbon caicined at 950°C is more than 3 times the capacity of original samples. On the other hand, the modified carbon caicined at 950°C also has a high capacity for the simultaneous adsorption/oxidation of methyl mercaptan and hydrogen sulfide.The introduce of basic nitrogen groups siginificantly increases the desulfurization since it can facilitate the electron transfer process between sulfur and oxygen. The structure and chemical properties are characterized using Boehm titration, N2 adsorption-desorption method, thermal analysis and elemental analysis. The results showed that the major oxidation products were dimethyl disulfide and methanesulfonic acid which adsorbed in the activated carbon.

  14. Effects of temperature on the heterogeneous oxidation of sulfur dioxide by ozone on calcium carbonate

    Directory of Open Access Journals (Sweden)

    L. Y. Wu

    2011-07-01

    Full Text Available The heterogeneous oxidation of sulfur dioxide by ozone on CaCO3 was studied as a function of temperature (230 to 298 K at ambient pressure. Oxidation reactions were followed in real time using diffuse reflectance infrared Fourier transform spectrometry (DRIFTS to obtain kinetic and mechanistic data. From the analysis of the spectral features, the formation of sulfate was identified on the surface in the presence of O3 and SO2 at different temperatures from 230 to 298 K. The results showed that the heterogeneous oxidation and the rate of sulfate formation were sensitive to temperature. An interesting stage-transition region was observed at temperatures ranging from 230 to 257 K, but it became ambiguous gradually above 257 K. The reactive uptake coefficients at different temperatures from 230 to 298 K were acquired for the first time, which can be used directly in atmospheric chemistry modeling studies to predict the formation of secondary sulfate aerosol in the troposphere. Furthermore, the rate of sulfate formation had a turning point at about 250 K. The sulfate concentration at 250 K was about twice as large as that at 298 K. The rate of sulfate formation increased with decreasing temperature at temperatures above 250 K, while there is a contrary temperature effect at temperatures below 250 K. The activation energy for heterogeneous oxidation at temperatures from 245 K to 230 K was determined to be 14.63 ± 0.20 kJ mol−1. A mechanism for the temperature dependence was proposed and the atmospheric implications were discussed.

  15. One-Step Extraction of Antimony in Low Temperature from Stibnite Concentrate Using Iron Oxide as Sulfur-Fixing Agent

    Directory of Open Access Journals (Sweden)

    Yun Li

    2016-07-01

    Full Text Available A new process for one-step extraction of antimony in low temperature from stibnite concentrate by reductive sulfur-fixation smelting in sodium molten salt, using iron oxide as sulfur-fixing agent, was presented. The influences of molten salt addition and composition, ferric oxide dosage, smelting temperature and duration on extraction efficiency of antimony were investigated in details, respectively. The optimum conditions were determined as follows: 1.0 time stoichiometric requirement (α of mixed sodium salt (αsalt = 1.0, WNaCl:Wsalt = 40%, αFe2O3 = 1.0, Wcoke:Wstibnite = 40%, where W represents weight, smelting at 850 °C (1123 K for 60 min. Under the optimum conditions, the direct recovery rate of antimony can reach 91.48%, and crude antimony with a purity of 96.00% has been achieved. 95.31% of sulfur is fixed in form of FeS in the presence of iron oxide. Meanwhile, precious metals contained in stibnite concentrate are enriched and recovered comprehensively in crude antimony. In comparison to traditional antimony pyrometallurgical process, the smelting temperature of present process is reduced from 1150–1200 °C (1423–1473 K to 850–900 °C (1123–1173 K. Sulfur obtained in stibnite is fixed in FeS which avoids SO2 emission owing to the sulfur-fixing agent. Sodium salt can be regenerated and recycled in smelting system when the molten slag is operated to filter solid residue. The solid residue is subjected to mineral dressing operation to obtain iron sulfide concentrate which can be sold directly or roasted to regenerate into iron oxide.

  16. Micro-Arc oxidation of Ti in a solution of sulfuric acid and Ti+3 salt

    International Nuclear Information System (INIS)

    Ragalevicius, Rimas; Stalnionis, Giedrius; Niaura, Gediminas; Jagminas, Arunas

    2008-01-01

    A comparative study was performed on the behavior of titanium electrode in a sulfuric acid solution with and without Ti +3 during micro-arc oxidation under the constant current density control regime. The composition and microstructure of the obtained micro-arc films were analyzed using scanning electron microscopy, glancing-angle X-ray diffractometry, Raman and energy-dispersive X-ray spectroscopies. We have shown that addition of a Ti +3 salt extends the region of current densities (j a ) can be used for micro-arc oxidation of Ti and results in an obvious change of sparking behavior from extensive, large and long-played sparks to numerous, small and short sparks. As a consequence, the titania films formed in the Ti +3 -containing solutions are relatively thick, more uniform, composed of almost pure crystalline anatase and rutile phases of TiO 2 , and contain a network of evenly distributed small pores. It has also been shown that these films are promising for applications in catalysis, sensors and optoelectronics. The Raman spectra indicate that an increase in the electrolysis time of titanium in the Ti +3 -containing solution leads to the increase in rutile content, as expected

  17. Permanganate oxidation of sulfur compounds to prevent poisoning of Pd catalysts in water treatment processes.

    Science.gov (United States)

    Angeles-Wedler, Dalia; Mackenzie, Katrin; Kopinke, Frank-Dieter

    2008-08-01

    The practical application of Pd-catalyzed water treatment processes is impeded by catalyst poisoning by reduced sulfur compounds (RSCs). In this study, the potential of permanganate as a selective oxidant for the removal of microbially generated RSCs in water and as a regeneration agent for S-poisoned catalysts was evaluated. Hydrodechlorination using Pd/Al2O3 was carried out as a probe reaction in permanganate-pretreated water. The activity of the Pd catalysts in the successfully pretreated reaction medium was similar to that in deionized water. The catalyst showed no deactivation behavior in the presence of permanganate at a concentration level or = 0.08 mM, a significant but temporary inhibition of the catalytic dechlorination was observed. Unprotected Pd/Al2O3, which had been completely poisoned by sulfide, was reactivated by a combined treatment with permanganate and hydrazine. However, the anthropogenic water pollutants thiophene and carbon disulfide were resistant against permanganate. Together with the preoxidation of catalyst poisons, hydrophobic protection of the catalysts was studied. Pd/zeolite and various hydrophobically coated catalysts showed a higher stability against ionic poisons and permanganate than the uncoated catalyst. By means of a combination of oxidative water pretreatment and hydrophobic catalyst protection, we provide a new tool to harness the potential of Pd-catalyzed hydrodehalogenation for the treatment of real waters.

  18. Effect of Iron Oxides (Ordinary and Nano and Municipal Solid Waste Compost (MSWC Coated Sulfur on Wheat (Triticum aestivum L. Plant Iron Concentration and Growth

    Directory of Open Access Journals (Sweden)

    S Mazaherinia

    2011-02-01

    Full Text Available Abstract A greenhouse study was conducted to compare the effects of ordinary iron oxide (0.02-0.06 mm and nano iron oxide (25-250 nm and five levels of both iron oxides (0, 0.05, 0.1, 0.5, and 1.0 %w/w and two levels of sulfurous granular compost (MSW (0 and 2% w/w on plant height, spike length, grain weight per spike, total plant dry matter weight and thousands grain weight of wheat. The experimental factors were combined in factorial arrangement in a completely randomized design with 3 replications. Results showed that nano iron oxide was superior over ordinary iron oxide in all parameters studied. Fe concentration, spike length, plant height, grain weight per spike, total plant dry weight and thousands grain weight showed increasing trend per increase in both of iron oxides levels. Also, all parameters studied in sulfurous granular compost (MSW treatment were superior over granular compost without sulfurous (MSW. This increase in all parameters were significantly higher when urban solid waste compost coated with sulfur coupled with nano iron oxide compared to urban sulfurous granular compost (MSW along with ordinary iron oxide. Keywords: Sulfurous granular compost (MSW, Nano and ordinary iron oxides, Wheat

  19. Surface structure-dependent pyrite oxidation in relatively dry and moist air: Implications for the reaction mechanism and sulfur evolution

    Science.gov (United States)

    Zhu, Jianxi; Xian, Haiyang; Lin, Xiaoju; Tang, Hongmei; Du, Runxiang; Yang, Yiping; Zhu, Runliang; Liang, Xiaoliang; Wei, Jingming; Teng, H. Henry; He, Hongping

    2018-05-01

    Pyrite oxidation not only is environmentally significant in the formation of acid mine (or acid rock) drainage and oxidative acidification of lacustrine sediment but also is a critical stage in geochemical sulfur evolution. The oxidation process is always controlled by the reactivity of pyrite, which in turn is controlled by its surface structure. In this study, the oxidation behavior of naturally existing {1 0 0}, {1 1 1}, and {2 1 0} facets of pyrite was investigated using a comprehensive approach combining X-ray photoelectron spectroscopy, diffuse reflectance Fourier transform infrared spectroscopy, and time-of-flight secondary-ion mass spectrometry with periodic density functional theoretical (DFT) calculations. The experimental results show that (i) the initial oxidation rates of both pyrite {1 1 1} and {2 1 0} are much greater than that of pyrite {1 0 0}; (ii) the initial oxidation rate of pyrite {2 1 0} is greater than that of pyrite {1 1 1} in low relative humidity, which is reversed in high relative humidity; and (iii) inner sphere oxygen-bearing sulfur species are originally generated from surface reactions and then converted to outer sphere species. The facet dependent rate law can be expressed as: r{hkl} =k{hkl}haP0.5(t + 1) - 0.5 , where r{hkl} is the orientation dependent reaction rate, k{hkl} is the orientation dependent rate constant, h is the relative humidity, P is the oxygen partial pressure, and t is the oxidation time in seconds. {1 1 1} is the most sensitive facet for pyrite oxidation. Combined with DFT theoretical investigations, water catalyzed electron transfer is speculated as the rate-limiting step. These findings disclose the structure-reactivity dependence of pyrite, which not only presents new insight into the mechanism of pyrite oxidation but also provides fundamental data to evaluate sulfur speciation evolution, suggesting that the surface structure sensitivity should be considered to estimate the reactivity at the mineral

  20. Enhanced metabolic versatility of planktonic sulfur-oxidizing γ-proteobacteria in an oxygen-deficient coastal ecosystem

    Directory of Open Access Journals (Sweden)

    Alejandro A. Murillo

    2014-07-01

    Full Text Available Sulfur-oxidizing Gamma-proteobacteria are abundant in marine oxygen-deficient waters, and appear to play a key role in a previously unrecognized cryptic sulfur cycle. Metagenomic analyses of members of the uncultured SUP05 lineage in the Canadian seasonally anoxic fjord Saanich Inlet (SI, hydrothermal plumes in the Guaymas Basin (GB and single cell genomics analysis of two ARCTIC96BD-19 representatives from the South Atlantic Sub-Tropical Gyre (SASG have shown them to be metabolically versatile. However, SI and GB SUP05 bacteria seem to be obligate chemolithoautotrophs, whereas ARCTIC96BD-19 has the genetic potential for aerobic respiration. Here, we present results of a metagenomic analysis of sulfur-oxidizing Gamma-proteobacteria (GSO, closely related to the SUP05/ARCTIC96BD-19 clade, from a coastal ecosystem in the eastern South Pacific (ESP. This ecosystem experiences seasonal anoxia and accumulation of nitrite and ammonium at depth, with a corresponding increase in the abundance of GSO representatives. The ESP-GSOs appear to have a significantly different gene complement than those from Saanich Inlet, Guaymas Basin and SASG. Genomic analyses of de novo assembled contigs indicate the presence of a complete aerobic respiratory complex based on the cytochrome bc1 oxidase. Furthermore, they appear to encode a complete TCA cycle and several transporters for dissolved organic carbon species, suggesting a mixotrophic lifestyle. Thus, the success of sulfur-oxidizing Gamma-proteobacteria in oxygen-deficient marine ecosystems appears due not only to their previously recognized anaerobic metabolic versatility, but also to their capacity to function under aerobic conditions using different carbon sources. Finally, members of ESP-GSO cluster also have the genetic potential for reducing nitrate to ammonium based on the nirBD genes, and may therefore facilitate a tighter coupling of the nitrogen and sulfur cycles in oxygen-deficient waters.

  1. Facilitated and selective oxidation of thiophenic sulfur compounds using MoOx/Al₂O₃-H₂O₂ system under ultrasonic irradiation.

    Science.gov (United States)

    Akbari, Azam; Omidkhah, Mohammadreza; Towfighi Darian, Jafar

    2015-03-01

    Oxidative desulfurization of thiophenic sulfur compounds of benzothiophene (BT), dibenzothiophene (DBT) and 4,6-dimethyl dibenzothiophene (4,6-DMDBT) with MoOx/Al₂O₃ catalyst and H₂O₂ oxidant has been facilitated and more selective under ultrasonic irradiation. The catalyst with the optimum 10% of Mo loading consisted of isolated tetrahedral molybdenum oxide species based on FTIR analysis. The increase of Mo loading to 15% and 20% caused to generation of polymolybdate and MoO₃ crystals which decreased desulfurization activity. Sonication enhanced the apparent reaction rate constants in oxidation of all three sulfur compounds. An increase in the Arrhenius factor (A0), which is the total number of collisions per second, could explain the acceleration in the rate constants by sonication. The apparent activated energy (Ea) of BT oxidation was reduced from 96.6 to 75.3 kJ/mol by using ultrasound. This indicated that ultrasound had also a chemical effect, like a catalytic influence, in the acceleration of BT removal. DBT oxidation was reduced when investigated in the presence of tetralin, naphthalene and 2-methyl naphthalene as the model aromatic compounds of actual light oils. A higher selectivity toward DBT elimination in the presence of aromatics was obtained by sonication when compared with the silent treatment. Ultrasound cleaned the catalyst surface from adsorbed aromatics. On the basis of the obtained results, a mechanistic proposal for this desulfurization was explained. Oxidation was performed by nucleophilic attack of sulfur atom to the molybdenum peroxide species of tetrahedral molybdates, which was more advanced by sonication. Copyright © 2014 Elsevier B.V. All rights reserved.

  2. Effective bioleaching of chromium in tannery sludge with an enriched sulfur-oxidizing bacterial community.

    Science.gov (United States)

    Zeng, Jing; Gou, Min; Tang, Yue-Qin; Li, Guo-Ying; Sun, Zhao-Yong; Kida, Kenji

    2016-10-01

    In this study, a sulfur-oxidizing community was enriched from activated sludge generated in tannery wastewater treatment plants. Bioleaching of tannery sludge containing 0.9-1.2% chromium was investigated to evaluate the effectiveness of the enriched community, the effect of chromium binding forms on bioleaching efficiency, and the dominant microbes contributing to chromium bioleaching. Sludge samples inoculated with the enriched community presented 79.9-96.8% of chromium leaching efficiencies, much higher than those without the enriched community. High bioleaching efficiencies of over 95% were achieved for chromium in reducible fraction, while 60.9-97.9% were observed for chromium in oxidizable and residual fractions. Acidithiobacillus thiooxidans, the predominant bacteria in the enriched community, played an important role in bioleaching, whereas some indigenous heterotrophic species in sludge might have had a supporting role. The results indicated that A. thiooxidans-dominant enriched microbial community had high chromium bioleaching efficiency, and chromium binding forms affected the bioleaching performance. Copyright © 2016 Elsevier Ltd. All rights reserved.

  3. Sulfur polymer cement encapsulation of RCRA toxic metals and metal oxides

    International Nuclear Information System (INIS)

    Calhoun, C.L. Jr.; Nulf, L.E.; Gorin, A.H.

    1995-06-01

    A study was conducted to determine the suitability of Sulfur Polymer Cement (SPC) encapsulation technology for the stabilization of RCRA toxic metal and metal oxide wastes. In a series of bench-scale experiments, the effects of sodium sulfide additions to the waste mixture, residence time, and temperature profile were evaluated. In addition, an effort was made to ascertain the degree to which SPC affords chemical stabilization as opposed to physical encapsulation. Experimental results have demonstrated that at the 25 wt % loading level, SPC can effectively immobilize Cr, Cr 2 O 3 , Hg, Pb, and Se to levels below regulatory limits. SPC encapsulation also has been shown to significantly reduce the leachability of other toxic compounds including PbO, PbO 2 , As 2 O 3 , BaO, and CdO. In addition, data has confirmed sulfide conversion of Hg, Pb, PbO, PbO 2 , and BaO as the product of their reaction with SPC

  4. Management of industrial sulfur dioxide and nitrogen oxides emissions in Alberta - description of the existing system

    International Nuclear Information System (INIS)

    Macdonald, W.S.; Bietz, B.F.

    1999-01-01

    In addition to being key primary air contaminants, sulfur dioxide and nitrogen oxides are also major contributors to acidic deposition. The current management system for controlling industrial sources of SO(2) and NO(x) emissions in Alberta was developed in the late 1960s/early 1970s. The focus is on control of point source emissions through the use of appropriate technology. The approach taken for managing SO(2) and NO(x) emissions is similar to the approach taken to other industrial air and wastewater pollutants in Alberta. It is a command and control regulatory system. There are three main industry categories in Alberta which emit SO(2): sour gas processing, oil sand plants and thermal power plants. For NO(x) emissions, the two main categories with emissions: are natural gas production and thermal power plants. The two main goals of the existing industrial air quality management systems are to ensire that: (1) emissions from industrial facilities are minimized through the use of best available demonstrated technology, and (2) ambient levels of air contaminants in the vicinity of industrial facilities do not exceed Alberta guidelines. The four main policies which support these two goals of the existing management system are described. There are a number of key components of the existing management system including: ambient guideline levels, source emission standards, plume dispersion modelling, ambient air and source emission monitoring, environmental reporting, emission inventories, and approvals. 32 refs., 13 figs

  5. Evaluation of haloalkaliphilic sulfur-oxidizing microorganisms with potential application in the effluent treatment of the petroleum industry.

    Science.gov (United States)

    Olguín-Lora, P; Le Borgne, S; Castorena-Cortés, G; Roldán-Carrillo, T; Zapata-Peñasco, I; Reyes-Avila, J; Alcántara-Pérez, S

    2011-02-01

    Haloalkaliphilic sulfur-oxidizing mixed cultures for the treatment of alkaline-saline effluents containing sulfide were characterized and evaluated. The mixed cultures (IMP-PB, IMP-XO and IMP-TL) were obtained from Mexican alkaline soils collected in Puebla (PB), Xochimilco (XO) and Tlahuac (TL), respectively. The Ribosomal Intergenic Spacer Analysis (RISA) revealed bacteria related to Thioalkalibacterium and Thioalkalivibrio in IMP-XO and IMP-PB mixed cultures. Halomonas strains were detected in IMP-XO and IMP-TL. In addition, an uncultured Bacteroides bacterium was present in IMP-TL. Mixed cultures were evaluated at different pH and NaCl concentrations at 30°C. IMP-PB and IMP-TL expressed thiosulfate-oxidizing activity in the 7.5-10.5 pH range, whereas IMP-XO presented its maximal activity with 19.0 mg O₂ g (protein)⁻¹ min⁻¹, at pH 10.6; it was not affected by NaCl concentrations up to 1.7 M. In continuous culture, IMP-XO showed a growth rate of 15 day⁻¹, productivity of 433.4 mg(protein) l⁻¹ day⁻¹ and haloalkaliphilic sulfur-oxidizing activity was also detected up to 170 mM by means of N-methyl-diethanolamine (MDEA). Saline-alkaline soil samples are potential sources of haloalkaliphilic sulfur-oxidizing bacteria and the mixed cultures could be applied in the treatment of inorganic sulfur compounds in petroleum industry effluents under alkaline-saline conditions.

  6. Control and treatment of sulfur oxides emissions; Prevention et traitement des emissions d`oxydes de soufre

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-12-01

    The conference on the control and treatment of sulfur oxides emissions has held in Le Havre the 4. and 5. december, 1997. The aim of this conference was to promote the information on the different treatment technologies and to contribute on the one hand to the supporting and revival of the environmental protection and on the other hand to the desulfurization programs. It has allowed to recall too the technical and financial support of the Ademe to the manufacturers. (O.M.)

  7. Denitrification of groundwater using a sulfur-oxidizing autotrophic denitrifying anaerobic fluidized-bed MBR: performance and bacterial community structure.

    Science.gov (United States)

    Zhang, Lili; Zhang, Chao; Hu, Chengzhi; Liu, Huijuan; Qu, Jiuhui

    2015-03-01

    This paper investigates a novel sulfur-oxidizing autotrophic denitrifying anaerobic fluidized bed membrane bioreactor (AnFB-MBR) that has the potential to overcome the limitations of conventional sulfur-oxidizing autotrophic denitrification systems. The AnFB-MBR produced consistent high-quality product water when fed by a synthetic groundwater with NO3 (-)-N ranging 25-80 mg/L and operated at hydraulic retention times of 0.5-5.0 h. A nitrate removal rate of up to 4.0 g NO3 (-)-N/Lreactord was attained by the bioreactor, which exceeded any reported removal capacity. The flux of AnFB-MBR was maintained in the range of 1.5-15 L m(-2) h(-1). Successful membrane cleaning was practiced with cleaning cycles of 35-81 days, which had no obvious effect on the AnFB-MBR performance. The (15) N-tracer analyses elucidated that nitrogen was converted into (15) N2-N and (15) N-biomass accounting for 88.1-93.1 % and 6.4-11.6 % of the total nitrogen produced, respectively. Only 0.3-0.5 % of removed nitrogen was in form of (15)N2O-N in sulfur-oxidizing autotrophic denitrification process, reducing potential risks of a significant amount of N2O emissions. The sulfur-oxidizing autotrophic denitrifying bacterial consortium was composed mainly of bacteria from Proteobacteria, Chlorobi, and Chloroflexi phyla, with genera Thiobacillus, Sulfurimonas, and Ignavibacteriales dominating the consortium. The pyrosequencing assays also suggested that the stable microbial communities corresponded to the elevated performance of the AnFB-MBR. Overall, this research described relatively high nitrate removal, acceptable flux, indicating future potential for the technology in practice.

  8. Study of the chemistry of sulfur- and nitrogen oxides at fluidized bed combustion. Final report

    International Nuclear Information System (INIS)

    Lindqvist, O.

    1995-01-01

    Research has been carried out concerning chemistry of nitrogen and sulfur oxides, with relevance to fluidized bed combustion. Studies of the heterogeneous decomposition reactions of NO and N 2 O molecules have also been carried out. The effect of O 2 on the heterogeneous reactions has been investigated and the results indicate that NO can deteriorate only in the reducing zones of a FBC. The formation of NO and N 2 O as well as the question of what parameters affect this formation have been studied in a series of combustion experiments. In addition, it has also been demonstrated that the volatiles and the char are about equally important for the NO and N 2 O formation. Quantum chemical calculations have been used to study the surface processes of the nitrogen oxides. Investigations of the desulfurization reactions at high percentages of CO 2 with special regard to the PFBC technique have been made. In addition, the same reaction has been studied with e.g. spectroscopic methods at normal CO 2 percentages, but with varying amounts of O 2 and CO. CaSO 3 has been demonstrated to be an intermediary and CaS as being one of the products. An important part of the project activities is the analytical work which primarily supports the full scale experiments on the 12 MW th CTH FBC boiler. As a link between the CTH boiler and our analytical laboratory, a chemical engineer also has been employed. In this activity is also included the development of sampling and analytical methods, e.g. NH 3 and HCN sampling in the combustor. Time has also been allocated to measuring corrosive alkali metals (Na and K) in flue gases from a PFBC plant. 29 refs, 4 figs, 1 tab

  9. Performance of a pilot-scale packed bed reactor for perchlorate reduction using a sulfur oxidizing bacterial consortium.

    Science.gov (United States)

    Boles, Amber R; Conneely, Teresa; McKeever, Robert; Nixon, Paul; Nüsslein, Klaus R; Ergas, Sarina J

    2012-03-01

    A novel sulfur-utilizing perchlorate reducing bacterial consortium successfully treated perchlorate (ClO₄⁻) in prior batch and bench-scale packed bed reactor (PBR) studies. This study examined the scale up of this process for treatment of water from a ClO ₄⁻ and RDX contaminated aquifer in Cape Cod Massachusetts. A pilot-scale upflow PBR (∼250-L) was constructed with elemental sulfur and crushed oyster shell packing media. The reactor was inoculated with sulfur oxidizing ClO₄⁻ reducing cultures enriched from a wastewater seed. Sodium sulfite provided a good method of dissolved oxygen removal in batch cultures, but was found to promote the growth of bacteria that carry out sulfur disproportionation and sulfate reduction, which inhibited ClO₄⁻ reduction in the pilot system. After terminating sulfite addition, the PBR successfully removed 96% of the influent ClO₄⁻ in the groundwater at an empty bed contact time (EBCT) of 12 h (effluent ClO₄⁻ of 4.2 µg L(-1)). Simultaneous ClO₄⁻ and NO₃⁻ reduction was observed in the lower half of the reactor before reactions shifted to sulfur disproportionation and sulfate reduction. Analyses of water quality profiles were supported by molecular analysis, which showed distinct groupings of ClO₄⁻ and NO₃⁻ degrading organisms at the inlet of the PBR, while sulfur disproportionation was the primary biological process occurring in the top potion of the reactor. Copyright © 2011 Wiley Periodicals, Inc.

  10. Persistence of oxidation state III of gold in thione coordination

    Science.gov (United States)

    Jääskeläinen, Sirpa; Koskinen, Laura; Kultamaa, Matti; Haukka, Matti; Hirva, Pipsa

    2017-05-01

    Ligands N,N'-tetramethylthiourea and 2-mercapto-1-methyl-imidazole form stable Au(III) complexes [AuCl3(N,N'-tetramethylthiourea)] (1) and [AuCl3(2-mercapto-1-methyl-imidazole)] (2) instead of reducing the Au(III) metal center into Au(I), which would be typical for the attachment of sulfur donors. Compounds 1 and 2 were characterized by spectroscopic methods and by X-ray crystallography. The spectroscopic details were explained by simulation of the UV-Vis spectra via the TD-DFT method. Additionally, computational DFT studies were performed in order to find the reason for the unusual oxidation state in the crystalline materials. The preference for Au(III) can be explained via various weak intra- and intermolecular interactions present in the solid state structures. The nature of the interactions was further investigated by topological charge density analysis via the QTAIM method.

  11. Molecular Analysis of the Diversity of Sulfate-Reducing and Sulfur-Oxidizing Prokaryotes in the Environment, Using aprA as Functional Marker Gene▿ †

    Science.gov (United States)

    Meyer, Birte; Kuever, Jan

    2007-01-01

    The dissimilatory adenosine-5′-phosposulfate reductase is a key enzyme of the microbial sulfate reduction and sulfur oxidation processes. Because the alpha- and beta-subunit-encoding genes, aprBA, are highly conserved among sulfate-reducing and sulfur-oxidizing prokaryotes, they are most suitable for molecular profiling of the microbial community structure of the sulfur cycle in environment. In this study, a new aprA gene-targeting assay using a combination of PCR and denaturing gradient gel electrophoresis is presented. The screening of sulfate-reducing and sulfur-oxidizing reference strains as well as the analyses of environmental DNA from diverse habitats (e.g., microbial mats, invertebrate tissue, marine and estuarine sediments, and filtered hydrothermal water) by the new primer pair revealed an improved microbial diversity coverage and less-pronounced template-to-PCR product bias in direct comparison to those of the previously published primer set (B. Deplancke, K. R. Hristova, H. A. Oakley, V. J. McCracken, R. Aminov, R. I. Mackie, and H. R. Gaskins, Appl. Environ. Microbiol. 66:2166-2174, 2000). The concomitant molecular detection of sulfate-reducing and sulfur-oxidizing prokaryotes was confirmed. The new assay was applied in comparison with the 16S rRNA gene-based analysis to investigate the microbial diversity of the sulfur cycle in sediment, seawater, and manganese crust samples from four study sites in the area of the Lesser Antilles volcanic arc, Caribbean Sea (Caribflux project). The aprA gene-based approach revealed putative sulfur-oxidizing Alphaproteobacteria of chemolithoheterotrophic lifestyle to have been abundant in the nonhydrothermal sediment and water column. In contrast, the sulfur-based microbial community that inhabited the surface of the volcanic manganese crust was more complex, consisting predominantly of putative chemolithoautotrophic sulfur oxidizers of the Betaproteobacteria and Gammaproteobacteria. PMID:17921272

  12. Molecular analysis of the diversity of sulfate-reducing and sulfur-oxidizing prokaryotes in the environment, using aprA as functional marker gene.

    Science.gov (United States)

    Meyer, Birte; Kuever, Jan

    2007-12-01

    The dissimilatory adenosine-5'-phosphosulfate reductase is a key enzyme of the microbial sulfate reduction and sulfur oxidation processes. Because the alpha- and beta-subunit-encoding genes, aprBA, are highly conserved among sulfate-reducing and sulfur-oxidizing prokaryotes, they are most suitable for molecular profiling of the microbial community structure of the sulfur cycle in environment. In this study, a new aprA gene-targeting assay using a combination of PCR and denaturing gradient gel electrophoresis is presented. The screening of sulfate-reducing and sulfur-oxidizing reference strains as well as the analyses of environmental DNA from diverse habitats (e.g., microbial mats, invertebrate tissue, marine and estuarine sediments, and filtered hydrothermal water) by the new primer pair revealed an improved microbial diversity coverage and less-pronounced template-to-PCR product bias in direct comparison to those of the previously published primer set (B. Deplancke, K. R. Hristova, H. A. Oakley, V. J. McCracken, R. Aminov, R. I. Mackie, and H. R. Gaskins, Appl. Environ. Microbiol. 66:2166-2174, 2000). The concomitant molecular detection of sulfate-reducing and sulfur-oxidizing prokaryotes was confirmed. The new assay was applied in comparison with the 16S rRNA gene-based analysis to investigate the microbial diversity of the sulfur cycle in sediment, seawater, and manganese crust samples from four study sites in the area of the Lesser Antilles volcanic arc, Caribbean Sea (Caribflux project). The aprA gene-based approach revealed putative sulfur-oxidizing Alphaproteobacteria of chemolithoheterotrophic lifestyle to have been abundant in the nonhydrothermal sediment and water column. In contrast, the sulfur-based microbial community that inhabited the surface of the volcanic manganese crust was more complex, consisting predominantly of putative chemolithoautotrophic sulfur oxidizers of the Betaproteobacteria and Gammaproteobacteria.

  13. Rational Design of a Water-Storable Hierarchical Architecture Decorated with Amorphous Barium Oxide and Nickel Nanoparticles as a Solid Oxide Fuel Cell Anode with Excellent Sulfur Tolerance.

    Science.gov (United States)

    Song, Yufei; Wang, Wei; Ge, Lei; Xu, Xiaomin; Zhang, Zhenbao; Julião, Paulo Sérgio Barros; Zhou, Wei; Shao, Zongping

    2017-11-01

    Solid oxide fuel cells (SOFCs), which can directly convert chemical energy stored in fuels into electric power, represent a useful technology for a more sustainable future. They are particularly attractive given that they can be easily integrated into the currently available fossil fuel infrastructure to realize an ideal clean energy system. However, the widespread use of the SOFC technology is hindered by sulfur poisoning at the anode caused by the sulfur impurities in fossil fuels. Therefore, improving the sulfur tolerance of the anode is critical for developing SOFCs for use with fossil fuels. Herein, a novel, highly active, sulfur-tolerant anode for intermediate-temperature SOFCs is prepared via a facile impregnation and limited reaction protocol. During synthesis, Ni nanoparticles, water-storable BaZr 0.4 Ce 0.4 Y 0.2 O 3- δ (BZCY) perovskite, and amorphous BaO are formed in situ and deposited on the surface of a Sm 0.2 Ce 0.8 O 1.9 (SDC) scaffold. More specifically, a porous SDC scaffold is impregnated with a well-designed proton-conducting perovskite oxide liquid precursor with the nominal composition of Ba(Zr 0.4 Ce 0.4 Y 0.2 ) 0.8 Ni 0.2 O 3- δ (BZCYN), calcined and reduced in hydrogen. The as-synthesized hierarchical architecture exhibits high H 2 electro-oxidation activity, excellent operational stability, superior sulfur tolerance, and good thermal cyclability. This work demonstrates the potential of combining nanocatalysts and water-storable materials in advanced electrocatalysts for SOFCs.

  14. Mixing-assisted oxidative desulfurization of model sulfur compounds using polyoxometalate/H2O2 catalytic system

    OpenAIRE

    Angelo Earvin Sy Choi; Susan Roces; Nathaniel Dugos; Meng-Wei Wan

    2016-01-01

    Desulfurization of fossil fuel derived oil is needed in order to comply with environmental regulations. Dibenzothiophene and benzothiophene are among the predominant sulfur compound present in raw diesel oil. In this study, mixing-assisted oxidative desulfurization of dibenzothiophene and benzothiophene were carried out using polyoxometalate/H2O2 systems and a phase transfer agent. The effects of reaction time (2–30 min) and temperature (30–70 °C) were examined in the oxidation of model sulfu...

  15. Method of removing and recovering elemental sulfur from highly reducing gas streams containing sulfur gases

    Science.gov (United States)

    Gangwal, Santosh K.; Nikolopoulos, Apostolos A.; Dorchak, Thomas P.; Dorchak, Mary Anne

    2005-11-08

    A method is provided for removal of sulfur gases and recovery of elemental sulfur from sulfur gas containing supply streams, such as syngas or coal gas, by contacting the supply stream with a catalyst, that is either an activated carbon or an oxide based catalyst, and an oxidant, such as sulfur dioxide, in a reaction medium such as molten sulfur, to convert the sulfur gases in the supply stream to elemental sulfur, and recovering the elemental sulfur by separation from the reaction medium.

  16. Environmental politics in the US: a study of state sulfur dioxide standards

    International Nuclear Information System (INIS)

    Davis, M.

    2005-01-01

    What determines the environmental regulatory regime of a country or region? This paper addresses the question in detail, using the US and its widely varying environmental policies as the case study. What factors lead some US states to pass strict environmental regulations, while others are content with the baseline standards required at the national level? This work outlines the state environmental choice as a trade-off between the desires of consumers (who want better environmental quality) and of producers (who want less restrictive environmental standards). A rational state legislator maximises her chances of being re-elected by balancing these two competing forces when setting environmental policy. I test this model by directly analysing the state decision to adopt more restrictive sulfur dioxide regulations than those required by the federal government under the Environmental Protection Agency's ''National Ambient Air Quality Standards'' program. The statistical results suggest that legislators weigh the relative influence of consumer and producer groups when setting sulfur dioxide standards, in addition to accounting for meteorological influences that affect the cost of compliance with stricter environmental regulations. Limited evidence is also provided to support an inverted-U shaped relationship between income levels and environmental regulations. (author)

  17. Sulfur-oxidizing autotrophic and mixotrophic denitrification processes for drinking water treatment: elimination of excess sulfate production and alkalinity requirement.

    Science.gov (United States)

    Sahinkaya, Erkan; Dursun, Nesrin

    2012-09-01

    This study evaluated the elimination of alkalinity need and excess sulfate generation of sulfur-based autotrophic denitrification process by stimulating simultaneous autotrophic and heterotrophic (mixotrophic) denitrification process in a column bioreactor by methanol supplementation. Also, denitrification performances of sulfur-based autotrophic and mixotrophic processes were compared. In autotrophic process, acidity produced by denitrifying sulfur-oxidizing bacteria was neutralized by the external NaHCO(3) supplementation. After stimulating mixotrophic denitrification process, the alkalinity need of the autotrophic process was satisfied by the alkalinity produced by heterotrophic denitrifiers. Decreasing and lastly eliminating the external alkalinity supplementation did not adversely affect the process performance. Complete denitrification of 75 mg L(-1) NO(3)-N under mixotrophic conditions at 4 h hydraulic retention time was achieved without external alkalinity supplementation and with effluent sulfate concentration lower than the drinking water guideline value of 250 mg L(-1). The denitrification rate of mixotrophic process (0.45 g NO(3)-N L(-1) d(-1)) was higher than that of autotrophic one (0.3 g NO(3)-N L(-1) d(-1)). Batch studies showed that the sulfur-based autotrophic nitrate reduction rate increased with increasing initial nitrate concentration and transient accumulation of nitrite was observed. Copyright © 2012 Elsevier Ltd. All rights reserved.

  18. Chemical trapping and characterization of small oxoacids of sulfur (SOS) generated in aqueous oxidations of H2S.

    Science.gov (United States)

    Kumar, Murugaeson R; Farmer, Patrick J

    2018-04-01

    Small oxoacids of sulfur (SOS) are elusive molecules like sulfenic acid, HSOH, and sulfinic acid, HS(O)OH, generated during the oxidation of hydrogen sulfide, H 2 S, in aqueous solution. Unlike their alkyl homologs, there is a little data on their generation and speciation during H 2 S oxidation. These SOS may exhibit both nucleophilic and electrophilic reactivity, which we attribute to interconversion between S(II) and S(IV) tautomers. We find that SOS may be trapped in situ by derivatization with nucleophilic and electrophilic trapping agents and then characterized by high resolution LC MS. In this report, we compare SOS formation from H 2 S oxidation by a variety of biologically relevant oxidants. These SOS appear relatively long lived in aqueous solution, and thus may be involved in the observed physiological effects of H 2 S. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

  19. The application of an isotopic ratio technique to a study of the atmospheric oxidation of sulfur dioxide in the plume from a coal fired power plant

    International Nuclear Information System (INIS)

    Newman, L.; Forrest, J.; Manowitz, B.

    1975-01-01

    The extent of oxidation of sulfur dioxide to sulfate in the plume of a coal fired plant has been studied by using sampling with a single engine aircraft. A technique employing isotopic ratio measurements was utilized in conjunction with simultaneous concentration measurements of sulfur dioxide and sulfate. The use of sulfur hexafluroide as a conservative tracer was explored. The heterogeneous mechanism postulated in an oil fired plume study appears to pertain to the coal fired plume. However, the extent of oxidation seldom exceeded 5% and is limited by the relatively low particulate content of the coal fired plume. Evidence is presented for the apparent dropping out of sulfate from the plume. Implications pertaining to the ambient oxidation of sulfur dioxide are presented. (author)

  20. INFLUENCE OF ELEMENTAL SULFUR AND/OR INOCULATION WITH SULFUR OXIDIZING BACTERIA ON GROWTH, AND NUTRIENT CONTENT OF SORGHUM PLANTS GROWN ON DIFFERENT SOILS

    Directory of Open Access Journals (Sweden)

    Hala Kandil

    2011-12-01

    Full Text Available A pot experiment was conducted to study the effect of elemental sulfur(E.S rates (300 and 600 ppm and/or sulfur oxidizing bacteria (S.O.B. ATCC 8158 on growth and nutrients content of sorghum plants grown on different soils (sandy soils(I & II and clay loam soil.The obtained results could be summarized in the followings:Sorghum plants:Significant increases over the control were observed in fresh and dry weights of sorghum plant as well as its content of SO4=, N, P, K, Fe, Mn, Zn and Cu by using all the sulfur and/or the oxidizing bacteria treatments. Addition of E.S (300 & 600 ppm in combination with S.O.B. ATCC 8158 significantly increased both fresh and dry weights as well as SO4=, N, P, K, Fe, Mn, Zn and Cu contents of sorghum plants grown on the used soils as compared with either of them alone.E.S rates (300 & 600 ppm significantly increased the fresh and dry weights as well as all the studied nutrients content (SO4=, N, P, K, Fe, Mn, Zn and Cu of sorghum plants grown on the different soils as compared with S.O.B. ATCC 8158 treatment alone. The highest rate of E.S (600 ppm significantly increased all the previous parameters under study as compared with the lower rate (300 ppm. The highest values of fresh and dry weights as well as nutrients content (SO4=, N, P, K, Fe, Mn, Zn and Cu of sorghum plants grown on the used soils were obtained by 600 ppm E.S + S.O.B. ATCC 8158 treatment followed by 600 ppm E.S; 300 ppm E.S + S.O.B. ATCC 8158; 300 ppm E.S; S.O.B. ATCC 8158 and control treatments in decreasing order.The used soils:E.S rates (300 & 600 ppm and/or S.O.B. ATCC 8158 decreased pH values of the used soils after 3, 6 and 9 weeks from sowing as compared with their corresponding control treatments. The values of pH of sand soil (I and clay loam soil slightly decreased by time i.e they decreased from 3 weeks to 9 weeks from plantation. E.S rates (300 & 600 ppm with or without inoculation the used soils with S.O.B. ATCC 8158 significantly

  1. Catalytic removal of sulfur dioxide from dibenzothiophene sulfone over Mg-Al mixed oxides supported on mesoporous silica.

    Science.gov (United States)

    You, Nansuk; Kim, Min Ji; Jeong, Kwang-Eun; Jeong, Soon-Yong; Park, Young-Kwon; Jeon, Jong-Ki

    2010-05-01

    Dibenzothiophene sulfone (DBTS), one of the products of the oxidative desulfurization of heavy oil, can be removed through extraction as well as by an adsorption process. It is necessary to utilize DBTS in conjunction with catalytic cracking. An object of the present study is to provide an Mg-Al-mesoporous silica catalyst for the removal of sulfur dioxide from DBTS. The characteristics of the Mg-Al-mesoporous silica catalyst were investigated through N2 adsorption, XRD, ICP, and XRF. An Mg-Al-mesoporous silica catalyst formulated in a direct incorporation method showed higher catalytic performance compared to pure MgO during the catalytic removal of sulfur dioxide from DBTS. The higher dispersion of Mg as well as the large surface area of the Mg-Al-mesoporous silica catalyst strongly influenced the catalyst basicity in DBTS cracking.

  2. Chemiluminescence behavior based on oxidation reaction of rhodamine B with cerium(IV) in sulfuric acid medium

    International Nuclear Information System (INIS)

    Ma Yongjun; Jin Xiaoyong; Zhou Min; Zhang Ziyu; Teng Xiulan; Chen Hui

    2003-01-01

    The chemiluminescence (CL) of the rhodamine B (RhB)-cerium(IV) system was investigated by flow-injection. Rhodamine B was suggested to be a suitable chemiluminescent reagent in acidic conditions. When the concentration of rhodamine B was 100 mg l -1 and cerium sulfate was 1.6 mmol l -1 in sulfuric acid, the chemiluminescent intensity was found to be highest by using 0.3 mol l -1 sulfuric acid as a carrier solution. The particular chemiluminescent system could tolerate such distinct acidic environments that it was utilized for detecting many compounds that are stable in acidic solutions. Furthermore, by virtue of IR, UV-Vis and luminescence spectroscopic measurements, the chemiluminescent behavior of rhodamine B was studied and a possible mechanism for this chemiluminescent reaction was proposed. The emitter was affirmed to be a radical species due to one of the oxidation products of RhB; the chemiluminescent emissive wavelength was about 425 nm

  3. Sulfur-oxidizing bacteria dominate the microbial diversity shift during the pyrite and low-grade pyrolusite bioleaching process.

    Science.gov (United States)

    Han, Yifan; Ma, Xiaomei; Zhao, Wei; Chang, Yunkang; Zhang, Xiaoxia; Wang, Xingbiao; Wang, Jingjing; Huang, Zhiyong

    2013-10-01

    The microbial ecology of the pyrite-pyrolusite bioleaching system and its interaction with ore has not been well-described. A 16S rRNA gene clone library was created to evaluate changes in the microbial community at different stages of the pyrite-pyrolusite bioleaching process in a shaken flask. The results revealed that the bacterial community was disturbed after 5 days of the reaction. Phylogenetic analysis of 16S rRNA sequences demonstrated that the predominant microorganisms were members of a genus of sulfur-oxidizing bacteria, Thiomonas sp., that subsequently remained dominant during the bioleaching process. Compared with iron-oxidizing bacteria, sulfur-oxidizing bacteria were more favorable to the pyrite-pyrolusite bioleaching system. Decreased pH due to microbial acid production was an important condition for bioleaching efficiency. Iron-oxidizing bacteria competed for pyrite reduction power with Mn(IV) in pyrolusite under specific conditions. These results extend our knowledge of microbial dynamics during pyrite-pyrolusite bioleaching, which is a key issue to improve commercial applications. Copyright © 2013 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

  4. Bioenergetic studies of coal sulfur oxidation by extremely thermophilic bacteria. Final report, September 15, 1992--August 31, 1997

    Energy Technology Data Exchange (ETDEWEB)

    Kelly, R.M.; Han, C.J.

    1997-12-31

    Thermoacidophilic microorganisms have been considered for inorganic sulfur removal from coal because of expected improvements in rates of both biotic and abiotic sulfur oxidation reactions with increasing temperature. In this study, the bioenergetic response of the extremely thermoacidophilic archaeon, Metallosphaera sedula, to environmental changes have been examined in relation to its capacity to catalyze pyrite oxidation in coal. Given an appropriate bioenergetic challenge, the metabolic response was to utilize additional amounts of energy sources (i.e., pyrite) to survive. Of particular interest were the consequences of exposing the organism to various forms of stress (chemical, nutritional, thermal, pH) in the presence of coal pyrite. Several approaches to take advantage of stress response to accelerate pyrite oxidation by this organism were examined, including attempts to promote acquired thermal tolerance to extend its functional range, exposure to chemical uncouplers and decouplers, and manipulation of heterotrophic and chemolithotrophic tendencies to optimize biomass concentration and biocatalytic activity. Promising strategies were investigated in a continuous culture system. This study identified environmental conditions that promote better coupling of biotic and abiotic oxidation reactions to improve biosulfurization rates of thermoacidophilic microorganisms.

  5. Microbial Desulfurization of a Crude Oil Middle-Distillate Fraction: Analysis of the Extent of Sulfur Removal and the Effect of Removal on Remaining Sulfur

    Science.gov (United States)

    Grossman, M. J.; Lee, M. K.; Prince, R. C.; Garrett, K. K.; George, G. N.; Pickering, I. J.

    1999-01-01

    Rhodococcus sp. strain ECRD-1 was evaluated for its ability to desulfurize a 232 to 343°C middle-distillate (diesel range) fraction of Oregon basin (OB) crude oil. OB oil was provided as the sole source of sulfur in batch cultures, and the extent of desulfurization and the chemical fate of the residual sulfur in the oil after treatment were determined. Gas chromatography (GC), flame ionization detection, and GC sulfur chemiluminesce detection analysis were used to qualitatively evaluate the effect of Rhodococcus sp. strain ECRD-1 treatment on the hydrocarbon and sulfur content of the oil, respectively. Total sulfur was determined by combustion of samples and measurement of released sulfur dioxide by infrared absorption. Up to 30% of the total sulfur in the middle distillate cut was removed, and compounds across the entire boiling range of the oil were affected. Sulfur K-edge X-ray absorption-edge spectroscopy was used to examine the chemical state of the sulfur remaining in the treated OB oil. Approximately equal amounts of thiophenic and sulfidic sulfur compounds were removed by ECRD-1 treatment, and over 50% of the sulfur remaining after treatment was in an oxidized form. The presence of partially oxidized sulfur compounds indicates that these compounds were en route to desulfurization. Overall, more than two-thirds of the sulfur had been removed or oxidized by the microbial treatment. PMID:9872778

  6. The uptake and excretion of partially oxidized sulfur expands the repertoire of energy resources metabolized by hydrothermal vent symbioses.

    Science.gov (United States)

    Beinart, R A; Gartman, A; Sanders, J G; Luther, G W; Girguis, P R

    2015-05-07

    Symbiotic associations between animals and chemoautotrophic bacteria crowd around hydrothermal vents. In these associations, symbiotic bacteria use chemical reductants from venting fluid for the energy to support autotrophy, providing primary nutrition for the host. At vents along the Eastern Lau Spreading Center, the partially oxidized sulfur compounds (POSCs) thiosulfate and polysulfide have been detected in and around animal communities but away from venting fluid. The use of POSCs for autotrophy, as an alternative to the chemical substrates in venting fluid, could mitigate competition in these communities. To determine whether ESLC symbioses could use thiosulfate to support carbon fixation or produce POSCs during sulfide oxidation, we used high-pressure, flow-through incubations to assess the productivity of three symbiotic mollusc genera-the snails Alviniconcha spp. and Ifremeria nautilei, and the mussel Bathymodiolus brevior-when oxidizing sulfide and thiosulfate. Via the incorporation of isotopically labelled inorganic carbon, we found that the symbionts of all three genera supported autotrophy while oxidizing both sulfide and thiosulfate, though at different rates. Additionally, by concurrently measuring their effect on sulfur compounds in the aquaria with voltammetric microelectrodes, we showed that these symbioses excreted POSCs under highly sulfidic conditions, illustrating that these symbioses could represent a source for POSCs in their habitat. Furthermore, we revealed spatial disparity in the rates of carbon fixation among the animals in our incubations, which might have implications for the variability of productivity in situ. Together, these results re-shape our thinking about sulfur cycling and productivity by vent symbioses, demonstrating that thiosulfate may be an ecologically important energy source for vent symbioses and that they also likely impact the local geochemical regime through the excretion of POSCs.

  7. Homology modeling of dissimilatory APS reductases (AprBA of sulfur-oxidizing and sulfate-reducing prokaryotes.

    Directory of Open Access Journals (Sweden)

    Birte Meyer

    Full Text Available BACKGROUND: The dissimilatory adenosine-5'-phosphosulfate (APS reductase (cofactors flavin adenine dinucleotide, FAD, and two [4Fe-4S] centers catalyzes the transformation of APS to sulfite and AMP in sulfate-reducing prokaryotes (SRP; in sulfur-oxidizing bacteria (SOB it has been suggested to operate in the reverse direction. Recently, the three-dimensional structure of the Archaeoglobus fulgidus enzyme has been determined in different catalytically relevant states providing insights into its reaction cycle. METHODOLOGY/PRINCIPAL FINDINGS: Full-length AprBA sequences from 20 phylogenetically distinct SRP and SOB species were used for homology modeling. In general, the average accuracy of the calculated models was sufficiently good to allow a structural and functional comparison between the beta- and alpha-subunit structures (78.8-99.3% and 89.5-96.8% of the AprB and AprA main chain atoms, respectively, had root mean square deviations below 1 A with respect to the template structures. Besides their overall conformity, the SRP- and SOB-derived models revealed the existence of individual adaptations at the electron-transferring AprB protein surface presumably resulting from docking to different electron donor/acceptor proteins. These structural alterations correlated with the protein phylogeny (three major phylogenetic lineages: (1 SRP including LGT-affected Archaeoglobi and SOB of Apr lineage II, (2 crenarchaeal SRP Caldivirga and Pyrobaculum, and (3 SOB of the distinct Apr lineage I and the presence of potential APS reductase-interacting redox complexes. The almost identical protein matrices surrounding both [4Fe-4S] clusters, the FAD cofactor, the active site channel and center within the AprB/A models of SRP and SOB point to a highly similar catalytic process of APS reduction/sulfite oxidation independent of the metabolism type the APS reductase is involved in and the species it has been originated from. CONCLUSIONS: Based on the comparative

  8. Oxidation-state maxima in plutonium chemistry

    International Nuclear Information System (INIS)

    Silver, G.L.

    2013-01-01

    Maxima in the fractions of the trivalent and hexavalent oxidation states of plutonium are inherent in the algebra of its disproportionation reactions. The maxima do not support overall disproportionation equations as satisfactory representations of aqueous plutonium. (author)

  9. Determination of the products from the oxidation of aqueous hydrogen sulfide by sulfur K-edge XANES spectroscopy

    International Nuclear Information System (INIS)

    Vairavamurthy, A.; Manowitz, B.; Jeon, Yongseog; Zhou, Weiqing.

    1993-01-01

    The application of synchrotron radiation based XANES spectroscopy is described for determining the products formed from oxidation of aqueous sulfide.This technique allows simultaneous characterization of all the different forms of sulfur both qualitatively and quantitatively. Thus, it is superior to other commonly used techniques, such as chromatography, which are usually targeted at specific compounds. Since the use of XANES-based technique is relatively new in geochemistry, we present here an overview of the principles of the technique as well as the approach used for quantitative analysis. We studied the sulfide oxidation under conditions of high sulfide to oxygen ratio using 0.1 M sulfide solutions and the catalytic effects of sea sand, Fe 2+ , and Ni 2+ , were also examined. Significant results obtained from this study are presented to illustrate the value of the XANES technique for the determination of the products formed from the oxidation of sulfide at high concentrations

  10. The origin of efficient triplet state population in sulfur-substituted nucleobases

    Science.gov (United States)

    Mai, Sebastian; Pollum, Marvin; Martínez-Fernández, Lara; Dunn, Nicholas; Marquetand, Philipp; Corral, Inés; Crespo-Hernández, Carlos E.; González, Leticia

    2016-10-01

    Elucidating the photophysical mechanisms in sulfur-substituted nucleobases (thiobases) is essential for designing prospective drugs for photo- and chemotherapeutic applications. Although it has long been established that the phototherapeutic activity of thiobases is intimately linked to efficient intersystem crossing into reactive triplet states, the molecular factors underlying this efficiency are poorly understood. Herein we combine femtosecond transient absorption experiments with quantum chemistry and nonadiabatic dynamics simulations to investigate 2-thiocytosine as a necessary step to unravel the electronic and structural elements that lead to ultrafast and near-unity triplet-state population in thiobases in general. We show that different parts of the potential energy surfaces are stabilized to different extents via thionation, quenching the intrinsic photostability of canonical DNA and RNA nucleobases. These findings satisfactorily explain why thiobases exhibit the fastest intersystem crossing lifetimes measured to date among bio-organic molecules and have near-unity triplet yields, whereas the triplet yields of canonical nucleobases are nearly zero.

  11. Multi-temperature state-dependent equivalent circuit discharge model for lithium-sulfur batteries

    DEFF Research Database (Denmark)

    Propp, Karsten; Marinescu, Monica; Auger, Daniel J.

    2016-01-01

    Lithium-sulfur (Li-S) batteries are described extensively in the literature, but existing computational models aimed at scientific understanding are too complex for use in applications such as battery management. Computationally simple models are vital for exploitation. This paper proposes a non......-linear state-of-charge dependent Li-S equivalent circuit network (ECN) model for a Li-S cell under discharge. Li-S batteries are fundamentally different to Li-ion batteries, and require chemistry-specific models. A new Li-S model is obtained using a ‘behavioural’ interpretation of the ECN model; as Li...... pulse profile at four temperatures from 10 °C to 50 °C, giving linearized ECN parameters for a range of states-of-charge, currents and temperatures. These are used to create a nonlinear polynomial-based battery model suitable for use in a battery management system. When the model is used to predict...

  12. Lithium Azide as an Electrolyte Additive for All-Solid-State Lithium-Sulfur Batteries.

    Science.gov (United States)

    Eshetu, Gebrekidan Gebresilassie; Judez, Xabier; Li, Chunmei; Bondarchuk, Oleksandr; Rodriguez-Martinez, Lide M; Zhang, Heng; Armand, Michel

    2017-11-27

    Of the various beyond-lithium-ion battery technologies, lithium-sulfur (Li-S) batteries have an appealing theoretical energy density and are being intensely investigated as next-generation rechargeable lithium-metal batteries. However, the stability of the lithium-metal (Li°) anode is among the most urgent challenges that need to be addressed to ensure the long-term stability of Li-S batteries. Herein, we report lithium azide (LiN 3 ) as a novel electrolyte additive for all-solid-state Li-S batteries (ASSLSBs). It results in the formation of a thin, compact and highly conductive passivation layer on the Li° anode, thereby avoiding dendrite formation, and polysulfide shuttling. It greatly enhances the cycling performance, Coulombic and energy efficiencies of ASSLSBs, outperforming the state-of-the-art additive lithium nitrate (LiNO 3 ). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Synthetic modeling chemistry of iron-sulfur clusters in nitric oxide signaling.

    Science.gov (United States)

    Fitzpatrick, Jessica; Kim, Eunsuk

    2015-08-18

    Nitric oxide (NO) is an important signaling molecule that is involved in many physiological and pathological functions. Iron-sulfur proteins are one of the main reaction targets for NO, and the [Fe-S] clusters within these proteins are converted to various iron nitrosyl species upon reaction with NO, of which dinitrosyl iron complexes (DNICs) are the most prevalent. Much progress has been made in identifying the origin of cellular DNIC generation. However, it is not well-understood which other products besides DNICs may form during [Fe-S] cluster degradation nor what effects DNICs and other degradation products can have once they are generated in cells. Even more elusive is an understanding of the manner by which cells cope with unwanted [Fe-S] modifications by NO. This Account describes our synthetic modeling efforts to identify cluster degradation products derived from the [2Fe-2S]/NO reaction in order to establish their chemical reactivity and repair chemistry. Our intent is to use the chemical knowledge that we generate to provide insight into the unknown biological consequences of cluster modification. Our recent advances in three different areas are described. First, new reaction conditions that lead to the formation of previously unrecognized products during the reaction of [Fe-S] clusters with NO are identified. Hydrogen sulfide (H2S), a gaseous signaling molecule, can be generated from the reaction between [2Fe-2S] clusters and NO in the presence of acid or formal H• (e(-)/H(+)) donors. In the presence of acid, a mononitrosyl iron complex (MNIC) can be produced as the major iron-containing product. Second, cysteine analogues can efficiently convert MNICs back to [2Fe-2S] clusters without the need for any other reagents. This reaction is possible for cysteine analogues because of their ability to labilize NO from MNICs and their capacity to undergo C-S bond cleavage, providing the necessary sulfide for [2Fe-2S] cluster formation. Lastly, unique dioxygen

  14. Retention of sulfur and nitrogen oxides from the exhaust gases by radiolysis, a modern method of environmental protection

    International Nuclear Information System (INIS)

    Macarie, Rodica; Zissulescu, Ecaterina; Martin, Diana; Radoiu, Marilena

    2000-01-01

    Industry, especially the power industry, is a great generator of gaseous pollutants (SO x , NO x , CO 2 , CO). The oxides are responsible for the 'acid rains' which have a great negative impact on the environment, human beings and animals, while CO 2 emissions contribute to the increase of the greenhouse effect. Retention of the sulfur and nitrogen oxides from the exhaust gases can be carried out either by conventional methods (using chemical adsorbents) or by non-conventional ones (radiolysis). Recently, non-conventional methods have bee given priority, including exhaust gas irradiation with an accelerated electron beam as a more efficient alternative to the gas desulfurization. In order to increase the efficiency of the accelerated electron beam injected into the exhaust gas, the effect of microwave utilization has been investigated. The company S.C. ICPET S.A.-Bucuresti, in cooperation with INFLPR-Bucuresti, investigated the retention by radiolysis of the sulfur and nitrogen oxides from a synthetic mixture of exhaust gases in an installation developed in the laboratory by means of accelerated electron beams, microwaves and by the accelerated electron beams and microwave combined. The paper presents the results obtained in the laboratory experiments and the advantages of radiolysis in comparison with the chemical conventional methods, namely: simultaneous removal of SO 2 and NO x , solid by-products that can be used as fertilizers in agriculture, simple technologies that do not imply catalysts or adsorbents, no waste waters. (authors)

  15. Investigation of sulfur interactions on a conventional nickel-based solid oxide fuel cell anode during methane steam and dry reforming

    Science.gov (United States)

    Jablonski, Whitney S.

    Solid oxide fuel cells (SOFC) are an attractive energy source because they do not have undesirable emissions, are scalable, and are feedstock flexible, which means they can operate using a variety of fuel mixtures containing H2 and hydrocarbons. In terms of fuel flexibility, most potential fuel sources contain sulfur species, which severely poison the nickel-based anode. The main objective of this thesis is to systematically evaluate sulfur interactions on a conventional Ni/YSZ anode and compare sulfur poisoning during methane steam and dry reforming (SMR and DMR) to a conventional catalyst (Sud Chemie, Ni/K2O-CaAl2O4). Reforming experiments (SMR and DMR) were carried out in a packed bed reactor (PBR), and it was demonstrated that Ni/YSZ is much more sensitive to sulfur poisoning than Ni/K2O-CaAl2O4 as evidenced by the decline in activity to zero in under an hour for both SMR and DMR. Adsorption and desorption of H2S and SO2 on both catalysts was evaluated, and despite the low amount of accessible nickel on Ni/YSZ (14 times lower than Ni/K2O-CaAl2O4), it adsorbs 20 times more H2S and 50 times more SO2 than Ni/K 2O-CaAl2O4. A one-dimensional, steady state PBR model (DetchemPBED) was used to evaluate SMR and DMR under poisoning conditions using the Deutschmann mechanism and a recently published sulfur sub-mechanism. To fit the observed deactivation in the presence of 1 ppm H2S, the adsorption/desorption equilibrium constant was increased by a factor 16,000 for Ni/YSZ and 96 for Ni/K2O-CaAl2O4. A tubular SAE reactor was designed and fabricated for evaluating DMR in a reactor that mimics an SOFC. Evidence of hydrogen diffusion through a supposedly impermeable layer indicated that the tubular SAE reactor has a major flaw in which gases diffuse to unintended parts of the tube. It was also found to be extremely susceptible to coking which leads to cell failure even in operating regions that mimic real biogas. These problems made it impossible to validate the tubular SAE

  16. Genomic features of "Candidatus Venteria ishoeyi", a new sulfur-oxidizing macrobacterium from the Humboldt Sulfuretum off Chile.

    Directory of Open Access Journals (Sweden)

    Alexis Fonseca

    Full Text Available The Humboldt Sulfuretum (HS, in the productive Humboldt Eastern Boundary Current Upwelling Ecosystem, extends under the hypoxic waters of the Peru-Chile Undercurrent (ca. 6°S and ca. 36°S. Studies show that primeval sulfuretums held diverse prokaryotic life, and, while rare today, still sustain species-rich giant sulfur-oxidizing bacterial communities. We here present the genomic features of a new bacteria of the HS, "Candidatus Venteria ishoeyi" ("Ca. V. ishoeyi" in the family Thiotrichaceae.Three identical filaments were micro-manipulated from reduced sediments collected off central Chile; their DNA was extracted, amplified, and sequenced by a Roche 454 GS FLX platform. Using three sequenced libraries and through de novo genome assembly, a draft genome of 5.7 Mbp, 495 scaffolds, and a N50 of 70 kbp, was obtained. The 16S rRNA gene phylogenetic analysis showed that "Ca. V. ishoeyi" is related to non-vacuolate forms presently known as Beggiatoa or Beggiatoa-like forms. The complete set of genes involved in respiratory nitrate-reduction to dinitrogen was identified in "Ca. V. ishoeyi"; including genes likely leading to ammonification. As expected, the sulfur-oxidation pathway reported for other sulfur-oxidizing bacteria were deduced and also, key inorganic and organic carbon acquisition related genes were identified. Unexpectedly, the genome of "Ca. V. ishoeyi" contained numerous CRISPR repeats and an I-F CRISPR-Cas type system gene coding array. Findings further show that, as a member of an eons-old marine ecosystem, "Ca. V. ishoeyi" contains the needed metabolic plasticity for life in an increasingly oxygenated and variable ocean.

  17. Using Demonstrations Involving Combustion and Acid-Base Chemistry to Show Hydration of Carbon Dioxide, Sulfur Dioxide, and Magnesium Oxide and Their Relevance for Environmental Climate Science

    Science.gov (United States)

    Shaw, C. Frank, III; Webb, James W.; Rothenberger, Otis

    2016-01-01

    The nature of acidic and basic (alkaline) oxides can be easily illustrated via a series of three straightforward classroom demonstrations for high school and general chemistry courses. Properties of carbon dioxide, sulfur dioxide, and magnesium oxide are revealed inexpensively and safely. Additionally, the very different kinetics of hydration of…

  18. A novel acidophilic, thermophilic iron and sulfur-oxidizing archaeon isolated from a hot spring of tengchong, yunnan, China

    Directory of Open Access Journals (Sweden)

    Jiannan Ding

    2011-06-01

    Full Text Available A novel thermoacidophilic iron and sulfur-oxidizing archaeon, strain YN25, was isolated from an in situ enriched acid hot spring sample collected in Yunnan, China. Cells were irregular cocci, about 0.9-1.02 µm×1.0-1.31 µm in the medium containing elemental sulfur and 1.5-2.22 µm×1.8-2.54 µm in ferrous sulfate medium. The ranges of growth and pH were 50-85 (optimum 65 and pH 1.0-6.0 (optimum 1.5-2.5. The acidophile was able to grow heterotrophically on several organic substrates, including various monosaccharides, alcohols and amino acids, though the growth on single substrate required yeast extract as growth factor. Growth occurred under aerobic conditions or via anaerobic respiration using elemental sulfur as terminal electron acceptor. Results of morphology, physiology, fatty acid analysis and analysis based on 16S rRNA gene sequence indicated that the strain YN25 should be grouped in the species Acidianus manzaensis. Bioleaching experiments indicated that this strain had excellent leaching capacity, with a copper yielding ratio up to 79.16% in 24 d. The type strain YN25 was deposited in China Center for Type Culture Collection (=CCTCCZNDX0050.

  19. Sulfite-oxido-reductase is involved in the oxidation of sulfite in Desulfocapsa sulfoexigens during disproportionation of thiosulfate and elemental sulfur.

    Science.gov (United States)

    Frederiksen, Trine-Maria; Finster, Kai

    2003-06-01

    The enzymatic pathways of elemental sulfur and thiosulfate disproportionation were investigated using cell-free extract of Desulfocapsa sulfoexigens. Sulfite was observed to be an intermediate in the metabolism of both compounds. Two distinct pathways for the oxidation of sulfite have been identified. One pathway involves APS reductase and ATP sulfurylase and can be described as the reversion of the initial steps of the dissimilatory sulfate reduction pathway. The second pathway is the direct oxidation of sulfite to sulfate by sulfite oxidoreductase. This enzyme has not been reported from sulfate reducers before. Thiosulfate reductase, which cleaves thiosulfate into sulfite and sulfide, was only present in cell-free extract from thiosulfate disproportionating cultures. We propose that this enzyme catalyzes the first step in thiosulfate disproportionation. The initial step in sulfur disproportionation was not identified. Dissimilatory sulfite reductase was present in sulfur and thiosulfate disproportionating cultures. The metabolic function of this enzyme in relation to elemental sulfur or thiosulfate disproportionation was not identified. The presence of the uncouplers HQNO and CCCP in growing cultures had negative effects on both thiosulfate and sulfur disproportionation. CCCP totally inhibited sulfur disproportionation and reduced thiosulfate disproportionation by 80% compared to an unamended control. HQNO reduced thiosulfate disproportionation by 80% and sulfur disproportionation by 90%.

  20. Prevention of formation of acid drainage from high-sulfur coal refuse by inhibition of iron- and sulfur-oxidizing microorganisms. II. Inhibition in run of mine refuse under simulated field conditions

    Energy Technology Data Exchange (ETDEWEB)

    Dugan, P.R.

    1987-01-01

    The combination of sodium lauryl sulfate and benzoic acid effectively inhibits iron- and sulfur-oxidizing bacteria in coal refuse and prevents the conversion of iron pyrite to sulfate, ferric iron, and sulfuric acid, thereby significantly reducing the formation of acidic drainage from coal refuse. The inhibitors were effective in a concentration of 1.1. mg/kg refuse, and data indicate that the SLS was in excess of the concentration required. The treatment was compatible with the use of lime for neutralization of acid present prior to inhibition of its formation.

  1. Iron-sulfur clusters as biological sensors: the chemistry of reactions with molecular oxygen and nitric oxide.

    Science.gov (United States)

    Crack, Jason C; Green, Jeffrey; Thomson, Andrew J; Le Brun, Nick E

    2014-10-21

    Iron-sulfur cluster proteins exhibit a range of physicochemical properties that underpin their functional diversity in biology, which includes roles in electron transfer, catalysis, and gene regulation. Transcriptional regulators that utilize iron-sulfur clusters are a growing group that exploit the redox and coordination properties of the clusters to act as sensors of environmental conditions including O2, oxidative and nitrosative stress, and metabolic nutritional status. To understand the mechanism by which a cluster detects such analytes and then generates modulation of DNA-binding affinity, we have undertaken a combined strategy of in vivo and in vitro studies of a range of regulators. In vitro studies of iron-sulfur cluster proteins are particularly challenging because of the inherent reactivity and fragility of the cluster, often necessitating strict anaerobic conditions for all manipulations. Nevertheless, and as discussed in this Account, significant progress has been made over the past decade in studies of O2-sensing by the fumarate and nitrate reduction (FNR) regulator and, more recently, nitric oxide (NO)-sensing by WhiB-like (Wbl) and FNR proteins. Escherichia coli FNR binds a [4Fe-4S] cluster under anaerobic conditions leading to a DNA-binding dimeric form. Exposure to O2 converts the cluster to a [2Fe-2S] form, leading to protein monomerization and hence loss of DNA binding ability. Spectroscopic and kinetic studies have shown that the conversion proceeds via at least two steps and involves a [3Fe-4S](1+) intermediate. The second step involves the release of two bridging sulfide ions from the cluster that, unusually, are not released into solution but rather undergo oxidation to sulfane (S(0)) subsequently forming cysteine persulfides that then coordinate the [2Fe-2S] cluster. Studies of other [4Fe-4S] cluster proteins that undergo oxidative cluster conversion indicate that persulfide formation and coordination may be more common than previously

  2. Orbital physics in sulfur spinels: ordered, liquid and glassy ground states

    International Nuclear Information System (INIS)

    Buettgen, N; Hemberger, J; Fritsch, V; Krimmel, A; Muecksch, M; Nidda, H-A Krug von; Lunkenheimer, P; Fichtl, R; Tsurkan, V; Loidl, A

    2004-01-01

    Measurements of magnetization M(T, H), heat capacity C(T), NMR lineshift K(T) and linewidth Δ(T), neutron scattering S(Q, ω, T) and broadband dielectric spectroscopy ε(ω, T) provide experimental evidence of the different orbital ground states in the cubic sulfur spinels under investigation. In all compounds, the tetrahedrally coordinated Jahn-Teller ions Fe 2+ are characterized by a degeneracy of the orbital degrees of freedom. Particularly, we found a long-range orbital ordering in polycrystalline (PC) FeCr 2 S 4 , and a glassy freezing of the orbital degrees of freedom in FeCr 2 S 4 (single crystals) (SCs). In contrast, FeSc 2 S 4 belongs to the rare class of spin-orbital liquids, where quantum fluctuations accompanying the glassy freezing of the orbitals suppress long-range magnetic order

  3. Quantification of Sulfur by the Wet Oxidation for the Determination of 35S

    International Nuclear Information System (INIS)

    Lee, Heung N.; Kang, Sang Hoon; Ahn, Hong Joo; Han, Sun Ho; Jee, Kwang Yong

    2006-01-01

    Natural sulfur contains four stable isotopes. The main isotopes are 32 S (95.02%) and 34 S (4.21%). Beside the stable isotopes, there exist also a radioactive one 35 S (T 1/2 = 87.4 d, Emax = 167 keV, pure β - emitter). Sulfur- 35 is one of the cosmogenic radionuclides generated by cosmic rays through spallation of argon atoms. 35 S for the labeled compound such as 35 S-thiourea is produced from the pile irradiation of the neutron ( 35 Cl(n,p) 35 S). Most 35 S produced by cosmic rays is rapidly converted to sulfur dioxide (SO 2 ) and sulfate (SO 4 2- ), and attached on the ambient aerosols. The quantities of 35 S do not present a significant external exposure hazard since the low-energy emissions barely penetrate the outer dead layer of skin. For uptakes of inorganic sulfur, 15% is assumed to be retained with a 20 day biological half-life and 5% retained with a 2,000 day biological half-life. The remaining 80% is assumed to be rapidly excreted. Because of its relatively weak emission, 35 S is primarily an internal radiation hazard. TLDs are not effective and Geiger-Muller detectors can measure to low efficiency (∼10%) for detecting 35 S. Therefore, it is important to use careful handling and frequent monitoring, either with survey meters with thin- windows probes or by taking wipe samples and counting in a liquid scintillation counter (LSC)

  4. Antiinflammatory and neurological activity of pyrithione and related sulfur-containing pyridine N-oxides from Persian shallot (Allium stipitatum)

    DEFF Research Database (Denmark)

    Krejčová, Petra; Kučerová, Petra; Stafford, Gary Ivan

    2014-01-01

    ETHNOPHARMACOLOGICAL RELEVANCE: Persian shallot (Allium stipitatum) is a bulbous plant native to Turkey, Iran and Central Asia. It is frequently used in folk medicine for the treatment of a variety of disorders, including inflammation and stress. Antiinflammatory and neurological activities...... of pyrithione and four related sulfur-containing pyridine N-oxides which are prominent constituents of Allium stipitatum were tested. METHODS: The antiinflammatory activity was tested by the ability of the compounds to inhibit cyclooxygenase (COX-1 and COX-2), whereas the neurological activities were evaluated...... by assessing the compounds ability to inhibit monoamine oxidase-A (MAO-A) and acetylcholinesterase (AChE). The compounds׳ affinity for the serotonin transport protein (SERT) and the GABAA-benzodiazepine receptor were also investigated. RESULTS: 2-[(Methylthio)methyldithio]pyridine N-oxide showed very high...

  5. Effects of rare-earths additions on the breakdown of protective oxide scales in the presence of sulfur

    International Nuclear Information System (INIS)

    Srinivasan, V.; Goodman, D.E.

    1989-01-01

    Minor additions of rare-earths improve oxide scale adhesion in simple oxidation at high temperatures. The efficacy of such improvements and the role of such additions are not well understood in the presence of sulfur at 500-700 degrees C. Therefore, mixed gas corrosion tests were performed on model Fe-based alloys, with minor additions of rare-earths in an H 2 /H 2 S/H 2 O/Ar gas mixture at 700 degrees C up to 192 hours. The scale breakdown mechanisms were studied on preoxidized samples. The scales and the substrates were characterized by SEM/EDS, and scanning Auger microscopy (AES). The results are discussed

  6. Mixing-assisted oxidative desulfurization of model sulfur compounds using polyoxometalate/H2O2 catalytic system

    Directory of Open Access Journals (Sweden)

    Angelo Earvin Sy Choi

    2016-07-01

    Full Text Available Desulfurization of fossil fuel derived oil is needed in order to comply with environmental regulations. Dibenzothiophene and benzothiophene are among the predominant sulfur compound present in raw diesel oil. In this study, mixing-assisted oxidative desulfurization of dibenzothiophene and benzothiophene were carried out using polyoxometalate/H2O2 systems and a phase transfer agent. The effects of reaction time (2–30 min and temperature (30–70 °C were examined in the oxidation of model sulfur compounds mixed in toluene. A pseudo first-order reaction kinetic model and the Arrhenius equation were utilized in order to evaluate the kinetic rate constant and activation energy of each catalyst tested in the desulfurization process. Results showed the order of catalytic activity and activation energy of the different polyoxometalate catalysts to be H3PW12O40 > H3PM12O40 > H4SiW12O40 for both dibenzothiophene and benzothiophene.

  7. Silibinin attenuates sulfur mustard analog-induced skin injury by targeting multiple pathways connecting oxidative stress and inflammation.

    Directory of Open Access Journals (Sweden)

    Neera Tewari-Singh

    Full Text Available Chemical warfare agent sulfur mustard (HD inflicts delayed blistering and incapacitating skin injuries. To identify effective countermeasures against HD-induced skin injuries, efficacy studies were carried out employing HD analog 2-chloroethyl ethyl sulfide (CEES-induced injury biomarkers in skin cells and SKH-1 hairless mouse skin. The data demonstrate strong therapeutic efficacy of silibinin, a natural flavanone, in attenuating CEES-induced skin injury and oxidative stress. In skin cells, silibinin (10 µM treatment 30 min after 0.35/0.5 mM CEES exposure caused a significant (p90%, and activation of transcription factors NF-κB and AP-1 (complete reversal. Similarly, silibinin treatment was also effective in attenuating CEES-induced oxidative stress measured by 4-hydroxynonenal and 5,5-dimethyl-2-(8-octanoic acid-1-pyrolline N-oxide protein adduct formation, and 8-oxo-2-deoxyguanosine levels. Since our previous studies implicated oxidative stress, in part, in CEES-induced toxic responses, the reversal of CEES-induced oxidative stress and other toxic effects by silibinin in this study indicate its pleiotropic therapeutic efficacy. Together, these findings support further optimization of silibinin in HD skin toxicity model to develop a novel effective therapy for skin injuries by vesicants.

  8. All-Solid-State Lithium-Sulfur Battery based on a nanoconfined LiBH 4 Electrolyte

    NARCIS (Netherlands)

    Das, Supti; Ngene, Peter; Norby, Poul; Vegge, Tejs; de Jongh, P.E.; Blanchard, Didier

    2016-01-01

    In this work we characterize all-solid-state lithium-sulfur batteries based on nano-confined LiBH4in mesoporous silica as solid electrolytes. The nano-confined LiBH4has fast ionic lithium conductivity at room temperature, 0.1 mScm-1, negligible electronic conductivity and its cationic transport

  9. Isotopic composition of reduced and oxidized sulfur in the Canary Islands: implications for the mantle S cycle

    Science.gov (United States)

    Beaudry, P.; Longpre, M. A.; Wing, B. A.; Bui, T. H.; Stix, J.

    2017-12-01

    The Earth's mantle contains distinct sulfur reservoirs, which can be probed by sulfur isotope analyses of volcanic rocks and gases. We analyzed the isotopic composition of reduced and oxidized sulfur in a diverse range of volcanically derived materials spanning historical volcanism in the Canary Islands. Our sample set consists of subaerial volcanic tephras from three different islands, mantle and sedimentary xenoliths, as well as lava balloon samples from the 2011-2012 submarine El Hierro eruption and associated crystal separates. This large sample set allows us to differentiate between the various processes responsible for sulfur isotope heterogeneity in the Canary archipelago. Our results define an array in triple S isotope space between the compositions of the MORB and seawater sulfate reservoirs. Specifically, the sulfide values are remarkably homogeneous around d34S = -1 ‰ and D33S = -0.01 ‰, while sulfate values peak at d34S = +4 ‰ and D33S = +0.01 ‰. Lava balloons from the El Hierro eruption have highly enriched sulfate d34S values up to +19.3 ‰, reflecting direct interaction between seawater sulfate and the erupting magma. Several sulfate data points from the island of Lanzarote also trend towards more positive d34S up to +13.8 ‰, suggesting interaction with seawater sulfate-enriched lithologies or infiltration of seawater within the magmatic system. On the other hand, the modal values and relative abundances of S2- and S6+ in crystal separates suggest that the Canary Island mantle source has a d34S around +3 ‰, similar to the S-isotopic composition of a peridotite xenolith from Lanzarote. We infer that the S2- and S6+ modes reflect isotopic equilibrium between those species in the magmatic source, which requires 80 % of the sulfide to become oxidized after melting, consistent with measured S speciation. This 34S enrichment of the source could be due to the recycling of hydrothermally-altered oceanic crust, which has been previously suggested

  10. Iron and Sulfur Species and Sulfur Isotopic Compositions of Authigenic Pyrite in Gas Hydrate-Bearing Sediments from Hydrate Ridge, Cascadia Margin (ODP Leg 204): A Proposal of Conceptual Models to Indicate the Non-Steady State Depositional and Diagenetic Processes

    Science.gov (United States)

    Liu, C.; Jiang, S. Y.; Su, X.

    2017-12-01

    Two accretionary sediment sequences from Sites 1245 and 1252 recovered during Ocean Drilling Program (ODP) Leg 204 at Hydrate Ridge, Cascadia Margin were investigated to explore the non-steady state depositional and diagenetic history. Five iron species and three sulfur species were chemically extracted, and their concentrations and the sulfur isotopic compositions of pyrite were determined. After the mineral recognitions of these species and detailed comparative analyses, the aerobic history of bottom seawater has been determined. The formation of pyrite is thought to be controlled by the limited production of hydrogen sulfide relative to the supply of reactive iron. Also, the intrusion of oxygen by bioturbation would oxidize the reduced sulfur species and further suppress pyritization. To explain the geochemical relationship between pyrite and siderite and the sulfur isotope characteristics of pyrite, we propose seven conceptual models based on the variations in depositional rate and methane flux, and the models succeed in explaining the geochemical results and are validated by the observed non-steady state events. These models may contribute to the reconstruction of the non-steady state processes in other research areas in the future.

  11. Sulfonation of polyester fabrics by gaseous sulfur oxide activated by UV irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Kordoghli, Bessem [Laboratory of Applied Chemical and Environment (UR-CAE) - University of Monastir (Tunisia); Textile Research Laboratory (LRT) - ISET Kasr Hellal, University of Monastir (Tunisia); Khiari, Ramzi, E-mail: khiari_ramzi2000@yahoo.fr [Laboratory of Applied Chemical and Environment (UR-CAE) - University of Monastir (Tunisia); LGP2 - Laboratory of Pulp and Paper Science, 461, Rue de la Papeterie - BP 65, 38402 Saint Martin d' Heres Cedex (France); Mhenni, Mohamed Farouk [Laboratory of Applied Chemical and Environment (UR-CAE) - University of Monastir (Tunisia); Sakli, Faouzi [Textile Research Laboratory (LRT) - ISET Kasr Hellal, University of Monastir (Tunisia); Belgacem, Mohamed Naceur [LGP2 - Laboratory of Pulp and Paper Science, 461, Rue de la Papeterie - BP 65, 38402 Saint Martin d' Heres Cedex (France)

    2012-10-01

    Highlights: Black-Right-Pointing-Pointer In this paper, an original technique was present to improve the hydrophilic properties of polyester fibres. Black-Right-Pointing-Pointer The modification of PET fabric was carried out using gaseous sulfur trioxide activated by UV irradiations. Black-Right-Pointing-Pointer We fully characterized the modified and untreated fabrics. - Abstract: This paper describes an original technique aiming to improve the hydrophilic properties of polyester fibres. In this method, the sulfonation of the aromatic rings is carried out using gaseous sulfur trioxide activated by UV irradiations. Thus, exposing the polyester textile fabric to the UVC light (wavelength around 254 nm) under a stream of sulfur trioxide leads to the fixation of -SO{sub 3}H groups. The amounts of the fixed sulfonate groups depended on the reaction conditions. Evidence of grafting deduced from the measurements of hygroscopic properties was carried out by contact angle measurement, moisture regain as well as by measuring the rate of retention. SEM and FT-IR analysis, DSC and DTA/TGA thermograms showed that no significant modifications have occurred in the bulk of the treated PET fabrics.

  12. Sulfonation of polyester fabrics by gaseous sulfur oxide activated by UV irradiation

    International Nuclear Information System (INIS)

    Kordoghli, Bessem; Khiari, Ramzi; Mhenni, Mohamed Farouk; Sakli, Faouzi; Belgacem, Mohamed Naceur

    2012-01-01

    Highlights: ► In this paper, an original technique was present to improve the hydrophilic properties of polyester fibres. ► The modification of PET fabric was carried out using gaseous sulfur trioxide activated by UV irradiations. ► We fully characterized the modified and untreated fabrics. - Abstract: This paper describes an original technique aiming to improve the hydrophilic properties of polyester fibres. In this method, the sulfonation of the aromatic rings is carried out using gaseous sulfur trioxide activated by UV irradiations. Thus, exposing the polyester textile fabric to the UVC light (wavelength around 254 nm) under a stream of sulfur trioxide leads to the fixation of -SO 3 H groups. The amounts of the fixed sulfonate groups depended on the reaction conditions. Evidence of grafting deduced from the measurements of hygroscopic properties was carried out by contact angle measurement, moisture regain as well as by measuring the rate of retention. SEM and FT-IR analysis, DSC and DTA/TGA thermograms showed that no significant modifications have occurred in the bulk of the treated PET fabrics.

  13. Ahead of his time: Jacob Lipman's 1930 estimate of atmospheric sulfur deposition for the conterminous United States

    Science.gov (United States)

    Landa, Edward R.; Shanley, James B.

    2015-01-01

    A 1936 New Jersey Agricultural Experiment Station Bulletin provided an early quantitative assessment of atmospheric deposition of sulfur for the United States that has been compared in this study with more recent assessments. In the early 20th century, anthropogenic sulfur additions from the atmosphere to the soil by the combustion of fossil fuels were viewed as part of the requisite nutrient supply of crops. Jacob G. Lipman, the founding editor of Soil Science, and his team at Rutgers University, made an inventory of such additions to soils of the conterminous United States during the economic depression of the 1930s as part of a federally funded project looking at nutrient balances in soils. Lipman's team gathered data compiled by the US Bureau of Mines on coal and other fuel consumption by state and calculated the corresponding amounts of sulfur emitted. Their work pioneered a method of assessment that became the norm in the 1970s to 1980s—when acid rain emerged as a national issue. Lipman's estimate of atmospheric sulfur deposition in the 1930 is in reasonable agreement with recent historic reconstructions.

  14. Thermodynamic Ground States of Complex Oxide Heterointerfaces

    DEFF Research Database (Denmark)

    Gunkel, F.; Hoffmann-Eifert, S.; Heinen, R. A.

    2017-01-01

    The formation mechanism of 2-dimensional electron gases (2DEGs) at heterointerfaces between nominally insulating oxides is addressed with a thermodynamical approach. We provide a comprehensive analysis of the thermodynamic ground states of various 2DEG systems directly probed in high temperature...

  15. Higher Americium Oxidation State Research Roadmap

    Energy Technology Data Exchange (ETDEWEB)

    Mincher, Bruce J. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Law, Jack D. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Goff, George S. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Moyer, Bruce A. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Burns, Jon D. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Lumetta, Gregg J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Sinkov, Sergey I. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Shehee, Thomas C. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Hobbs, David T. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2015-12-18

    The partitioning of hexavalent Am from dissolved nuclear fuel requires the ability to efficiently oxidize Am(III) to Am(VI) and to maintain that oxidation state for a length of time sufficient to perform the separation. Several oxidants have been, or are being developed. Chemical oxidants include Ag-catalyzed ozone, Ag-catalyzed peroxydisulfate, Cu(III) periodate, and sodium bismuthate. Hexavalent americium has also now successfully been prepared by electrolysis, using functionalized electrodes. So-called auto-reduction rates of Am(VI) are sufficiently slow to allow for separations. However, for separations based on solvent extraction or ion exchange using organic resins, the high valence state must be maintained under the reducing conditions of the organic phase contact, and a holding oxidant is probably necessary. Until now, only Cu(III) periodate and sodium bismuthate oxidation have been successfully combined with solvent extraction separations. Bismuthate oxidation provided the higher DAm, since it acts as its own holding oxidant, and a successful hot test using centrifugal contactors was performed. For the other oxidants, Ag-catalyzed peroxydisulfate will not oxidize americium in nitric acid concentrations above 0.3 M, and it is not being further investigated. Peroxydisulfate in the absence of Ag catalysis is being used to prepare Am(V) in ion exchange work, discussed below. Preliminary work with Ag-catalyzed ozone has been unsuccessful for extractions of Am(VI) from 6.5 M HNO3, and only one attempt at extraction, also from 6.5 M HNO3, using the electrolytic oxidation has been attempted. However, this high acid concentration was based on the highest Am extraction efficiency using the bismuthate oxidant; which is only sparingly soluble, and thus the oxidation yield is based on bismuthate solubility. Lower acid concentrations may be sufficient with alternative oxidants and work with Ag-ozone, Cu(III) and electrolysis is on-going. Two non

  16. Synthesis and Application of Iron Oxide/Silica Gel Nanocomposite for Removal of Sulfur Dyes from Aqueous Solutions

    Directory of Open Access Journals (Sweden)

    Naser Tavassoli

    2017-03-01

    Full Text Available Background & Aims of the Study: water pollution by synthetic organic dyes is mainly regarded as environmental and ecological critical issues worldwide. In this research, magnetite iron oxide/silica gel nanocomposite (termed as Fe3O4/SG was synthesized chemically and then used as an effective adsorbent for removal of sulfur dyes from aqueous solution. Materials and Methods: The various parameters such as pH, sorbent dosage, initial dye concentration, contact time and dye solution temperature were investigated in a batch system. The equilibrium data were analyzed by Langmuir and Freundlich isotherm models. Results: The experimental data fit well with pseudo-second-order kinetic model (R2≥0.998 and conformed better to Langmuir isotherm model (R2≥0.997. The maximum adsorption capacity for Fe3O4/SG obtained from the Langmuir model was 11.1mg/g. Evaluation of thermodynamic parameters proved that the adsorption process was normally feasible, spontaneous and exothermic. Conclusion: It can be concluded that the Fe3O4/SG can be considered as a cost-effective and an environmental friendly adsorbent for efficient removal of sulfur dyes from aqueous solutions.

  17. Chemiluminescence behavior based on oxidation reaction of rhodamine B with cerium(IV) in sulfuric acid medium

    Energy Technology Data Exchange (ETDEWEB)

    Ma Yongjun; Jin Xiaoyong; Zhou Min; Zhang Ziyu; Teng Xiulan; Chen Hui

    2003-08-18

    The chemiluminescence (CL) of the rhodamine B (RhB)-cerium(IV) system was investigated by flow-injection. Rhodamine B was suggested to be a suitable chemiluminescent reagent in acidic conditions. When the concentration of rhodamine B was 100 mg l{sup -1} and cerium sulfate was 1.6 mmol l{sup -1} in sulfuric acid, the chemiluminescent intensity was found to be highest by using 0.3 mol l{sup -1} sulfuric acid as a carrier solution. The particular chemiluminescent system could tolerate such distinct acidic environments that it was utilized for detecting many compounds that are stable in acidic solutions. Furthermore, by virtue of IR, UV-Vis and luminescence spectroscopic measurements, the chemiluminescent behavior of rhodamine B was studied and a possible mechanism for this chemiluminescent reaction was proposed. The emitter was affirmed to be a radical species due to one of the oxidation products of RhB; the chemiluminescent emissive wavelength was about 425 nm.

  18. Carbon deposition and sulfur poisoning during CO2 electrolysis in nickel-based solid oxide cell electrodes

    Science.gov (United States)

    Skafte, Theis Løye; Blennow, Peter; Hjelm, Johan; Graves, Christopher

    2018-01-01

    Reduction of CO2 to CO and O2 in the solid oxide electrolysis cell (SOEC) has the potential to play a crucial role in closing the CO2 loop. Carbon deposition in nickel-based cells is however fatal and must be considered during CO2 electrolysis. Here, the effect of operating parameters is investigated systematically using simple current-potential experiments. Due to variations of local conditions, it is shown that higher current density and lower fuel electrode porosity will cause local carbon formation at the electrochemical reaction sites despite operating with a CO outlet concentration outside the thermodynamic carbon formation region. Attempts at mitigating the issue by coating the composite nickel/yttria-stabilized zirconia electrode with carbon-inhibiting nanoparticles and by sulfur passivation proved unsuccessful. Increasing the fuel electrode porosity is shown to mitigate the problem, but only to a certain extent. This work shows that a typical SOEC stack converting CO2 to CO and O2 is limited to as little as 15-45% conversion due to risk of carbon formation. Furthermore, cells operated in CO2-electrolysis mode are poisoned by reactant gases containing ppb-levels of sulfur, in contrast to ppm-levels for operation in fuel cell mode.

  19. The Role of Oxidative Stress in Severity of Obstructive Pulmonary Complications in Sputum of Sulfur Mustard-Injured Patients

    Directory of Open Access Journals (Sweden)

    Javad Heydari

    2017-09-01

    Full Text Available Background: Sulfur mustard (SM is a strong bifunctional alkylating agent that causes delayed complications in organs such as lung. Oxidative stress plays a pivotal role in the pathogenesis and progression of many pulmonary diseases. The aim of this study was to investigate the oxidative stress in sputum of SM exposed patients with mild, moderate and severe pulmonary dysfunction and assessing their relationship with pulmonary function. Methods: In this cross–sectional study, oxidative stress biomarkers in sputum were examined on 26 patients with SM-induced bronchiolitis obliterans (9 mild, 14 moderate and 3 severe and 12 matched healthy controls referred to Baqiyatallah Hospital, Tehran between October 2015 and April 2016. Results: Sputum superoxide dismutase, catalase and glutathione S-transferase activities and malondialdehyde level in moderate and severe groups were significantly higher than in the control group (P=0.002, P=0.004, P=0.014 and P=0.009, respectively. Glutathione (GSH level in moderate (22.29%, P=0.025 and severe (45.07%, P=0.004 groups were significantly lower than the control. A decreased in GSH level in severe (41.7% groups was observed as compared with the mild group. Pearson analysis revealed strong correlations between disease severity and oxidative stress biomarkers in sputum of patients with moderate and severe injuries. Conclusions: Oxidative stress is involved in the pathogenesis of patients with moderate and severe pulmonary dysfunction following SM exposure. The presence of enhanced oxidative stress relates to the decline lung function and the progression of the disease. Sputum induction in SM-injured patients can be used to the assessment of the antioxidant status of bronchial secretions.

  20. Sulfur Earth

    Science.gov (United States)

    de Jong, B. H.

    2007-12-01

    Variations in surface tension affect the buoyancy of objects floating in a liquid. Thus an object floating in water will sink deeper in the presence of dishwater fluid. This is a very minor but measurable effect. It causes for instance ducks to drown in aqueous solutions with added surfactant. The surface tension of liquid iron is very strongly affected by the presence of sulfur which acts as a surfactant in this system varying between 1.9 and 0.4 N/m at 10 mass percent Sulfur (Lee & Morita (2002), This last value is inferred to be the maximum value for Sulfur inferred to be present in the liquid outer core. Venting of Sulfur from the liquid core manifests itself on the Earth surface by the 105 to 106 ton of sulfur vented into the atmosphere annually (Wedepohl, 1984). Inspection of surface Sulfur emission indicates that venting is non-homogeneously distributed over the Earth's surface. The implication of such large variation in surface tension in the liquid outer core are that at locally low Sulfur concentration, the liquid outer core does not wet the predominantly MgSiO3 matrix with which it is in contact. However at a local high in Sulfur, the liquid outer core wets this matrix which in the fluid state has a surface tension of 0.4 N/m (Bansal & Doremus, 1986), couples with it, and causes it to sink. This differential and diapiric movement is transmitted through the essentially brittle mantle (1024 Pa.s, Lambeck & Johnson, 1998; the maximum value for ice being about 1030 Pa.s at 0 K, in all likely hood representing an upper bound of viscosity for all materials) and manifests itself on the surface by the roughly 20 km differentiation, about 0.1 % of the total mantle thickness, between topographical heights and lows with concomitant lateral movement in the crust and upper mantle resulting in thin skin tectonics. The brittle nature of the medium though which this movement is transmitted suggests that the extremes in topography of the D" layer are similar in range to

  1. Carbon deposition and sulfur poisoning during CO2 electrolysis in nickel-based solid oxide cell electrodes

    DEFF Research Database (Denmark)

    Skafte, Theis Løye; Blennow, Peter; Hjelm, Johan

    2017-01-01

    is investigated systematically using simple current-potential experiments. Due to variations of local conditions, it is shown that higher current density and lower fuel electrode porosity will cause local carbon formation at the electrochemical reaction sites despite operating with a CO outlet concentration...... outside the thermodynamic carbon formation region. Attempts at mitigating the issue by coating the composite nickel/yttria-stabilized zirconia electrode with carbon-inhibiting nanoparticles and by sulfur passivation proved unsuccessful. Increasing the fuel electrode porosity is shown to mitigate......Reduction of CO2 to CO and O2 in the solid oxide electrolysis cell (SOEC) has the potential to play a crucial role in closing the CO2 loop. Carbon deposition in nickel-based cells is however fatal and must be considered during CO2 electrolysis. Here, the effect of operating parameters...

  2. Partial genome sequence of Thioalkalivibrio thiocyanodenitrificans ARhD 1T, a chemolithoautotrophic haloalkaliphilic sulfur-oxidizing bacterium capable of complete denitrification

    NARCIS (Netherlands)

    Berben, T.; Sorokin, D.Y.; Ivanova, N.; Pati, A.; Kyrpides, N.; Goodwin, L.A; Woyke, T.; Muyzer, G.

    2015-01-01

    Thioalkalivibrio thiocyanodenitrificans strain ARhD 1 T is a motile, Gram-negative bacterium isolated from soda lakes that belongs to the Gammaproteobacteria. It derives energy for growth and carbon fixation from the oxidation of sulfur compounds, most notably thiocyanate, and so is a

  3. EFFECTS OF ALKALINE SANDY LOAM ON SULFURIC SOIL ACIDITY AND SULFIDIC SOIL OXIDATION

    Directory of Open Access Journals (Sweden)

    Patrick S. Michael

    2015-08-01

    Full Text Available  In poor soils, addition of alkaline sandy loam containing an adequate proportion of sand, silt and clay would add value by improving the texture, structure and organic matter (OM for general use of the soils. In acid sulfate soils (ASS, addition of alkaline sandy would improve the texture and leach out salts as well as add a sufficient proportion of OM for vegetation establishment. In this study, addition of alkaline sandy loam into sulfuric soil effectively increased the pH, lowered the redox and reduced the sulfate content, the magnitude of the effects dependent on moisture content. Addition of alkaline sandy loam in combination with OM was highly effective than the effects of the lone alkaline sandy loam. When alkaline sandy was added alone or in combination with OM into sulfidic soil, the effects on pH and the redox were similar as in the sulfuric soil but the effect on sulfate content was variable. The effects under aerobic conditions were higher than under anaerobic conditions. The findings of this study have important implications for the general management of ASS where lime availability is a concern and its application is limited.International Journal of Environment Volume-4, Issue-3, June-August 2015Page: 42-54

  4. Lithiated Nafion as polymer electrolyte for solid-state lithium sulfur batteries using carbon-sulfur composite cathode

    Science.gov (United States)

    Gao, Jing; Sun, Chunshui; Xu, Lei; Chen, Jian; Wang, Chong; Guo, Decai; Chen, Hao

    2018-04-01

    Due to flexible property and light weight, the lithiated Nafion membrane swollen with PC (PC-Li-Nafion) has been employed as both solid-state electrolyte and separator to fabricate solid-state Li-S cells. The electrochemical measurements of PC-Li-Nafion membrane show that its Li-ion transference number is 0.928, ionic conductivity of 2.1 × 10-4 S cm-1 can be achieved at 70 °C and its electrochemical window is 0 ∼ +4.1 V vs. Li+/Li. It is observed that the Li dendrites are suppressed by using PC-Li-Nafion membrane due to its single-ion conducting property. The amounts of Li-Nafion resin binder and conductive carbon in the cathode are optimized as 40% and 10% respectively to make a balance of ionic and electronic conductivities. A thin-layer Li-Nafion resin with a thickness of around 2 μm is fabricated between the cathode and PC-Li-Nafion membrane to improve the interfacial contact and further enhance the specific capacity of the cell. When measured at 70 °C, the Li-S cell delivers a reversible specific capacity of 1072.8 mAh g-1 (S) at 0.05 C and 895 mAh g-1 (S) at 1 C. The capacity retention at 1 C is 89% after 100 cycles. These results suggest that high-performance solid-state Li-S cells can be fabricated with the Li-Nafion polymer electrolyte.

  5. Enhancing Sulfur Tolerance of Ni-Based Cermet Anodes of Solid Oxide Fuel Cells by Ytterbium-Doped Barium Cerate Infiltration.

    Science.gov (United States)

    Li, Meng; Hua, Bin; Luo, Jing-Li; Jiang, San Ping; Pu, Jian; Chi, Bo; Li, Jian

    2016-04-27

    Conventional anode materials for solid oxide fuel cells (SOFCs) are Ni-based cermets, which are highly susceptible to deactivation by contaminants in hydrocarbon fuels. Hydrogen sulfide is one of the commonly existed contaminants in readily available natural gas and gasification product gases of pyrolysis of biomasses. Development of sulfur tolerant anode materials is thus one of the critical challenges for commercial viability and practical application of SOFC technologies. Here we report a viable approach to enhance substantially the sulfur poisoning resistance of a Ni-gadolinia-doped ceria (Ni-GDC) anode through impregnation of proton conducting perovskite BaCe0.9Yb0.1O3-δ (BCYb). The impregnation of BCYb nanoparticles improves the electrochemical performance of the Ni-GDC anode in both H2 and H2S containing fuels. Moreover, more importantly, the enhanced stability is observed in 500 ppm of H2S/H2. The SEM and XPS analysis indicate that the infiltrated BCYb fine particles inhibit the adsorption of sulfur and facilitate sulfur removal from active sites, thus preventing the detrimental interaction between sulfur and Ni-GDC and the formation of cerium sulfide. The preliminary results of the cell with the BCYb+Ni-GDC anode in methane fuel containing 5000 ppm of H2S show the promising potential of the BCYb infiltration approach in the development of highly active and stable Ni-GDC-based anodes fed with hydrocarbon fuels containing a high concentration of sulfur compounds.

  6. Sulfur poisoning of Ni/Gadolinium-doped ceria anodes: A long-term study outlining stable solid oxide fuel cell operation

    Science.gov (United States)

    Riegraf, Matthias; Zekri, Atef; Knipper, Martin; Costa, Rémi; Schiller, Günter; Friedrich, K. Andreas

    2018-03-01

    This work presents an analysis of the long-term behavior of nickel/gadolinium-doped ceria (CGO) anode-based solid oxide fuel cells (SOFC) under sulfur poisoning conditions. A parameter study of sulfur-induced irreversible long-term degradation of commercial, high-performance single cells was carried out at 900 °C for different H2/N2/H2S fuel gas atmospheres, current densities and Ni/CGO anodes. The poisoning periods of the cells varied from 200 to 1500 h. The possibility of stable long-term Ni/CGO anode operation under sulfur exposure is established and the critical operating regime is outlined. Depending on the operating conditions, two degradation phenomena can be observed. Small degradation of the ohmic resistance was witnessed for sulfur exposure times of approximately 1000 h. Moreover, degradation of the anode charge transfer resistance was observed to be triggered by the combination of a small anodic potential step and high sulfur coverage on Ni. The microstructural evolution of altered Ni/CGO anodes was examined post-mortem by means of SEM and FIB/SEM, and is correlated to the anode performance degradation under critical operating conditions, establishing Ni depletion, porosity increase and a tripe phase boundary density decrease in the anode functional layer. It is shown that short-term sulfur poisoning behavior can be used to assess long-term stability.

  7. A case study of the relative effects of power plant nitrogen oxides and sulfur dioxide emission reductions on atmospheric nitrogen deposition.

    Science.gov (United States)

    Vijayaraghavan, Krish; Seigneur, Christian; Bronson, Rochelle; Chen, Shu-Yun; Karamchandani, Prakash; Walters, Justin T; Jansen, John J; Brandmeyer, Jo Ellen; Knipping, Eladio M

    2010-03-01

    The contrasting effects of point source nitrogen oxides (NOx) and sulfur dioxide (SO2) air emission reductions on regional atmospheric nitrogen deposition are analyzed for the case study of a coal-fired power plant in the southeastern United States. The effect of potential emission reductions at the plant on nitrogen deposition to Escambia Bay and its watershed on the Florida-Alabama border is simulated using the three-dimensional Eulerian Community Multiscale Air Quality (CMAQ) model. A method to quantify the relative and individual effects of NOx versus SO2 controls on nitrogen deposition using air quality modeling results obtained from the simultaneous application of NOx and SO2 emission controls is presented and discussed using the results from CMAQ simulations conducted with NOx-only and SO2-only emission reductions; the method applies only to cases in which ambient inorganic nitrate is present mostly in the gas phase; that is, in the form of gaseous nitric acid (HNO3). In such instances, the individual effects of NOx and SO2 controls on nitrogen deposition can be approximated by the effects of combined NOx + SO2 controls on the deposition of NOy, (the sum of oxidized nitrogen species) and reduced nitrogen species (NHx), respectively. The benefit of controls at the plant in terms of the decrease in nitrogen deposition to Escambia Bay and watershed is less than 6% of the overall benefit due to regional Clean Air Interstate Rule (CAIR) controls.

  8. An oxidative desulfurization method using ultrasound/Fenton's reagent for obtaining low and/or ultra-low sulfur diesel fuel

    Energy Technology Data Exchange (ETDEWEB)

    Dai, Yongchuan; Qi, Yutai [Department of Applied Chemistry, School of Science, Harbin Institute of Technology, Harbin 115001 (China); Zhao, Dezhi [Department of Petroleum Chemical Engineering, Liaoning Shihua University, Fushun 113001 (China); Zhang, Huicheng [Fushun Research Institute of Petroleum and Petrochemicals of SINOPEC Corp., Fushun 113001 (China)

    2008-10-15

    The total development trend in the world is towards continuously lower of sulfur content as a quality standard of diesel fuels. Integrating of an oxidative desulfurization unit with a conventional hydrotreating unit can bring benefits to producing low and/or ultra-low sulfur diesel fuels. Using the hydrotreated Middle East diesel fuel as a feedstock, four processes of the oxidative desulfurization have been studied: a hydrogen peroxide-acetic acid system and a Fenton's reagent system both without/with ultrasound. Results showed that the oxidative desulfurization reaction mechanics fitted apparent first-order kinetics. The addition of Fenton's reagent could enhance the oxidative desulfurization efficiency for diesel fuels and sono-oxidation treatment in combination with Fenton's reagent shows a good synergistic effect. Under our best operating condition for the oxidative desulfurization: temperature 313 K, ultrasonic power 200 W, ultrasonic frequency 28 kHz, Fe{sup 2+}/H{sub 2}O{sub 2} 0.05 mol/mol, pH 2.10 in aqueous phase and reaction time 15 min, the sulfur content in the diesel fuels was decreased from 568.75 {mu}g/g to 9.50 {mu}g/g. (author)

  9. Evidences of oxidative stress during hydrogen photoproduction in sulfur-deprived cultures of Chlamydomonas reinhardtii

    Czech Academy of Sciences Publication Activity Database

    Sáens, M. E.; Bišová, Kateřina; Touloupakis, E.; Faraloni, C.; Dario Di Marzio, W.; Torzillo, G.

    2015-01-01

    Roč. 40, č. 30 (2015), s. 10410-10417 ISSN 0360-3199 Institutional support: RVO:61388971 Keywords : Oxidative stress * Chlamydomonas reinhardtii * H-2 production Subject RIV: EE - Microbiology, Virology Impact factor: 3.205, year: 2015

  10. Genomic analysis reveals versatile heterotrophic capacity of a potentially symbiotic sulfur-oxidizing bacterium in sponge

    KAUST Repository

    Tian, Renmao; Wang, Yong; Bougouffa, Salim; Gao, Zhaoming; Cai, Lin; Bajic, Vladimir B.; Qian, Peiyuan

    2014-01-01

    coevolved with the ancient host during establishment of their association. Exclusive distribution in sponge, bacterial detoxification for the host (sulfide oxidation) and the enrichment for symbiotic characteristics (genes-encoding ankyrin) in the SOB genome

  11. Oxidation of alginate and pectate biopolymers by cerium(IV) in perchloric and sulfuric acid solutions: A comparative kinetic and mechanistic study.

    Science.gov (United States)

    Fawzy, Ahmed

    2016-03-15

    The kinetics of oxidation of alginate (Alg) and pectate (Pec) carbohydrate biopolymers was studied by spectrophotometry in aqueous perchloric and sulfuric acid solutions at fixed ionic strengths and temperature. In both acids, the reactions showed a first order dependence on [Ce(IV)], whereas the orders with respect to biopolymer concentrations are less than unity. In perchloric acid, the reactions exhibited less than unit orders with respect to [H(+)] whereas those proceeded in sulfuric acid showed negative fractional-first order dependences on [H(+)]. The effect of ionic strength and dielectric constant was studied. Probable mechanistic schemes for oxidation reactions were proposed. In both acids, the final oxidation products were characterized as mono-keto derivatives of both biopolymers. The activation parameters with respect to the slow step of the mechanisms were computed and discussed. The rate laws were derived and the reaction constants involved in the different steps of the mechanisms were calculated. Copyright © 2015 Elsevier Ltd. All rights reserved.

  12. Simultaneous removal of nitrogen oxide/nitrogen dioxide/sulfur dioxide from gas streams by combined plasma scrubbing technology.

    Science.gov (United States)

    Chang, Moo Been; Lee, How Ming; Wu, Feeling; Lai, Chi Ren

    2004-08-01

    Oxides of nitrogen (NOx) [nitrogen oxide (NO) + nitrogen dioxide (NO2)] and sulfur dioxide (SO2) are removed individually in traditional air pollution control technologies. This study proposes a combined plasma scrubbing (CPS) system for simultaneous removal of SO2 and NOx. CPS consists of a dielectric barrier discharge (DBD) and wet scrubbing in series. DBD is used to generate nonthermal plasmas for converting NO to NO2. The water-soluble NO2 then can be removed by wet scrubbing accompanied with SO2 removal. In this work, CPS was tested with simulated exhausts in the laboratory and with diesel-generator exhausts in the field. Experimental results indicate that DBD is very efficient in converting NO to NO2. More than 90% removal of NO, NOx, and SO2 can be simultaneously achieved with CPS. Both sodium sulfide (Na2S) and sodium sulfite (Na2SO3) scrubbing solutions are good for NO2 and SO2 absorption. Energy efficiencies for NOx and SO2 removal are 17 and 18 g/kWh, respectively. The technical feasibility of CPS for simultaneous removal of NO, NO2, and SO2 from gas streams is successfully demonstrated in this study. However, production of carbon monoxide as a side-product (approximately 100 ppm) is found and should be considered.

  13. Corrosion by concentrated sulfuric acid in carbon steel pipes and tanks: state of the art

    Energy Technology Data Exchange (ETDEWEB)

    Panossian, Zehbour; Almeida, Neusvaldo Lira de; Sousa, Raquel Maria Ferreira de [Instituto de Pesquisas Tecnologicas (IPT), Sao Paulo, SP (Brazil); Pimenta, Gutemberg de Souza [PETROBRAS S.A., Rio de Janeiro, RJ (Brazil). Centro de Pesquisas e Desenvolvimento (CENPES); Marques, Leandro Bordalo Schmidt [PETROBRAS Engenharia, Rio de Janeiro, RJ (Brazil)

    2009-07-01

    PETROBRAS, allied to the policy of reduction of emission of pollutants, has been adjusting the processes of the new refineries to obtain products with lower sulfur content. Thus, the sulfur dioxide, extracted from the process gases of a new refinery to be built in the Northeast, will be used to produce sulfuric acid with concentration between (94-96) %. This acid will be stored in carbon steel tanks and transported through a buried 8-km carbon steel pipe from the refinery to a pier, where it will be loaded onto ships and sent to the consumer markets. Therefore, the corrosion resistance of carbon steel by concentrated acid will become a great concern for the mentioned storage and transportation. When the carbon steel comes into contact with concentrated sulfuric acid, there is an immediate acid attack with the formation of hydrogen gas and ferrous ions which, in turn, forms a protective layer of FeSO{sub 4} on the metallic surface. The durability of the tanks and pipes made of carbon steel will depend on the preservation of this protective layer. This work presents a review of the carbon steel corrosion in concentrated sulfuric acid and discusses the preventive methods against this corrosion, including anodic protection. (author)

  14. The coordination of sulfur in synthetic and biogenic Mg calcites: The red coral case

    Science.gov (United States)

    Perrin, J.; Rivard, C.; Vielzeuf, D.; Laporte, D.; Fonquernie, C.; Ricolleau, A.; Cotte, M.; Floquet, N.

    2017-01-01

    Sulfur has been recognized in biogenic calcites for a long time. However, its structural position is matter of debate. For some authors, sulfur is a marker of the organic matrix while it is part of the calcite structure itself for others. To better understand the place of sulfur in calcite, sulfated magnesian calcites (S-MgCalcite) have been synthetized at high pressure and temperature and studied by μ-XANES spectroscopy. S-MgCalcite XANES spectra show two different types of sulfur: sulfate (SO42-) as a predominant species and a small contribution of sulfite (SO32-), both substituting for carbonate ions in the calcite structure. To address the question of the position of sulfur in biogenic calcites, the oxidation states of sulfur in the skeleton and organic tissues of Corallium rubrum have been investigated by micro X-ray fluorescence (μ-XRF) and sulfur K-edge micro X-ray absorption near edge structure (μ-XANES) spectroscopy at the European Synchrotron Radiation Facility (ESRF, Grenoble, France) on beamline ID21. In the skeleton, sulfur is mainly present as oxidized sulfur SO42- (+VI), plus a weak sulfite contribution. XANES spectra indicate that sulfur is inorganically incorporated as sulfur structurally substituted to carbonate ions (SSS). Although an organic matrix is present in the red coral skeleton, reduced organic sulfur could not be detected by μ-XANES spectroscopy in the skeleton probably due to low organic/inorganic sulfur ratio. In the organic tissues surrounding the skeleton, several sulfur oxidation states have been detected including disulfide (S-S), thioether (R-S-CH3), sulfoxide (SO2), sulfonate (SO2O-) and sulfate (SO42-). The unexpected occurrence of inorganic sulfate within the organic tissues suggests the presence of pre-organized organic/inorganic complexes in the circulatory system of the red coral, precursors to biomineralization ahead of the growth front.

  15. A kinetic and mechanistic study on the oxidation of l-methionine and N-acetyl l-methionine by cerium(IV) in sulfuric acid medium

    OpenAIRE

    T. Sumathi; P. Shanmugasundaram; G. Chandramohan

    2016-01-01

    The kinetics of oxidation of l-methionine and N-acetyl l-methionine by Ce(IV) in sulfuric acid–sulfate media in the range of 288.1–298.1 K has been investigated. The major oxidation products of methionine and N-acetyl l-methionine have been identified as methionine sulfoxide and N-acetyl methionine sulfoxide. The major oxidation products have been confirmed by qualitative analysis and boiling point. The reaction was first order with respect to l-methionine, N-acetyl l-methionine and Ce(IV). I...

  16. Method of making sulfur tolerant composite cermet electrodes for solid oxide electrochemical cells

    Science.gov (United States)

    Isenberg, Arnold O.

    1989-01-01

    An electrochemical apparatus is made containing an exterior electorde bonded to the exterior of a tubular, solid, oxygen ion conducting electrolyte where the electrolyte is also in contact with an interior electrode, said exterior electrode comprising particles of an electronic conductor contacting the electrolyte, where a ceramic metal oxide coating partially surrounds the particles and is bonded to the electrolyte, and where a coating of an ionic-electronic conductive material is attached to the ceramic metal oxide coating and to the exposed portions of the particles.

  17. Sources of carbon and sulfur nutrition for consumers in three meromictic lakes of New York State

    International Nuclear Information System (INIS)

    Fry, B.

    1986-01-01

    The trophic importance of bacterioplankton as a source of carbon and sulfur nutrition for consumers in meromictic lakes was tested using stable carbon (delta 13 C) and sulfur (delta 34 S) isotopic measurements. Studies in three lakes near Syracuse, New York, showed that most consumers ultimately derive their C and S nutrition from a mixture of terrestrial detritus, phytoplankton, and littoral vegetation, rather than from bacterioplankton. Food webs in these meromictic lakes are thus similar to those in other lakes that lack dense populations of bacterioplankton

  18. Electrochemical evaluation of sulfur poisoning in a methane-fuelled solid oxide fuel cell: Effect of current density and sulfur concentration

    DEFF Research Database (Denmark)

    Hagen, Anke; Johnson, Gregory B.; Hjalmarsson, Per

    2014-01-01

    , the effect of sulfur was less pronounced on mass transfer/fuel reforming processes but quite significant on the charge transfer/TPB processes. Overall, sulfur related performance loss was more severe at the highest current density (1 A cm−2), due to the deactivation of catalytic fuel reforming reactions......A Ni/ScYSZ based SOFC was tested at 1, 0.5, 0.25, and 0 (OCV) A cm−2 in methane fuel containing 0–100 ppm H2S. Analysis of cell voltage loss during short-term H2S poisoning showed that SOFC performance loss was generally larger at higher current loads. Separating the effect of H2S on catalytic...... reforming and electrochemical activity by evaluating the relevant area specific resistances and charge transfer processes based on impedance spectroscopy revealed that the poisoning of electrochemical activity was not dependent on current density. Two major anode processes were significantly affected...

  19. Keep your Sox on: Community genomics-directed isolation and microscopic characterization of the dominant subsurface sulfur-oxidizing bacterium in a sediment aquifer

    Science.gov (United States)

    Mullin, S. W.; Wrighton, K. C.; Luef, B.; Wilkins, M. J.; Handley, K. M.; Williams, K. H.; Banfield, J. F.

    2012-12-01

    Community genomics and proteomics (proteogenomics) can be used to predict the metabolic potential of complex microbial communities and provide insight into microbial activity and nutrient cycling in situ. Inferences regarding the physiology of specific organisms then can guide isolation efforts, which, if successful, can yield strains that can be metabolically and structurally characterized to further test metagenomic predictions. Here we used proteogenomic data from an acetate-stimulated, sulfidic sediment column deployed in a groundwater well in Rifle, CO to direct laboratory amendment experiments to isolate a bacterial strain potentially involved in sulfur oxidation for physiological and microscopic characterization (Handley et al, submitted 2012). Field strains of Sulfurovum (genome r9c2) were predicted to be capable of CO2 fixation via the reverse TCA cycle and sulfur oxidation (Sox and SQR) coupled to either nitrate reduction (Nap, Nir, Nos) in anaerobic environments or oxygen reduction in microaerobic (cbb3 and bd oxidases) environments; however, key genes for sulfur oxidation (soxXAB) were not identified. Sulfidic groundwater and sediment from the Rifle site were used to inoculate cultures that contained various sulfur species, with and without nitrate and oxygen. We isolated a bacterium, Sulfurovum sp. OBA, whose 16S rRNA gene shares 99.8 % identity to the gene of the dominant genomically characterized strain (genome r9c2) in the Rifle sediment column. The 16S rRNA gene of the isolate most closely matches (95 % sequence identity) the gene of Sulfurovum sp. NBC37-1, a genome-sequenced deep-sea sulfur oxidizer. Strain OBA grew via polysulfide, colloidal sulfur, and tetrathionate oxidation coupled to nitrate reduction under autotrophic and mixotrophic conditions. Strain OBA also grew heterotrophically, oxidizing glucose, fructose, mannose, and maltose with nitrate as an electron acceptor. Over the range of oxygen concentrations tested, strain OBA was not

  20. Geochemical mass balance for sulfur- and nitrogen-bearing acid components: Eastern United States

    International Nuclear Information System (INIS)

    Bischoff, W.D.; Mackenzie, F.T.; Paterson, V.L.

    1984-01-01

    The impact on a geographical region of SO 2 and nitrogen oxides (NO /SUB x/ ) emissions to the atmosphere because of man's activities (e.g., burning of fossil fuels and smelting of sulfide ores) usually has not been considered in terms of a regional geochemical mass balance model. Mass balance models, however, have been employed extensively on a global scale. The models evaluate reservoir sizes, processes and fluxes associated with the transfer of a substance within a system of interest. The models may be steady- or transient-state, and include assessment of historical (geologic), present and future data and processes. In this chapter a geochemical mass balance model is applied to constituents of acid precipitation (H + , NO - 3 and SO 2- ) to evaluate the impact of acid precipitation on the eastern United States

  1. Release of dissolved cadmium and sulfur nanoparticles from oxidizing sulfide minerals

    Science.gov (United States)

    Cadmium enrichment (relative to Fe and Zn) in paddy rice grain occurs during the pre-harvest drainage of flooded soil, which causes oxidative dissolution of sulfide minerals present in reduced soil. We investigated this process over a range of environmentally realistic Cdcontain...

  2. Galvanic detection of sulfur dioxide in ambient air at trace levels by anodic oxidation

    NARCIS (Netherlands)

    Lindqvist, F.

    1978-01-01

    A continuous method for the measurement of SO2 in ambient air at trace levels is described. The principle of detection is based on the anodic oxidation of SO2 in a galvanic cell. A differential measuring technique with a cell with two anodes and one cathode is used; background and noise current are

  3. A method for nitric oxide radical scavenging properties of sulfur containing compounds.

    NARCIS (Netherlands)

    Vriesman, M.F.; Haenen, G.R.M.M.; Westerveld, G.J.; Paquay, J.B.G.; Voss, H.P.; Bast, A.

    1997-01-01

    A new method for the quantification of the nitric oxide (NO) scavenging activity of compounds in aqueous solutions is described using an amperometric NO sensor. After correction for the spontaneous degradation of NO, second-order rate kinetics of the scavenging reaction are observed.

  4. The role of support and promoter on the oxidation of sulfur dioxide using platinum based catalysts

    DEFF Research Database (Denmark)

    Koutsopoulos, Sotiris; Rasmussen, Søren Birk; Eriksen, Kim Michael

    2006-01-01

    The catalytic oxidation of SO2 to SO3 was studied over platinum based catalysts in the absence and the presence of dopants. The active metal was supported on silica gel or titania (anatase) by impregnation. The activities of the silica supported catalysts were found to follow the order PtRh/SiO2 ...

  5. Sulfur Poisoning of the Water Gas Shift Reaction on Anode Supported Solid Oxide Fuel Cells

    DEFF Research Database (Denmark)

    Hagen, Anke

    2013-01-01

    resistance increased both in the high and low frequency region, which indicates a strong poisoning of the water gas shift reaction and thus a lack of hydrogen fuel in addition to the poisoning of the electrochemical hydrogen oxidation. All poisoning effects are reversible under the applied operating...

  6. Kinetics and mechanism of heterogeneous oxidation of sulfur dioxide by ozone on surface of calcium carbonate

    Directory of Open Access Journals (Sweden)

    L. Li

    2006-01-01

    Full Text Available Sulfate particles play a key role in the air quality and the global climate, but the heterogeneous formation mechanism of sulfates on surfaces of atmospheric particles is not well established. Carbonates, which act as a reactive component in mineral dust due to their special chemical properties, may contribute significantly to the sulfate formation by heterogeneous processes. This paper presents a study on the oxidation of SO2 by O3 on CaCO3 particles. Using Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS, the formation of sulfite and sulfate on the surface was identified, and the roles of O3 and water in oxidation processes were determined. The results showed that in the presence of O3, SO2can be oxidized to sulfate on the surface of CaCO3 particles. The reaction is first order in SO2 and zero order in O3. The reactive uptake coefficient for SO2 [(0.6–9.8×1014 molecule cm-3] oxidation by O3 [(1.2–12×1014 molecule cm-3] was determined to be (1.4±0.3×10-7 using the BET area as the reactive area and (7.7±1.6×10-4 using the geometric area. A two-stage mechanism that involves adsorption of SO2 followed by O3 oxidation is proposed and the adsorption of SO2 on the CaCO3 surface is the rate-determining step. The proposed mechanism can well explain the experiment results. The atmospheric implications were explored based on a box model calculation. It was found that the heterogeneous reaction might be an important pathway for sulfate formation in the atmosphere.

  7. Reaction Mechanism for m- Xylene Oxidation in the Claus Process by Sulfur Dioxide

    KAUST Repository

    Sinha, Sourab

    2015-09-24

    In the Claus process, the presence of aromatic contaminants such benzene, toluene, and xylenes (BTX), in the H2S feed stream has a detrimental effect on catalytic reactors, where BTX form soot particles and clog and deactivate the catalysts. Among BTX, xylenes are proven to be most damaging contaminant for catalysts. BTX oxidation in the Claus furnace, before they enter catalyst beds, provides a solution to this problem. A reaction kinetics study on m-xylene oxidation by SO2, an oxidant present in Claus furnace, is presented. The density functional theory is used to study the formation of m-xylene radicals (3-methylbenzyl, 2,6-dimethylphenyl, 2,4-dimethylphenyl, and 3,5-dimethylphenyl) through H-abstraction and their oxidation by SO2. The mechanism begins with SO2 addition on the radicals through an O-atom rather than the S-atom with the release of 180.0-183.1 kJ/mol of reaction energies. This exothermic reaction involves energy barriers in the range 3.9-5.2 kJ/mol for several m-xylene radicals. Thereafter, O-S bond scission takes place to release SO, and the O-atom remaining on aromatics leads to CO formation. Among four m-xylene radicals, the resonantly stabilized 3-methylbenzyl exhibited the lowest SO2 addition and SO elimination rates. The reaction rate constants are provided to facilitate Claus process simulations to find conditions suitable for BTX oxidation. © 2015 American Chemical Society.

  8. Reaction Mechanism for m- Xylene Oxidation in the Claus Process by Sulfur Dioxide

    KAUST Repository

    Sinha, Sourab; Raj, Abhijeet; Al Shoaibi, Ahmed S.; Chung, Suk-Ho

    2015-01-01

    In the Claus process, the presence of aromatic contaminants such benzene, toluene, and xylenes (BTX), in the H2S feed stream has a detrimental effect on catalytic reactors, where BTX form soot particles and clog and deactivate the catalysts. Among BTX, xylenes are proven to be most damaging contaminant for catalysts. BTX oxidation in the Claus furnace, before they enter catalyst beds, provides a solution to this problem. A reaction kinetics study on m-xylene oxidation by SO2, an oxidant present in Claus furnace, is presented. The density functional theory is used to study the formation of m-xylene radicals (3-methylbenzyl, 2,6-dimethylphenyl, 2,4-dimethylphenyl, and 3,5-dimethylphenyl) through H-abstraction and their oxidation by SO2. The mechanism begins with SO2 addition on the radicals through an O-atom rather than the S-atom with the release of 180.0-183.1 kJ/mol of reaction energies. This exothermic reaction involves energy barriers in the range 3.9-5.2 kJ/mol for several m-xylene radicals. Thereafter, O-S bond scission takes place to release SO, and the O-atom remaining on aromatics leads to CO formation. Among four m-xylene radicals, the resonantly stabilized 3-methylbenzyl exhibited the lowest SO2 addition and SO elimination rates. The reaction rate constants are provided to facilitate Claus process simulations to find conditions suitable for BTX oxidation. © 2015 American Chemical Society.

  9. Photochemical oxidants: state of the science.

    Science.gov (United States)

    Kley, D; Kleinmann, M; Sanderman, H; Krupa, S

    1999-01-01

    Atmospheric photochemical processes resulting in the production of tropospheric ozone (O(3)) and other oxidants are described. The spatial and temporal variabilities in the occurrence of surface level oxidants and their relationships to air pollution meteorology are discussed. Models of photooxidant formation are reviewed in the context of control strategies and comparisons are provided of the air concentrations of O(3) at select geographic locations around the world. This overall oxidant (O(3)) climatology is coupled to human health and ecological effects. The discussion of the effects includes both acute and chronic responses, mechanisms of action, human epidemiological and plant population studies and briefly, efforts to establish cause-effect relationships through numerical modeling. A short synopsis is provided of the interactive effects of O(3) with other abiotic and biotic factors. The overall emphasis of the paper is on identifying the current uncertainties and gaps in our understanding of the state of the science and some suggestions as to how they may be addressed.

  10. Plutonium disproportionation. Hydrolysis and local oxidation-state maxima

    International Nuclear Information System (INIS)

    Silver, G.L.

    2014-01-01

    Local maxima in the fractions of the trivalent and hexavalent oxidation states are inherent in the algebra of Pu disproportionation reactions. A new method predicts the pH and the oxidation-state fractions at maximum. Tabulated results illustrate the effects of the Pu oxidation number and Pu(IV) hydrolysis on the maxima. This method suggests a new laboratory approach for discovering Pu oxidation-state maxima. (author)

  11. Radiation-chemical removal of exhaust gases of thermal power stations from nitrogen and sulfur oxides

    International Nuclear Information System (INIS)

    Gerasimov, G.Ya.; Gerasimova, T.S.; Tokmacheva, I.P.; Fadeev, S.A.; Faminskaya, M.V.

    1991-01-01

    Problem related to numerical simulation of kinetic processes occuring in waste flue gases of heat and power plants when they are treated by fast electrons are considered. The system of gas-phase chemical reactions describing kinetics of NO transformation in the presence of ammonia was studied. Different groups of reactions resulting in SO 2 oxidation were analyzed. Results of the calculations are compared with experimental data

  12. European scale modeling of sulfur, oxidized nitrogen and photochemical oxidants. Model development and evaluation for the 1994 growing season

    Energy Technology Data Exchange (ETDEWEB)

    Langner, J.; Bergstroem, R. [Swedish Meteorological and Hydrological Inst., Norrkoeping (Sweden); Pleijel, K. [Swedish Environmental Research Inst., Goeteborg (Sweden)

    1998-09-01

    A chemical mechanism, including the relevant reactions leading to the production of ozone and other photochemical oxidants, has been implemented in the MATCH regional tracer transport/chemistry/deposition model. The aim has been to develop a model platform that can be used as a basis for a range of regional scale studies involving atmospheric chemistry, including assessment of the importance of different sources of pollutants to the levels of photochemical oxidants and air pollutant forecasting. Meteorological input data to the model were taken from archived output from the operational version of HIRLAM at SMHI. Evaluation of model calculations over Europe for a six month period in 1994 for a range of chemical components show good results considering known sources of error and uncertainties in input data and model formulation. With limited further work the system is sufficiently good to be applied for scenario studies and for regional scale air pollutant forecasts 42 refs, 24 figs, 17 tabs

  13. Repeatedly evolved host-specific ectosymbioses between sulfur-oxidizing bacteria and amphipods living in a cave ecosystem.

    Directory of Open Access Journals (Sweden)

    Jan Bauermeister

    Full Text Available Ectosymbioses between invertebrates and sulfur-oxidizing bacteria are widespread in sulfidic marine environments and have evolved independently in several invertebrate phyla. The first example from a freshwater habitat, involving Niphargus ictus amphipods and filamentous Thiothrix ectosymbionts, was recently reported from the sulfide-rich Frasassi caves in Italy. Subsequently, two new Niphargus species, N. frasassianus and N. montanarius, were discovered within Frasassi and found to co-occur with N. ictus. Using a variety of microscopic and molecular techniques, we found that all three Frasassi-dwelling Niphargus species harbor Thiothrix ectosymbionts, which belong to three distinct phylogenetic clades (named T1, T2, and T3. T1 and T3 Thiothrix dominate the N. frasassianus ectosymbiont community, whereas T2 and T3 are prevalent on N. ictus and N. montanarius. Relative distribution patterns of the three ectosymbionts are host species-specific and consistent over different sampling locations and collection years. Free-living counterparts of T1-T3 are rare or absent in Frasassi cave microbial mats, suggesting that ectosymbiont transmission among Niphargus occurs primarily through inter- or intraspecific inoculations. Phylogenetic analyses indicate that the Niphargus-Thiothrix association has evolved independently at least two times. While ectosymbioses with T1 and T2 may have been established within Frasassi, T3 ectosymbionts seem to have been introduced to the cave system by Niphargus.

  14. Oxidation of sulfur (IV by oxygen in aqueous solution: role of some metal ions

    Directory of Open Access Journals (Sweden)

    Martins Claudia R.

    1999-01-01

    Full Text Available Catalytic effect of metal ions: Cr(VI, Cr(III, Cd(II, V(V and chloride anion, on the oxidation of S(IV in aqueous solution, at concentrations of metal ions and S(IV usually found in urban atmospheres, were studied under controlled experimental conditions (pH (2.1 - 4,5, T (25.0 - 35.0 °C, air flow rate, concentration of reactants, etc.... The kinetic constant determined at 25.0 °C and pH range (2.1 - 4.5, using ultra pure water was 8.0 ± 0.5 x 10-4 s-1. This value was considered as a reference for the oxidation reaction rate. The kinetic constants determined in the presence of Cr(VI revealed that the oxidation reaction of S(IV is quite influenced by the acidity. At pH = 2.1 (K = 2.3 x 10-2 mg-1 L s-1 the reaction is carried out with a rate five times greater when compared to pH = 2.6 (K = 4.3 x 10-3 mg-1 L s-1 and thirty times greater when compared to pH = 3.4 (K= 8.0 x 10 -4 mg-1 L s-1. The following rate expression was obtained at pH = 2.6: -r(S(IV =K [Cr(VI] [S(IV] and the activation energy found was: Ea =70.3KJ/mol. No catalytic effects were observed for Cd(II or chloride ion, while inhibitory effects were observed for Cr(III and V(V ions.

  15. Effect of alloying elements on characteristics of iron passive state in sulfuric acid

    International Nuclear Information System (INIS)

    Rejes Jola, O.; Mustafa-Zade, F.M.; Sukhotin, A.M.; Tchannikova, O.A.

    1981-01-01

    The curves of anodic polarization of iron binary alloys with Cr, Mo, W, Ni, Si, Co, Mn, Re, Ti, Al, Cu, Bi, Zn, In, V, Sb, Ta, Hf, Pb, Sn, Zr, Nb, Ce, B, P, S in 0.5 MH 2 SO 4 are studied. Passivation potentials, potentials of total passivation, transpassivity and current density are determined in the passivity region. All alloys had alpha-structure, the content of alloying elements was close to solubility in solid solution. Elements are classified according to the type of their effect on passive state of iron. Character of this effect does not have a direct connection with passivation ability the elements themselves, it is determined, probably, by a possibility to form stable passivating ruixed oxides of the ferrospinel type [ru

  16. Oxidation of SO2 by stabilized Criegee intermediate (sCI radicals as a crucial source for atmospheric sulfuric acid concentrations

    Directory of Open Access Journals (Sweden)

    M. Boy

    2013-04-01

    Full Text Available The effect of increased reaction rates of stabilized Criegee intermediates (sCIs with SO2 to produce sulfuric acid is investigated using data from two different locations, SMEAR II, Hyytiälä, Finland, and Hohenpeissenberg, Germany. Results from MALTE, a zero-dimensional model, show that using previous values for the rate coefficients of sCI + SO2, the model underestimates gas phase H2SO4 by up to a factor of two when compared to measurements. Using the rate coefficients recently calculated by Mauldin et al. (2012 increases sulfuric acid by 30–40%. Increasing the rate coefficient for formaldehyde oxide (CH2OO with SO2 according to the values recommended by Welz et al. (2012 increases the H2SO4 yield by 3–6%. Taken together, these increases lead to the conclusion that, depending on their concentrations, the reaction of stabilized Criegee intermediates with SO2 could contribute as much as 33–46% to atmospheric sulfuric acid gas phase concentrations at ground level. Using the SMEAR II data, results from SOSA, a one-dimensional model, show that the contribution from sCI reactions to sulfuric acid production is most important in the canopy, where the concentrations of organic compounds are the highest, but can have significant effects on sulfuric acid concentrations up to 100 m. The recent findings that the reaction of sCI + SO2 is much faster than previously thought together with these results show that the inclusion of this new oxidation mechanism could be crucial in regional as well as global models.

  17. Tetrathionate and Elemental Sulfur Shape the Isotope Composition of Sulfate in Acid Mine Drainage

    Directory of Open Access Journals (Sweden)

    Nurgul Balci

    2017-08-01

    Full Text Available Sulfur compounds in intermediate valence states, for example elemental sulfur, thiosulfate, and tetrathionate, are important players in the biogeochemical sulfur cycle. However, key understanding about the pathways of oxidation involving mixed-valance state sulfur species is still missing. Here we report the sulfur and oxygen isotope fractionation effects during the oxidation of tetrathionate (S4O62− and elemental sulfur (S° to sulfate in bacterial cultures in acidic conditions. Oxidation of tetrathionate by Acidithiobacillus thiooxidans produced thiosulfate, elemental sulfur and sulfate. Up to 34% of the tetrathionate consumed by the bacteria could not be accounted for in sulfate or other intermediate-valence state sulfur species over the experiments. The oxidation of tetrathionate yielded sulfate that was initially enriched in 34S (ε34SSO4−S4O6 by +7.9‰, followed by a decrease to +1.4‰ over the experiment duration, with an average ε34SSO4−S4O6 of +3.5 ± 0.2‰ after a month of incubation. We attribute this significant sulfur isotope fractionation to enzymatic disproportionation reactions occurring during tetrathionate decomposition, and to the incomplete transformation of tetrathionate into sulfate. The oxygen isotope composition of sulfate (δ18OSO4 from the tetrathionate oxidation experiments indicate that 62% of the oxygen in the formed sulfate was derived from water. The remaining 38% of the oxygen was either inherited from the supplied tetrathionate, or supplied from dissolved atmospheric oxygen (O2. During the oxidation of elemental sulfur, the product sulfate became depleted in 34S between −1.8 and 0‰ relative to the elemental sulfur with an average for ε34SSO4−S0 of −0.9 ± 0.2‰ and all the oxygen atoms in the sulfate derived from water with an average normal oxygen isotope fractionation (ε18OSO4−H2O of −4.4‰. The differences observed in δ18OSO4 and the sulfur isotope composition of sulfate (δ34SSO4

  18. Comparative study of the oxidation behavior of sulfur-containing amino acids and glutathione by electrochemistry-mass spectrometry in the presence and absence of cisplatin.

    Science.gov (United States)

    Zabel, Robert; Weber, Günther

    2016-02-01

    Small sulfur-containing compounds are involved in several important biochemical processes, including-but not limited to-redox regulation and drug conjugation/detoxification. While methods for stable redox pairs of such compounds (thiols/disulfides) are available, analytical data on more labile and short-lived redox intermediates are scarce, due to highly challenging analytical requirements. In this study, we employ the direct combination of reagentless electrochemical oxidation and mass spectrometric (EC-MS) identification for monitoring oxidation reactions of cysteine, N-acetylcysteine, methionine, and glutathione under simulated physiological conditions (pH 7.4, 37 °C). For the first time, all theoretically expected redox intermediates-with only one exception-are detected simultaneously and in situ, including sulfenic, sulfinic, and sulfonic acids, disulfides, thiosulfinates, thiosulfonates, and sulfoxides. By monitoring the time/potential-dependent interconversion of sulfur species, mechanistic oxidation routes are confirmed and new reactions detected, e.g., sulfenamide formation due to reaction with ammonia from the buffer. Furthermore, our results demonstrate a highly significant impact of cisplatin on the redox reactivity of sulfur species. Namely, the amount of thiol oxidation to sulfonic acid via sulfenic and sulfinic acid intermediates is diminished for glutathione in the presence of cisplatin in favor of the disulfide formation, while for N-acetylcysteine the contrary applies. N-acetylcysteine is the only ligand which displays enhanced oxidation currents upon cisplatin addition, accompanied by increased levels of thiosulfinate and thiosulfonate species. This is traced back to thiol reactivity and highlights the important role of sulfenic acid intermediates, which may function as a switch between different oxidation routes.

  19. Sulfuric acid intercalated-mechanical exfoliation of reduced graphene oxide from old coconut shell

    Science.gov (United States)

    Islamiyah, Wildatun; Nashirudin, Luthfi; Baqiya, Malik A.; Cahyono, Yoyok; Darminto

    2018-04-01

    We report a fecile preparation of reduced grapheme oxide (rGO) from an old coconut shell by rapid reduction of heating at 400°C, chemical exfoliation using H2SO4 and HCl intercalating and mechanical exfoliation using ultrasonication. The produced samples consist of random stacks of nanometer-sized sheets. The dispersions prepared from H2SO4 had broader size distributions and larger particle sizes than the that from HCl. An average size of rGO in H2SO4 and HCl is respectively 23.62 nm and 570.4 nm. Furthermore, sample prepared in H2SO4 exhibited a high electronical conductivity of 1.1 × 10-3 S/m with a low energy gap of 0.11 eV.

  20. ADVANCED SULFUR CONTROL CONCEPTS

    Energy Technology Data Exchange (ETDEWEB)

    Apostolos A. Nikolopoulos; Santosh K. Gangwal; William J. McMichael; Jeffrey W. Portzer

    2003-01-01

    Conventional sulfur removal in integrated gasification combined cycle (IGCC) power plants involves numerous steps: COS (carbonyl sulfide) hydrolysis, amine scrubbing/regeneration, Claus process, and tail-gas treatment. Advanced sulfur removal in IGCC systems involves typically the use of zinc oxide-based sorbents. The sulfides sorbent is regenerated using dilute air to produce a dilute SO{sub 2} (sulfur dioxide) tail gas. Under previous contracts the highly effective first generation Direct Sulfur Recovery Process (DSRP) for catalytic reduction of this SO{sub 2} tail gas to elemental sulfur was developed. This process is currently undergoing field-testing. In this project, advanced concepts were evaluated to reduce the number of unit operations in sulfur removal and recovery. Substantial effort was directed towards developing sorbents that could be directly regenerated to elemental sulfur in an Advanced Hot Gas Process (AHGP). Development of this process has been described in detail in Appendices A-F. RTI began the development of the Single-step Sulfur Recovery Process (SSRP) to eliminate the use of sorbents and multiple reactors in sulfur removal and recovery. This process showed promising preliminary results and thus further process development of AHGP was abandoned in favor of SSRP. The SSRP is a direct Claus process that consists of injecting SO{sub 2} directly into the quenched coal gas from a coal gasifier, and reacting the H{sub 2}S-SO{sub 2} mixture over a selective catalyst to both remove and recover sulfur in a single step. The process is conducted at gasifier pressure and 125 to 160 C. The proposed commercial embodiment of the SSRP involves a liquid phase of molten sulfur with dispersed catalyst in a slurry bubble-column reactor (SBCR).

  1. All-solid-state lithium-sulfur battery based on a nanoconfined LiBH4 electrolyte

    DEFF Research Database (Denmark)

    Das, Supti; Ngene, Peter; Norby, Poul

    2016-01-01

    In this work we characterize all-solid-state lithium-sulfur batteries based on nano-confined LiBH4 in mesoporous silica as solid electrolytes. The nano-confined LiBH4 has fast ionic lithium conductivity at room temperature, 0.1 mScm-1, negligible electronic conductivity and its cationic transport...... number (t+ = 0.96), close to unity, demonstrates a purely cationic conductor. The electrolyte has an excellent stability against lithium metal. The behavior of the batteries is studied by cyclic voltammetry and repeated charge/discharge cycles in galvanostatic conditions. The batteries show very good...

  2. Kinetics and mechanism of OsOsub(4) catalyzed oxidation of chalcones by Cesub(4) in aqueous acetic sulfuric acid media

    International Nuclear Information System (INIS)

    Srinivasulu, P.V.; Adinarayana, M.; Sethuram, B.; Rao, T.N.

    1985-01-01

    Kinetics of OsOsub(4) catalyzed oxidation of chalcones by Cesup(4+) was studied in aqueous acetic-sulfuric acid medium in the temperature range 313 to 338 K. The order in oxidant is zero while the order with respect to substrate and catalyst are each fractional. The rate of the reaction decreased with increase in percentage of acetic acid while [Hsup(+)] had practically no effect on the rate. The rates of various substituted chalcones are given. A mechanism in which formation of a cyclic ester between chalcone and OsOsub(4) in a fast step followed by its decomposition in a rate-determining step is envisaged. (author)

  3. Detecting decompositions of sulfur hexafluoride using reduced graphene oxide decorated with Pt nanoparticles

    Science.gov (United States)

    Chen, Dachang; Tang, Ju; Zhang, Xiaoxing; Fang, Jiani; Li, Yi; Zhuo, Ran

    2018-05-01

    The resistance-typed gas sensing material of Pt nanoparticles (PtNPs) decorated reduced graphene oxide (RGO) synthesized by one-step chemical reduction for the detection of four types of SF6 decompositions was explored. The PtNPs disperse uniformly on RGO with particle size near 2–4 nm and a small number of particles are larger than 10 nm. Gas sensing tests suggest that the introduction of PtNPs increases the response to SO2, SOF2 and H2S compared to pure RGO and PtNPs-RGO experiences resistance reducing in SO2 and SOF2 while presenting the opposite case in H2S. Elevating the temperature enhances the recovery properties to SO2 and H2S but lowers the sensitivity. The sensing mechanism for Pt-RGO in low oxygen and water environment depends mainly on the charge transfer between gas and adsorbent and the solvent on material surface. The work provides experimental investigation of Pt-RGO to detect SF6 decompositions.

  4. Sulfur-doped porous reduced graphene oxide hollow nanosphere frameworks as metal-free electrocatalysts for oxygen reduction reaction and as supercapacitor electrode materials.

    Science.gov (United States)

    Chen, Xi'an; Chen, Xiaohua; Xu, Xin; Yang, Zhi; Liu, Zheng; Zhang, Lijie; Xu, Xiangju; Chen, Ying; Huang, Shaoming

    2014-11-21

    Chemical doping with foreign atoms is an effective approach to significantly enhance the electrochemical performance of the carbon materials. Herein, sulfur-doped three-dimensional (3D) porous reduced graphene oxide (RGO) hollow nanosphere frameworks (S-PGHS) are fabricated by directly annealing graphene oxide (GO)-encapsulated amino-modified SiO2 nanoparticles with dibenzyl disulfide (DBDS), followed by hydrofluoric acid etching. The XPS and Raman spectra confirmed that sulfur atoms were successfully introduced into the PGHS framework via covalent bonds. The as-prepared S-PGHS has been demonstrated to be an efficient metal-free electrocatalyst for oxygen reduction reaction (ORR) with the activity comparable to that of commercial Pt/C (40%) and much better methanol tolerance and durability, and to be a supercapacitor electrode material with a high specific capacitance of 343 F g(-1), good rate capability and excellent cycling stability in aqueous electrolytes. The impressive performance for ORR and supercapacitors is believed to be due to the synergistic effect caused by sulfur-doping enhancing the electrochemical activity and 3D porous hollow nanosphere framework structures facilitating ion diffusion and electronic transfer.

  5. Complete Oxidation of Propionate, Valerate, Succinate, and Other Organic Compounds by Newly Isolated Types of Marine, Anaerobic, Mesophilic, Gram-Negative, Sulfur-Reducing Eubacteria

    Science.gov (United States)

    Finster, Kai; Bak, Friedhelm

    1993-01-01

    Anaerobic enrichment cultures with either propionate, succinate, lactate, or valerate and elemental sulfur and inocula from shallow marine or deep-sea sediments were dominated by rod-shaped motile bacteria after three transfers. By application of deep-agar dilutions, five eubacterial strains were obtained in pure culture and designated Kyprop, Gyprop, Kysw2, Gylac, and Kyval. All strains were gram negative and grew by complete oxidation of the electron donors and concomitant stoichiometric reduction of elemental sulfur to hydrogen sulfide. The isolates used acetate, propionate, succinate, lactate, pyruvate, oxaloacetate, maleate, glutamate, alanine, aspartate, and yeast extract. All isolates, except strain Gylac, used citrate as an electron donor but valerate was oxidized only by strain Kyval. Fumarate and malate were degraded by all strains without an additional electron donor or acceptor. Kyprop, Gyprop, and Gylac utilized elemental sulfur as the sole inorganic electron acceptor, while Kysw2 and Kyval also utilized nitrate, dimethyl sulfoxide, or Fe(III)-citrate as an electron acceptor. Images PMID:16348934

  6. Partial oxidation of jet fuels over Rh/Al_2O_3. Design and reaction kinetics of sulfur-containing surrogates

    International Nuclear Information System (INIS)

    Baer, Julian Nicolaas

    2016-01-01

    The conversion of logistic fuels via catalytic partial oxidation (CPOX) on Rh/Al_2O_3 at short contact times is an efficient method for generating hydrogen-rich synthesis gas. Depending on the inlet conditions, fuel, and catalyst, high syngas yields, low by-product formation, and rates of high fuel conversion can be achieved. CPOX is relevant for mobile hydrogen generation, e.g., on board of airplanes in order to increase the fuel efficiency via fuel cell-based auxiliary power units. Jet fuels contain hundreds of different hydrocarbons and a significant amount of sulfur. The hydrocarbon composition and sulfur content of a jet fuel vary depending on distributor, origin, and refinement of the crude oil. Little is known about the influence of the various compounds on the synthesis-gas yield and the impact of sulfur on the product yield. In this work, the influence of three main chemical compounds of a jet fuel (aromatics, alkanes, and sulfur compounds) on syngas selectivity, the catalyst deactivation process, and reaction sequence is unraveled. As representative components of alkanes and aromatics, n-dodecane and 1,2,4-trimethylbenzene were chosen for ex-situ and in-situ investigations on the CPOX over Rh/Al_2O_3, respectively. Additionally, for a fixed paraffin-to-aromatics ratio, benzothiophene or dibenzothiophene were added as a sulfur component in three different concentrations. The knowledge gained about the catalytic partial oxidation of jet fuels and their surrogates is used to identify requirements for jet fuels in mobile applications based on CPOX and to optimize the overall system efficiency. The results show an influence of the surrogate composition on syngas selectivity. The tendency for syngas formation increases with higher paraffin contents. A growing tendency for by-product formation can be observed with increasing aromatics contents in the fuel. The impact of sulfur on the reaction system shows an immediate change in the product distribution. An

  7. Partial oxidation of jet fuels over Rh/Al{sub 2}O{sub 3}. Design and reaction kinetics of sulfur-containing surrogates

    Energy Technology Data Exchange (ETDEWEB)

    Baer, Julian Nicolaas

    2016-07-01

    The conversion of logistic fuels via catalytic partial oxidation (CPOX) on Rh/Al{sub 2}O{sub 3} at short contact times is an efficient method for generating hydrogen-rich synthesis gas. Depending on the inlet conditions, fuel, and catalyst, high syngas yields, low by-product formation, and rates of high fuel conversion can be achieved. CPOX is relevant for mobile hydrogen generation, e.g., on board of airplanes in order to increase the fuel efficiency via fuel cell-based auxiliary power units. Jet fuels contain hundreds of different hydrocarbons and a significant amount of sulfur. The hydrocarbon composition and sulfur content of a jet fuel vary depending on distributor, origin, and refinement of the crude oil. Little is known about the influence of the various compounds on the synthesis-gas yield and the impact of sulfur on the product yield. In this work, the influence of three main chemical compounds of a jet fuel (aromatics, alkanes, and sulfur compounds) on syngas selectivity, the catalyst deactivation process, and reaction sequence is unraveled. As representative components of alkanes and aromatics, n-dodecane and 1,2,4-trimethylbenzene were chosen for ex-situ and in-situ investigations on the CPOX over Rh/Al{sub 2}O{sub 3}, respectively. Additionally, for a fixed paraffin-to-aromatics ratio, benzothiophene or dibenzothiophene were added as a sulfur component in three different concentrations. The knowledge gained about the catalytic partial oxidation of jet fuels and their surrogates is used to identify requirements for jet fuels in mobile applications based on CPOX and to optimize the overall system efficiency. The results show an influence of the surrogate composition on syngas selectivity. The tendency for syngas formation increases with higher paraffin contents. A growing tendency for by-product formation can be observed with increasing aromatics contents in the fuel. The impact of sulfur on the reaction system shows an immediate change in the product

  8. Aircraft exhaust sulfur emissions

    Energy Technology Data Exchange (ETDEWEB)

    Brown, R C; Anderson, M R; Miake-Lye, R C; Kolb, C E [Aerodyne Research, Inc., Billerica, MA (United States). Center for Chemical and Environmental Physics; Sorokin, A A; Buriko, Y I [Scientific Research Center ` Ecolen` , Moscow (Russian Federation)

    1998-12-31

    The extent to which fuel sulfur is converted to SO{sub 3} during combustion and the subsequent turbine flow in supersonic and subsonic aircraft engines is estimated numerically. The analysis is based on: a flamelet model with non-equilibrium sulfur chemistry for the combustor, and a one-dimensional, two-stream model with finite rate chemical kinetics for the turbine. The results indicate that between 2% and 10% of the fuel sulfur is emitted as SO{sub 3}. It is also shown that, for a high fuel sulfur mass loading, conversion in the turbine is limited by the level of atomic oxygen at the combustor exit, leading to higher SO{sub 2} oxidation efficiency at lower fuel sulfur loadings. While SO{sub 2} and SO{sub 3} are the primary oxidation products, the model results further indicate H{sub 2}SO{sub 4} levels on the order of 0.1 ppm for supersonic expansions through a divergent nozzle. This source of fully oxidized S(6) (SO{sub 3} + H{sub 2}SO{sub 4}) exceeds previously calculated S(6) levels due to oxidation of SO{sub 2} by OH in the exhaust plume outside the engine nozzle. (author) 26 refs.

  9. Aircraft exhaust sulfur emissions

    Energy Technology Data Exchange (ETDEWEB)

    Brown, R.C.; Anderson, M.R.; Miake-Lye, R.C.; Kolb, C.E. [Aerodyne Research, Inc., Billerica, MA (United States). Center for Chemical and Environmental Physics; Sorokin, A.A.; Buriko, Y.I. [Scientific Research Center `Ecolen`, Moscow (Russian Federation)

    1997-12-31

    The extent to which fuel sulfur is converted to SO{sub 3} during combustion and the subsequent turbine flow in supersonic and subsonic aircraft engines is estimated numerically. The analysis is based on: a flamelet model with non-equilibrium sulfur chemistry for the combustor, and a one-dimensional, two-stream model with finite rate chemical kinetics for the turbine. The results indicate that between 2% and 10% of the fuel sulfur is emitted as SO{sub 3}. It is also shown that, for a high fuel sulfur mass loading, conversion in the turbine is limited by the level of atomic oxygen at the combustor exit, leading to higher SO{sub 2} oxidation efficiency at lower fuel sulfur loadings. While SO{sub 2} and SO{sub 3} are the primary oxidation products, the model results further indicate H{sub 2}SO{sub 4} levels on the order of 0.1 ppm for supersonic expansions through a divergent nozzle. This source of fully oxidized S(6) (SO{sub 3} + H{sub 2}SO{sub 4}) exceeds previously calculated S(6) levels due to oxidation of SO{sub 2} by OH in the exhaust plume outside the engine nozzle. (author) 26 refs.

  10. Obligate sugar oxidation in Mesotoga spp., phylum Thermotogae, in the presence of either elemental sulfur or hydrogenotrophic sulfate-reducers as electron acceptor.

    Science.gov (United States)

    Fadhlaoui, Khaled; Ben Hania, Wagdi; Armougom, Fabrice; Bartoli, Manon; Fardeau, Marie-Laure; Erauso, Gaël; Brasseur, Gaël; Aubert, Corinne; Hamdi, Moktar; Brochier-Armanet, Céline; Dolla, Alain; Ollivier, Bernard

    2018-01-01

    Mesotoga prima strain PhosAc3 is a mesophilic representative of the phylum Thermotogae comprising only fermentative bacteria so far. We show that while unable to ferment glucose, this bacterium is able to couple its oxidation to reduction of elemental sulfur. We demonstrate furthermore that M. prima strain PhosAc3 as well as M. prima strain MesG1 and Mesotoga infera are able to grow in syntrophic association with sulfate-reducing bacteria (SRB) acting as hydrogen scavengers through interspecies hydrogen transfer. Hydrogen production was higher in M. prima strain PhosAc3 cells co-cultured with SRB than in cells cultured alone in the presence of elemental sulfur. We propose that the efficient sugar-oxidizing metabolism by M. prima strain PhosAc3 in syntrophic association with a hydrogenotrophic sulfate-reducing bacterium can be extrapolated to all members of the Mesotoga genus. Genome comparison of Thermotogae members suggests that the metabolic difference between Mesotoga and Thermotoga species (sugar oxidation versus fermentation) is mainly due to the absence of the bifurcating [FeFe]-hydrogenase in the former. Such an obligate oxidative process for using sugars, unusual within prokaryotes, is the first reported within the Thermotogae. It is hypothesized to be of primary ecological importance for growth of Mesotoga spp. in the environments that they inhabit. © 2017 Society for Applied Microbiology and John Wiley & Sons Ltd.

  11. Performance Factors and Sulfur Tolerance of Metal Supported Solid Oxide Fuel Cells with Nanostructured Ni:GDC Infiltrated Anodes

    DEFF Research Database (Denmark)

    Nielsen, Jimmi; Sudireddy, Bhaskar Reddy; Hagen, Anke

    2015-01-01

    at a current load of 0.25Acm-2. The results were compared with literature on the sulfur tolerance of the conventional SOFC Ni/YSZ cermet anode. The comparison in terms of absolute cell resistance increase and relative anode polarization resistance increase indicate, that the nanostructured Ni:GDC MS-SOFC based...... anode is significantly more sulfur tolerant than the conventional Ni/YSZ cermet anode. © 2015 ECS - The Electrochemical Society...

  12. Quantitative evaluation of the effect of H2O degassing on the oxidation state of magmas

    Science.gov (United States)

    Lange, R. A.; Waters, L.

    2014-12-01

    The extent to which degassing of the H2O component affects the oxidation state of hydrous magmas is widely debated. Several researchers have examined how degassing of mixed H-C-O-S-Cl fluids may change the Fe3+/FeT ratio of various magmas, whereas our focus is on the H2O component. There are two ways that degassing of H2O by itself may cause oxidation: (1) the reaction: H2O (melt) + 2FeO (melt) = H2 (fluid) + Fe2O3 (melt), and/or (2) if dissolved water preferentially enhances the activity of ferrous vs. ferric iron in magmatic liquids. In this study, a comparison is made between the pre-eruptive oxidation states of 14 crystal-poor, jet-black obsidian samples (obtained from two Fe-Ti oxides) and their post-eruptive values (analyzed with the Wilson 1960 titration method tested against USGS standards). The obsidians are from Medicine Lake (CA), Long Valley (CA), and the western Mexican arc; all have low FeOT (1.1-2.1 wt%), rendering their Fe2+/Fe3+ ratios highly sensitive to the possible effects of substantial H2O degassing. The Fe-Ti oxide thermometer/oxybarometer of Ghiorso and Evans, (2008) gave temperatures for the 14 samples that range for 720 to 940°C and ΔNNO values of -0.9 to +1.4. With temperature known, the plagioclase-liquid hygrometer was applied and show that ≤ 6.5 wt% H2O was dissolved in the melts prior to eruption. In addition, pre-eruptive Cl and S concentrations were constrained on the basis of apatite analyses (Webster et al., 2009) and sulfur concentrations needed for saturation with pyrrhotite (Clemente et al., 2004), respectively. Maximum pre-eruptive chlorine and sulfur contents are 6000 and 200 ppm, respectively. After eruption, the rhyolites lost nearly all of their volatiles. Our results indicate no detectable change between pre- and post-eruptive Fe2+ concentrations, with an average deviation of ± 0.1 wt % FeO. Although degassing of large concentrations of S and/or Cl may affect the oxidation state of magmas, at the pre-eruptive levels

  13. A Nanophase-Separated, Quasi-Solid-State Polymeric Single-Ion Conductor: Polysulfide Exclusion for Lithium–Sulfur Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Jinhong; Song, Jongchan; Lee, Hongkyung; Noh, Hyungjun; Kim, Yun-Jung; Kwon, Sung Hyun; Lee, Seung Geol; Kim, Hee-Tak

    2017-04-19

    Formation of soluble polysulfide (PS), which is a key feature of lithium sulfur (Li–S) batteries, provides a fast redox kinetic based on a liquid–solid mechanism; however, it imposes the critical problem of PS shuttle. Here, we address the dilemma by exploiting a solvent-swollen polymeric single-ion conductor (SPSIC) as the electrolyte medium of the Li–S battery. The SPSIC consisting of a polymeric single-ion conductor and lithium salt-free organic solvents provides Li ion hopping by forming a nanoscale conducting channel and suppresses PS shuttle according to the Donnan exclusion principle when being employed for Li–S batteries. The organic solvents at the interface of the sulfur/carbon composite and SPSIC eliminate the poor interfacial contact and function as a soluble PS reservoir for maintaining the liquid–solid mechanism. Furthermore, the quasi-solid-state SPSIC allows the fabrication of a bipolar-type stack, which promises the realization of a high-voltage and energy-dense Li–S battery.

  14. Electric circuit modeling of lithium-sulfur batteries during discharging state

    DEFF Research Database (Denmark)

    Stroe, Daniel-Ioan; Knap, Vaclav; Swierczynski, Maciej Jozef

    2017-01-01

    Lithium-ion batteries are characterized by having very good performance in terms of efficiency, lifetime, and selfdischarge, which allowed them to become the major player in the electric vehicle applications. However, they were not able to totally overcome the EV range anxiety. Thus, research...... is carried out nowadays to develop batteries with even higher gravimetric energy density, which should allow a substantial range increase. One of the technologies, which should be able to meet the range requirements is the Lithium-Sulfur (Li-S) battery. Thanks to the extensive research and development...... static and pulse discharge profiles, showing a good accuracy in predicting the voltage of the tested Li-S battery cell....

  15. Io's theothermal (sulfur) - Lithosphere cycle inferred from sulfur solubility modeling of Pele's magma supply

    Science.gov (United States)

    Battaglia, Steven M.; Stewart, Michael A.; Kieffer, Susan W.

    2014-06-01

    Surface deposits of volatile compounds such as water (Earth) or sulfur (Io) on volcanically active bodies suggest that a magmatic distillation process works to concentrate volatiles in surface reservoirs. On Earth, this is the combined hydrologic and tectonic cycle. On Io, sulfurous compounds are transferred from the interior to the surface reservoirs through a combination of a mantle-sourced magmatic system, vertical cycling of the lithosphere, and a sulfur-dominated crustal thermal system that we here call the "theothermal" system. We present a geochemical analysis of this process using previously inferred temperature and oxygen fugacity constraints of Pele's basaltic magma to determine the behavior of sulfur in the ionian magmas. Sulfate to sulfide ratios of Pele's magma are -4.084 ± 0.6 and -6.442 ± 0.7 log10 units, comparable to or lower than those of mid-ocean ridge basalts. This reflects the similarity of Io's oxidation state with Earth's depleted mantle as previously suggested by Zolotov and Fegley (Zolotov, M.Y., Fegley, B. [2000]. Geophys. Res. Lett. 27, 2789-2792). Our calculated limits of sulfur solubility in melts from Pele's patera (˜1100-1140 ppm) are also comparable to terrestrial mid-ocean ridge basalts, reflecting a compositional similarity of mantle sources. We propose that the excess sulfur obvious on Io's surface comes from two sources: (1) an insoluble sulfide liquid phase in the magma and (2) theothermal near-surface recycling.

  16. A three-electrode column for Pd-catalytic oxidation of TCE in groundwater with automatic pH-regulation and resistance to reduced sulfur compound foiling.

    Science.gov (United States)

    Yuan, Songhu; Chen, Mingjie; Mao, Xuhui; Alshawabkeh, Akram N

    2013-01-01

    A hybrid electrolysis and Pd-catalytic oxidation process is evaluated for degradation of trichloroethylene (TCE) in groundwater. A three-electrode, one anode and two cathodes, column is employed to automatically develop a low pH condition in the Pd vicinity and a neutral effluent. Simulated groundwater containing up to 5 mM bicarbonate can be acidified to below pH 4 in the Pd vicinity using a total of 60 mA with 20 mA passing through the third electrode. By packing 2 g of Pd/Al(2)O(3) pellets in the developed acidic region, the column efficiency for TCE oxidation in simulated groundwater (5.3 mg/L TCE) increases from 44 to 59 and 68% with increasing Fe(II) concentration from 0 to 5 and 10 mg/L, respectively. Different from Pd-catalytic hydrodechlorination under reducing conditions, this hybrid electrolysis and Pd-catalytic oxidation process is advantageous in controlling the fouling caused by reduced sulfur compounds (RSCs) because the in situ generated reactive oxidizing species, i.e., O(2), H(2)O(2) and OH, can oxidize RSCs to some extent. In particular, sulfite at concentrations less than 1 mM even greatly increases TCE oxidation by the production of SO(4)(•-), a strong oxidizing radical, and more OH. Copyright © 2012 Elsevier Ltd. All rights reserved.

  17. Evolution of insoluble eutectic Si particles in anodic oxidation films during adipic-sulfuric acid anodizing processes of ZL114A aluminum alloys

    Science.gov (United States)

    Hua, Lei; Liu, Jian-hua; Li, Song-mei; Yu, Mei; Wang, Lei; Cui, Yong-xin

    2015-03-01

    The effects of insoluble eutectic Si particles on the growth of anodic oxide films on ZL114A aluminum alloy substrates were investigated by optical microscopy (OM) and scanning electron microscopy (SEM). The anodic oxidation was performed at 25°C and a constant voltage of 15 V in a solution containing 50 g/L sulfuric acid and 10 g/L adipic acid. The thickness of the formed anodic oxidation film was approximately 7.13 μm. The interpore distance and the diameters of the major pores in the porous layer of the film were within the approximate ranges of 10-20 nm and 5-10 nm, respectively. Insoluble eutectic Si particles strongly influenced the morphology of the anodic oxidation films. The anodic oxidation films exhibited minimal defects and a uniform thickness on the ZL114A substrates; in contrast, when the front of the oxide oxidation films encountered eutectic Si particles, defects such as pits and non-uniform thickness were observed, and pits were observed in the films.

  18. Carbon monoxide oxidation over three different states of copper: Development of a model metal oxide catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Jernigan, Glenn Geoffrey [California Univ., Berkeley, CA (United States). Dept. of Chemistry

    1994-10-01

    Carbon monoxide oxidation was performed over the three different oxidation states of copper -- metallic (Cu), copper (I) oxide (Cu2O), and copper (II) oxide (CuO) as a test case for developing a model metal oxide catalyst amenable to study by the methods of modern surface science and catalysis. Copper was deposited and oxidized on oxidized supports of aluminum, silicon, molybdenum, tantalum, stainless steel, and iron as well as on graphite. The catalytic activity was found to decrease with increasing oxidation state (Cu > Cu2O > CuO) and the activation energy increased with increasing oxidation state (Cu, 9 kcal/mol < Cu2O, 14 kcal/mol < CuO, 17 kcal/mol). Reaction mechanisms were determined for the different oxidation states. Lastly, NO reduction by CO was studied. A Cu and CuO catalyst were exposed to an equal mixture of CO and NO at 300--350 C to observe the production of N2 and CO2. At the end of each reaction, the catalyst was found to be Cu2O. There is a need to study the kinetics of this reaction over the different oxidation states of copper.

  19. Study and modeling of the reduction of sulfur dioxide, nitrogen oxides and hydrogen chloride by dry injection technologies

    Energy Technology Data Exchange (ETDEWEB)

    Wang Wuyin

    1997-05-01

    The potential and mechanism to reduce acid gases, such as sulfur dioxide (SO{sub 2}), nitrogen oxides (NO{sub x}) and hydrogen chloride (HCl), by dry Ca-based sorbents have been studied to improve the efficiency of the process and sorbent utilization. Several natural limestones were tested for SO{sub 2} removal. Calcium conversion as high as 45 % was achieved in the first 0.3 s at 1000 deg C, 1000 ppm SO{sub 2} and Ca/S=1. A SO{sub 2} removal efficiency of 95 % was reached at Ca/S=2. Two models for estimating the sulfation of CaO at high temperature are presented. Short-residence-time sulfation is described by a pore size distribution model and long-residence-time sulfation by a particle expansion model. The pore size distribution model explains the effects of particle size, pore size distribution and partial pressure of SO{sub 2}, suggesting these three factors be the most important for CaO conversion. For particles larger than 1-2 {mu}m in furnace sorbent injection, pore diameters of 50-300 Aa are desirable. When large particles or long residence times are used, as in fluidized bed combustion, the particle expansion model shows the particle size and the sorbent type to be the main factors affecting the reaction. By using the selected limestone and additives the simultaneous SO{sub 2}/NO{sub x} removal was also measured. Several ammonium salts as well as urea were tested. Urea was found to give the highest NO{sub x} removal efficiency. To fully utilize the unreacted Ca-based sorbents, the spent sorbents from SO{sub 2} reduction processes were tested in a fixed-bed reactor to measure the capacity for HCl removal at 150-600 deg C. The results showed that all spent materials could react with HCl to some extent. After being calcined and slaked, they even showed the same reactivity as pure Ca(OH){sub 2}. A shrinking core model was derived for fixed-bed reactor. For the best sorbent tested, the multiple sorbent utilization reached about 80 %. 100 refs, 42 figs, 12 tabs

  20. Obligate sugar oxidation in Mesotoga spp., phylum Thermotogae, in the presence of either elemental sulfur or hydrogenotrophic sulfate-reducers as electron acceptor

    OpenAIRE

    Fadhlaoui, K.; Ben Hania, W.; Armougom, Fabrice; Bartoli, M.; Fardeau, Marie-Laure; Erauso, G.; Brasseur, G.; Aubert, C.; Hamdi, M.; Brochier-Armanet, C.; Dolla, A.; Ollivier, Bernard

    2018-01-01

    Mesotoga prima strain PhosAc3 is a mesophilic representative of the phylum Thermotogae comprising only fermentative bacteria so far. We show that while unable to ferment glucose, this bacterium is able to couple its oxidation to reduction of elemental sulfur. We demonstrate furthermore that M. prima strain PhosAc3 as well as M. prima strain MesG1 and Mesotoga infera are able to grow in syntrophic association with sulfate-reducing bacteria (SRB) acting as hydrogen scavengers through interspeci...

  1. A Lithium-Ion Battery using a 3 D-Array Nanostructured Graphene-Sulfur Cathode and a Silicon Oxide-Based Anode.

    Science.gov (United States)

    Benítez, Almudena; Di Lecce, Daniele; Elia, Giuseppe Antonio; Caballero, Álvaro; Morales, Julián; Hassoun, Jusef

    2018-05-09

    An efficient lithium-ion battery was assembled by using an enhanced sulfur-based cathode and a silicon oxide-based anode and proposed as an innovative energy-storage system. The sulfur-carbon composite, which exploits graphene carbon with a 3 D array (3DG-S), was synthesized by a reduction step through a microwave-assisted solvothermal technique and was fully characterized in terms of structure and morphology, thereby revealing suitable features for lithium-cell application. Electrochemical tests of the 3DG-S electrode in a lithium half-cell indicated a capacity ranging from 1200 to 1000 mAh g -1 at currents of C/10 and 1 C, respectively. Remarkably, the Li-alloyed anode, namely, Li y SiO x -C prepared by the sol-gel method and lithiated by surface treatment, showed suitable performance in a lithium half-cell by using an electrolyte designed for lithium-sulfur batteries. The Li y SiO x -C/3DG-S battery was found to exhibit very promising properties with a capacity of approximately 460 mAh g S -1 delivered at an average voltage of approximately 1.5 V over 200 cycles, suggesting that the characterized materials would be suitable candidates for low-cost and high-energy-storage applications. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Effect of Silica Sol on Boric-sulfuric Acid Anodic Oxidation of LY12CZ Aluminum Alloy

    Directory of Open Access Journals (Sweden)

    LIU Hui-cong

    2016-07-01

    Full Text Available Aluminum alloy anodizing coatings were prepared for LY12CZ in the boric-sulfuric acid solution (45g/L sulfuric acid,8g/L boric acid with the addition of 10%,20%,30% (volume fractionsilica sol,with the gradient voltage of 15V. The current and voltage transients of the anodizing process were collected by data collection instrument. The surface morphologies,microstructure and chemical composition of the anodic coatings were characterized by scanning electron microscopy (SEM. The corrosion resistance was examined by neutral salt spray,electrochemical impedance spectroscopy (EIS test and titrating test. The results show that the different concentration of silica sol addition can influence the forming and dissolution of anodizing coatings,improve the compactness smoothness and corrosion resistance during the anodizing process in the boric-sulfuric acid solution.

  3. Performance Factors and Sulfur Tolerance of Metal Supported Solid Oxide Fuel Cells with Nanostructured Ni:GDC Infiltrated Anodes

    DEFF Research Database (Denmark)

    Nielsen, Jimmi; Sudireddy, Bhaskar Reddy; Hagen, Anke

    2016-01-01

    galvanostatic operation at a current load of 0.25 Acm−2. The results were compared with literature on the sulfur tolerance of conventional SOFC Ni/YSZ cermet anode. The comparison in terms of absolute cell resistance increase and relative anode polarization resistance increase indicates, that the nanostructured...... Ni:GDC MS-SOFC based anode is significantly more sulfur tolerant than the conventional Ni/YSZ cermet anode. Furthermore, it was shown that the believed extension of the electrochemical three-phase-boundary reaction zone in the presence of GDC must be very limited and cannot account for the higher...

  4. Sulfur equilibrium desulfurization of sulfur containing products of combustion

    International Nuclear Information System (INIS)

    Woodroffe, J.A.; Abichandani, J.S.

    1990-01-01

    This patent describes the method for the combustion of a carbon- and sulfur-containing fuel for substantially reducing emission of gaseous sulfur compounds formed during combustion of the fuel in a combustion zone. The zone having one or more fuel inlets and one or more oxidizer inlets, and having a combustion products outlet spaced therefrom, and having one or more inorganic sorbent inlets downstream of the fuel inlet(s) and oxidizer inlet(s) and upstream of the combustion products outlet

  5. Biologically removing sulfur from dilute gas flows

    Science.gov (United States)

    Ruitenberg, R.; Dijkman, H.; Buisman, C. J. N.

    1999-05-01

    A biological process has been developed to clean off-gases containing sulfur dioxide from industrial installations. The sulfur dioxide is converted into hydrogen sulfide, which can then be oxidized to elemental sulfur if not used on-site. The process produces no waste products that require disposal and has a low reagent consumption.

  6. Method of distillation of sulfurous bituminous shales

    Energy Technology Data Exchange (ETDEWEB)

    Hallback, A J.S.; Bergh, S V

    1918-04-22

    A method of distillation of sulfur-containing bituminous shales is characterized by passing the hot sulfur-containing and oil-containing gases and vapors formed during the distillation through burned shale containing iron oxide, so that when these gases and vapors are thereafter cooled they will be, as far as possible, free from sulfur compounds. The patent contains six more claims.

  7. Ultra Low Sulfur Home Heating Oil Demonstration Project

    Energy Technology Data Exchange (ETDEWEB)

    Batey, John E. [Energy Research Center, Inc., Easton, CT (United States); McDonald, Roger [Brookhaven National Lab. (BNL), Upton, NY (United States)

    2015-09-30

    This Ultra Low Sulfur (ULS) Home Heating Oil Demonstration Project was funded by the New York State Energy Research and Development Authority (NYSERDA) and has successfully quantified the environmental and economic benefits of switching to ULS (15 PPM sulfur) heating oil. It advances a prior field study of Low Sulfur (500 ppm sulfur) heating oil funded by NYSERDA and laboratory research conducted by Brookhaven National Laboratory (BNL) and Canadian researchers. The sulfur oxide and particulate matter (PM) emissions are greatly reduced as are boiler cleaning costs through extending cleaning intervals. Both the sulfur oxide and PM emission rates are directly related to the fuel oil sulfur content. The sulfur oxide and PM emission rates approach near-zero levels by switching heating equipment to ULS fuel oil, and these emissions become comparable to heating equipment fired by natural gas. This demonstration project included an in-depth review and analysis of service records for both the ULS and control groups to determine any difference in the service needs for the two groups. The detailed service records for both groups were collected and analyzed and the results were entered into two spreadsheets that enabled a quantitative side-by-side comparison of equipment service for the entire duration of the ULS test project. The service frequency for the ULS and control group were very similar and did indicate increased service frequency for the ULS group. In fact, the service frequency with the ULS group was slightly less (7.5 percent) than the control group. The only exception was that three burner fuel pump required replacement for the ULS group and none were required for the control group.

  8. Simultaneous heterotrophic and sulfur-oxidizing autotrophic denitrification process for drinking water treatment: control of sulfate production.

    Science.gov (United States)

    Sahinkaya, Erkan; Dursun, Nesrin; Kilic, Adem; Demirel, Sevgi; Uyanik, Sinan; Cinar, Ozer

    2011-12-15

    A long-term performance of a packed-bed bioreactor containing sulfur and limestone was evaluated for the denitrification of drinking water. Autotrophic denitrification rate was limited by the slow dissolution rate of sulfur and limestone. Dissolution of limestone for alkalinity supplementation increased hardness due to release of Ca(2+). Sulfate production is the main disadvantage of the sulfur autotrophic denitrification process. The effluent sulfate concentration was reduced to values below drinking water guidelines by stimulating the simultaneous heterotrophic and autotrophic denitrification with methanol supplementation. Complete removal of 75 mg/L NO(3)-N with effluent sulfate concentration of around 225 mg/L was achieved when methanol was supplemented at methanol/NO(3)-N ratio of 1.67 (mg/mg), which was much lower than the theoretical value of 2.47 for heterotrophic denitrification. Batch studies showed that sulfur-based autotrophic NO(2)-N reduction rate was around three times lower than the reduction rate of NO(3)-N, which led to NO(2)-N accumulation at high loadings. Copyright © 2011 Elsevier Ltd. All rights reserved.

  9. Danburite decomposition by sulfuric acid

    International Nuclear Information System (INIS)

    Mirsaidov, U.; Mamatov, E.D.; Ashurov, N.A.

    2011-01-01

    Present article is devoted to decomposition of danburite of Ak-Arkhar Deposit of Tajikistan by sulfuric acid. The process of decomposition of danburite concentrate by sulfuric acid was studied. The chemical nature of decomposition process of boron containing ore was determined. The influence of temperature on the rate of extraction of boron and iron oxides was defined. The dependence of decomposition of boron and iron oxides on process duration, dosage of H 2 SO 4 , acid concentration and size of danburite particles was determined. The kinetics of danburite decomposition by sulfuric acid was studied as well. The apparent activation energy of the process of danburite decomposition by sulfuric acid was calculated. The flowsheet of danburite processing by sulfuric acid was elaborated.

  10. Expression of Critical Sulfur- and Iron-Oxidation Genes and the Community Dynamics During Bioleaching of Chalcopyrite Concentrate by Moderate Thermophiles.

    Science.gov (United States)

    Zhou, Dan; Peng, Tangjian; Zhou, Hongbo; Liu, Xueduan; Gu, Guohua; Chen, Miao; Qiu, Guanzhou; Zeng, Weimin

    2015-07-01

    Sulfate adenylyltransferase gene and 4Fe-4S ferredoxin gene are the key genes related to sulfur and iron oxidations during bioleaching system, respectively. In order to better understand the bioleaching and microorganism synergistic mechanism in chalcopyrite bioleaching by mixed culture of moderate thermophiles, expressions of the two energy metabolism genes and community dynamics of free and attached microorganisms were investigated. Specific primers were designed for real-time quantitative PCR to study the expression of these genes. Real-time PCR results showed that sulfate adenylyltransferase gene was more highly expressed in Sulfobacillus thermosulfidooxidans than that in Acidithiobacillus caldus, and expression of 4Fe-4S ferredoxin gene was higher in Ferroplasma thermophilum than that in S. thermosulfidooxidans and Leptospirillum ferriphilum. The results indicated that in the bioleaching system of chalcopyrite concentrate, sulfur and iron oxidations were mainly performed by S. thermosulfidooxidans and F. thermophilum, respectively. The community dynamics results revealed that S. thermosulfidooxidans took up the largest proportion during the whole period, followed by F. thermophilum, A. caldus, and L. ferriphilum. The CCA analysis showed that 4Fe-4S ferredoxin gene expression was mainly affected (positively correlated) by high pH and elevated concentration of ferrous ion, while no factor was observed to prominently influence the expression of sulfate adenylyltransferase gene.

  11. A novel fabrication methodology for sulfur-doped ZnO nanorods as an active photoanode for improved water oxidation in visible-light regime

    Science.gov (United States)

    Khan, A.; Ahmed, M. I.; Adam, A.; Azad, A.-M.; Qamar, M.

    2017-02-01

    Incorporation of foreign moiety in the lattice of semiconductors significantly alters their optoelectronic behavior and opens a plethora of new applications. In this paper, we report the synthesis of sulfur-doped zinc oxide (S-doped ZnO) nanorods by reacting ZnO nanorods with diammonium sulfide in vapor phase. Microscopic investigation revealed that the morphological features, such as, the length (2-4 μm) and width (100-250 nm) of the original hexagonal ZnO nanorods remained intact post-sulfidation. X-ray photoelectron spectroscopy analysis of the sulfide sample confirmed the incorporation of sulfur into ZnO lattice. The optical measurements suggested the extension of absorption threshold into visible region upon sulfidation. Photoelectrochemical (PEC) activities of pure and S-doped ZnO nanorods were compared for water oxidation in visible light (λ > 420 nm), which showed several-fold increment in the performance of S-doped ZnO sample; the observed amelioration in the PEC activity was rationalized in terms of preferred visible light absorption and low resistance of sulfide sample, as evidenced by optical and electrochemical impedance spectroscopy.

  12. Magnetite Crisis in Miniature: Vanadium, Sulfur, and Iron Valence State Measurements in Melt Inclusions from Nyamuragira Volcano (D.R. Congo, Africa)

    Science.gov (United States)

    Head, E.; Lanzirotti, A.; Sutton, S.; Newville, M.

    2017-12-01

    Sulfur (S), vanadium (V), and iron (Fe) K-edge micro-X-ray absorption near edge structure (micro-XANES) spectroscopy of melt inclusions (MI) from Nyamuragira volcano (D.R. Congo, Africa) shows that diffusive loss of H from olivine-hosted melt inclusions may lead to crystallization of submicron magnetite and sulfide crystallites that are imperceptible petrographically or via electron microscopy. Micro-XANES was used to constrain the evolution of oxygen fugacity (fO2) and sulfur speciation for MI preserved in Nyamuragira tephra (1986 and 2006) and lava (1938 and 1948). The S, V, and Fe valence state oxybarometry for 1938, 1948, and 2006 MI are all consistent with equilibration at FMQ-1, and sulfur in MI from these three eruptions are sulfide-dominated (water loss in olivine-hosted MIs.

  13. Ultrafast Photodissociation Dynamics of the F State of Sulfur Dioxide by Femtosecond Time-Resolved Pump-Probe Method

    International Nuclear Information System (INIS)

    Zhang Dong-Dong; Ni Qiang; Luo Si-Zuo; Zhang Jing; Liu Hang; Xu Hai-Feng; Jin Ming-Xing; Ding Da-Jun

    2011-01-01

    A femtosecond pump-probe method is employed to study the dissociation dynamics of sulfur dioxide. SO 2 molecules are excited to the F state by absorbing two photons of 267 nm femtosecond laser pulses, and ionized by 400 nm laser pulses at different delay times between the two lasers. Transients of both parent ions (SO + 2 ) and the fragment ions (SO + , S + and O + ) are observed. The SO + 2 transient can be well fitted to a biexponential decay comprising a fast and a slow component of 280 fs and 2.97 ps lifetimes, respectively. The SO + transient consists of two growth components of 270 fs and 2.50 ps. The results clearly show that the F state of SO 2 dissociates along an S-O bond. The transients of S + and O + , however, have different behavior, which consist of a fast growth and a long decay component. A possible mechanism of the fragment formation is discussed to understand the dissociation dynamics of the F state of SO 2 . (atomic and molecular physics)

  14. Sulfur Tolerant Solid Oxide Fuel Cell for Coal Syngas Application: Experimental Study on Diverse Impurity Effects and Fundamental Modeling of Electrode Kinetics

    Science.gov (United States)

    Gong, Mingyang

    With demand over green energy economy, fuel cells have been developed as a promising energy conversion technology with higher efficiency and less emission. Solid oxide fuel cells (SOFC) can utilize various fuels in addition to hydrogen including coal derived sygas, and thus are favored for future power generation due to dependence on coal in electrical industry. However impurities such as sulfur and phosphorous present in coal syngas in parts per million (p.p.m.) levels can severely poison SOFC anode typically made of Ni/yttria-stabilized-zirconia (Ni-YSZ) and limit SOFC applicability in economically derivable fuels. The focus of the research is to develop strategy for application of high performance SOFC in coal syngas with tolerance against trace impurities such as H2S and PH3. To realize the research goal, the experimental study on sulfur tolerant anode materials and examination of various fuel impurity effects on SOFC anode are combined with electrochemical modeling of SOFC cathode kinetics in order to benefit design of direct-coal-syngas SOFC. Tolerant strategy for SOFC anode against sulfur is studied by using alternative materials which can both mitigate sulfur poisoning and function as active anode components. The Ni-YSZ anode was modified by incorporation of lanthanum doped ceria (LDC) nano-coatings via impregnation. Cell test in coal syngas containing 20 ppm H2S indicated the impregnated LDC coatings inhibited on-set of sulfur poisoning by over 10hrs. Cell analysis via X-ray photon spectroscopy (XPS), X-ray diffraction (XRD) and electrochemistry revealed LDC coatings reacted with H2S via chemisorptions, resulting in less sulfur blocking triple--phase-boundary and minimized performance loss. Meanwhile the effects of PH3 impurity on SOFC anode is examined by using Ni-YSZ anode supported SOFC. Degradation of cell is found to be irreversible due to adsorption of PH3 on TPB and further reaction with Ni to form secondary phases with low melting point. The

  15. Demonstration of Selective Catalytic Reduction Technology to Control Nitrogen Oxide Emissions From High-Sulfur, Coal-Fired Boilers: A DOE Assessment

    International Nuclear Information System (INIS)

    Federal Energy Technology Center

    1999-01-01

    The goal of the U.S. Department of Energy (DOE) Clean Coal Technology (CCT) program is to furnish the energy marketplace with a number of advanced, more efficient, and environmentally responsible coal utilization technologies through demonstration projects. These projects seek to establish the commercial feasibility of the most promising advanced coal technologies that have developed beyond the proof-of-concept stage. This document serves as a DOE post-project assessment of a project selected in CCT Round 2. The project is described in the report ''Demonstration of Selective Catalytic Reduction (SCR) Technology for the Control of Nitrogen Oxide (NO(sub x)) Emissions from High-Sulfur, Coal-Fired Boilers'' (Southern Company Services 1990). In June 1990, Southern Company Services (Southern) entered into a cooperative agreement to conduct the study. Southern was a cofunder and served as the host at Gulf Power Company's Plant Crist. Other participants and cofunders were EPRI (formerly the Electric Power Research Institute) and Ontario Hydro. DOE provided 40 percent of the total project cost of$23 million. The long-term operation phase of the demonstration was started in July 1993 and was completed in July 1995. This independent evaluation is based primarily on information from Southern's Final Report (Southern Company Services 1996). The SCR process consists of injecting ammonia (NH(sub 3)) into boiler flue gas and passing the 3 flue gas through a catalyst bed where the NO(sub x) and NH(sub 3) react to form nitrogen and water vapor. The objectives of the demonstration project were to investigate: Performance of a wide variety of SCR catalyst compositions, geometries, and manufacturing methods at typical U.S. high-sulfur coal-fired utility operating conditions; Catalyst resistance to poisoning by trace metal species present in U.S. coals but not present, or present at much lower concentrations, in fuels from other countries; and Effects on the balance-of-plant equipment

  16. The Global Redox Responding RegB/RegA Signal Transduction System Regulates the Genes Involved in Ferrous Iron and Inorganic Sulfur Compound Oxidation of the Acidophilic Acidithiobacillus ferrooxidans

    Directory of Open Access Journals (Sweden)

    Danielle Moinier

    2017-07-01

    Full Text Available The chemical attack of ore by ferric iron and/or sulfuric acid releases valuable metals. The products of these reactions are recycled by iron and sulfur oxidizing microorganisms. These acidophilic chemolithotrophic prokaryotes, among which Acidithiobacillus ferrooxidans, grow at the expense of the energy released from the oxidation of ferrous iron and/or inorganic sulfur compounds (ISCs. In At. ferrooxidans, it has been shown that the expression of the genes encoding the proteins involved in these respiratory pathways is dependent on the electron donor and that the genes involved in iron oxidation are expressed before those responsible for ISCs oxidation when both iron and sulfur are present. Since the redox potential increases during iron oxidation but remains stable during sulfur oxidation, we have put forward the hypothesis that the global redox responding two components system RegB/RegA is involved in this regulation. To understand the mechanism of this system and its role in the regulation of the aerobic respiratory pathways in At. ferrooxidans, the binding of different forms of RegA (DNA binding domain, wild-type, unphosphorylated and phosphorylated-like forms of RegA on the regulatory region of different genes/operons involved in ferrous iron and ISC oxidation has been analyzed. We have shown that the four RegA forms are able to bind specifically the upstream region of these genes. Interestingly, the phosphorylation of RegA did not change its affinity for its cognate DNA. The transcriptional start site of these genes/operons has been determined. In most cases, the RegA binding site(s was (were located upstream from the −35 (or −24 box suggesting that RegA does not interfere with the RNA polymerase binding. Based on the results presented in this report, the role of the RegB/RegA system in the regulation of the ferrous iron and ISC oxidation pathways in At. ferrooxidans is discussed.

  17. The Global Redox Responding RegB/RegA Signal Transduction System Regulates the Genes Involved in Ferrous Iron and Inorganic Sulfur Compound Oxidation of the Acidophilic Acidithiobacillus ferrooxidans

    Science.gov (United States)

    Moinier, Danielle; Byrne, Deborah; Amouric, Agnès; Bonnefoy, Violaine

    2017-01-01

    The chemical attack of ore by ferric iron and/or sulfuric acid releases valuable metals. The products of these reactions are recycled by iron and sulfur oxidizing microorganisms. These acidophilic chemolithotrophic prokaryotes, among which Acidithiobacillus ferrooxidans, grow at the expense of the energy released from the oxidation of ferrous iron and/or inorganic sulfur compounds (ISCs). In At. ferrooxidans, it has been shown that the expression of the genes encoding the proteins involved in these respiratory pathways is dependent on the electron donor and that the genes involved in iron oxidation are expressed before those responsible for ISCs oxidation when both iron and sulfur are present. Since the redox potential increases during iron oxidation but remains stable during sulfur oxidation, we have put forward the hypothesis that the global redox responding two components system RegB/RegA is involved in this regulation. To understand the mechanism of this system and its role in the regulation of the aerobic respiratory pathways in At. ferrooxidans, the binding of different forms of RegA (DNA binding domain, wild-type, unphosphorylated and phosphorylated-like forms of RegA) on the regulatory region of different genes/operons involved in ferrous iron and ISC oxidation has been analyzed. We have shown that the four RegA forms are able to bind specifically the upstream region of these genes. Interestingly, the phosphorylation of RegA did not change its affinity for its cognate DNA. The transcriptional start site of these genes/operons has been determined. In most cases, the RegA binding site(s) was (were) located upstream from the −35 (or −24) box suggesting that RegA does not interfere with the RNA polymerase binding. Based on the results presented in this report, the role of the RegB/RegA system in the regulation of the ferrous iron and ISC oxidation pathways in At. ferrooxidans is discussed. PMID:28747899

  18. Graphene-supported zinc oxide solid-phase microextraction coating with enhanced selectivity and sensitivity for the determination of sulfur volatiles in Allium species.

    Science.gov (United States)

    Zhang, Suling; Du, Zhuo; Li, Gongke

    2012-10-19

    A graphene-supported zinc oxide (ZnO) solid-phase microextraction (SPME) fiber was prepared via a sol-gel approach. Graphite oxide (GO), with rich oxygen-containing groups, was selected as the starting material to anchor ZnO on its nucleation center. After being deoxidized by hydrazine, the Zn(OH)2/GO coating was dehydrated at high temperature to give the ZnO/graphene coating. Sol-gel technology could efficiently incorporate ZnO/graphene composites into the sol-gel network and provided strong chemical bonding between sol-gel polymeric SPME coating and silica fiber surface, which enhanced the durability of the fiber and allowed more than 200 replicate extractions. Results indicated that pure ZnO coated fiber did not show adsorption selectivity toward sulfur compounds, which might because the ZnO nanoparticles were enwrapped in the sol-gel network, and the strong coordination action between Zn ion and S ion was therefore blocked. The incorporation of graphene into ZnO based sol-gel network greatly enlarged the BET surface area from 1.2 m2/g to 169.4 m2/g and further increased the adsorption sites. Combining the superior properties of extraordinary surface area of graphene and the strong coordination action of ZnO to sulfur compounds, the ZnO/graphene SPME fiber showed much higher adsorption affinity to 1-octanethiol (enrichment factor, EF, 1087) than other aliphatic compounds without sulfur-containing groups (EFsPDMS) and polydimethylsiloxane/divinylbenzene (PDMS/DVB) SPME fibers. Several most abundant sulfur volatiles in Chinese chive and garlic sprout were analyzed using the ZnO/graphene SPME fiber in combination with gas chromatography-mass spectrometry (GC-MS). Their limits of detection were 0.1-0.7 μg/L. The relative standard deviation (RSD) using one fiber ranged from 3.6% to 9.1%. The fiber-to-fiber reproducibility for three parallel prepared fibers was 4.8-10.8%. The contents were in the range of 1.0-46.4 μg/g with recoveries of 80.1-91.6% for four main

  19. Performance Factors and Sulfur Tolerance of Metal Supported Solid Oxide Fuel Cells with Nanostructured Ni:GDC Infiltrated Anodes

    DEFF Research Database (Denmark)

    Nielsen, Jimmi; Persson, Åsa Helen; Sudireddy, Bhaskar Reddy

    2015-01-01

    poisoning. The ceria can be incorporated as a Ni:GDC cermet anode, but also via infiltration of ceria and doped ceria into the conventional Ni:YSZ cermet anode. Both approaches have been reported to improve the tolerance towards sulfur poisoning [1-3]. In the present study we report the performance...... concentrations of 2, 5 and 10 ppm in hydrogen fuel, during galvanostatic operation at a current load of 0.25 Acm-2. The results are illustrated and compared with the conventional SOFC Ni:YSZ cermet anode in figure 1, where the relative increase in anode polarization resistance as a function of Ni sulfur coverage...... is shown. The comparison indicate the MS-SOFC anode of the present study to be more tolerant towards sulfur poisoning than the conventional Ni:YSZ cermet anode. [1] K. Sasaki et al., J. Electrochem. Soc., 153, A2023–A2029 (2006). [2] L. Zhang et al., International Journal of Hydrogen Energy, 35, 12359...

  20. Density functional theory analysis of the reaction pathway for methane oxidation to acetic acid catalyzed by Pd2+ in sulfuric acid.

    Science.gov (United States)

    Chempath, Shaji; Bell, Alexis T

    2006-04-12

    Density functional theory has been used to investigate the thermodynamics and activation barriers associated with the direct oxidation of methane to acetic acid catalyzed by Pd2+ cation in concentrated sulfuric acid. Pd2+ cations in such solutions are ligated by two bisulfate anions and by one or two molecules of sulfuric acid. Methane oxidation is initiated by the addition of CH4 across one of the Pd-O bonds of a bisulfate ligand to form Pd(HSO4)(CH3)(H2SO4)2. The latter species will react with CO to produce Pd(HSO4)(CH3CO)(H2SO4)2. The most likely path to the final products is found to be via oxidation of Pd(HSO4)(CH3)(H2SO4)2 and Pd(HSO4)(CH3CO)(H2SO4)2 to form Pd(eta2-HSO4)(HSO4)2(CH3)(H2SO4) and Pd(eta2-HSO4)(HSO4)2(CH3CO)(H2SO4), respectively. CH3HSO4 or CH3COHSO4 is then produced by reductive elimination from the latter two species, and CH(3)COOH is then formed by hydrolysis of CH3COHSO4. The loss of Pd2+ from solution to form Pd(0) or Pd-black is predicted to occur via reduction with CO. This process is offset, though, by reoxidation of palladium by either H2SO4 or O2.

  1. A kinetic and mechanistic study on the oxidation of l-methionine and N-acetyl l-methionine by cerium(IV in sulfuric acid medium

    Directory of Open Access Journals (Sweden)

    T. Sumathi

    2016-09-01

    Full Text Available The kinetics of oxidation of l-methionine and N-acetyl l-methionine by Ce(IV in sulfuric acid–sulfate media in the range of 288.1–298.1 K has been investigated. The major oxidation products of methionine and N-acetyl l-methionine have been identified as methionine sulfoxide and N-acetyl methionine sulfoxide. The major oxidation products have been confirmed by qualitative analysis and boiling point. The reaction was first order with respect to l-methionine, N-acetyl l-methionine and Ce(IV. Increase in [H+], ionic strength and HSO4- did not affect the reaction rate. Under the experimental conditions, Ce4+ was the effective oxidizing species of cerium. Increase in dielectric constant of the medium decreased the reaction rate. Under nitrogen atmosphere, the reaction system can initiate polymerization of acrylonitrile, indicating the generation of free radicals. Activation parameters associated with the overall reaction have been calculated.

  2. Nanostructure-Directed Chemical Sensing: The IHSAB Principle and the Effect of Nitrogen and Sulfur Functionalization on Metal Oxide Decorated Interface Response

    Directory of Open Access Journals (Sweden)

    James L. Gole

    2013-08-01

    Full Text Available The response matrix, as metal oxide nanostructure decorated n-type semiconductor interfaces are modified in situ through direct amination and through treatment with organic sulfides and thiols, is demonstrated. Nanostructured TiO2, SnOx, NiO and CuxO (x = 1,2, in order of decreasing Lewis acidity, are deposited to a porous silicon interface to direct a dominant electron transduction process for reversible chemical sensing in the absence of significant chemical bond formation. The metal oxide sensing sites can be modified to decrease their Lewis acidity in a process appearing to substitute nitrogen or sulfur, providing a weak interaction to form the oxynitrides and oxysulfides. Treatment with triethylamine and diethyl sulfide decreases the Lewis acidity of the metal oxide sites. Treatment with acidic ethane thiol modifies the sensor response in an opposite sense, suggesting that there are thiol (SH groups present on the surface that provide a Brønsted acidity to the surface. The in situ modification of the metal oxides deposited to the interface changes the reversible interaction with the analytes, NH3 and NO. The observed change for either the more basic oxynitrides or oxysulfides or the apparent Brønsted acid sites produced from the interaction of the thiols do not represent a simple increase in surface basicity or acidity, but appear to involve a change in molecular electronic structure, which is well explained using the recently developed inverse hard and soft acids and bases (IHSAB model.

  3. Observation of new particle formation and measurement of sulfuric acid, ammonia, amines and highly oxidized organic molecules at a rural site in central Germany

    Directory of Open Access Journals (Sweden)

    A. Kürten

    2016-10-01

    Full Text Available The exact mechanisms for new particle formation (NPF under different boundary layer conditions are not known yet. One important question is whether amines and sulfuric acid lead to efficient NPF in the atmosphere. Furthermore, it is not clear to what extent highly oxidized organic molecules (HOMs are involved in NPF. We conducted field measurements at a rural site in central Germany in the proximity of three larger dairy farms to investigate whether there is a connection between NPF and the presence of amines and/or ammonia due to the local emissions from the farms. Comprehensive measurements using a nitrate chemical ionization–atmospheric pressure interface time-of-flight (CI-APi-TOF mass spectrometer, a proton-transfer-reaction mass spectrometer (PTR-MS, particle counters and differential mobility analyzers (DMAs, as well as measurements of trace gases and meteorological parameters, were performed. We demonstrate here that the nitrate CI-APi-TOF is suitable for sensitive measurements of sulfuric acid, amines, a nitrosamine, ammonia, iodic acid and HOMs. NPF was found to correlate with sulfuric acid, while an anti-correlation with RH, amines and ammonia is observed. The anti-correlation between NPF and amines could be due to the efficient uptake of these compounds by nucleating clusters and small particles. Much higher HOM dimer (C19/C20 compounds concentrations during the night than during the day indicate that these HOMs do not efficiently self-nucleate as no nighttime NPF is observed. Observed iodic acid probably originates from an iodine-containing reservoir substance, but the iodine signals are very likely too low to have a significant effect on NPF.

  4. Diversity and Transcriptional Levels of RuBisCO Form II of Sulfur-Oxidizing γ-Proteobacteria in Coastal-Upwelling Waters with Seasonal Anoxia

    Directory of Open Access Journals (Sweden)

    Bárbara Léniz

    2017-07-01

    Full Text Available Seasonal wind-driven upwelling, high primary production in surface waters, and oxygen deficiency in subsurface waters characterize the coastal ecosystem of the subtropical eastern South Pacific (ESP, and shape the nature and dynamics of the microbial community structure and function. We investigated the diversity, abundance, and transcriptional levels of the gene encoding the large subunit form II of the RuBisCO enzyme (cbbM in the pelagic microbial community at a continental-shelf site off central Chile over 2 years. We focused on cbbM genes affiliated with the sulfur-oxidizing γ-proteobacteria cluster, whose members are known to dominate in oxygen-deficient marine environments and are highly abundant in the study area. Phylogenetic analysis of cbbM sequences suggests the presence of a novel group of chemolithoautotrophs, closely related to the SUP05/ARCTIC96BD-19 clade. Through (RT-qPCR, we studied the cbbM gene abundance and transcript dynamics over an annual cycle, finding a significantly higher number of cbbM copies per unit volume in months of active upwelling and at depths in which oxygen was scarce or absent. The same temporal pattern was observed at the transcriptional level. We also analyzed the relative expression of key genes for carbon, nitrogen and sulfur cycling in six metatranscriptomic datasets, for two characteristic periods within the annual cycle: the anoxic upwelling and the suboxic downwelling. Our results indicate that coastal waters of the subtropical ESP contain transcriptionally active populations of carbon fixing pelagic bacteria, whose dynamics is controlled, in large part, by fluctuations in oxygen levels. They also suggest that chemolithoautotrophic processes coupled to the sulfur and nitrogen cycles become increasingly important for the carbon economy of marine coastal waters as oxygen concentrations decline.

  5. Ge{sub 0.83}Sn{sub 0.17} p-channel metal-oxide-semiconductor field-effect transistors: Impact of sulfur passivation on gate stack quality

    Energy Technology Data Exchange (ETDEWEB)

    Lei, Dian; Wang, Wei; Gong, Xiao, E-mail: elegong@nus.edu.sg, E-mail: yeo@ieee.org; Liang, Gengchiau; Yeo, Yee-Chia, E-mail: elegong@nus.edu.sg, E-mail: yeo@ieee.org [Department of Electrical and Computer Engineering, National University of Singapore, Singapore 117576 (Singapore); Zhang, Zheng; Pan, Jisheng [Institute of Material Research and Engineering, A*STAR (Agency for Science, Technology and Research), 3 Research Link, Singapore 117602 (Singapore); Tok, Eng-Soon [Department of Physics, National University of Singapore, Singapore 117551 (Singapore)

    2016-01-14

    The effect of room temperature sulfur passivation of the surface of Ge{sub 0.83}Sn{sub 0.17} prior to high-k dielectric (HfO{sub 2}) deposition is investigated. X-ray photoelectron spectroscopy (XPS) was used to examine the chemical bonding at the interface of HfO{sub 2} and Ge{sub 0.83}Sn{sub 0.17}. Sulfur passivation is found to be effective in suppressing the formation of both Ge oxides and Sn oxides. A comparison of XPS results for sulfur-passivated and non-passivated Ge{sub 0.83}Sn{sub 0.17} samples shows that sulfur passivation of the GeSn surface could also suppress the surface segregation of Sn atoms. In addition, sulfur passivation reduces the interface trap density D{sub it} at the high-k dielectric/Ge{sub 0.83}Sn{sub 0.17} interface from the valence band edge to the midgap of Ge{sub 0.83}Sn{sub 0.17}, as compared with a non-passivated control. The impact of the improved D{sub it} is demonstrated in Ge{sub 0.83}Sn{sub 0.17} p-channel metal-oxide-semiconductor field-effect transistors (p-MOSFETs). Ge{sub 0.83}Sn{sub 0.17} p-MOSFETs with sulfur passivation show improved subthreshold swing S, intrinsic transconductance G{sub m,int}, and effective hole mobility μ{sub eff} as compared with the non-passivated control. At a high inversion carrier density N{sub inv} of 1 × 10{sup 13 }cm{sup −2}, sulfur passivation increases μ{sub eff} by 25% in Ge{sub 0.83}Sn{sub 0.17} p-MOSFETs.

  6. Non-equilibrium oxidation states of zirconium during early stages of metal oxidation

    International Nuclear Information System (INIS)

    Ma, Wen; Yildiz, Bilge; Herbert, F. William; Senanayake, Sanjaya D.

    2015-01-01

    The chemical state of Zr during the initial, self-limiting stage of oxidation on single crystal zirconium (0001), with oxide thickness on the order of 1 nm, was probed by synchrotron x-ray photoelectron spectroscopy. Quantitative analysis of the Zr 3d spectrum by the spectrum reconstruction method demonstrated the formation of Zr 1+ , Zr 2+ , and Zr 3+ as non-equilibrium oxidation states, in addition to Zr 4+ in the stoichiometric ZrO 2 . This finding resolves the long-debated question of whether it is possible to form any valence states between Zr 0 and Zr 4+ at the metal-oxide interface. The presence of local strong electric fields and the minimization of interfacial energy are assessed and demonstrated as mechanisms that can drive the formation of these non-equilibrium valence states of Zr

  7. Sulfur Mustard

    Science.gov (United States)

    ... in of the vapors can cause chronic respiratory disease, repeated respiratory infections, or death. Extensive eye exposure can cause permanent blindness. Exposure to sulfur mustard may increase a person’s risk for lung and respiratory cancer. ...

  8. Sulfur isotopes of host strata for Howards Pass (Yukon–Northwest Territories) Zn-Pb deposits implicate anaerobic oxidation of methane, not basin stagnation

    Science.gov (United States)

    Johnson, Craig A.; Slack, John F.; Dumoulin, Julie A.; Kelley, Karen Duttweiler; Falck, Hendrik

    2018-01-01

    A new sulfur isotope stratigraphic profile has been developed for Ordovician-Silurian mudstones that host the Howards Pass Zn-Pb deposits (Canada) in an attempt to reconcile the traditional model of a stagnant euxinic basin setting with new contradictory findings. Our analyses of pyrite confirm the up-section 34S enrichment reported previously, but additional observations show parallel depletion of carbonate 13C, an increase in organic carbon weight percent, and a change in pyrite morphology. Taken together, the data suggest that the 34S enrichment reflects a transition in the mechanism of pyrite formation during diagenesis, not isotopic evolution of a stagnant water mass. Low in the stratigraphic section, pyrite formed mainly in the sulfate reduction zone in association with organic matter–driven bacterial sulfate reduction. In contrast, starting just below the Zn-Pb mineralized horizon, pyrite formed increasingly within the sulfate-methane transition zone in association with anaerobic oxidation of methane. Our new insights on diagenesis have implications for (1) the setting of Zn-Pb ore formation, (2) the reliability of redox proxies involving metals, and (3) the source of ore sulfur for Howards Pass, and potentially for other stratiform Zn-Pb deposits contained in carbonaceous strata.

  9. Unprecedented Oxidative Addition of Highly Active Manganese into the Oxygen-Sulfur Bond of Coumarin and Pyrone 4-Tosylates

    Energy Technology Data Exchange (ETDEWEB)

    Shin, Ueon Sang; Joo, Seong-Ryu; Kim, Seung-Hoi [Dankook University , Cheonan (Korea, Republic of)

    2016-06-15

    Novel organomanganese reagents, 2-oxo-2H-chromen-4-yloxy tosylmanganese (A1), and 6-methyl-2-oxo-2H-pyran-4-yloxy tosylmanganese (A2), were obtained by the reaction of highly active Mn with 2-oxo-2H-chromen-4-yl 4-methylbenzenesulfonate (I) and 6-methyl-2-oxo-2H-pyran-4-yl-4-methylbenzenesulfonate (II), respectively. This was accomplished by the insertion of Mn into the oxygen-sulfur bond. Of interest, subsequent cross-coupling reactions of the thus-obtained organomanganese reagents afforded two different products, esters and sulfones, depending on the electrophile used under mild conditions.

  10. Acidophilic sulfur disproportionation

    Science.gov (United States)

    Hardisty, Dalton S.; Olyphant, Greg A.; Bell, Jonathan B.; Johnson, Adam P.; Pratt, Lisa M.

    2013-07-01

    Bacterial disproportionation of elemental sulfur (S0) is a well-studied metabolism and is not previously reported to occur at pH values less than 4.5. In this study, a sediment core from an abandoned-coal-mine-waste deposit in Southwest Indiana revealed sulfur isotope fractionations between S0 and pyrite (Δ34Ses-py) of up to -35‰, inferred to indicate intense recycling of S0 via bacterial disproportionation and sulfide oxidation. Additionally, the chemistry of seasonally collected pore-water profiles were found to vary, with pore-water pH ranging from 2.2 to 3.8 and observed seasonal redox shifts expressed as abrupt transitions from Fe(III) to Fe(II) dominated conditions, often controlled by fluctuating water table depths. S0 is a common product during the oxidation of pyrite, a process known to generate acidic waters during weathering and production of acid mine drainage. The H2S product of S0 disproportionation, fractionated by up to -8.6‰, is rapidly oxidized to S0 near redox gradients via reaction with Fe(III) allowing for the accumulation of isotopically light S0 that can then become subject to further sulfur disproportionation. A mass-balance model for S0 incorporating pyrite oxidation, S0 disproportionation, and S0 oxidation readily explains the range of observed Δ34Ses-py and emphasizes the necessity of seasonally varying pyrite weathering and metabolic rates, as indicated by the pore water chemistry. The findings of this research suggest that S0 disproportionation is potentially a common microbial process at a pH < 4.5 and can create large sulfur isotope fractionations, even in the absence of sulfate reduction.

  11. EnviroAtlas - Atmospheric Nitrogen and Sulfur Deposition by 12-digit HUC for the Conterminous United States (2011)

    Data.gov (United States)

    U.S. Environmental Protection Agency — This EnviroAtlas dataset includes annual nitrogen and sulfur deposition within each 12-digit HUC subwatershed for the year 2011. Values are provided for total...

  12. Oxidatively generated DNA/RNA damage in psychological stress states

    DEFF Research Database (Denmark)

    Jørgensen, Anders

    2013-01-01

    age-related somatic disorders. The overall aim of the PhD project was to investigate the relation between psychopathology, psychological stress, stress hormone secretion and oxidatively generated DNA and RNA damage, as measured by the urinary excretion of markers of whole-body DNA/RNA oxidation (8...... between the 24 h urinary cortisol excretion and the excretion of 8-oxodG/8-oxoGuo, determined in the same samples. Collectively, the studies could not confirm an association between psychological stress and oxidative stress on nucleic acids. Systemic oxidatively generated DNA/RNA damage was increased......Both non-pathological psychological stress states and mental disorders are associated with molecular, cellular and epidemiological signs of accelerated aging. Oxidative stress on nucleic acids is a critical component of cellular and organismal aging, and a suggested pathogenic mechanism in several...

  13. Charge state of oxide layer of SIMOX-structures

    CERN Document Server

    Askinazi, A Y; Dmitriev, V A; Miloglyadova, L V

    2001-01-01

    The charge state of the oxide layer of the SIMOX-structures, obtained in the course of forming the oxide layers, bricked up in the silicon volume, through the oxygen ions implantation into the Si, is studied. The charge state of the given structures is studied through the method of the layer-by-layer profiling, which makes it possible to obtain the dependence of the plane zones potential on the oxide layer thickness. It is established, that during the process of the SIMOX-structures formation in the oxide layer near the boundary with the Si there appear defects, responsible for the charge. The radiation from the near-the-ultraviolet (NUV) area without the applied electric field neutralizes the given charge. The simultaneous impact of the NUV-radiation and electric field leads to the formation of significantly positive charge

  14. Large fractions of CO2-fixing microorganisms in pristine limestone aquifers appear to be involved in the oxidation of reduced sulfur and nitrogen compounds

    Science.gov (United States)

    Herrmann, Martina; Rusznyák, Anna; Akob, Denise M.; Schulze, Isabel; Opitz, Sebastian; Totsche, Kai Uwe; Küsel, Kirsten

    2015-01-01

    The traditional view of the dependency of subsurface environments on surface-derived allochthonous carbon inputs is challenged by increasing evidence for the role of lithoautotrophy in aquifer carbon flow. We linked information on autotrophy (Calvin-Benson-Bassham cycle) with that from total microbial community analysis in groundwater at two superimposed—upper and lower—limestone groundwater reservoirs (aquifers). Quantitative PCR revealed that up to 17% of the microbial population had the genetic potential to fix CO2 via the Calvin cycle, with abundances of cbbM and cbbL genes, encoding RubisCO (ribulose-1,5-bisphosphate carboxylase/oxygenase) forms I and II, ranging from 1.14 × 103 to 6 × 106 genes liter−1 over a 2-year period. The structure of the active microbial communities based on 16S rRNA transcripts differed between the two aquifers, with a larger fraction of heterotrophic, facultative anaerobic, soil-related groups in the oxygen-deficient upper aquifer. Most identified CO2-assimilating phylogenetic groups appeared to be involved in the oxidation of sulfur or nitrogen compounds and harbored both RubisCO forms I and II, allowing efficient CO2 fixation in environments with strong oxygen and CO2 fluctuations. The genera Sulfuricellaand Nitrosomonas were represented by read fractions of up to 78 and 33%, respectively, within the cbbM and cbbL transcript pool and accounted for 5.6 and 3.8% of 16S rRNA sequence reads, respectively, in the lower aquifer. Our results indicate that a large fraction of bacteria in pristine limestone aquifers has the genetic potential for autotrophic CO2 fixation, with energy most likely provided by the oxidation of reduced sulfur and nitrogen compounds.

  15. Characterization of desulfurization, denitrogenation and process sulfur transfer during hydropyrolysis of Chinese high sulfur coals

    Energy Technology Data Exchange (ETDEWEB)

    Sun Chenggong; Li Baoqing [Chinese Academy of Sciences, Taiyuan (China). State Key Lab. of Coal Conversion; Snape, C.E. [Strathclyde Univ., Glasgow (United Kingdom). Dept. of Pure and Applied Chemistry

    1997-12-31

    The process desulphurization and denitrogenation of Chinese high sulfur coals and the characteristics of sulfur transformation during non-catalytic hydropyrolysis were investigated by a 10 g fixed-bed reactor and a small-scaled reactor with online spectrometry respectively. It was indicated that more than 70% of the total sulfur of the two high sulfur coals and almost all pyritic sulfur are removed as H{sub 2}S, leaving the char and tar products with much less sulfur distribution. The liability of sulfur transformation to tar products is closely related to the thiophenic structure forms rather than sulfidic forms. At the same time, the formation of trace amount of sulfur dioxide indicates the presence of inherent sulfur oxidation reactions inside coal frame structures even under H{sub 2} pressure. (orig.)

  16. Demand outlook for sulfur and high-sulfur petroleum coke

    Energy Technology Data Exchange (ETDEWEB)

    Koshkarov, V.Ya.; Danil' yan, P.G.; Feotov, V.E.; Gimaev, R.N.; Koshkarova, M.E.; Sadykova, S.R.; Vodovichenko, N.S.

    1980-01-01

    The feasibility of using sulfur and high-sulfur petroleum coke fines in pyrometallurgical processes and also in the chemical and coal-tar chemical industry is examined. Results of industrial tests on briquetting fines of petroleum coke with a petroleum binder are presented. The feasibility of using the obtained briquets in shaft furnace smelting of oxidized nickel ores, production of anode stock, and also in the chemical industry are demonstrated.

  17. Effect of microorganisms on the plutonium oxidation states

    International Nuclear Information System (INIS)

    Lukšienė, Benedikta; Druteikienė, Rūta; Pečiulytė, Dalia; Baltrūnas, Dalis; Remeikis, Vidmantas; Paškevičius, Algimantas

    2012-01-01

    Particular microbes from substrates at the low-level radioactive waste repository in the Ignalina NPP territory were exposed to 239 Pu (IV) at low pH under aerobic conditions. Pu(III) and Pu(IV) were separated and quantitatively evaluated using the modified anion exchange method and alpha spectrometry. Tested bacteria Bacillus mycoides and Serratia marcescens were more effective in Pu reduction than Rhodococcus fascians. Fungi Paecillomyces lilacinus and Absidia spinosa var. spinosa as well as bacterium Rhodococcus fascians did not alter the plutonium oxidation state. - Highlights: ► Particular microbes from low-level radioactive waste repository were exposed to Pu (IV). ► Some tested bacteria induced slight Pu (IV) reduction at low pH under aerobic conditions. ► Tested fungi did not show peculiarities to alter Pu oxidation state. ► The modified radiochemical method was applied to differentiate Pu oxidation states.

  18. Effect of microorganisms on the plutonium oxidation states

    Energy Technology Data Exchange (ETDEWEB)

    Luksiene, Benedikta, E-mail: bena@ar.fi.lt [Center for Physical Sciences and Technology, Savanoriu ave 231, LT-02300 Vilnius (Lithuania); Druteikiene, Ruta [Center for Physical Sciences and Technology, Savanoriu ave 231, LT-02300 Vilnius (Lithuania); Peciulyte, Dalia [Nature Research Centre, Akademijos street 2, LT-08412 Vilnius (Lithuania); Baltrunas, Dalis; Remeikis, Vidmantas [Center for Physical Sciences and Technology, Savanoriu ave 231, LT-02300 Vilnius (Lithuania); Paskevicius, Algimantas [Nature Research Centre, Akademijos street 2, LT-08412 Vilnius (Lithuania)

    2012-03-15

    Particular microbes from substrates at the low-level radioactive waste repository in the Ignalina NPP territory were exposed to {sup 239}Pu (IV) at low pH under aerobic conditions. Pu(III) and Pu(IV) were separated and quantitatively evaluated using the modified anion exchange method and alpha spectrometry. Tested bacteria Bacillus mycoides and Serratia marcescens were more effective in Pu reduction than Rhodococcus fascians. Fungi Paecillomyces lilacinus and Absidia spinosa var. spinosa as well as bacterium Rhodococcus fascians did not alter the plutonium oxidation state. - Highlights: Black-Right-Pointing-Pointer Particular microbes from low-level radioactive waste repository were exposed to Pu (IV). Black-Right-Pointing-Pointer Some tested bacteria induced slight Pu (IV) reduction at low pH under aerobic conditions. Black-Right-Pointing-Pointer Tested fungi did not show peculiarities to alter Pu oxidation state. Black-Right-Pointing-Pointer The modified radiochemical method was applied to differentiate Pu oxidation states.

  19. Structural and Redox Properties of Vanadium Complexes in Molten Salts of Interest for the Catalytic Oxidation of Sulfur Dioxide

    DEFF Research Database (Denmark)

    Boghosian, S.; Chrissanthopoulos, A.; Fehrmann, Rasmus

    2000-01-01

    Electronic absorption (UV/VIS) spectra have been obtained at 450 degrees C from V2O5-K2S2O7 molten mixtures in SO2 ( P-SO2 = 0 - 1.2 atm) gas atmospheres. The data are in agreement with the V-V reversible arrow V-IV equilibrium: (VO)(2)O(SO4)(4)(4-)(l) + SO2(g) - 2VO(SO4)(2)(2-)(l) + SO3(g). Sulfur...... and vibrational properties of the vanadium complexes formed in the molten salt-gas system V2O5-M2S2O7-M2SO4/SO2-O-2 (M = K or Cs). The spectral features and the exploitation of the relative Raman intensities indicate that the (VO)(2)O(SO4)(4)(+) dimeric complex unit which possesses a V-O-V bridge is formed...

  20. In Situ Scanning Tunneling Microscopy Topography Changes of Gold (111) in Aqueous Sulfuric Acid Produced by Electrochemical Surface Oxidation and Reduction and Relaxation Phenomena

    Science.gov (United States)

    Pasquale, M. A.; Nieto, F. J. Rodríguez; Arvia, A. J.

    The electrochemical formation and reduction of O-layers on gold (111) films in 1 m sulfuric acid under different potentiodynamic routines are investigated utilizing in situ scanning tunneling microscopy. The surface dynamics is interpreted considering the anodic and cathodic reaction pathways recently proposed complemented with concurrent relaxation phenomena occurring after gold (111) lattice mild disruption (one gold atom deep) and moderate disruption (several atoms deep). The dynamics of both oxidized and reduced gold topographies depends on the potentiodynamic routine utilized to form OH/O surface species. The topography resulting from a mild oxidative disruption is dominated by quasi-2D holes and hillocks of the order of 5 nm, involving about 500-600 gold atoms each, and their coalescence. A cooperative turnover process at the O-layer, in which the anion ad-layer and interfacial water play a key role, determines the oxidized surface topography. The reduction of these O-layers results in gold clusters, their features depending on the applied potential routine. A moderate oxidative disruption produces a surface topography of hillocks and holes several gold atoms high and deep, respectively. The subsequent reduction leads to a spinodal gold pattern. Concurrent coalescence appears to be the result of an Ostwald ripening that involves the surface diffusion of both gold atoms and clusters. These processes produce an increase in surface roughness and an incipient gold faceting. The dynamics of different topographies can be qualitatively explained employing the arguments from colloidal science theory. For 1.1 V ≤ E ≅ Epzc weak electrostatic repulsions favor gold atom/cluster coalescence, whereas for E < Epzc the attenuated electrostatic repulsions among gold surfaces stabilize small clusters over the substrate producing string-like patterns.

  1. Shifts in oxidation states of cerium oxide nanoparticles detected inside intact hydrated cells and organelles

    Energy Technology Data Exchange (ETDEWEB)

    Szymanski, Craig J.; Munusamy, Prabhakaran; Mihai, Cosmin; Xie, Yumei; Hu, Dehong; Gilles, Marry K.; Tyliszczak, T.; Thevuthasan, Suntharampillai; Baer, Donald R.; Orr, Galya

    2015-09-01

    Cerium oxide nanoparticles (CNPs) have been shown to induce diverse biological effects, ranging from toxic to beneficial. The beneficial effects have been attributed to the potential antioxidant activity of CNPs via certain redox reactions, depending on their oxidation state or Ce3+/Ce4+ ratio. However, this ratio is strongly dependent on the environment and age of the nanoparticles and it is unclear whether and how the complex intracellular environment impacts this ratio and the possible redox reactions of CNPs. To identify any changes in the oxidation state of CNPs in the intracellular environment and better understand their intracellular reactions, we directly quantified the oxidation states of CNPs outside and inside intact hydrated cells and organelles using correlated scanning transmission x-ray and super resolution fluorescence microscopies. By analyzing hundreds of small CNP aggregates, we detected a shift to a higher Ce3+/Ce4+ ratio in CNPs inside versus outside the cells, indicating a net reduction of CNPs in the intracellular environment. We further found a similar ratio in the cytoplasm and in the lysosomes, indicating that the net reduction occurs earlier in the internalization pathway. Together with oxidative stress and toxicity measurements, our observations identify a net reduction of CNPs in the intracellular environment, which is consistent with their involvement in potentially beneficial oxidation reactions, but also point to interactions that can negatively impact the health of cells.

  2. Sulfur activation in Hiroshima

    International Nuclear Information System (INIS)

    Kerr, G.D.; Pace, J.V. III.

    1987-01-01

    In 1979, we attempted to establish the validity of source terms for the Hiroshima and Nagasaki bombs using experimental data on sulfur activation. Close agreement was observed between measured and calculated values for test firings of Nagasaki-type bombs. The calculated values were based on source terms developed by W.E. Preeg at the Los Alamos National Laboratory (LANL). A discrepancy was found, however, when we compared calculated values for the two bombs because a 1956 report by R.R. Wilson stated that sulfur acitvation by fast neutrons in Hiroshima was approximately three times greater than in Nagasaki. Our calculations based on Preeg's source-term data predicted about equal sulfur activation in the two cities

  3. The Impact of HCl Precleaning and Sulfur Passivation on the Al2O3/Ge Interface in Ge Metal-Oxide-Semiconductor Capacitors

    International Nuclear Information System (INIS)

    Xue Bai-Qing; Chang Hu-Dong; Sun Bing; Wang Sheng-Kai; Liu Hong-Gang

    2012-01-01

    Surface treatment for Ge substrates using hydrogen chlorine cleaning and chemical passivation are investigated on AuTi/Al 2 O 3 /Ge metal-oxide-semiconductor capacitors. After hydrogen chlorine cleaning, a smooth Ge surface almost free from native oxide is demonstrated by atomic force microscopy and x-ray photoelectron spectroscopy observations. Passivation using a hydrogen chlorine solution is found to form a chlorine-terminated surface, while aqueous ammonium sulfide pretreatment results in a surface terminated by Ge-S bonding. Compared with chlorine-passivated samples, the sulfur-passivated ones show less frequency dispersion and better thermal stability based on capacitance-voltage characterizations. The samples with HCl pre-cleaning and (NH 4 ) 2 S passivation show less frequency dispersion than the HF pre-cleaning and (NH 4 ) 2 S passivated ones. The surface treatment process using hydrogen chlorine cleaning followed by aqueous ammonium sulfide passivation demonstrates a promising way to improve gate dielectric/Ge interface quality. (condensed matter: structure, mechanical and thermal properties)

  4. Effects of Reduced Sulfur Compounds on Pd-catalytic Hydrodechlorination of TCE in Groundwater by Cathodic H2 under Electrochemically-induced Oxidizing Conditions

    Science.gov (United States)

    Yuan, Songhu; Chen, Mingjie; Mao, Xuhui; Alshawabkeh, Akram N.

    2014-01-01

    Reduced sulfur compounds (RSCs) poison Pd catalysts for catalytic hydrodechlorination of contaminants in anoxic groundwater. This study investigates the effects of RSCs on Pd-catalytic hydrodechlorination of trichloroethylene (TCE) in oxic groundwater. Water electrolysis in an undivided electrolytic cell is used to produce H2 for TCE hydrodechlorination under oxidizing conditions. TCE is efficiently hydrodechlorinated to ethane, with significant accumulation of H2O2 under acidic conditions. Presence of sulfide at concentrations less than 93.8 μM moderately inhibits TCE hydrodechlorination and H2O2 production. Presence of sulfite at low concentrations (≤ 1 mM) significantly enhances TCE decay, while at high concentration (3 mM) inhibits initially and enhances afterwards when sulfite concentration declines to less than 1 mM. Using radical scavenging experiments and electron spin resonance assay, SO3•− which is generated from sulfite under oxidizing conditions is validated as the new reactive species contributing to the enhancement. This study reveals a distinct mechanism of effect of sulfite on TCE hydrodechlorination by Pd and H2 in oxic groundwater and presents an alternative approach to increasing resistance of Pd to RSCs poisoning. PMID:23962132

  5. Relationships among oxidation-reduction and acid-base properties of the actinides in high oxidation states

    International Nuclear Information System (INIS)

    Morss, L.R.

    1992-01-01

    The first chemical identification of plutonium, its subsequent isolation on the macroscopic scale, and more recent chemical separation schemes were achieved by taking advantage of the differences among the oxidation states of uranium, neptunium, and plutonium. Many acid-base properties modify the relative stabilities of oxidation states of the actinides. In the solid state, strongly basic compounds such as Cs 2 O yield complex oxides with oxidation states of Np(VII), Pu(VI), and Am(VI) whereas more acidic compounds such as CsF yield complex fluorides with lower oxidation states. In aqueous solution, high basicity and strongly covalent complexes favor high oxidation states. In nonaqueous solvent systems, high acidity generally favors low oxidation states. This paper elucidates and attempts to interpret the effects of these acid-base properties in a systematic fashion

  6. Impact of reduced graphene oxide on MoS{sub 2} grown by sulfurization of sputtered MoO{sub 3} and Mo precursor films

    Energy Technology Data Exchange (ETDEWEB)

    Pacley, Shanee, E-mail: shanee.pacley@us.af.mil; Brausch, Jacob; Beck-Millerton, Emory [U.S. Air Force Research Laboratory (AFRL)/Wright Patterson Air Force Base, Wright Patterson, Ohio 45433-7707 (United States); Hu, Jianjun; Jespersen, Michael [University of Dayton Research Institute, 300 College Park, Dayton, Ohio 45469 (United States); Hilton, Al [Wyle Laboratories, 4200 Colonel Glenn Hwy, Beavercreek, Ohio 45431 (United States); Waite, Adam [University Technology Corporation, 1270 N Fairfield Rd., Beavercreek, Ohio 45432 (United States); Voevodin, Andrey A. [Department of Materials Science and Engineering, University of North Texas, 1155 Union Circle, Denton, Texas 76203 (United States)

    2016-07-15

    Monolayer molybdenum disulfide (MoS{sub 2}), a two dimensional semiconducting dichalcogenide material with a bandgap of 1.8–1.9 eV, has demonstrated promise for future use in field effect transistors and optoelectronics. Various approaches have been used for MoS{sub 2} processing, the most common being chemical vapor deposition. During chemical vapor deposition, precursors such as Mo, MoO{sub 3}, and MoCl{sub 5} have been used to form a vapor reaction with sulfur, resulting in thin films of MoS{sub 2}. Currently, MoO{sub 3} ribbons and powder, and MoCl{sub 5} powder have been used. However, the use of ribbons and powder makes it difficult to grow large area-continuous films. Sputtering of Mo is an approach that has demonstrated continuous MoS{sub 2} film growth. In this paper, the authors compare the structural properties of MoS{sub 2} grown by sulfurization of pulse vapor deposited MoO{sub 3} and Mo precursor films. In addition, they have studied the effects that reduced graphene oxide (rGO) has on MoS{sub 2} structure. Reports show that rGO increases MoS{sub 2} grain growth during powder vaporization. Herein, the authors report a grain size increase for MoS{sub 2} when rGO was used during sulfurization of both sputtered Mo and MoO{sub 3} precursors. In addition, our transmission electron microscopy results show a more uniform and continuous film growth for the MoS{sub 2} films produced from Mo when compared to the films produced from MoO{sub 3}. Atomic force microscopy images further confirm this uniform and continuous film growth when Mo precursor was used. Finally, x-ray photoelectron spectroscopy results show that the MoS{sub 2} films produced using both precursors were stoichiometric and had about 7–8 layers in thickness, and that there was a slight improvement in stoichiometry when rGO was used.

  7. Photoelectron Spectroscopy and Density Functional Theory Studies of Iron Sulfur (FeS)m- (m = 2-8) Cluster Anions: Coexisting Multiple Spin States.

    Science.gov (United States)

    Yin, Shi; Bernstein, Elliot R

    2017-10-05

    Iron sulfur cluster anions (FeS) m - (m = 2-8) are studied by photoelectron spectroscopy (PES) at 3.492 eV (355 nm) and 4.661 eV (266 nm) photon energies, and by density functional theory (DFT) calculations. The most probable structures and ground state spin multiplicities for (FeS) m - (m = 2-8) clusters are tentatively assigned through a comparison of their theoretical and experiment first vertical detachment energy (VDE) values. Many spin states lie within 0.5 eV of the ground spin state for the larger (FeS) m - (m ≥ 4) clusters. Theoretical VDEs of these low lying spin states are in good agreement with the experimental VDE values. Therefore, multiple spin states of each of these iron sulfur cluster anions probably coexist under the current experimental conditions. Such available multiple spin states must be considered when evaluating the properties and behavior of these iron sulfur clusters in real chemical and biological systems. The experimental first VDEs of (FeS) m - (m = 1-8) clusters are observed to change with the cluster size (number m). The first VDE trends noted can be related to the different properties of the highest singly occupied molecular orbitals (NBO, HSOMOs) of each cluster anion. The changing nature of the NBO/HSOMO of these (FeS) m - (m = 1-8) clusters from a p orbital on S, to a d orbital on Fe, and to an Fe-Fe bonding orbital is probably responsible for the observed increasing trend for their first VDEs with respect to m.

  8. Optimization of LC-DRC-ICP-MS for the speciation of selenotrisulfides with simultaneous detection of sulfur and selenium as oxides combined with determination of elemental and isotope ratios

    DEFF Research Database (Denmark)

    Sturup, S.; Bendahl, L.; Gammelgaard, B.

    2006-01-01

    A LC-DRC-ICP-MS method for the simultaneous detection of selenium and Sulfur in the selenotrisulfides selenocysteineglutathione (Cys-Se-SG) and selenodiglutathione (GS-Se-SG) is described. Both sulfur and selenium are reacted with oxygen in the dynamic reaction cell (DRC) and detected as oxides....... The selenotrisulfides were separated applying a 30 rnin gradient liquid chromatographic (LC) method with a formic acid/methanol eluent. The detection limits for sulfur (as (SO+)-S-32-O-16) and selenium (as (SeO+)-Se-80-O-16) in the chromatographic system were 4.0 and 0.2 mu g L-1 (100 and 5 ng in absolute mass units...

  9. Formation and Control of Sulfur Oxides in Sour Gas Oxy-Combustion: Prediction Using a Reactor Network Model

    KAUST Repository

    Bongartz, Dominik

    2015-11-19

    © 2015 American Chemical Society. Sour natural gas currently requires expensive gas cleanup before it can be used in power generation because it contains large amounts of hydrogen sulfide (H2S) and carbon dioxide (CO2) that entail a low heating value and highly corrosive combustion products. A potential alternative is to use the gas directly in a gas turbine process employing oxy-fuel combustion, which could eliminate the need for gas cleanup while also enabling the application of carbon capture and sequestration, possibly combined with enhanced oil recovery (EOR). However, the exact influence of an oxy-fuel environment on the combustion products of sour gas has not been quantified yet. In this work, we used a reactor network model for the combustor and the gas turbine together with our recently assembled and validated detailed chemical reaction mechanism for sour gas combustion to investigate the influence of some basic design parameters on the combustion products of natural gas and sour gas in CO2 or H2O diluted oxy-fuel combustion as well as in conventional air combustion. Our calculations show that oxy-fuel combustion produces up to 2 orders of magnitude less of the highly corrosive product sulfur trioxide (SO3) than air combustion, which clearly demonstrates its potential in handling sulfur containing fuels. Unlike in air combustion, in oxy-fuel combustion, SO3 is mainly formed in the flame zone of the combustor and is then consumed as the combustion products are cooled in the dilution zone of the combustor and the turbine. In oxy-fuel combustion, H2O dilution leads to a higher combustion efficiency than CO2 dilution. However, if the process is to be combined with EOR, CO2 dilution makes it easier to comply with the very low levels of oxygen (O2) required in the EOR stream. Our calculations also show that it might even be beneficial to operate slightly fuel-rich because this simultaneously decreases the O2 and SO3 concentration further. The flame zone

  10. Catalytic oxidation of methanol on Pt/X (X = CaTP, NaTP electrodes in sulfuric acid solution

    Directory of Open Access Journals (Sweden)

    Said Benmokhtar

    2013-10-01

    Full Text Available In this paper, we report the synthesis and characterization of electrodes based on NASICON type phosphates. The study of the electrochemical oxidation of methanol at ambient temperature on electrodes based on NASICON type Ca0,5Ti2(PO43 (CaTP and Na5Ti(PO43 (NaTP compared to that of the platinum electrode model has been conducted by cyclic voltammetry in acidic medium. The results showed a significant increase of current density on the electro oxidation of methanol on the material developed based NASICON structure CaTP, cons deactivation of the electro oxidation is observed the closed structure type NaTP.

  11. The Social Cost of Trading: Measuring the Increased Damages from Sulfur Dioxide Trading in the United States

    Science.gov (United States)

    Henry, David D., III; Muller, Nicholas Z.; Mendelsohn, Robert O.

    2011-01-01

    The sulfur dioxide (SO[subscript 2]) cap and trade program established in the 1990 Clean Air Act Amendments is celebrated for reducing abatement costs ($0.7 to $2.1 billion per year) by allowing emissions allowances to be traded. Unfortunately, places with high marginal costs also tend to have high marginal damages. Ton-for-ton trading reduces…

  12. Bioleaching of metals from soils or sediments using the microbial sulfur cycle

    NARCIS (Netherlands)

    Tichy, R.

    1998-01-01

    Reduced inorganic sulfur species like elemental sulfur or sulfide are sensitive to changes in oxidative environments. Generally, inorganic reduced sulfur exists in natural environments in a solid phase, whereas its oxidation leads to sulfur solubilization and a production of acidity. This

  13. Participation of oxidized sulfur center in intramolecular free radical processes in the model organic compounds of biological importance

    International Nuclear Information System (INIS)

    Pogocki, D.M.

    2004-01-01

    The pathogenesis of neurodegenerative diseases such as prion diseases (Creutzfeldt-Jacob disease) and Alzheimer's disease is strongly associated with the presence of β-amyloid peptide (βA) and prion protein (hPrP) in the brain tissue. Both macromolecules contain methionine (Met) residues. Their presence seems to be responsible for unique redox properties of βA and hPrP. These residues may undergo relatively easy autooxidation and/or metal-catalysed oxidation. The presented studies were focused on the potential function of Met residues as antioxidants or pro-oxidants and on their role in radical-mediated oxidation of peptides and proteins. The role of S-, O-, N- and C-centered radicals generated in various oligopeptides containing Met and relevant model compounds has been examined in detail with respect to formation of 2c-3e bonds, redox processes, fragmentation and their mutual interconversion. In order to achieve these goals several experimental radiation, photochemical, and molecular modelling methods were applied. The experimental and molecular modelling results show significant influence of functional neighbouring groups and conformational flexibility of a peptide backbone on the oxidative reduction pathway in oligopeptides containing single and multiple Met residues. The results presented here allow for better understanding of the known propensities of βA and hPrP to reduce transition metals and to form reactive oxygen species and free radicals. (author)

  14. Oxidative Stress and Heart Failure in Altered Thyroid States

    Directory of Open Access Journals (Sweden)

    Pallavi Mishra

    2012-01-01

    Full Text Available Increased or reduced action of thyroid hormone on certain molecular pathways in the heart and vasculature causes relevant cardiovascular derangements. It is well established that hyperthyroidism induces a hyperdynamic cardiovascular state, which is associated with a faster heart rate, enhanced left ventricular systolic and diastolic function whereas hypothyroidism is characterized by the opposite changes. Hyperthyroidism and hypothyroidism represent opposite clinical conditions, albeit not mirror images. Recent experimental and clinical studies have suggested the involvement of ROS tissue damage under altered thyroid status. Altered-thyroid state-linked changes in heart modify their susceptibility to oxidants and the extent of the oxidative damage they suffer following oxidative challenge. Chronic increase in the cellular levels of ROS can lead to a catastrophic cycle of DNA damage, mitochondrial dysfunction, further ROS generation and cellular injury. Thus, these cellular events might play an important role in the development and progression of myocardial remodeling and heart failure in altered thyroid states (hypo- and hyper-thyroidism. The present review aims at elucidating the various signaling pathways mediated via ROS and their modulation under altered thyroid state and the possibility of antioxidant therapy.

  15. Oxidative decarboxylation of glycolic and phenylacetic acids with cerium(4) catalyzed by silver ions in the sulfuric acid media

    International Nuclear Information System (INIS)

    Venkatesvar Rao, G.; Nagardzhun Rao, Ch.; Sajprakash, P.K.

    1981-01-01

    Oxidative decarboxylation of glycolic and phenylacetic acids by cerium (4) in the presence of Ag + ions is studied. The Ce(4) order equals 1, glycolic acid order in the absence of a catalyst also equals 1 and is fractional (0.5) for a catalytic reaction. The phenylacetic acid order is fractional (0.75). The Ag + ion reaction order is fractional and constitutes 0.32 for glycolic and 0.36 for phenylacetic acids. The reaction mechanism is proposed [ru

  16. Micellar effect on the kinetics of oxidation of methyl blue by Ce(IV in sulfuric acid medium

    Directory of Open Access Journals (Sweden)

    Mohammed Hassan

    2015-01-01

    Full Text Available The kinetics of oxidation of methyl blue (MB by Ce(IV in aqueous and surfactant media has been carried out to explore the micellar effect on the rate and kinetic parameters of the reaction. The reaction was found to be first order with respect to both oxidant and substrate and fractional order with respect to H+. The active kinetic species of the oxidant was found to be Ce(SO4+2 based on the effect of ionic strength and sulfate ion on the rate of the reaction. The presence of micelles was found to inhibit the reaction and this effect has been explained by the association of one of the reactants with the micelles leaving the other reactant in the bulk solution. The binding constant and first order rate constant in micellar medium has been obtained by the application of pseudo-phase model to the experimental data. Interestingly, the temperature dependence of the reaction reveals that the reaction has negative activation energy in the absence of micelles, which turns to a positive value in the presence of micelles.

  17. Evolution of the Oxidation State of the Earth's Mantle

    Science.gov (United States)

    Danielson, L. R.; Righter, K.; Keller, L.; Christoffersen, E.; Rahman, Z.

    2015-01-01

    The oxidation state of the Earth's mantle during formation remains an unresolved question, whether it was constant throughout planetary accretion, transitioned from reduced to oxidized, or from oxidized to reduced. We investigate the stability of Fe3(+) at depth, in order to constrain processes (water, late accretion, dissociation of FeO) which may reduce or oxidize the Earth's mantle. In our previous experiments on shergottite compositions, variable fO2, T, and P less than 4 GPa, Fe3(+)/sigma Fe decreased slightly with increasing P, similar to terrestrial basalt. For oxidizing experiments less than 7GPa, Fe3(+)/sigma Fe decreased as well, but it's unclear from previous modelling whether the deeper mantle could retain significant Fe3(+). Our current experiments expand our pressure range deeper into the Earth's mantle and focus on compositions and conditions relevant to the early Earth. Preliminary multi-anvil experiments with Knippa basalt as the starting composition were conducted at 5-7 GPa and 1800 C, using a molybdenum capsule to set the fO2 near IW, by buffering with Mo-MoO3. TEM and EELS analyses revealed the run products quenched to polycrystalline phases, with the major phase pyroxene containing approximately equal to Fe3(+)/2(+). Experiments are underway to produce glassy samples that can be measured by EELS and XANES, and are conducted at higher pressures.

  18. Peatland Acidobacteria with a dissimilatory sulfur metabolism.

    Science.gov (United States)

    Hausmann, Bela; Pelikan, Claus; Herbold, Craig W; Köstlbacher, Stephan; Albertsen, Mads; Eichorst, Stephanie A; Glavina Del Rio, Tijana; Huemer, Martin; Nielsen, Per H; Rattei, Thomas; Stingl, Ulrich; Tringe, Susannah G; Trojan, Daniela; Wentrup, Cecilia; Woebken, Dagmar; Pester, Michael; Loy, Alexander

    2018-02-23

    Sulfur-cycling microorganisms impact organic matter decomposition in wetlands and consequently greenhouse gas emissions from these globally relevant environments. However, their identities and physiological properties are largely unknown. By applying a functional metagenomics approach to an acidic peatland, we recovered draft genomes of seven novel Acidobacteria species with the potential for dissimilatory sulfite (dsrAB, dsrC, dsrD, dsrN, dsrT, dsrMKJOP) or sulfate respiration (sat, aprBA, qmoABC plus dsr genes). Surprisingly, the genomes also encoded DsrL, which so far was only found in sulfur-oxidizing microorganisms. Metatranscriptome analysis demonstrated expression of acidobacterial sulfur-metabolism genes in native peat soil and their upregulation in diverse anoxic microcosms. This indicated an active sulfate respiration pathway, which, however, might also operate in reverse for dissimilatory sulfur oxidation or disproportionation as proposed for the sulfur-oxidizing Desulfurivibrio alkaliphilus. Acidobacteria that only harbored genes for sulfite reduction additionally encoded enzymes that liberate sulfite from organosulfonates, which suggested organic sulfur compounds as complementary energy sources. Further metabolic potentials included polysaccharide hydrolysis and sugar utilization, aerobic respiration, several fermentative capabilities, and hydrogen oxidation. Our findings extend both, the known physiological and genetic properties of Acidobacteria and the known taxonomic diversity of microorganisms with a DsrAB-based sulfur metabolism, and highlight new fundamental niches for facultative anaerobic Acidobacteria in wetlands based on exploitation of inorganic and organic sulfur molecules for energy conservation.

  19. Comparative Genomics of Green Sulfur Bacteria

    DEFF Research Database (Denmark)

    Ussery, David; Davenport, C; Tümmler, B

    2010-01-01

    Eleven completely sequenced Chlorobi genomes were compared in oligonucleotide usage, gene contents, and synteny. The green sulfur bacteria (GSB) are equipped with a core genome that sustains their anoxygenic phototrophic lifestyle by photosynthesis, sulfur oxidation, and CO(2) fixation. Whole...... weight of 10(6), and are probably instrumental for the bacteria to generate their own intimate (micro)environment....

  20. Corrosion-product transport, oxidation state and remedial measures

    International Nuclear Information System (INIS)

    Sawicki, J.A.; Brett, M.E.; Tapping, R.L.

    1998-10-01

    The issues associated with monitoring and controlling corrosion-product transport (CPT) in the balance-of-plant (BOP) and steam generators (SG) of CANDU stations are briefly reviewed. Efforts are focused on minimizing corrosion of carbon steel, which is used extensively in the CANDU primary and secondary systems. Emphasis is placed on the corrosion-product oxidation state as a monitor of water chemistry effectiveness and as a monitor of system corrosion effects. The discussion is based mostly on the results of observations from Ontario Hydro plants, and their comparisons with pressurized-water reactors. The effects of low oxygen and elevated hydrazine chemistry are reviewed, as well as the effects of layup and various startup conditions. Progress in monitoring electrochemical potential (ECP) at Ontario Hydro plants and its relationship to the oxidation state of corrosion products is reviewed. Observations on CPT on the primary side of SGs are also discussed. (author)

  1. Corrosion-product transport, oxidation state and remedial measures

    International Nuclear Information System (INIS)

    Sawicki, J.A.; Brett, M.E.; Tapping, R.L.

    1998-01-01

    The issues associated with monitoring and controlling corrosion-product transport (CPT) in the balance-of-plant (BOP) and steam generators (SG) of CANDU stations are briefly reviewed. The efforts are focused on minimizing corrosion of carbon steel, which is used extensively in the CANDU primary and secondary systems. Emphasis is placed on the corrosion-product oxidation state as a monitor of water chemistry effectiveness, and as a monitor of system corrosion effects. The discussion is based mostly on the results and observations from Ontario Hydro plants, and their comparisons with PWRs. The effects of low oxygen and elevated hydrazine chemistry are reviewed, as well as the effects of lay-up and various start-up conditions. Progress in monitoring electrochemical potential (ECP) at Ontario Hydro plants and its relationship to the oxidation state of corrosion products is reviewed. Observations on corrosion-product transport on the primary side of steam generators are also discussed. (author)

  2. Influence of oxidation state on the pH dependence of hydrous iridium oxide films

    International Nuclear Information System (INIS)

    Steegstra, Patrick; Ahlberg, Elisabet

    2012-01-01

    Many electrochemical reactions taking place in aqueous solution consume or produce protons. The pH in the diffusion layer can therefore be significantly altered during the reaction and there is a need for in situ pH measurements tracing this near surface pH. In the present paper the rotating ring disc technique was used to measure near surface pH changes during oxygen reduction, utilising hydrous iridium oxide as the pH sensing probe. Before such experiments a good understanding of the pH sensing properties of these films is required and the impact of the oxidation state of the film on the pH sensing properties was investigated as well as the influence of solution redox species. The pH sensitivity (depicted by dE/dpH) was found to depend on the average oxidation state of the film in a manner resembling the cyclic voltammetry response. In all cases the pH response is “supernernstian” with more than one proton per electron. The origin of this behaviour is discussed in the context of acid-base properties of the film and the existence of both hydrous and anhydrous oxide phases. The pH response depends also on the redox properties of the solution but can be optimised for various purposes by conditioning the film at different potentials. This was clearly illustrated by adding hydrogen peroxide, an intermediate in the oxygen reduction reaction, to the solution. It was shown that hydrous iridium oxide can be used as a reliable in situ pH sensor provided that care is taken to optimise the oxidation state of the film.

  3. Pentavalent Uranium Chemistry - Synthetic Pursuit Of A Rare Oxidation State

    Energy Technology Data Exchange (ETDEWEB)

    Graves, Christopher R [Los Alamos National Laboratory; Kiplinger, Jaqueline L [Los Alamos National Laboratory

    2009-01-01

    This feature article presents a comprehensive overview of pentavalent uranium systems in non-aqueous solution with a focus on the various synthetic avenues employed to access this unusual and very important oxidation state. Selected characterization data and theoretical aspects are also included. The purpose is to provide a perspective on this rapidly evolving field and identify new possibilities for future developments in pentavalent uranium chemistry.

  4. Study of uranium oxidation states in geological material.

    Science.gov (United States)

    Pidchenko, I; Salminen-Paatero, S; Rothe, J; Suksi, J

    2013-10-01

    A wet chemical method to determine uranium (U) oxidation states in geological material has been developed and tested. The problem faced in oxidation state determinations with wet chemical methods is that U redox state may change when extracted from the sample material, thereby leading to erroneous results. In order to quantify and monitor U redox behavior during the acidic extraction in the procedure, an analysis of added isotopic redox tracers, (236)U(VI) and (232)U(IV), and of variations in natural uranium isotope ratio ((234)U/(238)U) of indigenous U(IV) and U(VI) fractions was performed. Two sample materials with varying redox activity, U bearing rock and U-rich clayey lignite sediment, were used for the tests. The Fe(II)/Fe(III) redox-pair of the mineral phases was postulated as a potentially disturbing redox agent. The impact of Fe(III) on U was studied by reducing Fe(III) with ascorbic acid, which was added to the extraction solution. We observed that ascorbic acid protected most of the U from oxidation. The measured (234)U/(238)U ratio in U(IV) and U(VI) fractions in the sediment samples provided a unique tool to quantify U oxidation caused by Fe(III). Annealing (sample heating) to temperatures above 500 °C was supposed to heal ionizing radiation induced defects in the material that can disturb U redox state during extraction. Good agreement between two independent methods was obtained for DL-1a material: an average 38% of U(IV) determined by redox tracer corrected wet chemistry and 45% for XANES. Copyright © 2013 Elsevier Ltd. All rights reserved.

  5. Evaluation of nitrous oxide as a substitute for sulfur hexafluoride to reduce global warming impacts of ANSI/HPS N13.1 gaseous uniformity testing

    Science.gov (United States)

    Yu, Xiao-Ying; Barnett, J. Matthew; Amidan, Brett G.; Recknagle, Kurtis P.; Flaherty, Julia E.; Antonio, Ernest J.; Glissmeyer, John A.

    2018-03-01

    The ANSI/HPS N13.1-2011 standard requires gaseous tracer uniformity testing for sampling associated with stacks used in radioactive air emissions. Sulfur hexafluoride (SF6), a greenhouse gas with a high global warming potential, has long been the gas tracer used in such testing. To reduce the impact of gas tracer tests on the environment, nitrous oxide (N2O) was evaluated as a potential replacement to SF6. The physical evaluation included the development of a test plan to record percent coefficient of variance and the percent maximum deviation between the two gases while considering variables such as fan configuration, injection position, and flow rate. Statistical power was calculated to determine how many sample sets were needed, and computational fluid dynamic modeling was utilized to estimate overall mixing in stacks. Results show there are no significant differences between the behaviors of the two gases, and SF6 modeling corroborated N2O test results. Although, in principle, all tracer gases should behave in an identical manner for measuring mixing within a stack, the series of physical tests guided by statistics was performed to demonstrate the equivalence of N2O testing to SF6 testing in the context of stack qualification tests. The results demonstrate that N2O is a viable choice leading to a four times reduction in global warming impacts for future similar compliance driven testing.

  6. Sulfate reduction and methane oxidation activity below the sulfate-methane transition zone in Alaskan Beaufort Sea continental margin sediments: Implications for deep sulfur cycling

    Science.gov (United States)

    Treude, Tina; Krause, Stefan; Maltby, Johanna; Dale, Andrew W.; Coffin, Richard; Hamdan, Leila J.

    2014-11-01

    Two ∼6 m long sediment cores were collected along the ∼300 m isobath on the Alaskan Beaufort Sea continental margin. Both cores showed distinct sulfate-methane transition zones (SMTZ) at 105 and 120 cm below seafloor (cmbsf). Sulfate was not completely depleted below the SMTZ but remained between 30 and 500 μM. Sulfate reduction and anaerobic oxidation of methane (AOM) determined by radiotracer incubations were active throughout the methanogenic zone. Although a mass balance could not explain the source of sulfate below the SMTZ, geochemical profiles and correlation network analyses of biotic and abiotic data suggest a cryptic sulfur cycle involving iron, manganese and barite. Inhibition experiments with molybdate and 2-bromoethanesulfonate (BES) indicated decoupling of sulfate reduction and AOM and competition between sulfate reducers and methanogens for substrates. While correlation network analyses predicted coupling of AOM to iron reduction, the addition of manganese or iron did not stimulate AOM. Since none of the classical archaeal anaerobic methanotrophs (ANME) were abundant, the involvement of unknown or unconventional phylotypes in AOM is conceivable. The resistance of AOM activity to inhibitors implies deviation from conventional enzymatic pathways. This work suggests that the classical redox cascade of electron acceptor utilization based on Gibbs energy yields does not always hold in diffusion-dominated systems, and instead biotic processes may be more strongly coupled to mineralogy.

  7. Inhibitory effect of self-generated extracellular dissolved organic carbon on carbon dioxide fixation in sulfur-oxidizing bacteria during a chemoautotrophic cultivation process and its elimination.

    Science.gov (United States)

    Wang, Ya-Nan; Tsang, Yiu Fai; Wang, Lei; Fu, Xiaohua; Hu, Jiajun; Li, Huan; Le, Yiquan

    2018-03-01

    The features of extracellular dissolved organic carbon (EDOC) generation in two typical aerobic sulfur-oxidizing bacteria (Thiobacillus thioparus DSM 505 and Halothiobacillus neapolitanus DSM 15147) and its impact on CO 2 fixation during chemoautotrophic cultivation process were investigated. The results showed that EDOC accumulated in both strains during CO 2 fixation process. Large molecular weight (MW) EDOC derived from cell lysis and decay was dominant during the entire process in DSM 505, whereas small MW EDOC accounted for a large proportion during initial and middle stages of DSM 15147 as its cytoskeleton synthesis rate did not keep up with CO 2 assimilation rate. The self-generated EDOC feedback repressed cbb gene transcription and thus decreased total bacterial cell number and CO 2 fixation yield in both strains, but DSM 505 was more sensitive to this inhibition effect. Moreover, the membrane bioreactor effectively decreased the EDOC/TOC ratio and improved carbon fixation yield of DSM 505. Copyright © 2017 Elsevier Ltd. All rights reserved.

  8. Titania Supported Pt and Pt/Pd Nano-particle Catalysts for the Oxidation of Sulfur Dioxide

    DEFF Research Database (Denmark)

    Koutsopoulos, Sotiris; Johannessen, Tue; Eriksen, Kim Michael

    2006-01-01

    Several types of titania (anatase) were used as supports for pure platinum and Pt–Pd bimetallic alloy catalysts. The preparation methods, normal wet impregnation technique and flame aerosol synthesis, obtained metal loadings of 2% by weight. The prepared catalysts were tested for SO2 oxidation...... activity at atmospheric pressure in the temperature range 250–600 °C. The SO2 to SO3 conversion efficiency of the Pt–Pd alloy was significantly higher than that of the individual metals. The effects of the preparation method and the titania type used on the properties and activity of the resulting catalyst...

  9. Catalysts for liquid phase oxidation of olefins and sulfur compounds; Catalyseurs pour l'oxydation en phase liquide d'olefines et de composes soufres

    Energy Technology Data Exchange (ETDEWEB)

    Palomeque Santiago, J.F.

    2002-07-01

    Several basic, acid and acid-base catalysts were studied for the epoxidation of olefins activated or not and dibenzo-thiophene.Hydrotalcite activation by thermic treatment and in situ re-hydration improves catalytic activity for 2-cyclohexene-1-one and isophorone. Bronsted basic sites were found to be more active than Lewis sites. Total conversion of 2-cyclohexene-1-one is reached in 1.5 h in polar solvents. W{sub 7}O{sub 24}{sup 6-} Iso-poly-anion was exchanged onto a meixnerite by a new preparation method, A meso-porous solid was obtained with good catalytic properties for cyclohexene epoxidation 100% selective to epoxide. W{sub 7}O{sub 24}{sup 6-} and WO{sub 5}{sup 2-} anions and phenyl and dodecyl-phospho-tungstates were grafted on hydrotalcites. Due to the acid-base characteristics of these solid catalysts, cyclohexene yields products of allylic reactions. Mg-La, and Mg-Al-La mixed oxides were synthesized and mixed phases were gotten. Their basic characteristics account for hydrogen peroxide decomposition which prevents DBT oxidation reaction to sulfone. On the contrary, Mg-Al re-hydrated hydrotalcites are very active for this reaction and remove 100% of sulfur compounds in 1 hour. New catalyst W-ZrO{sub 2} were synthesized with high acid properties. stable structure with temperature and high DBT conversion in less than 5 minutes of reaction. These catalytic systems can be applied for hydrocarbon desulfurization of fuels like naphtha, gas oil and kerosene. (author)

  10. Study of the chemistry of sulfur- and nitrogen oxides at fluidized bed combustion. Final report; Studier avseende svavel- och kvaeveoxidernas kemi vid fluidiserad foerbraenning

    Energy Technology Data Exchange (ETDEWEB)

    Lindqvist, O [Chalmers Univ. of Technology and Goeteborg Univ. (Sweden). Dept. of Inorganic Chemistry

    1995-12-01

    Research has been carried out concerning chemistry of nitrogen and sulfur oxides, with relevance to fluidized bed combustion. Studies of the heterogeneous decomposition reactions of NO and N{sub 2}O molecules have also been carried out. The effect of O{sub 2} on the heterogeneous reactions has been investigated and the results indicate that NO can deteriorate only in the reducing zones of a FBC. The formation of NO and N{sub 2}O as well as the question of what parameters affect this formation have been studied in a series of combustion experiments. In addition, it has also been demonstrated that the volatiles and the char are about equally important for the NO and N{sub 2}O formation. Quantum chemical calculations have been used to study the surface processes of the nitrogen oxides. Investigations of the desulfurization reactions at high percentages of CO{sub 2} with special regard to the PFBC technique have been made. In addition, the same reaction has been studied with e.g. spectroscopic methods at normal CO{sub 2} percentages, but with varying amounts of O{sub 2} and CO. CaSO{sub 3} has been demonstrated to be an intermediary and CaS as being one of the products. An important part of the project activities is the analytical work which primarily supports the full scale experiments on the 12 MW{sub th} CTH FBC boiler. As a link between the CTH boiler and our analytical laboratory, a chemical engineer also has been employed. In this activity is also included the development of sampling and analytical methods, e.g. NH{sub 3} and HCN sampling in the combustor. Time has also been allocated to measuring corrosive alkali metals (Na and K) in flue gases from a PFBC plant. 29 refs, 4 figs, 1 tab

  11. The Oxidation State of Fe in Glasses from the Galapagos Archipelago: Variable Oxygen Fugacity as a Function of Mantle Source

    Science.gov (United States)

    Peterson, M. E.; Kelley, K. A.; Cottrell, E.; Saal, A. E.; Kurz, M. D.

    2015-12-01

    The oxidation state of the mantle plays an intrinsic role in the magmatic evolution of the Earth. Here we present new μ-XANES measurements of Fe3+/ΣFe ratios (a proxy for ƒO2) in a suite of submarine glasses from the Galapagos Archipelago. Using previously presented major, trace, and volatile elements and isotopic data for 4 groups of glass that come from distinct mantle sources (depleted upper mantle, 2 recycled, and a primitive mantle source) we show that Fe3+/ΣFe ratios vary both with the influence of shallow level processes and with variations in mantle source. Fe3+/ΣFe ratios increase with differentiation (i.e. decreasing MgO), but show a large variation at a given MgO. Progressive degassing of sulfur accompanies decreasing Fe3+/ΣFe ratios, while assimilation of hydrothermally altered crust (as indicated by increasing Sr/Sr*) is shown to increase Fe3+/ΣFe ratios. After taking these processes into account, there is still variability in the Fe3+/ΣFe ratios of the isotopically distinct sample suites studied, yielding a magmatic ƒO2 that ranges from ΔQFM = +0.16 to +0.74 (error ITE = enriched Sr and Pb isotopes) shows evidence of mixing between oxidized and reduced sources (ITE oxidized end-member = 0.177). This suggests that mantle sources in the Galapagos that are thought to contain recycled components (i.e., WD and ITE groups) have distinct oxidation states. The high 3He/4He Fernandina samples (HHe group) are shown to be the most oxidized (ave. 0.175 ± 0.006). With C/3He ratios an order of magnitude greater than MORB this suggests that the primitive mantle is a more carbonated and oxidized source than the depleted upper mantle.

  12. Fuel processor integrated H{sub 2}S catalytic partial oxidation technology for sulfur removal in fuel cell power plants

    Energy Technology Data Exchange (ETDEWEB)

    Gardner, T.H.; Berry, D.A.; Lyons, K.D.; Beer, S.K.; Freed, A.D. [U.S. Department of Energy, Morgantown, WV (USA). National Energy Technology Laboratory

    2002-12-01

    H{sub 2}S catalytic partial oxidation technology with an activated carbon catalyst was found to be a promising method for the removal of hydrogen sulfide from fuel cell hydrocarbon feedstocks. Three different fuel cell feedstocks were considered for analysis: sour natural gas, sour effluent from a liquid middle distillate fuel processor and a Texaco O{sub 2}-blown coal-derived synthesis gas. The H{sub 2}S catalytic partial oxidation reaction, its integratability into fuel cell power plants with different hydrocarbon feedstocks and its salient features are discussed. Experimental results indicate that H{sub 2}S concentration can be removed down to the part-per-million level in these plants. Additionally, a power law rate expression was developed and reaction kinetics compared to prior literature. The activation energy for this reaction was determined to be 34.4 kJ/g mol with the reaction being first order in H{sub 2}S and 0.3 order in O{sub 2}. 18 refs., 14 figs., 3 tabs.

  13. Heterogeneous oxidation of SO2 in the radiation chemical purification of exhaust gases of thermoelectric power plants from oxides of nitrogen and sulfur

    International Nuclear Information System (INIS)

    Gerasimova, T.S.; Gerasimov, G.Ya.; Tokmacheva, I.P.

    1992-01-01

    Questions associated with numerical modeling of the heterogeneous oxidation of SO 2 in exhaust gases of thermoelectric power plants, induced by irradiation of the gas with a flux of fast electrons, are discussed. In constructing a mathematical model of the process it is considered that a phase equilibrium exists between the gas and the aerosol drops formed in the gas under the radiation influence, and the rate of the process is determined by the rate of liquid-phase oxidation of SO 2 by nitrogen dioxide in dissolved form. 7 refs., 4 figs

  14. Studies of the Tc oxidation states in humic acid solutions

    International Nuclear Information System (INIS)

    Wang Bo; Liu Dejun; Yao Jun

    2010-01-01

    The oxidation state is an important aspect of the speciation of Tc in groundwater that contained organic substances due to it control the precipitation, complexation, sorption and colloid formation behavior of the Tc under HWL geological disposal conditions. In present work, the oxidation states of Tc were investigated using the LaCl 3 coagulation method and solution extraction method in aqueous solutions in which the humic acid concentration range is from 0 to 20 mg L -1 and the Tc (Ⅶ) concentration range is about 10 -8 mol l -1 . The radiocounting of 99 Tc was determined using liquid scintillation spectrometry. The humic acid will influence the radiocounting ratio of 99 Tc apparently, however, the quenching effect can be restrained once keep the volume of the cocktail to about twenty times of the sample volume. The LaCl 3 coagulation methods were carried out for the investigation of Tc oxidation states in humic acid aqueous systems at about pH 8. The tetraphenylarsonium chloride (IPA)-chloroform extraction method was used also simultaneously to investigation the concentrations of Tc (Ⅳ) and Tc (Ⅶ) for the availability of the LaCl 3 precipitation method, and the experimental results demonstrate that tetravalent technetium and pertechnetate concentrations are well agreement with the LaCl 3 precipitation method. These two experimental results demonstrated that Tc (Ⅶ) is very stable in the Tc (Ⅶ)-humic acid system during a 350 days experimental period, and the Tc (Ⅳ) concentrations are very lower, that is indicate that there didn't oxidizing reactions between the Fluka humic acid and Tc (Ⅶ) in aqueous solutions under anaerobic conditions. That is means the presence of humic acids even in anaerobic groundwater is disadvantage for the retardance of radionuclides. (authors)

  15. Studies of Tc oxidation states in humic acid solutions

    International Nuclear Information System (INIS)

    Wang Bo; Liu Dejun; Yao Jun

    2011-01-01

    The oxidation state of Tc is an important aspect of the speciation in groundwater which contained organic substances due to it control the precipitation, complexation, sorption and colloid formation behavior of the Tc under HWL geological disposal conditions. In present work, the oxidation states of Tc were investigated using the LaCl 3 coagulation method and solution extraction method in aqueous solutions in which the humic acid concentration range is from 0 to 20 mg/L and the Tc (VII) concentration is about 10 -8 mol/L. The radiocounting of 99 Tc was determined using liquid scintillation spectrometry. The humic acid will influence the radiocounting ratio of 99 Tc apparently, however, the quenching effect can be restrained once keep the volume of the cocktail to about twenty times of the sample volume. The LaCl 3 coagulation method was carried out for the investigation of Tc oxidation states in humic acid aqueous systems at about pH 8. The tetraphenylarsonium chloride (TPA)-chloroform extraction method was used also simultaneously to investigation the concentrations of Tc (IV) and Tc (VII) for the availability of the LaCl 3 precipitation method, and the experimental results demonstrate that tetravalent technetium and pertechnetate concentration are well agreement with the LaCl 3 precipitation method. These two experimental results demonstrated that Tc (VII) is very stable in the Tc (VII)-humic acid system during a 350 days experimental period, and the Tc (IV) concentrations are very lower, that is indicate that there didn't oxidizing reactions between the Fluka humic acid and Tc (VII) in aqueous solutions under anaerobic conditions. That means the presence of humic acids even in anaerobic groundwater is disadvantage for the retardance of radionuclides. (authors)

  16. Diurnal Variation and Spatial Distribution Effects on Sulfur Speciation in Aerosol Samples as Assessed by X-Ray Absorption Near-Edge Structure (XANES

    Directory of Open Access Journals (Sweden)

    Siwatt Pongpiachan

    2012-01-01

    Full Text Available This paper focuses on providing new results relating to the impacts of Diurnal variation, Vertical distribution, and Emission source on sulfur K-edge XANES spectrum of aerosol samples. All aerosol samples used in the diurnal variation experiment were preserved using anoxic preservation stainless cylinders (APSCs and pressure-controlled glove boxes (PCGBs, which were specially designed to prevent oxidation of the sulfur states in PM10. Further investigation of sulfur K-edge XANES spectra revealed that PM10 samples were dominated by S(VI, even when preserved in anoxic conditions. The “Emission source effect” on the sulfur oxidation state of PM10 was examined by comparing sulfur K-edge XANES spectra collected from various emission sources in southern Thailand, while “Vertical distribution effects” on the sulfur oxidation state of PM10 were made with samples collected from three different altitudes from rooftops of the highest buildings in three major cities in Thailand. The analytical results have demonstrated that neither “Emission source” nor “Vertical distribution” appreciably contribute to the characteristic fingerprint of sulfur K-edge XANES spectrum in PM10.

  17. Augmented ingestion of carbon monoxide and sulfur oxides by occupants of vehicles while idling in drive-up facility lines

    Energy Technology Data Exchange (ETDEWEB)

    Myronuk, D J

    1977-02-01

    For a line-up of automobiles waiting for a period of time at a drive-up facility, the idling engine emissions are expelled in a rearward direction and tend to envelope the vehicles at the end portion of the queue. Factors that affect these highly localized pollutant accumulation episodes include local meteorological conditions, number, age and tune-up condition of the cars, exhaust pipe location, interior air handling equipment, vehicle separation distances and natural or artificial barriers that form troughs in which vehicular emissions can accumulate or be trapped. In a series of typical vehicle line-ups, local CO concentrations were measured. With Santa Clara Valley background levels of 2 to 5 ppm, the 15 min average driver-area concentration levels ranged from 15 ppm to 95 ppm with short term peaks between 100 and 1000 ppm. The exposure of humans to these concentrations of CO can result in mild headache or nausea, failure to react quickly to stimuli (like oncoming traffic) as well as setting a strain on the heart and lungs. These effects are temporary and reversible. A far more serious local air quality and health problem arises in the growing production of SO/sub x/ and sulfate compounds attributable to the legislated use of oxidizing catalytic mufflers for new car emission control and oxidation of the elemental S found in all gasoline. Using the CO levels as indicators of the accumulation of local automobile produced pollutants, when a majority of cars are equipped with catalytic converters, the anticipated adverse effects of SO/sub x/ concentrations, irritation and inflammation of healthy lung tissue of young and old people alike, as well as aggrevation of preexisting conditions of lung or heart impairment, will be a most undesirable feature of drive-up facility services. Potential reductions in the extent of this developing problem include S removal, SO/sub x/ traps and exhaust system redesign.

  18. Study on the solid state chemistry of ternary uranium oxides

    International Nuclear Information System (INIS)

    Yamashita, Toshiyuki

    1988-03-01

    With the increase of burnup of uranium oxide fuels, various kinds of fission products are formed, and the oxygen atoms combined with the consumed heavy atoms are freed. The solid state chemical and/or thermodynamic properties of these elements at high temperatures are complex, and have not been well clarified. In the present report, an approach was taken that the chemical interactions between UO 2 and these fission products can be regarded as causing overlapped effects of composing ternary uranium oxides, and formation reactions and phase behavior were studied for several ternary uranium oxides with typical fission product elements such as alkaline earth metals and rare earth elements. Precise determination methods for the composition of ternary uranium oxides were developed. The estimated accuracies for x and y values in M y U 1-y O 2+x were ± 0.006 and ± 0.004, respectively. The thermodynamic properties and the lattice parameters of the phases in the Ca-U-O and Pr-U-O systems were discussed in relation to the composition determined by the methods. Crystal structure analyses of cadmium monouranates were made with X-ray diffraction method. (author) 197 refs

  19. Optoelectronic properties of valence-state-controlled amorphous niobium oxide

    Science.gov (United States)

    Onozato, Takaki; Katase, Takayoshi; Yamamoto, Akira; Katayama, Shota; Matsushima, Koichi; Itagaki, Naho; Yoshida, Hisao; Ohta, Hiromichi

    2016-06-01

    In order to understand the optoelectronic properties of amorphous niobium oxide (a-NbO x ), we have investigated the valence states, local structures, electrical resistivity, and optical absorption of a-NbO x thin films with various oxygen contents. It was found that the valence states of Nb ion in a-NbO x films can be controlled from 5+  to 4+  by reducing oxygen pressure during film deposition at room temperature, together with changing the oxide-ion arrangement around Nb ion from Nb2O5-like to NbO2-like local structure. As a result, a four orders of magnitude reduction in the electrical resistivity of a-NbO x films was observed with decreasing oxygen content, due to the carrier generation caused by the appearance and increase of an oxygen-vacancy-related subgap state working as an electron donor. The tunable optoelectronic properties of a-NbO x films by valence-state-control with oxygen-vacancy formation will be useful for potential flexible optoelectronic device applications.

  20. Predicting spent fuel oxidation states in a tuff repository

    International Nuclear Information System (INIS)

    Einziger, R.E.; Woodley, R.E.

    1987-01-01

    Nevada Nuclear Waste Storage Investigations Project (NNWSI) is studying the suitability of the tuffaceous rocks at Yucca Mountain as a waste repository for spent fuel disposal. The oxidation state of the LWR spent fuel in the moist air environment of a tuff repository could be a significant factor in determining its leaching and dissolution characteristics. Predictions as to which oxidation states would be present are important in analyzing such a repository and thus the present study was undertaken. A set of TGA (thermogravimetric analysis) tests were conducted on well-controlled samples of irradiated PWR fuel with time and temperature as the only variables. The tests were conducted between 140 and 225 0 C for a duration up to 2200 hours. The weight gain curves were analyzed in terms of diffusion through a layer of U 3 O 7 , diffusion into the grains to form a solid solution, a simplified empirical representation of a combination of grain boundary diffusion and bulk grain oxidation. Reaction rate constants were determined in each case, but analysis of these data could not establish a definitive mechanism. 21 refs., 10 figs., 3 tabs

  1. Multi-scale modeling study of the source contributions to near-surface ozone and sulfur oxides levels over California during the ARCTAS-CARB period

    Directory of Open Access Journals (Sweden)

    M. Huang

    2011-04-01

    Full Text Available Chronic high surface ozone (O3 levels and the increasing sulfur oxides (SOx = SO2+SO4 ambient concentrations over South Coast (SC and other areas of California (CA are affected by both local emissions and long-range transport. In this paper, multi-scale tracer, full-chemistry and adjoint simulations using the STEM atmospheric chemistry model are conducted to assess the contribution of local emission sourcesto SC O3 and to evaluate the impacts of transported sulfur and local emissions on the SC sulfur budgetduring the ARCTAS-CARB experiment period in 2008. Sensitivity simulations quantify contributions of biogenic and fire emissions to SC O3 levels. California biogenic and fire emissions contribute 3–4 ppb to near-surface O3 over SC, with larger contributions to other regions in CA. During a long-range transport event from Asia starting from 22 June, high SOx levels (up to ~0.7 ppb of SO2 and ~1.3 ppb of SO4 is observed above ~6 km, but they did not affect CA surface air quality. The elevated SOx observed at 1–4 km is estimated to enhance surface SOx over SC by ~0.25 ppb (upper limit on ~24 June. The near-surface SOx levels over SC during the flight week are attributed mostly to local emissions. Two anthropogenic SOx emission inventories (EIs from the California Air Resources Board (CARB and the US Environmental Protection Agency (EPA are compared and applied in 60 km and 12 km chemical transport simulations, and the results are compared withobservations. The CARB EI shows improvements over the National Emission Inventory (NEI by EPA, but generally underestimates surface SC SOx by about a factor of two. Adjoint sensitivity analysis indicated that SO2 levels at 00:00 UTC (17:00 local time at six SC surface sites were influenced by previous day maritime emissions over the

  2. SULFUR POLYMER ENCAPSULATION

    International Nuclear Information System (INIS)

    KALB, P.

    2001-01-01

    Sulfur polymer cement (SPC) is a thermoplastic polymer consisting of 95 wt% elemental sulfur and 5 wt% organic modifiers to enhance long-term durability. SPC was originally developed by the U.S. Bureau of Mines as an alternative to hydraulic cement for construction applications. Previous attempts to use elemental sulfur as a construction material in the chemical industry failed due to premature degradation. These failures were caused by the internal stresses that result from changes in crystalline structure upon cooling of the material. By reacting elemental sulfur with organic polymers, the Bureau of Mines developed a product that successfully suppresses the solid phase transition and significantly improves the stability of the product. SPC, originally named modified sulfur cement, is produced from readily available, inexpensive waste sulfur derived from desulfurization of both flue gases and petroleum. The commercial production of SPC is licensed in the United States by Martin Resources (Odessa, Texas) and is marketed under the trade name Chement 2000. It is sold in granular form and is relatively inexpensive ((approx)$0.10 to 0.12/lb). Application of SPC for the treatment of radioactive, hazardous, and mixed wastes was initially developed and patented by Brookhaven National Laboratory (BNL) in the mid-1980s (Kalb and Colombo, 1985; Colombo et al., 1997). The process was subsequently investigated by the Commission of the European Communities (Van Dalen and Rijpkema, 1989), Idaho National Engineering Laboratory (Darnell, 1991), and Oak Ridge National Laboratory (Mattus and Mattus, 1994). SPC has been used primarily in microencapsulation applications but can also be used for macroencapsulation of waste. SPC microencapsulation has been demonstrated to be an effective treatment for a wide variety of wastes, including incinerator hearth and fly ash; aqueous concentrates such as sulfates, borates, and chlorides; blowdown solutions; soils; and sludges. It is not

  3. The surface evolution of La0.4Sr0.6TiO3+δ anode in solid oxide fuel cells: Understanding the sulfur-promotion effect

    Science.gov (United States)

    Yan, Ning; Zanna, Sandrine; Klein, Lorena H.; Roushanafshar, Milad; Amirkhiz, Babak S.; Zeng, Yimin; Rothenberg, Gadi; Marcus, Philippe; Luo, Jing-Li

    2017-03-01

    The ideal solid oxide fuel cells (SOFCs) can be powered by readily available hydrocarbon fuels containing impurities. While this is commonly recognized as a key advantage of SOFC, it also, together with the elevated operating temperature, becomes the main barrier impeding the in-situ or operando investigations of the anode surface chemistry. Here, using a well-designed quenching experiment, we managed to characterize the near-surface structure of La0.4Sr0.6TiO3+δ (LST) anode in SOFCs fuelled by H2S-containing methane. This new method enabled us to clearly observe the surface amorphization and sulfidation of LST under simulated SOFC operating conditions. The ∼1 nm-thick two dimensional sulfur-adsorbed layer was on top of the disordered LST, containing -S, -SH and elemental sulfur species. In SOFC test, such "poisoned" anode showed increased performances: a ten-fold enhanced power density enhancement (up to 30 mW cm-2) and an improved open circuit voltage (from 0.69 V to 1.17 V). Moreover, its anodic polarization resistance in methane decreased to 21.53 Ω cm2, a difference of 95% compared with the sulfur-free anode. Control experiments confirmed that once the adsorbed sulfur species were removed electrochemically, methane conversion slowed down simultaneously till full stop.

  4. Synthesis and characterization of sulfur functionalized graphene oxide nanosheets as efficient sorbent for removal of Pb2+, Cd2+, Ni2+ and Zn2+ ions from aqueous solution: A combined thermodynamic and kinetic studies

    Science.gov (United States)

    Pirveysian, Mahtab; Ghiaci, Mehran

    2018-01-01

    A very simple, one pot method was used for preparation of sulfur functionalized graphene oxide (GO-SOxR) with sodium sulfide and water in reflux condition. The elemental analysis data showed high sulfur content up to 15%. EDS and XPS analysis also proved introduction of sulfur element. To make the sorbent more efficient operationally, the GO-SOxR was coated with a mesoporous shell of TiO2 or SiO2. The prepared sorbents were characterized by SEM, TEM, TGA, XPS, XRD, IR and EDS. GO-SOxR@TiO2 and GO-SOxR@SiO2 composites were tested for removal of Pb(II), Cd(II), Ni(II) and Zn(II) as heavy metal ions from aqueous solution in batch method. Adsorption of the heavy metal ions was studied kinetically, and the adsorption capacities of GO-SOxR, GO-SOxR@TiO2, and GO-SOxR@SiO2 were evaluated using equilibrium adsorption isotherms, and compared to other adsorbents used for removal of these heavy metals. Kinetic studies showed that the experimental data was fitted with pseudo second order model. The adsorption capacity of GO was significantly improved by sulfur functionalization and TiO2 coating.

  5. Novel Metal-Sulfur-Based Air-Stable Passivation of GaAs with Very Low Surface State Densities

    Energy Technology Data Exchange (ETDEWEB)

    Ashby, Carol I.H.; Baca, Albert G.; Chang, P.-C; Hafich, M.J.; Hammons, B.E.; Zavadil, Kevin R.

    1999-08-09

    A new air-stable electronic surface passivation for GaAs and other III-V compound semiconductors that employs sulfur and a suitable metal ion, e.g., Zn, and that is robust towards plasma dielectric deposition has been developed. Initial improvements in photoluminescence are twice that of S-only treatments and have been preserved for >11 months with SiO{sub x}N{sub y} dielectric encapsulation. Photoluminescence and X-ray photoelectron spectroscopies indicate that the passivation consists of two major components with one being stable for >2 years in air. This process improves heterojunction bipolar transistor current gain for both large and small area devices.

  6. Chelation and stabilization of berkelium in oxidation state +IV

    Science.gov (United States)

    Deblonde, Gauthier J.-P.; Sturzbecher-Hoehne, Manuel; Rupert, Peter B.; An, Dahlia D.; Illy, Marie-Claire; Ralston, Corie Y.; Brabec, Jiri; de Jong, Wibe A.; Strong, Roland K.; Abergel, Rebecca J.

    2017-09-01

    Berkelium (Bk) has been predicted to be the only transplutonium element able to exhibit both +III and +IV oxidation states in solution, but evidence of a stable oxidized Bk chelate has so far remained elusive. Here we describe the stabilization of the heaviest 4+ ion of the periodic table, under mild aqueous conditions, using a siderophore derivative. The resulting Bk(IV) complex exhibits luminescence via sensitization through an intramolecular antenna effect. This neutral Bk(IV) coordination compound is not sequestered by the protein siderocalin—a mammalian metal transporter—in contrast to the negatively charged species obtained with neighbouring trivalent actinides americium, curium and californium (Cf). The corresponding Cf(III)-ligand-protein ternary adduct was characterized by X-ray diffraction analysis. Combined with theoretical predictions, these data add significant insight to the field of transplutonium chemistry, and may lead to innovative Bk separation and purification processes.

  7. Some information needs for air quality modeling. [Environmental effects of sulfur compounds

    Energy Technology Data Exchange (ETDEWEB)

    Hill, F B

    1975-09-01

    The following topics were considered at the workshop: perturbation of the natural sulfur cycle by human activity; ecosystem responses to a given environmental dose of sulfur compounds; movement of sulfur compounds within the atmosphere; air quality models; contribution of biogenic sulfur compounds to atmospheric burden of sulfur; production of acid rain from sulfur dioxide; meteorological processes; and rates of oxidation of SO/sub 2/ via direct photo-oxidation, oxidation resulting from photo-induced free radical chemistry, and catalytic oxidation in cloud droplets and on dry particles. (HLW)

  8. Contribution of nitrogen oxide and sulfur dioxide exposure from power plant emissions on respiratory symptom and disease prevalence

    International Nuclear Information System (INIS)

    Amster, Eric D.; Haim, Maayan; Dubnov, Jonathan; Broday, David M.

    2014-01-01

    This study investigates the association between exposure to ambient NO x and SO 2 originating from power plant emissions and prevalence of obstructive pulmonary disease and related symptoms. The Orot Rabin coal-fired power plant is the largest power generating facility in the Eastern Mediterranean. Two novel methods assessing exposure to power plant-specific emissions were estimated for 2244 participants who completed the European Community Respiratory Health Survey. The “source approach” modeled emissions traced back to the power plant while the “event approach” identified peak exposures from power plant plume events. Respiratory symptoms, but not prevalence of asthma and COPD, were associated with estimates of power plant NO x emissions. The “source approach” yielded a better estimate of exposure to power plant emissions and showed a stronger dose–response relationship with outcomes. Calculating the portion of ambient pollution attributed to power plants emissions can be useful for air quality management purposes and targeted abatement programs. -- Highlights: • Two methods assessing NO x and SO 2 exposure attributed to a coal-fired power plant are utilized. • Exposure estimates are compared with respiratory outcomes in 2244 participants. • Power plant nitrogen oxide emissions are associated with respiratory symptoms. • Stack emission models correlated closest with health outcomes. -- Chronic cough, nocturnal dyspnea, chronic phlegm, and shortness of breath were significantly associated with exposure estimates of power plant-specific NO x emissions

  9. The partitioning of sulfur between multicomponent aqueous fluids and felsic melts

    Science.gov (United States)

    Binder, Bernd; Wenzel, Thomas; Keppler, Hans

    2018-02-01

    Sulfur partitioning between melt and fluid phase largely controls the environmental impact of volcanic eruptions. Fluid/melt partitioning data also provide the physical basis for interpreting changes in volcanic gas compositions that are used in eruption forecasts. To better constrain some variables that control the behavior of sulfur in felsic systems, in particular the interaction between different volatiles, we studied the partitioning of sulfur between aqueous fluids and haplogranitic melts at 200 MPa and 750-850 °C as a function of oxygen fugacity (Ni-NiO or Re-ReO2 buffer), melt composition (Al/(Na + K) ratio), and fluid composition (NaCl and CO2 content). The data confirm a first-order influence of oxygen fugacity on the partitioning of sulfur. Under "reducing conditions" (Ni-NiO buffer), D fluid/melt is nearly one order of magnitude larger (323 ± 14 for a metaluminous melt) than under "oxidizing conditions" (Re-ReO2 buffer; 74 ± 5 for a metaluminous melt). This effect is likely related to a major change in sulfur speciation in both melt and fluid. Raman spectra of the quenched fluids show the presence of H2S and HS- under reducing conditions and of SO4 2- and HSO4 - under oxidizing conditions, while SO2 is undetectable. The latter observation suggests that already at the Re-ReO2 buffer, sulfur in the fluid is almost completely in the S6+ state and, therefore, more oxidized than expected according to current models. CO2 in the fluid (up to x CO2 = 0.3) has no effect on the fluid/melt partitioning of sulfur, neither under oxidizing nor under reducing conditions. However, the effect of NaCl depends on redox state. While at oxidizing conditions, D fluid/melt is independent of x NaCl, the fluid/melt partition coefficient strongly decreases with NaCl content under reducing conditions, probably due to a change from H2S to NaSH as dominant sulfur species in the fluid. A decrease of D fluid/melt with alkali content in the melt is observed over the entire

  10. Facile Assembly of 3D Porous Reduced Graphene Oxide/Ultrathin MnO2 Nanosheets-S Aerogels as Efficient Polysulfide Adsorption Sites for High-Performance Lithium-Sulfur Batteries.

    Science.gov (United States)

    Zhao, Xiaojun; Wang, Hui; Zhai, Gaohong; Wang, Gang

    2017-05-23

    Rechargeable lithium-sulfur (Li-S) batteries are receiving much attention due to their high specific capacity, low cost, and environmental friendliness. Nonetheless, fast capacity decay and low specific capacity still limit their practical implementation. Herein, we report a facile strategy to overcome these challenges by the design and fabrication of 3D porous reduced graphene oxide/ultrathin MnO 2 nanosheets-S aerogel (rGM-SA) composites for Li-S batteries. By a simple solvothermal reaction process, nanosized S atoms are homogeneously decorated into the 3D scaffold formed by reduced graphene oxide (rGO) and MnO 2 nanosheets, which can form the homogeneous rGM-SA composites. In this porous network architecture, rGO serves as an electron and ion transfer pathway, a physical adsorption site for polysulfides, and provides structural stability. The ultrathin MnO 2 nanosheets provide strong binding sites for trapping polysulfide intermediates. The 3D porous rGO/MnO 2 architecture enables rapid ion transport and buffers volume expansion of sulfur during discharge. The rGM-SA composites can be directly used as lithium-sulfur battery cathodes without using binder and conductive additive. As a result of this multifunctional arrangement, the rGM-SA composites exhibit high and stable-specific capacities over 200 cycles and excellent high-rate performances. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Synthesis and characterization of ruthenium fluorides and oxide fluorides with high oxidation states

    International Nuclear Information System (INIS)

    Meublat, L.

    1989-10-01

    The synthesis of ruthenium fluorides and oxide fluorides with high oxidation states was attempted from dioxide RuO 2 and tetroxide RuO 4 . Three fluorinating agents were used: fluorine, chlorine trifluoride and krypton difluoride. The reactions were achieved in anhydrous hydrogen fluoride at room temperature. Thus, the reaction of RuO 4 with CIF 3 enabled us to prepare chloryl hexafluororuthenate (V), CIO 2 + RuF 6 - , a new compound well identified by vibrational spectroscopy (infra-red and Raman), the structure of which was determined. The reaction of KrF 2 with RuO 4 gave the oxide tetrafluoride RuOF 4 , the previously published syntheses and properties of which were not in agreement with each other. This compound was definitely characterized here by chemical analysis, infra-red spectroscopy and X-ray powder diffraction. The product of thermal decomposition (70 0 C) of RuOF 4 is presumably RuF 4 since only oxygen is liberated during this decomposition. At last, the reaction of KrF 2 with RuO 2 probably leads to the formation of the new oxide fluoride RuO 2 F 4 . Indeed, no oxygen is given off during this reaction, the chemical analysis of the red-orange coloured solid residue is almost in agreement with the one proposed and its infra-red absorption spectrum indicates the presence of ruthenium-oxygen and ruthenium-terminal and bridging fluorine bonds [fr

  12. Synthesis and characterization of ruthenium fluorides and oxide fluorides with high oxidation states

    International Nuclear Information System (INIS)

    Meublat, L.

    1989-01-01

    The synthesis of ruthenium fluorides and oxide fluorides with high oxidation states was attempted from dioxide RuO 2 and tetroxide RuO 4 . Three fluorinating agents were used: fluorine, chlorine trifluoride and krypton difluoride. The reactions were achieved in anhydrous hydrogen fluoride at room temperature. Thus, the reaction of RuO 4 with CIF 3 enabled us to prepare chloryl hexafluororuthenate (V), ClO 2 + RuF 6 - , a new compound well idendified by vibrational spectroscopy (infra-red and Raman), the structure of which was determined. The reaction of KrF 2 with RuO 4 gave the oxide tetrafluoride RuOF 4 , the previously published syntheses and properties of which were not in agreement with each other. This compound was definitely characterized here by chemical analysis, infra-red spectroscopy and X-ray powder diffraction. The product of thermal decomposition (70 0 C) of RuOF 4 is presumably RuF 4 since only oxygen is liberated during this decomposition. At last, the reaction of KrF 2 with RuO 2 probably leads to the formation of the new oxide fluoride RuO 2 F 4 . Indeed, no oxygen is given off during this reaction, the chemical analysis of the red-orange coloured solid residue is almost in agreement with the one proposed and its infra-red absorption spectrum indicates the presence of ruthenium-oxygen and ruthenium-terminal and bridging fluorine bonds [fr

  13. Relationship between corrosion and the biological sulfur cycle: A review

    Energy Technology Data Exchange (ETDEWEB)

    Little, B.J.; Ray, R.I.; Pope, R.K.

    2000-04-01

    Sulfur and sulfur compounds can produce pitting, crevice corrosion, dealloying, stress corrosion cracking, and stress-oriented hydrogen-induced cracking of susceptible metals and alloys. Even though the metabolic by-products of the biological sulfur cycle are extremely corrosive, there are no correlations between numbers and types of sulfur-related organisms and the probability or rate of corrosion, Determination of specific mechanisms for corrosion caused by microbiologically mediated oxidation and reduction of sulfur and sulfur compounds is complicated by the variety of potential metabolic-energy sources and by-products; the coexistence of reduced and oxidized sulfur species; competing reactions with inorganic and organic compounds; and the versatility and adaptability of microorganisms in biofilms. The microbial ecology of sulfur-rich environments is poorly understood because of the association of aerobes and anaerobes and the mutualism or succession of heterotrophs to autotrophs. The physical scale over which the sulfur cycle influences corrosion varies with the environment. The complete sulfur cycle of oxidation and reduction reactions can take place in macroenvironments, including sewers and polluted harbors, or within the microenvironment of biofilms. In this review, reactions of sulfur and sulfur compounds resulting in corrosion were discussed in the context of environmental processes important to corrosion.

  14. Radiation induced sulfur dioxide removal

    International Nuclear Information System (INIS)

    Chmielewski, A.G.

    2000-01-01

    The biggest source of air pollution is the combustion of fossil fuels, were pollutants such as particulate, sulfur dioxide (SO 2 ), nitrogen oxides (NO x ), and volatile organic compounds (VOC) are emitted. Among these pollutants, sulfur dioxide plays the main role in acidification of the environment. The mechanism of sulfur dioxide transformation in the environment is partly photochemical. This is not direct photooxidation, however, but oxidation through formed radicals. Heterogenic reactions play an important role in this transformation as well; therefore, observations from environmental chemistry can be used in air pollution control engineering. One of the most promising technologies for desulfurization of the flue gases (and simultaneous denitrification) is radiation technology with an electron accelerator application. Contrary to the nitrogen oxides (NO x ) removal processes, which is based on pure radiation induced reactions, sulfur dioxide removal depends on two pathways: a thermochemical reaction in the presence of ammonia/water vapor and a radiation set of radiochemical reactions. The mechanism of these reactions and the consequent technological parameters of the process are discussed in this paper. The industrial application of this radiation technology is being implemented in an industrial pilot plant operated by INCT at EPS Kaweczyn. A full-scale industrial plant is currently in operation in China, and two others are under development in Japan and Poland. (author)

  15. Intestinal Oxidative State Can Alter Nutrient and Drug Bioavailability

    Directory of Open Access Journals (Sweden)

    Faria Ana

    2009-01-01

    Full Text Available Organic cations (OCs are substances of endogenous (e.g., dopamine, choline or exogenous (e.g., drugs like cimetidine origin that are positively charged at physiological ph. since many of these compounds can not pass the cell membrane freely, their transport in or out of cells must be mediated by specific transport systems. Transport by organic cation transporters (OCTs can be regulated rapidly by altering their trafficking and/or affinities in response to stimuli. However, for example, a specific disease could lead to modifications in the expression of OCTs. Chronic exposure to oxidative stress has been suggested to alter regulation and functional activity of proteins through several pathways. According to results from a previous work, oxidation-reduction pathways were thought to be involved in intestinal organic cation uptake modulation. The present work was performed in order to evaluate the influence of oxidative stressors, especially glutathione, on the intestinal organic cation absorption. For this purpose, the effect of compounds with different redox potential (glutathione, an endogenous antioxidant, and procyanidins, diet antioxidants was assessed on MPP+ (1-methyl-4-phenylpyridinium iodide uptake in an enterocyte cell line (Caco-2. Caco-2 cells were subcultured with two different media conditions (physiological: 5 mM glucose, referred as control cells; and high-glucose: 25 mM glucose, referred as HG cells. In HG cells, the uptake was significantly lower than in control cells. Redox changing interventions affected Mpp+ uptake, both in control and in high-glucose Caco-2 cells. Cellular glutathione levels could have an important impact on membrane transporter activity. The results indicate that modifications in the cellular oxidative state modulate MPP+ uptake by Caco-2 cells. Such modifications may reflect in changes of nutrient and drug bioavailability.

  16. Sulfur-Hz(CHx)y(z = 0,1) functionalized metal oxide nanostructure decorated interfaces: Evidence of Lewis base and Brönsted acid sites – Influence on chemical sensing

    International Nuclear Information System (INIS)

    Laminack, William; Baker, Caitlin; Gole, James

    2015-01-01

    Nanostructure metal oxide decorated n-type extrinsic porous silicon (PS) semiconductor interfaces are modified through in-situ interaction with acidic ethane and butane thiols (EtSH, BuSH) and basic diethyl sulfide (Et 2 S). Highly sensitive conductometric sensor evaluations and X-ray Photoelectron Spectroscopy demonstrate the effect of sulfur group functionalization modifying the acidity of the metal oxides and their interaction with NH 3 . SEM micrographs demonstrate that the sulfur treated particles are less than 30 nm in size. EDAX studies confirm the chemical composition of the modified nanoparticles and suggest the surface interaction of the sulfides and thiols. The acidic thiols can form Brönsted acidic sites enhancing the acidity of the metal oxides, thus broadening the initial metal oxide acidity range. The sulfides interact to lower the Lewis acidity of nanostructured metal oxide sites. Conductometric response matrices with NH 3 at room temperature, corresponding to the thiol and sulfide treated nanostructures of the metal oxides TiO 2 , SnO x , Ni x O, Cu x O, and Au x O (x >> 1) are evaluated for a dominant electron transduction process forming the basis for reversible chemical sensing in the absence of chemical bond formation. Treatment with the acidic thiols enhances the metal center acidity. It is suggested that the thiols can interact to increase the Brönsted acidity of the doped metal oxide surface if they maintain SH bonds. This process may account for the shift in Lewis acidity as the Brönsted acid sites counter the decrease in Lewis acidity resulting from the interaction of S-(CH x ) y groups. In contrast, treatment with basic Et 2 S decreases the Lewis acidity of the metal oxide sites, enhancing the basicity of the decorated interface. XPS measurements indicate a change in binding energy (BE) of the metal and oxygen centers. The observed changes in conductometric response do not represent a simple increase in surface acidity or basicity but

  17. Proteomic indicators of oxidation and hydration state in colorectal cancer

    Directory of Open Access Journals (Sweden)

    Jeffrey M. Dick

    2016-07-01

    Full Text Available New integrative approaches are needed to harness the potential of rapidly growing datasets of protein expression and microbial community composition in colorectal cancer. Chemical and thermodynamic models offer theoretical tools to describe populations of biomacromolecules and their relative potential for formation in different microenvironmental conditions. The average oxidation state of carbon (ZC can be calculated as an elemental ratio from the chemical formulas of proteins, and water demand per residue ( ${\\overline{n}}_{{\\mathrm{H}}_{2}\\mathrm{O}}$ n ¯ H 2 O is computed by writing the overall formation reactions of proteins from basis species. Using results reported in proteomic studies of clinical samples, many datasets exhibit higher mean ZC or ${\\overline{n}}_{{\\mathrm{H}}_{2}\\mathrm{O}}$ n ¯ H 2 O of proteins in carcinoma or adenoma compared to normal tissue. In contrast, average protein compositions in bacterial genomes often have lower ZC for bacteria enriched in fecal samples from cancer patients compared to healthy donors. In thermodynamic calculations, the potential for formation of the cancer-related proteins is energetically favored by changes in the chemical activity of H2O and fugacity of O2 that reflect the compositional differences. The compositional analysis suggests that a systematic change in chemical composition is an essential feature of cancer proteomes, and the thermodynamic descriptions show that the observed proteomic transformations in host tissue could be promoted by relatively high microenvironmental oxidation and hydration states.

  18. Biogeochemistry of sulfur and iron in Thioploca-colonized surface sediments in the upwelling area off central chile

    Science.gov (United States)

    Zopfi, Jakob; Böttcher, Michael E.; Jørgensen, Bo Barker

    2008-02-01

    The biogeochemistry of sedimentary sulfur was investigated on the continental shelf off central Chile at water depths between 24 and 88 m under partial influence of an oxygen minimum zone. Dissolved and solid iron and sulfur species, including the sulfur intermediates sulfite, thiosulfate, and elemental sulfur, were analyzed at high resolution in the top 20 cm. All stations were characterized by high rates of sulfate reduction, but only the sediments within the Bay of Concepción contained dissolved sulfide. Due to advection and/or in-situ reoxidation of sulfide, dissolved sulfate was close to bottom water values. Whereas the concentrations of sulfite and thiosulfate were mostly in the submicromolar range, elemental sulfur was by far the dominant sulfur intermediate. Although the large nitrate- and sulfur-storing bacteria Thioploca were abundant, the major part of S 0 was located extracellularly. The distribution of sulfur species and dissolved iron suggests the reaction of sulfide with FeOOH as an important pathway for sulfide oxidation and sulfur intermediate formation. This is in agreement with the sulfur isotope composition of co-existing elemental sulfur and iron monosulfides. In the Bay of Concepción, sulfur isotope data suggest that pyrite formation proceeds via the reaction of FeS with polysulfides or H 2S. At the shelf stations, on the other hand, pyrite was significantly depleted in 34S relative to its potential precursors FeS and S 0. Isotope mass balance considerations suggest further that pyritization at depth includes light sulfide, potentially originating from bacterial sulfur disproportionation. The δ 34S-values of pyrite down to -38‰ vs. V-CDT are among the lightest found in organic-rich marine sediments. Seasonal variations in the sulfur isotope composition of dissolved sulfate indicated a dynamic non-steady-state sulfur cycle in the surface sediments. The 18O content of porewater sulfate increased with depth at all sites compared to the

  19. Charge-changing processes of heavy ions in matter. Non-equilibrium charge state distribution of sulfur ions after carbon foil penetration

    International Nuclear Information System (INIS)

    Imai, Makoto; Shibata, Hiromi; Sataka, Masao; Sugai, Hiroyuki; Nishio, Katsuhisa; Sugiyama, Koji; Komaki, Ken-ichiro

    2005-01-01

    Charge state distributions of 2.0 MeV/u (64 MeV) sulfur ions of various initial charge states (6+, 10+, 11+, 13+) after passing through 0.9, 1.1, 1.5, 2.0, 3.0, 4.7, 6.9 and 10 μg/cm 2 carbon foils have been studied experimentally using the heavy ion spectrometer 'ENMA'. Measured charge state distributions do not flat off to establish equilibrium within the measured thickness, proving to be the first systematic measurement of non-equilibrium charge state distribution using solid target at this energy range. The mean charge states and their distribution widths almost saturate to 12.4 and 1.03, respectively, for all initial charge states examined. Calculation with ETACHA code, developed by Rozet et al. [Nucl. Instr. and Meth. B 107 (1996) 67], is employed, although the present impact energy is lower than the assumed energy region for this code. It was also confirmed that a certain portion of 16 O q+ (q=3, 4, 7) beam is included in 32 S q+ (q=6, 8, 14) beam provided from the Tandem Accelerator, which originates in the Negative Ion Source forming O 2 - . (author)

  20. Oxidation states of Fe and Ti in blue sapphire

    International Nuclear Information System (INIS)

    Wongrawang, P; Wongkokua, W; Monarumit, N; Thammajak, N; Wathanakul, P

    2016-01-01

    X-ray absorption near-edge spectroscopy (XANES) can be used to study the oxidation state of a dilute system such as transition metal defects in solid-state samples. In blue sapphire, Fe and Ti are defects that cause the blue color. Inter-valence charge transfer (IVCT) between Fe 2+ and Ti 4+ has been proposed to describe the optical color’s origin. However, the existence of divalent iron cations has not been thoroughly investigated. Fluorescent XANES is therefore employed to study K-edge absorptions of Fe and Ti cations in various blue sapphire samples including natural, synthetic, diffused and heat-treated sapphires. All the samples showed an Fe absorption edge at 7124 eV, corresponding to the Fe 3+ state; and Ti at 4984 eV, corresponding to Ti 4+ . From these results, we propose Fe 3+ -Ti 4+ mixed acceptor states located at 1.75 eV and 2.14 eV above the valence band of corundum, that correspond to 710 nm and 580 nm bands of UV–vis absorption spectra, to describe the cause of the color of blue sapphire. (paper)

  1. Determination of the oxidation states of metals and metalloids: An analytical review

    Science.gov (United States)

    Vodyanitskii, Yu. N.

    2013-12-01

    The hazard of many heavy metals/metalloids in the soil depends on their oxidation state. The problem of determining the oxidation state has been solved due to the use of synchrotron radiation methods with the analysis of the X-ray absorption near-edge structure (XANES). The determination of the oxidation state is of special importance for some hazardous heavy elements (arsenic, antimony, selenium, chromium, uranium, and vanadium). The mobility and hazard of each of these elements depend on its oxidation state. The mobilities are higher at lower oxidation states of As, Cr, V, and Se and at higher oxidation states of Sb and U. The determination of the oxidation state of arsenic has allowed revealing its fixation features in the rhizosphere of hydrophytes. The known oxidation states of chromium and uranium are used for the retention of these elements on geochemical barriers. Different oxidation states have been established for vanadium displacing iron in goethite. The determination of the oxidation state of manganese in the rhizosphere and the photosynthetic apparatus of plants is of special importance for agricultural chemists.

  2. Arsenic Removal from Water Using Various Adsorbents: Magnetic Ion Exchange Resins, Hydrous Ion Oxide Particles, Granular Ferric Hydroxide, Activated Alumina, Sulfur Modified Iron, and Iron Oxide-Coated Microsand

    KAUST Repository

    Sinha, Shahnawaz

    2011-09-30

    The equilibrium and kinetic adsorption of arsenic on six different adsorbents were investigated with one synthetic and four natural types (two surface and two ground) of water. The adsorbents tested included magnetic ion exchange resins (MIEX), hydrous ion oxide particles (HIOPs), granular ferric hydroxide (GFH), activated alumina (AA), sulfur modified iron (SMI), and iron oxide-coated mic - rosand (IOC-M), which have different physicochemical properties (shape, charge, surface area, size, and metal content). The results showed that adsorption equilibriums were achieved within a contact period of 20 min. The optimal doses of adsorbents determined for a given equilibrium concentration of C eq = 10 μg/L were 500 mg/L for AA and GFH, 520–1,300 mg/L for MIEX, 1,200 mg/L for HIOPs, 2,500 mg/L for SMI, and 7,500 mg/L for IOC-M at a contact time of 60 min. At these optimal doses, the rate constants of the adsorbents were 3.9, 2.6, 2.5, 1.9, 1.8, and 1.6 1/hr for HIOPs, AA, GFH, MIEX, SMI, and IOC-M, respectively. The presence of silicate significantly reduced the arsenic removal efficiency of HIOPs, AA, and GFH, presumably due to the decrease in chemical binding affinity of arsenic in the presence of silicate. Additional experiments with natural types of water showed that, with the exception of IOC-M, the adsorbents had lower adsorption capacities in ground water than with surface and deionized water, in which the adsorption capacities decreased by approximately 60–95 % .

  3. Influence of vanadium oxidation states on the performance of V-Mg-Al mixed-oxide catalysts for the oxidative dehydrogenation of propane

    International Nuclear Information System (INIS)

    Schacht, L.; Navarrete, J.; Schacht, P.; Ramirez, M. A.

    2010-01-01

    V-Mg-Al mixed-oxide catalysts for oxidative dehydrogenation of propane were prepared by thermal decomposition of Mg-Al-layered double hydroxides with vanadium interlayer doping. The obtained catalysts were tested for the oxidative dehydrogenation of propane, obtaining good results in catalytic activity (conversion 16.55 % and selectivity 99.97 %) Results indicated that catalytic performance of these materials depends on how vanadium is integrated in the layered structure, which is determined by the Mg/Al ratio. Vanadium interlayer doping modifies the oxidation state of vanadium and consequently catalytic properties. Surface properties were studied by X-ray photoelectron spectroscopic and diffuse reflectance, UV-visible spectroscopy, and temperature programmed reduction. The analyses provided information about the oxidation state, before and after the reaction. From these results, it is suggested that selectivity to propylene and catalytic activity depend mainly of vanadium oxidation state. (Author)

  4. Influence of vanadium oxidation states on the performance of V-Mg-Al mixed-oxide catalysts for the oxidative dehydrogenation of propane

    Energy Technology Data Exchange (ETDEWEB)

    Schacht, L. [IPN, Escuela Superior de Fisica y Matematicas, Departamento de Ciencia de Materiales, Av. IPN s/n, Edificio 9, Col. Lindavista, 07738 Mexico D. F. (Mexico); Navarrete, J.; Schacht, P.; Ramirez, M. A., E-mail: pschacha@imp.m [Instituto Mexicano del Petroleo, Programa de Ingenieria Molecular, Eje Central Lazaro Cardenas No. 152, 07730 Mexico D. F. (Mexico)

    2010-07-01

    V-Mg-Al mixed-oxide catalysts for oxidative dehydrogenation of propane were prepared by thermal decomposition of Mg-Al-layered double hydroxides with vanadium interlayer doping. The obtained catalysts were tested for the oxidative dehydrogenation of propane, obtaining good results in catalytic activity (conversion 16.55 % and selectivity 99.97 %) Results indicated that catalytic performance of these materials depends on how vanadium is integrated in the layered structure, which is determined by the Mg/Al ratio. Vanadium interlayer doping modifies the oxidation state of vanadium and consequently catalytic properties. Surface properties were studied by X-ray photoelectron spectroscopic and diffuse reflectance, UV-visible spectroscopy, and temperature programmed reduction. The analyses provided information about the oxidation state, before and after the reaction. From these results, it is suggested that selectivity to propylene and catalytic activity depend mainly of vanadium oxidation state. (Author)

  5. Graphene-wrapped sulfur nanospheres with ultra-high sulfur loading for high energy density lithium–sulfur batteries

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Ya; Guo, Jinxin; Zhang, Jun, E-mail: zhangjun@zjnu.cn; Su, Qingmei; Du, Gaohui, E-mail: gaohuidu@zjnu.edu.cn

    2015-01-01

    Graphical abstract: - Highlights: • A graphene-wrapped sulfur nanospheres composite with 91 wt% S is prepared. • It shows highly improved electrochemical performance as cathode for Li–S cell. • The PVP coating and conductive graphene minimize polysulfides dissolution. • The flexible coatings with void space accommodate the volume expansion of sulfur. - Abstract: Lithium–sulfur (Li–S) battery with high theoretical energy density is one of the most promising energy storage systems for electric vehicles and intermittent renewable energy. However, due to the poor conductivity of the active material, considerable weight of the electrode is occupied by the conductive additives. Here we report a graphene-wrapped sulfur nanospheres composite (S-nanosphere@G) with sulfur content up to 91 wt% as the high energy density cathode material for Li–S battery. The sulfur nanospheres with diameter of 400–500 nm are synthesized through a solution-based approach with the existence of polyvinylpyrrolidone (PVP). Then the sulfur nanospheres are uniformly wrapped by conductive graphene sheets through the electrostatic interaction between graphene oxide and PVP, followed by reducing of graphene oxide with hydrazine. The design of graphene wrapped sulfur nanoarchitecture provides flexible conductive graphene coating with void space to accommodate the volume expansion of sulfur and to minimize polysulfide dissolution. As a result, the S-nanosphere@G nanocomposite with 91 wt% sulfur shows a reversible initial capacity of 970 mA h g{sup −1} and an average columbic efficiency > 96% over 100 cycles at a rate of 0.2 C. Taking the total mass of electrode into account, the S-nanosphere@G composite is a promising cathode material for high energy density Li–S batteries.

  6. Fractionation of sulfur isotopes during heterogeneous oxidation of SO2 on sea salt aerosol: a new tool to investigate non-sea salt sulfate production in the marine boundary layer

    Directory of Open Access Journals (Sweden)

    S. Borrmann

    2012-05-01

    Full Text Available The oxidation of SO2 to sulfate on sea salt aerosols in the marine environment is highly important because of its effect on the size distribution of sulfate and the potential for new particle nucleation from H2SO4 (g. However, models of the sulfur cycle are not currently able to account for the complex relationship between particle size, alkalinity, oxidation pathway and rate – which is critical as SO2 oxidation by O3 and Cl catalysis are limited by aerosol alkalinity, whereas oxidation by hypohalous acids and transition metal ions can continue at low pH once alkalinity is titrated. We have measured 34S/32S fractionation factors for SO2 oxidation in sea salt, pure water and NaOCl aerosol, as well as the pH dependency of fractionation. Oxidation of SO2 by NaOCl aerosol was extremely efficient, with a reactive uptake coefficient of ≈0.5, and produced sulfate that was enriched in 32S with αOCl = 0.9882±0.0036 at 19 °C. Oxidation on sea salt aerosol was much less efficient than on NaOCl aerosol, suggesting alkalinity was already exhausted on the short timescale of the experiments. Measurements at pH = 2.1 and 7.2 were used to calculate fractionation factors for each step from SO2(g → multiple steps → SOOCl2−. Oxidation on sea salt aerosol resulted in a lower fractionation factor than expected for oxidation of SO32− by O3 (αseasalt = 1.0124±0.0017 at 19 °C. Comparison of the lower fractionation during oxidation on sea salt aerosol to the fractionation factor for high pH oxidation shows HOCl contributed 29% of S(IV oxidation on sea salt in the short experimental timescale, highlighting the potential importance of hypohalous acids in the marine environment. The sulfur isotope fractionation factors measured in this study allow differentiation between the alkalinity-limited pathways – oxidation by O3 and by Cl catalysis (α34 = 1.0163±0.0018 at 19 °C in pure water or 1.0199±0.0024 at pH = 7.2 – which favour the heavy isotope, and

  7. Fractionation of sulfur isotopes during heterogeneous oxidation of SO2 on sea salt aerosol: a new tool to investigate non-sea salt sulfate production in the marine boundary layer

    Science.gov (United States)

    Harris, E.; Sinha, B.; Hoppe, P.; Foley, S.; Borrmann, S.

    2012-05-01

    The oxidation of SO2 to sulfate on sea salt aerosols in the marine environment is highly important because of its effect on the size distribution of sulfate and the potential for new particle nucleation from H2SO4 (g). However, models of the sulfur cycle are not currently able to account for the complex relationship between particle size, alkalinity, oxidation pathway and rate - which is critical as SO2 oxidation by O3 and Cl catalysis are limited by aerosol alkalinity, whereas oxidation by hypohalous acids and transition metal ions can continue at low pH once alkalinity is titrated. We have measured 34S/32S fractionation factors for SO2 oxidation in sea salt, pure water and NaOCl aerosol, as well as the pH dependency of fractionation. Oxidation of SO2 by NaOCl aerosol was extremely efficient, with a reactive uptake coefficient of ≈0.5, and produced sulfate that was enriched in 32S with αOCl = 0.9882±0.0036 at 19 °C. Oxidation on sea salt aerosol was much less efficient than on NaOCl aerosol, suggesting alkalinity was already exhausted on the short timescale of the experiments. Measurements at pH = 2.1 and 7.2 were used to calculate fractionation factors for each step from SO2(g) → multiple steps → SOOCl2-. Oxidation on sea salt aerosol resulted in a lower fractionation factor than expected for oxidation of SO32- by O3 (αseasalt = 1.0124±0.0017 at 19 °C). Comparison of the lower fractionation during oxidation on sea salt aerosol to the fractionation factor for high pH oxidation shows HOCl contributed 29% of S(IV) oxidation on sea salt in the short experimental timescale, highlighting the potential importance of hypohalous acids in the marine environment. The sulfur isotope fractionation factors measured in this study allow differentiation between the alkalinity-limited pathways - oxidation by O3 and by Cl catalysis (α34 = 1.0163±0.0018 at 19 °C in pure water or 1.0199±0.0024 at pH = 7.2) - which favour the heavy isotope, and the alkalinity non

  8. Sulfur isotope studies of biogenic sulfur emissions at Wallops Island, Virginia

    International Nuclear Information System (INIS)

    Hitchcock, D.R.; Black, M.S.; Herbst, R.P.

    1978-03-01

    This research attempted to determine whether it is possible to measure the stable sulfur isotope distributions of atmospheric particulate and gaseous sulphur, and to use this information together with measurements of the ambient levels of sulfur gases and particulate sulfate and sodium in testing certain hypotheses. Sulfur dioxide and particulate sulfur samples were collected at a coastal marine location and their delta (34)S values were determined. These data were used together with sodium concentrations to determine the presence of biogenic sulfur and the identity of the biological processes producing it. Excess (non-seasalt) sulfate levels ranged from 2 to 26 micrograms/cu m and SO2 from 1 to 9 ppb. Analyses of air mass origins and lead concentrations indicated that some anthropogenic contaminants were present on all days, but the isotope data revealed that most of the atmospheric sulfur originated locally from the metabolism of bacterial sulfate reducers on all days, and that the atmospheric reactions leading to the production of sulfate from this biogenic sulfur source are extremely rapid. Delta 34 S values of atmospheric sulfur dioxide correlated well with those of excess sulfate, and implied little or no sulfur isotope fractionation during the oxidation of sulfur gases to sulfate

  9. Genomic Insights into the Sulfur Metabolism of Phototrophic Green Sulfur Bacteria

    DEFF Research Database (Denmark)

    Frigaard, Niels-Ulrik; Bryant, Donald A.

    2008-01-01

    Green sulfur bacteria (GSB) utilize various combinations of sulfide, elemental sulfur, thiosulfate, ferrous iron, and hydrogen for anaerobic photoautotrophic growth. Genome sequence data is currently available for 12 strains of GSB. We present here a genome-based survey of the distribution...... and phylogenies of genes involved in oxidation of sulfur compounds in these strains. Sulfide:quinone reductase, encoded by sqr, is the only known sulfur-oxidizing enzyme found in all strains. All sulfide-utilizing strains contain the dissimilatory sulfite reductase dsrABCEFHLNMKJOPT genes, which appear...... to be involved in elemental sulfur utilization. All thiosulfate-utilizing strains have an identical sox gene cluster (soxJXYZAKBW). The soxCD genes found in certain other thiosulfate-utilizing organisms like Paracoccus pantotrophus are absent from GSB. Genes encoding flavocytochrome c (fccAB), adenosine-5...

  10. Manganese oxidation state mediates toxicity in PC12 cells

    International Nuclear Information System (INIS)

    Reaney, S.H.; Smith, D.R.

    2005-01-01

    The role of the manganese (Mn) oxidation state on cellular Mn uptake and toxicity is not well understood. Therefore, undifferentiated PC12 cells were exposed to 0-200 μM Mn(II)-chloride or Mn(III)-pyrophosphate for 24 h, after which cellular manganese levels were measured along with measures of cell viability, function, and cytotoxicity (trypan blue exclusion, medium lactate dehydrogenase (LDH), 8-isoprostanes, cellular ATP, dopamine, serotonin, H-ferritin, transferrin receptor (TfR), Mn-superoxide dismutase (MnSOD), and copper-zinc superoxide dismutase (CuZnSOD) protein levels). Exposures to Mn(III) >10 μM produced 2- to 5-fold higher cellular manganese levels than equimolar exposures to Mn(II). Cell viability and ATP levels both decreased at the highest Mn(II) and Mn(III) exposures (150-200 μM), while Mn(III) exposures produced increases in LDH activity at lower exposures (≥50 μM) than did Mn(II) (200 μM only). Mn(II) reduced cellular dopamine levels more than Mn(III), especially at the highest exposures (50% reduced at 200 μM Mn(II)). In contrast, Mn(III) produced a >70% reduction in cellular serotonin at all exposures compared to Mn(II). Different cellular responses to Mn(II) exposures compared to Mn(III) were also observed for H-ferritin, TfR, and MnSOD protein levels. Notably, these differential effects of Mn(II) versus Mn(III) exposures on cellular toxicity could not simply be accounted for by the different cellular levels of manganese. These results suggest that the oxidation state of manganese exposures plays an important role in mediating manganese cytotoxicity

  11. Solid-to-solid oxidation of a vanadium(IV) to a vanadium(V) compound: chemisty of a sulfur-containing siderophore.

    Science.gov (United States)

    Chatterjee, Pabitra B; Crans, Debbie C

    2012-09-03

    Visible light facilitates a solid-to-solid photochemical aerobic oxidation of a hunter-green microcrystalline oxidovanadium(IV) compound (1) to form a black powder of cis-dioxidovanadium(V) (2) at ambient temperature. The siderophore ligand pyridine-2,6-bis(thiocarboxylic acid), H(2)L, is secreted by a microorganism from the Pseudomonas genus. This irreversible transformation of a metal monooxo to a metal dioxo complex in the solid state in the absence of solvent is unprecedented. It serves as a proof-of-concept reaction for green chemistry occurring in solid matrixes.

  12. Solvent extraction of elemental sulfur from coal and a determination of its source using stable sulfur isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Hackley, K.C.; Buchanan, D.H.; Coombs, K.; Chaven, C.; Kruse, C.W. (Eastern Illinois University, Charleston, IL (USA). Chemistry Dept.)

    1990-01-01

    Hot tetrachloroethene (perchloroethylen PCE) extracts significant amounts of elemental sulfur (S{sup o}) from weathered coals but not from pristine coals. The objective of this study was to determine whether S{sup o} extracted by PCE is an oxidation product of pyrite or whether it originates in some way from unstable, organically-bound sulfur. The isotopic composition of the PCE-extracted S{sup o} was compared to the isotopic compositions of the pyritic and the organic sulfur in a coal. The S{sup o} was shown to have an isotopic signature similar to the pyritic sulfur. Additionally, the isotopic differences observed between the pyritic, S{sup o} and sulfatic sulfur were consistent with bacterial mediated oxidation of sulfide sulfur (pyrite) as the source of both the sulfatic and elemental sulfur. 21 refs., 2 tabs.

  13. Solvent extraction of elemental sulfur from coal and a determination of its source using stable sulfur isotopes

    Science.gov (United States)

    Hackley, Keith C.; Buchanan, D.H.; Coombs, K.; Chaven, C.; Kruse, C.W.

    1990-01-01

    Hot tetrachloroethene (perchloroethylene, PCE) extracts significant amounts of elemental sulfur (So) from weathered coals but not from pristine coals. The objective of this study was to determine whether So extracted by PCE is an oxidation product of pyrite or whether it originates in some way from unstable, organically-bound sulfur. The isotopic composition of the PCE-extracted So was compared to the isotopic compositions of the pyritic and the organic sulfur in a coal. The So was shown to have an isotopic signature similar to the pyritic sulfur. Additionally, the isotopic differences observed between the pyritic, So and sulfatic sulfur were consistent with bacterial mediated oxidation of sulfide sulfur (pyrite) as the source of both the sulfatic and elemental sulfur. ?? 1990.

  14. Measurement of soil carbon oxidation state and oxidative ratio by 13C nuclear magnetic resonance

    Science.gov (United States)

    Hockaday, W.C.; Masiello, C.A.; Randerson, J.T.; Smernik, R.J.; Baldock, J.A.; Chadwick, O.A.; Harden, J.W.

    2009-01-01

    The oxidative ratio (OR) of the net ecosystem carbon balance is the ratio of net O2 and CO2 fluxes resulting from photosynthesis, respiration, decomposition, and other lateral and vertical carbon flows. The OR of the terrestrial biosphere must be well characterized to accurately estimate the terrestrial CO2 sink using atmospheric measurements of changing O2 and CO2 levels. To estimate the OR of the terrestrial biosphere, measurements are needed of changes in the OR of aboveground and belowground carbon pools associated with decadal timescale disturbances (e.g., land use change and fire). The OR of aboveground pools can be measured using conventional approaches including elemental analysis. However, measuring the OR of soil carbon pools is technically challenging, and few soil OR data are available. In this paper we test three solid-state nuclear magnetic resonance (NMR) techniques for measuring soil OR, all based on measurements of the closely related parameter, organic carbon oxidation state (Cox). Two of the three techniques make use of a molecular mixing model which converts NMR spectra into concentrations of a standard suite of biological molecules of known C ox. The third technique assigns Cox values to each peak in the NMR spectrum. We assess error associated with each technique using pure chemical compounds and plant biomass standards whose Cox and OR values can be directly measured by elemental analyses. The most accurate technique, direct polarization solid-state 13C NMR with the molecular mixing model, agrees with elemental analyses to ??0.036 Cox units (??0.009 OR units). Using this technique, we show a large natural variability in soil Cox and OR values. Soil Cox values have a mean of -0.26 and a range from -0.45 to 0.30, corresponding to OR values of 1.08 ?? 0.06 and a range from 0.96 to 1.22. We also estimate the OR of the carbon flux from a boreal forest fire. Analysis of soils from nearby intact soil profiles imply that soil carbon losses associated

  15. Genomic and Evolutionary Perspectives on Sulfur Metabolism in Green Sulfur Bacteria

    DEFF Research Database (Denmark)

    Frigaard, Niels-Ulrik; Bryant, Donald A.

    2008-01-01

    Green sulfur bacteria (GSB) are anaerobic photoautotrophs that oxidize sulfide, elemental sulfur, thiosulfate, ferrous iron, and hydrogen for growth. We present here an analysis of the distribution and evolution of enzymes involved in oxidation of sulfur compounds in GSB based on genome sequence......, in combination with phylogenetic analyses, suggests that the Dsr system in GSB could be a recent acquisition, which was obtained by lateral gene transfer in part from sulfideoxidizing bacteria and in part from sulfate-reducing bacteria. All thiosulfate-utilizing GSB strains have an identical sox gene cluster...

  16. The problem of oxidation state stabilisation and some regularities of a Periodic system of the elements

    International Nuclear Information System (INIS)

    Kiselev, Yurii M; Tretyakov, Yuri D

    1999-01-01

    The general principles of the concept of oxidation state stabilisation are formulated. Problems associated with the preparation and provision of the highest valent forms of transition elements are considered. The empirical data concerning the synthesis of new compounds of rare-earth elements and d elements in unusually high oxidation states are analysed. The possibility of occurrence of the oxidation states + 9 and + 10 for some elements (for example, for iridium and platinum in tetraoxo ions) are discussed. Approaches to the realisation of these states are outlined and it is demonstrated that solid phases or matrices containing alkali metal cations are the most promising systems for the stabilisation of these high oxidation states. Selected thermodynamic features typical of metal halides and oxides and the regularities of the changes in the extreme oxidation states of d elements are considered. The bibliography includes 266 references.

  17. Demonstration of Selective Catalytic Reduction (SCR) technology for the control of nitrogen oxide (NO{sub x}) emissions from high-sulfur coal-fired boilers. Technical progress report, first and second quarters 1994

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1995-11-01

    The objective of this project is to demonstrate and evaluate commercially available Selective Catalytic Reduction (SCR) catalysts from U.S., Japanese and European catalyst suppliers on a high-sulfur U.S. coal-fired boiler. SCR is a post-combustion nitrogen oxide (NO{sub x}) control technology that involve injecting ammonia into the flue gas generated from coal combustion in a boiler. The flue gas containing ammonia is then passed through a reactor that contains a specialized catalyst. In the presence of the catalyst, the ammonia reacts with NO{sub x} to form nitrogen and water vapor. Although SCR is widely practiced in Japan and Europe on gas-, oil-, and low-sulfur coal-fired boilers, there are several technical uncertainties associated with applying SCR to U.S. coals. These uncertainties include: (1) potential catalyst deactivation due to poisoning by trace metal species present in U.S. coals that are not present in other fuels; (2) performance of the technology and effects on the balance-of-plant equipment in the presence of high amounts of SO{sub 2} and SO{sub 3}; and (3) performance of a wide variety of SCR catalyst compositions, geometries and methods of manufacture under typical high-sulfur coal-fired utility operating conditions. These uncertainties are being explored by operating a series of small-scale SCR reactors and simultaneously exposing different SCR catalysts to flue gas derived from the combustion of high sulfur U.S. coal. The project is being conducted in the following three phases: permitting, environmental monitoring plan and preliminary engineering; detailed design engineering and construction; and operation, testing, disposition and final report. The project was in the operation and testing phase during this reporting period. Accomplishments for this period are described.

  18. Innovative Clean Coal Technology (ICCT): Demonstration of selective catalytic reduction (SCR) technology for the control of nitrogen oxide (NO{sub x}) emissions from high-sulfur coal-fired boilers. Technical progress report, third and fourth quarters 1994

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1995-11-01

    The objective of this project is to demonstrate and evaluate commercially available selective catalytic reduction (SCR) catalysts from U.S., Japanese, and European catalyst suppliers on a high-sulfur U.S. Coal-fired boiler. SCR is a post-combustion nitrogen oxide (NO{sub x}) control technology that involves injecting ammonia into the flue gas generated from coal combustion in an electric utility boiler. The flue gas containing ammonia is then passed through a reactor that contains a specialized catalyst. In the presence of the catalyst, the ammonia reacts with NO{sub x} to form nitrogen and water vapor. Although SCR is widely practiced in Japan and European gas-, oil-, and low-sulfur coal-fired boilers, there are several technical uncertainties associated with applying SCR to U.S. coals. These uncertainties include: (1) potential catalyst deactivation due to poisoning by trace metal species present in U.S. coals that are not present in other fuels; (2) performance of the technology and effects on the balance-of-plant equipment in the presence of high amounts of SO{sub 2} and SO{sub 3}; performance of a wide variety of SCR catalyst compositions, geometries, and methods of manufacture under typical high-sulfur coal-fired utility operating conditions. These uncertainties are being explored by operating a series of small- scale SCR reactors and simultaneously exposing different SCR catalysts to flue gas derived from the combustion of high sulfur U.S. coal. The demonstration is being performed at Gulf Power Company`s Plant Crist Unit No. 5 (75 MW capacity) near Pensacola, Florida. The project is funded by the U.S. Department of Energy (DOE), Southern Company Services, Inc. (SCS on behalf of the entire Southern electric system), the Electric Power Research Institute (EPRI), and Ontario Hydro. SCS is the participant responsible for managing al aspects of this project. 1 ref., 69 figs., 45 tabs.

  19. Quadrupole moment of the 7/21- isomer state in 43S. Shell model study of sulfur isotopes around N=28

    International Nuclear Information System (INIS)

    Chevrier, Raphael

    2013-01-01

    The goal of this work consists in providing new insights in the shape coexistence expected in neutron-rich nuclei around the N=28 shell closure. In 43 S, recent experimental data as well as their interpretation in the shell model framework were used to predict the coexistence between a J π =3/2 1 - prolate deformed ground state and a 7/2 1 - rather spherical isomer state. We report on the quadrupole moment measurement Q s of the 7/2 1 - isomer state [E*=320.5(5) keV, T 1/2 =415(3) ns] in 43 S. The TDPAD method was applied on 43 S nuclei produced by the fragmentation of a 48 Ca primary beam at 345 A.MeV, and selected in-flight through the BigRIPS spectrometer at RIKEN (Japan). The measured value, |Q s |=23(3) efm 2 , is in remarkable agreement with that calculated in the shell model framework, although it is significantly larger than that expected for a single-particle state. In order to understand the nature of the correlations responsible for the departure of the isomer state from a pure spherical shape, we report on the results of a shell model study using the modern SDPF-U interaction of the neighbors sulfur isotopes 42,44,46 S. Those calculations allowed to identify a slight triaxial degree of freedom in the structure of these nuclei, although the latter happens to be highly hindered at N=28 in 44 S. Spectroscopic factor calculations show that this slight triaxial degree of freedom also impacts the low-lying structure in 43 S. It allows to better understand the deviation of the spectroscopic quadrupole moment value of the isomer state from the limit case of a pure spherical state. (author) [fr

  20. Effect of particle size on iron nanoparticle oxidation state

    International Nuclear Information System (INIS)

    Lombardo, Jeffrey J.; Lysaght, Andrew C.; Goberman, Daniel G.; Chiu, Wilson K.S.

    2012-01-01

    Selecting catalyst particles is a very important part of carbon nanotube growth, although the properties of these nanoscale particles are unclear. In this article iron nanoparticles are analyzed through the use of atomic force microscopy and x-ray photoelectron spectroscopy in order to understand how the size affects the chemical composition of nanoparticles and thus their physical structure. Initially, atomic force microscopy was used to confirm the presence of iron particles, and to determine the average size of the particles. Next an analytical model was developed to estimate particle size as a function of deposition time using inputs from atomic force microscopy measurement. X-ray photoelectron spectroscopy analysis was then performed with a focus on the spectra relating to the 2p Fe electrons to study the chemical state of the particles as a function of time. It was shown that as the size of nanoparticles decreased, the oxidation state of the particles changed due to a high proportion of atoms on the surface.

  1. A Cable-Shaped Lithium Sulfur Battery.

    Science.gov (United States)

    Fang, Xin; Weng, Wei; Ren, Jing; Peng, Huisheng

    2016-01-20

    A carbon nanostructured hybrid fiber is developed by integrating mesoporous carbon and graphene oxide into aligned carbon nanotubes. This hybrid fiber is used as a 1D cathode to fabricate a new cable-shaped lithium-sulfur battery. The fiber cathode exhibits a decent specific capacity and lifespan, which makes the cable-shaped lithium-sulfur battery rank far ahead of other fiber-shaped batteries. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. A primer on sulfur for the planetary geologist

    Science.gov (United States)

    Theilig, E.

    1982-01-01

    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.

  3. Influence of oxalic acid on the dissolution kinetics of manganese oxide

    Science.gov (United States)

    Godunov, E. B.; Artamonova, I. V.; Gorichev, I. G.; Lainer, Yu. A.

    2012-11-01

    The kinetics and electrochemical processes of the dissolution of manganese oxides with various oxidation states in sulfuric acid solutions containing oxalate ion additives is studied under variable conditions (concentration, pH, temperature). The parameters favoring a higher degree of the dissolution of manganese oxides in acidic media are determined. The optimal conditions are found for the dissolution of manganese oxides in acidic media in the presence of oxalate ions. The mechanism proposed for the dissolution of manganese oxides in sulfuric acid solutions containing oxalic acid is based on the results of kinetic and electrochemical studies. The steps of the dissolution mechanism are discussed.

  4. Quantum confinement-induced tunable exciton states in graphene oxide.

    Science.gov (United States)

    Lee, Dongwook; Seo, Jiwon; Zhu, Xi; Lee, Jiyoul; Shin, Hyeon-Jin; Cole, Jacqueline M; Shin, Taeho; Lee, Jaichan; Lee, Hangil; Su, Haibin

    2013-01-01

    Graphene oxide has recently been considered to be a potential replacement for cadmium-based quantum dots due to its expected high fluorescence. Although previously reported, the origin of the luminescence in graphene oxide is still controversial. Here, we report the presence of core/valence excitons in graphene-based materials, a basic ingredient for optical devices, induced by quantum confinement. Electron confinement in the unreacted graphitic regions of graphene oxide was probed by high resolution X-ray absorption near edge structure spectroscopy and first-principles calculations. Using experiments and simulations, we were able to tune the core/valence exciton energy by manipulating the size of graphitic regions through the degree of oxidation. The binding energy of an exciton in highly oxidized graphene oxide is similar to that in organic electroluminescent materials. These results open the possibility of graphene oxide-based optoelectronic device technology.

  5. Interfacial Reaction Dependent Performance of Hollow Carbon Nanosphere – Sulfur Composite as a Cathode for Li-S Battery

    International Nuclear Information System (INIS)

    Zheng, Jianming; Yan, Pengfei; Gu, Meng; Wagner, Michael J.; Hays, Kevin A.; Chen, Junzheng; Li, Xiaohong; Wang, Chongmin; Zhang, Ji-Guang; Liu, Jun; Xiao, Jie

    2015-01-01

    Lithium-sulfur (Li-S) battery is a promising energy storage system due to its high energy density, cost effectiveness, and environmental friendliness of sulfur. However, there are still a number of technical challenges, such as low Coulombic efficiency and poor long-term cycle life, impeding the commercialization of Li-S battery. The electrochemical performance of Li-S battery is closely related with the interfacial reactions occurring between hosting substrate and active sulfur species, which are poorly conducting at fully oxidized and reduced states. Here, we correlate the relationship between the performance and interfacial reactions in the Li-S battery system, using a hollow carbon nanosphere (HCNS) with highly graphitic character as hosting substrate for sulfur. With an appropriate amount of sulfur loading, HCNS/S composite exhibits excellent electrochemical performance because of the fast interfacial reactions between HCNS and the polysulfides. However, further increase of sulfur loading leads to increased formation of highly resistive insoluble reaction products (Li 2 S 2 /Li 2 S), which limits the reversibility of the interfacial reactions and results in poor electrochemical performances. These findings demonstrate the importance of the interfacial reaction reversibility in the whole electrode system on achieving high capacity and long cycle life of sulfur cathode for Li-S batteries.

  6. Interfacial Reaction Dependent Performance of Hollow Carbon Nanosphere – Sulfur Composite as a Cathode for Li-S Battery

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Jianming; Yan, Pengfei; Gu, Meng [Pacific Northwest National Laboratory, Richland, WA (United States); Wagner, Michael J.; Hays, Kevin A. [The George Washington University, Washington, DC (United States); Chen, Junzheng; Li, Xiaohong; Wang, Chongmin; Zhang, Ji-Guang; Liu, Jun; Xiao, Jie, E-mail: jie.xiao@pnnl.gov [Pacific Northwest National Laboratory, Richland, WA (United States)

    2015-05-26

    Lithium-sulfur (Li-S) battery is a promising energy storage system due to its high energy density, cost effectiveness, and environmental friendliness of sulfur. However, there are still a number of technical challenges, such as low Coulombic efficiency and poor long-term cycle life, impeding the commercialization of Li-S battery. The electrochemical performance of Li-S battery is closely related with the interfacial reactions occurring between hosting substrate and active sulfur species, which are poorly conducting at fully oxidized and reduced states. Here, we correlate the relationship between the performance and interfacial reactions in the Li-S battery system, using a hollow carbon nanosphere (HCNS) with highly graphitic character as hosting substrate for sulfur. With an appropriate amount of sulfur loading, HCNS/S composite exhibits excellent electrochemical performance because of the fast interfacial reactions between HCNS and the polysulfides. However, further increase of sulfur loading leads to increased formation of highly resistive insoluble reaction products (Li{sub 2}S{sub 2}/Li{sub 2}S), which limits the reversibility of the interfacial reactions and results in poor electrochemical performances. These findings demonstrate the importance of the interfacial reaction reversibility in the whole electrode system on achieving high capacity and long cycle life of sulfur cathode for Li-S batteries.

  7. Plasmon waveguide resonance spectroscopic evidence for differential binding of oxidized and reduced rhodobacter capsulatus cytochrome c(2) to the cytochrome bc(1) complex mediated by the conformation of the rieske iron-sulfur protein

    International Nuclear Information System (INIS)

    Devanathan, S.; Salamon, Z.; Tollin, G.; Fitch, J.C.; Meyer, T.E.; Berry, E.A.; Cusanovich, M.A.

    2007-01-01

    The dissociation constants for the binding of Rhodobacter capsulatus cytochrome c2 and its K93P mutant to the cytochrome bc1 complex embedded in a phospholipid bilayer were measured by plasmon waveguide resonance spectroscopy in the presence and absence of the inhibitor stigmatellin. The reduced form of cytochrome c2 strongly binds to reduced cytochrome bc1 (Kd = 0.02 M) but binds much more weakly to the oxidized form (Kd = 3.1 M). In contrast, oxidized cytochrome c2 binds to oxidized cytochrome bc1 in a biphasic fashion with Kd values of 0.11 and 0.58 M. Such a biphasic interaction is consistent with binding to two separate sites or conformations of oxidized cytochrome c2 and/or cytochrome bc1. However, in the presence of stigmatellin, we find that oxidized cytochrome c2 binds to oxidized cytochrome bc1 in a monophasic fashion with high affinity (Kd = 0.06 M) and reduced cytochrome c2 binds less strongly (Kd = 0.11 M) but ∼30-fold more tightly than in the absence of stigmatellin. Structural studies with cytochrome bc1, with and without the inhibitor stigmatellin, have led to the proposal that the Rieske protein is mobile, moving between the cytochrome b and cytochrome c1 components during turnover. In one conformation, the Rieske protein binds near the heme of cytochrome c1, while the cytochrome c2 binding site is also near the cytochrome c1 heme but on the opposite side from the Rieske site, where cytochrome c2 cannot directly interact with Rieske. However, the inhibitor, stigmatellin, freezes the Rieske protein iron-sulfur cluster in a conformation proximal to cytochrome b and distal to cytochrome c1. We conclude from this that the dual conformation of the Rieske protein is primarily responsible for biphasic binding of oxidized cytochrome c2 to cytochrome c1. This optimizes turnover by maximizing binding of the substrate, oxidized cytochrome c2, when the iron-sulfur cluster is proximal to cytochrome b and minimizing binding of the product, reduced cytochrome c

  8. Interfacial Engineered Polyaniline/Sulfur-doped TiO2 Nanotube Arrays for Ultralong Cycle Lifetime Fiber-Shaped, Solid-State Supercapacitors.

    Science.gov (United States)

    Li, Chun; Wang, Zhuanpei; Li, Shengwen; Cheng, Jianli; Zhang, Yanning; Zhou, Jingwen; Yang, Dan; Tong, Dong-Ge; Wang, Bin

    2018-05-04

    Fiber-shaped supercapacitors (FSCs) have great potential in wearable electronics applications. However, the limited specific surface area and inadequate structural stability caused by the weak interfacial interactions of the electrodes result in relatively low specific capacitance and unsatisfactory cycle lifetime. Herein, solid-state FSCs with high energy density and ultralong cycle lifetime based on polyaniline (PANI)/sulfur-doped TiO2 nanotubes array (PANI/S-TiO2) are fabricated by interfacial engineering. The experimental results and ab initio calculations reveal that S doping can effectively promote the conductivity of titania nanotubes and increase the binding energy of PANI anchored on the electrode surface, leading to much stronger binding of PANI on the surface of the electrode and excellent electrode structure stability. As a result, the FSCs using the PANI/S-TiO2 electrodes deliver a high specific capacitance of 91.9 mF cm-2, a capacitance retention of 93.78% after 12,000 charge/discharge cycles, and an areal energy density of 3.2 µWh cm-2, respectively. Meanwhile, the all-solid-state FSC device retains its excellent flexibility and stable electrochemical capacitance even after bending 150 cycles. The enhanced performances of FSCs could be attributed to the large surface area, short ion diffusion path, high electrical conductivity and engineered interfacial interaction of the rationally designed electrodes.

  9. Quantitative analysis of trap states through the behavior of the sulfur ions in MoS2 FETs following high vacuum annealing

    Science.gov (United States)

    Bae, Hagyoul; Jun, Sungwoo; Kim, Choong-Ki; Ju, Byeong-Kwon; Choi, Yang-Kyu

    2018-03-01

    Few-layer molybdenum disulfide (MoS2) has attracted a great deal of attention as a semiconductor material for electronic and optoelectronic devices. However, the presence of localized states inside the bandgap is a critical issue that must be addressed to improve the applicability of MoS2 technology. In this work, we investigated the density of states (DOS: g(E)) inside the bandgap of MoS2 FET by using a current-voltage (I-V) analysis technique with the aid of high vacuum annealing (HVA). The g(E) can be obtained by combining the trap density and surface potential (ψ S) extracted from a consistent subthreshold current (I D-sub). The electrical performance of MoS2 FETs is strongly dependent on the inherent defects, which are closely related to the g(E) in the MoS2 active layer. By applying the proposed technique to the MoS2 FETs, we were able to successfully characterize the g(E) after stabilization of the traps by the HVA, which reduces the hysteresis distorting the intrinsic g(E). Also, the change of sulfur ions in MoS2 film before and after the HVA treatment is investigated directly by Auger electron spectroscopy analysis. The proposed technique provides a new methodology for active channel engineering of 2D channel based FETs such as MoS2, MoTe2, WSe2, and WS2.

  10. Solid state solubility of copper oxides in hydroxyapatite

    Science.gov (United States)

    Zykin, Mikhail A.; Vasiliev, Alexander V.; Trusov, Lev A.; Dinnebier, Robert E.; Jansen, Martin; Kazin, Pavel E.

    2018-06-01

    Samples containing copper oxide doped hydroxyapatite with the composition Ca10(PO4)6(CuxOH1-x-δ)2, x = 0.054 - 0.582, in the mixture with CuO/Cu2O were prepared by a solid-state high-temperature treatment at varying annealing temperatures and at different partial water vapor and oxygen pressures. The crystal structures of the apatite compounds were refined using powder X-ray diffraction patterns and the content of copper ions x in the apatite was determined. Copper ions enter exclusively into the apatite trigonal channels formally substituting protons of OH-groups and the hexagonal cell parameters grow approximately linearly with x, the channel volume mostly expanding while the remaining volume of the crystal lattice changing only slightly. The equilibrium copper content in the apatite increases drastically, by almost a factor of 10 with the annealing temperature rising from 800° to 1200°C. The reduction of the water partial pressure leads to a further increase of x, while the dependence of x on the oxygen partial pressure exhibits a maximum. The observed relations are consistent with the proposed chemical reactions implying the copper introduction is followed by the release of a considerable quantity of gaseous products - water and oxygen. The analysis of interatomic distances suggests that the maximum content of copper ions in the channel cannot exceed 2/3.

  11. Stabilization of actinides and lanthanides in unusually high oxidation states

    International Nuclear Information System (INIS)

    Eller, P.G.; Penneman, R.A.

    1986-01-01

    Chemical environments can be chosen which stabilize actinides and lanthanides in unusually high or low oxidation states and in unusual coordination. In many cases, one can rationalize the observed species as resulting from strong charge/size influences provided by specific sites in host lattices (e.g., Tb(IV) in BaTbO 3 or Am(IV) in polytungstate anions). In other cases, the unusual species can be considered from an acid-base viewpoint (e.g., U(III) in AsF 5 /HF solution or Pu(VII) in Li 5 PuO 6 ). In still other cases, an interplay of steric and redox effects can lead to interesting comparisons (e.g., instability of double fluoride salts of Pu(V) and Pu(VI) relative to U, Np, and Am analogues). Generalized ways to rationalize compounds containing actinides and lanthanides in unusual valences (particularly high valences), including the above and numerous other examples, will form the focus of this paper. Recently developed methods for synthesizing high valent f-element fluorides using superoxidizers and superacids at low temperatures will also be described. 65 refs., 8 figs., 9 tabs

  12. Sulfur poisoning in cattle

    Energy Technology Data Exchange (ETDEWEB)

    Julian, R J; Harrison, K B

    1975-01-01

    A case of sulfur poisoning is described in which 12 of 20 cattle died following the feeding of sulfur. Respiratory distress and abdominal pain were the prominent signs. Examination of one animal revealed vasculitis and necrosis of the rumen and abomasal wall. The possible toxic effects of sulfur are discussed.

  13. Sulfur containing nanoporous materials, nanoparticles, methods and applications

    Science.gov (United States)

    Archer, Lynden A.; Navaneedhakrishnan, Jayaprakash

    2018-01-30

    Sulfur containing nanoparticles that may be used within cathode electrodes within lithium ion batteries include in a first instance porous carbon shape materials (i.e., either nanoparticle shapes or "bulk" shapes that are subsequently ground to nanoparticle shapes) that are infused with a sulfur material. A synthetic route to these carbon and sulfur containing nanoparticles may use a template nanoparticle to form a hollow carbon shape shell, and subsequent dissolution of the template nanoparticle prior to infusion of the hollow carbon shape shell with a sulfur material. Sulfur infusion into other porous carbon shapes that are not hollow is also contemplated. A second type of sulfur containing nanoparticle includes a metal oxide material core upon which is located a shell layer that includes a vulcanized polymultiene polymer material and ion conducting polymer material. The foregoing sulfur containing nanoparticle materials provide the electrodes and lithium ion batteries with enhanced performance.

  14. Modeling of a Large-Scale High Temperature Regenerative Sulfur Removal Process

    DEFF Research Database (Denmark)

    Konttinen, Jukka T.; Johnsson, Jan Erik

    1999-01-01

    model that does not account for bed hydrodynamics. The pilot-scale test run results, obtained in the test runs of the sulfur removal process with real coal gasifier gas, have been used for parameter estimation. The validity of the reactor model for commercial-scale design applications is discussed.......Regenerable mixed metal oxide sorbents are prime candidates for the removal of hydrogen sulfide from hot gasifier gas in the simplified integrated gasification combined cycle (IGCC) process. As part of the regenerative sulfur removal process development, reactor models are needed for scale......-up. Steady-state kinetic reactor models are needed for reactor sizing, and dynamic models can be used for process control design and operator training. The regenerative sulfur removal process to be studied in this paper consists of two side-by-side fluidized bed reactors operating at temperatures of 400...

  15. Regeneration of sulfated metal oxides and carbonates

    Science.gov (United States)

    Hubble, Bill R.; Siegel, Stanley; Cunningham, Paul T.

    1978-03-28

    Alkali metal or alkaline earth metal carbonates such as calcium carbonate and magnesium carbonate found in dolomite or limestone are employed for removal of sulfur dioxide from combustion exhaust gases. The sulfated carbonates are regenerated to oxides through use of a solid-solid reaction, particularly calcium sulfide with calcium sulfate to form calcium oxide and sulfur dioxide gas. The regeneration is performed by contacting the sulfated material with a reductant gas such as hydrogen within an inert diluent to produce calcium sulfide in mixture with the sulfate under process conditions selected to permit the sulfide-sulfate, solid-state reaction to occur.

  16. Sulfur dimers adsorbed on Au(111) as building blocks for sulfur octomers formation: A density functional study

    International Nuclear Information System (INIS)

    Hernandez-Tamargo, Carlos E.; Montero-Alejo, Ana Lilian; Pujals, Daniel Codorniu; Mikosch, Hans; Hernández, Mayra P.

    2014-01-01

    Experimental scanning tunneling microscopy (STM) studies have shown for more than two decades rectangular formations when sulfur atoms are deposited on Au(111) surfaces. The precursors have ranged from simple molecules or ions, such as SO 2 gas or sulfide anions, to more complex organosulfur compounds. We investigated, within the framework of the Density Functional Theory, the structure of these rectangular patterns assuming them entirely composed of sulfur atoms as the experimental evidence suggests. The sulfur coverage at which the simulations were carried out (0.67 ML or higher) provoked that the sulfur-sulfur association had to be taken into account for achieving a good agreement between the sets of simulated and experimental STM images. A combination of four sulfur dimers per rectangular formation properly explained the trends obtained by the experimental STM analysis which were related with the rectangles' size and shape fluctuations together with sulfur-sulfur distances within these rectangles. Finally, a projected density of states analysis showed that the dimers were capable of altering the Au(5d) electronic states at the same level as atomic sulfur adsorbed at low coverage. Besides, sulfur dimers states were perfectly distinguished, whose presence near and above the Fermi level can explain both: sulfur-sulfur bond elongation and dimers stability when they stayed adsorbed on the surface at high coverage

  17. Sulfur dimers adsorbed on Au(111) as building blocks for sulfur octomers formation: A density functional study

    Energy Technology Data Exchange (ETDEWEB)

    Hernandez-Tamargo, Carlos E.; Montero-Alejo, Ana Lilian [Laboratory of Computational and Theoretical Chemistry (LQCT), Faculty of Chemistry, Havana University, Havana 10400 (Cuba); Pujals, Daniel Codorniu [Higher Institute of Technologies and Applied Sciences (InSTEC), Havana 10400 (Cuba); Mikosch, Hans [Institute of Chemical Technologies and Analytics, Vienna University of Technology, Getreidemarkt 9/E164-EC, 1060 Vienna (Austria); Hernández, Mayra P., E-mail: mayrap@imre.oc.uh.cu [Instituto de Ciencias y Tecnologías de Materiales (IMRE), Havana 10400 (Cuba)

    2014-07-28

    Experimental scanning tunneling microscopy (STM) studies have shown for more than two decades rectangular formations when sulfur atoms are deposited on Au(111) surfaces. The precursors have ranged from simple molecules or ions, such as SO{sub 2} gas or sulfide anions, to more complex organosulfur compounds. We investigated, within the framework of the Density Functional Theory, the structure of these rectangular patterns assuming them entirely composed of sulfur atoms as the experimental evidence suggests. The sulfur coverage at which the simulations were carried out (0.67 ML or higher) provoked that the sulfur-sulfur association had to be taken into account for achieving a good agreement between the sets of simulated and experimental STM images. A combination of four sulfur dimers per rectangular formation properly explained the trends obtained by the experimental STM analysis which were related with the rectangles' size and shape fluctuations together with sulfur-sulfur distances within these rectangles. Finally, a projected density of states analysis showed that the dimers were capable of altering the Au(5d) electronic states at the same level as atomic sulfur adsorbed at low coverage. Besides, sulfur dimers states were perfectly distinguished, whose presence near and above the Fermi level can explain both: sulfur-sulfur bond elongation and dimers stability when they stayed adsorbed on the surface at high coverage.

  18. Effect of sulfur dioxide partial pressure on the reaction of iodine, sulfur dioxide and water

    International Nuclear Information System (INIS)

    Nakajima, Hayato; Imai, Yoshiyuki; Kasahara, Seiji; Kubo, Shinji; Onuki, Kaoru

    2007-01-01

    Effect of sulfur dioxide partial pressure on the reaction of iodine, sulfur dioxide and water, which is a unit reaction in the IS process for thermochemical hydrogen production, was studied experimentally at 323 K under iodine saturation. Quasi-equilibrium state was observed in the presence of sulfur dioxide gas at constant pressure. The composition of the poly-hydriodic acid solution formed was discussed assuming an ideal desulfurization by the reverse reaction of the Bunsen reaction. The value of HI/(HI+H 2 O) of the desulfurized solution was large at high sulfur dioxide pressure and reached the maximum of 15.7 ± 0.3 mol%. (author)

  19. Effect of sulfur content in a sulfur-activated carbon composite on the electrochemical properties of a lithium/sulfur battery

    Energy Technology Data Exchange (ETDEWEB)

    Park, Jin-Woo; Kim, Changhyeon; Ryu, Ho-Suk; Cho, Gyu-Bong; Cho, Kwon-Koo; Kim, Ki-Won [School of Materials Science and Engineering, Gyeongsang National University, Jinju (Korea, Republic of); Ahn, Jou-Hyeon [Department of Chemical & Biological Engineering, Gyeongsang National University, Jinju (Korea, Republic of); Wang, Guoxiu [School of Chemistry and Forensic Science, University of Technology Sydney, Sydney, NSW 2007 (Australia); Ahn, Jae-Pyeung [Advanced Analysis Center, Research Planning & Coordination Division, KIST, Seoul (Korea, Republic of); Ahn, Hyo-Jun, E-mail: ahj@gnu.ac.kr [School of Materials Science and Engineering, Gyeongsang National University, Jinju (Korea, Republic of)

    2015-09-15

    Highlights: • The content of sulfur in activated carbon was controlled by solution process. • The sulfur electrode with low sulfur content shows the best performance. • The Li/S battery has capacity of 1360 mAh/g at 1 C and 702 mAh/g at 10 C. - Abstract: The content of sulfur in sulfur/activated carbon composite is controlled from 32.37 wt.% to 55.33 wt.% by a one-step solution-based process. When the sulfur content is limited to 41.21 wt.%, it can be loaded into the pores of an activated carbon matrix in a highly dispersed state. On the contrary, when the sulfur content is 55.33 wt.%, crystalline sulfur can be detected on the surface of the activated carbon matrix. The best electrochemical performance can be obtained for a sulfur electrode with the lowest sulfur content. The sulfur/activated carbon composite with 32.37 wt.% sulfur afforded the highest first discharge capacity of 1360 mAh g{sup −1} at 1 C rate and a large reversible capacity of 702 mAh g{sup −1} at 10 C (16.75 A/g)

  20. The Behavior of the Ru-bda Water Oxidation Catalysts at Low Oxidation States.

    Science.gov (United States)

    Matheu, Roc; Ghaderian, Abolfazl; Francas, Laia; Chernev, Petko; Ertem, Mehmed; Benet-Buchholz, Jordi; Batista, Victor; Haumann, Michael; Gimbert-Suriñach, Carolina; Sala, Xavier; Llobet, Antoni

    2018-06-13

    The Ru complex [RuII(bda-κ-N2O2)(N-NH2)2], 1, (bda2- = (2,2'-bipyridine)-6,6'-dicarboxylate; N-NH2 = 4-(pyridin-4-yl)aniline) is used as a synthetic intermediate to prepare Ru-bda complexes that contain the NO+, acetonitrile (MeCN) or H2O ligands at oxidation states II and III. Complex 1 reacts with excess NO+ to form a Ru complex where the aryl amine ligands N-NH2 in 1 are transformed into diazonium salts (N-N2+ = 4-(pyridin-4-yl)benzenediazonium)) together with the formation of a new Ru-NO group at the equatorial zone, to generate [RuII(bda-κ-N2O)(NO)(N-N2)2]3+, 23+. Similarly, complex 1 can also react with a coordinating solvent, such as MeCN, at room temperature leading to complex [RuII(bda-κ-N2O)(MeCN)(N-NH2)2], 3. Finally in acidic aqueous solutions solvent water coordinates the Ru center forming {[RuII(bda-κ-(NO)3)(H2O)(N-NH3)2](H2O)n}2+, 42+, that is strongly hydrogen bonded with additional water molecules at the second coordination sphere. We have additionally characterized the one electron oxidized complex {[RuIII(bda-κ-(NO)3.5)(H2O)(N-NH3)2](H2O)n}3+, 53+. The coordination mode of the complexes has been studied both in the solid state and in solution through single-crystal XRD, X-ray absorption spectroscopy, variable-temperature NMR and DFT calculations. While the κ-N2O is the main coordination mode for 23+ and 3, an equilibrium that involves isomers with κ-N2O and κ-NO2 coordination modes and neighboring hydrogen bonded water molecules is observed for 42+ and 53+. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. A microbial-mineralization-inspired approach for synthesis of manganese oxide nanostructures with controlled oxidation states and morphologies

    Energy Technology Data Exchange (ETDEWEB)

    Oba, Manabu; Oaki, Yuya; Imai, Hiroaki [Department of Applied Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama 223-8522 (Japan)

    2010-12-21

    Manganese oxide nanostructures are synthesized by a route inspired by microbial mineralization in nature. The combination of organic molecules, which include antioxidizing and chelating agents, facilitates the parallel control of oxidation states and morphologies in an aqueous solution at room temperature. Divalent manganese hydroxide (Mn(OH){sub 2}) is selectively obtained as a stable dried powder by using a combination of ascorbic acid as an antioxidizing agent and other organic molecules with the ability to chelate to manganese ions. The topotactic oxidation of the resultant Mn(OH){sub 2} leads to the selective formation of trivalent manganese oxyhydroxide ({beta}-MnOOH) and trivalent/tetravalent sodium manganese oxide (birnessite, Na{sub 0.55}Mn{sub 2}O{sub 4}.1.5H{sub 2}O). For microbial mineralization in nature, similar synthetic routes via intermediates have been proposed in earlier works. Therefore, these synthetic routes, which include in the present study the parallel control over oxidation states and morphologies of manganese oxides, can be regarded as new biomimetic routes for synthesis of transition metal oxide nanostructures. As a potential application, it is demonstrated that the resultant {beta}-MnOOH nanostructures perform as a cathode material for lithium ion batteries. (Copyright copyright 2010 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  2. Sulfur-Containing Agrochemicals.

    Science.gov (United States)

    Devendar, Ponnam; Yang, Guang-Fu

    2017-10-09

    Modern agricultural chemistry has to support farmers by providing innovative agrochemicals. In this context, the introduction of sulfur atoms into an active ingredient is still an important tool in modulating the properties of new crop-protection compounds. More than 30% of today's agrochemicals contain at least one sulfur atom, mainly in fungicides, herbicides and insecticides. A number of recently developed sulfur-containing agrochemical candidates represent a novel class of chemical compounds with new modes of action, so we intend to highlight the emerging interest in commercially active sulfur-containing compounds. This chapter gives a comprehensive overview of selected leading sulfur-containing pesticidal chemical families namely: sulfonylureas, sulfonamides, sulfur-containing heterocyclics, thioureas, sulfides, sulfones, sulfoxides and sulfoximines. Also, the most suitable large-scale synthetic methods of the recently launched or provisionally approved sulfur-containing agrochemicals from respective chemical families have been highlighted.

  3. Method of burning sulfur-containing fuels in a fluidized bed boiler

    Science.gov (United States)

    Jones, Brian C.

    1982-01-01

    A method of burning a sulfur-containing fuel in a fluidized bed of sulfur oxide sorbent wherein the overall utilization of sulfur oxide sorbent is increased by comminuting the bed drain solids to a smaller average particle size, preferably on the order of 50 microns, and reinjecting the comminuted bed drain solids into the bed. In comminuting the bed drain solids, particles of spent sulfur sorbent contained therein are fractured thereby exposing unreacted sorbent surface. Upon reinjecting the comminuted bed drain solids into the bed, the newly-exposed unreacted sorbent surface is available for sulfur oxide sorption, thereby increasing overall sorbent utilization.

  4. S-containing copolymer as cathode material in poly(ethylene oxide)-based all-solid-state Li-S batteries

    Science.gov (United States)

    Gracia, Ismael; Ben Youcef, Hicham; Judez, Xabier; Oteo, Uxue; Zhang, Heng; Li, Chunmei; Rodriguez-Martinez, Lide M.; Armand, Michel

    2018-06-01

    Inverse vulcanization copolymers (p(S-DVB)) from the radical polymerization of elemental sulfur and divinylbenzene (DVB) have been studied as cathode active materials in poly(ethylene oxide) (PEO)-based all-solid-state Li-S cells. The Li-S cell comprising the optimized p(S-DVB) cathode (80:20 w/w S/DVB ratio) and lithium bis(fluorosulfonyl)imide/PEO (LiFSI/PEO) electrolyte shows high specific capacity (ca. 800 mAh g-1) and high Coulombic efficiency for 50 cycles. Most importantly, polysulfide (PS) shuttle is highly mitigated due to the strong interactions of PS species with polymer backbone in p(S-DVB). This is demonstrated by the stable cycling of the p(S-DVB)-based cell using lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)/PEO electrolyte, where successful charging cannot be achieved even at the first cycle with plain elemental S-based cathode material due to the severe PS shuttle phenomenon. These results suggest that inverse vulcanization copolymers are promising alternatives to elemental sulfur for enhancing the electrochemical performance of PEO-based all-solid-state Li-S cells.

  5. Steady-state sulfur critical loads and exceedances for protection of aquatic ecosystems in the U.S. Southern Appalachian Mountains.

    Science.gov (United States)

    McDonnell, Todd C; Sullivan, Timothy J; Hessburg, Paul F; Reynolds, Keith M; Povak, Nicholas A; Cosby, Bernard J; Jackson, William; Salter, R Brion

    2014-12-15

    Atmospherically deposited sulfur (S) causes stream water acidification throughout the eastern U.S. Southern Appalachian Mountain (SAM) region. Acidification has been linked with reduced fitness and richness of aquatic species and changes to benthic communities. Maintaining acid-base chemistry that supports native biota depends largely on balancing acidic deposition with the natural resupply of base cations. Stream water acid neutralizing capacity (ANC) is maintained by base cations that mostly originate from weathering of surrounding lithologies. When ambient atmospheric S deposition exceeds the critical load (CL) an ecosystem can tolerate, stream water chemistry may become lethal to biota. This work links statistical predictions of ANC and base cation weathering for streams and watersheds of the SAM region with a steady-state model to estimate CLs and exceedances. Results showed that 20.1% of the total length of study region streams displayed ANC high elevation, and cool and moist forested conditions, the percentage of stream length in exceedance was highest for mountain wilderness areas and in national parks, and lowest for privately owned valley bottom land. Exceedance results were summarized by 12-digit hydrologic unit code (subwatershed) for use in developing management goals and policy objectives, and for long-term monitoring. Copyright © 2014 Elsevier Ltd. All rights reserved.

  6. Electrochemical reduction of sulfur dioxide in sulfolane

    Energy Technology Data Exchange (ETDEWEB)

    Vorob' ev, A.S.; Gavrilova, A.A.; Kolosnitsyn, V.S.; Nikitin, Yu.E.

    1985-09-01

    Solutions of sulfur dioxide in aproptic media are promising electrolyte oxidizing agents for chemical current sources with anodes of active metals. This work describes the electrochemical reduction of sulfur dioxide in sulfolane in a lithium halide supporting electrolyte which was investigated by the methods of voltamperometry and chronopotentiometry. The dependence of the current of the cathodic peak on the concentration of the supporting electrolyte salts, sulfur dioxide and water, was studied. On the basis of the data obtained, a hypothesis was advanced on the nature of the limiting step. The investigation showed that at low polarizing current densities, a substantial influence on the reduction of sulfur dioxide in sulfolane in a lithium halide supporting electrolyte is exerted by blockage of the electrode surface by sparingly soluble reaction products.

  7. Effect of sulfur removal on scale adhesion to PWA 1480

    International Nuclear Information System (INIS)

    Smialek, J.L.; Tubbs, B.K.

    1995-01-01

    A commercial superalloy, PWA 1480, was annealed in hydrogen at 1,000 C to 1,300 C in order to remove a 10 ppmw sulfur impurity. This treatment was very successful above 1,200 C, resulting in residual sulfur contents below 0.1 ppmw. The degree of scale adhesion in subsequent 1,100 C cyclic oxidation tests was inversely related to residual sulfur content. Control of adhesion by desulfurization in the absence of reactive elements supports an adhesion mechanism based on oxide-metal bonding weakened by sulfur segregation. Attempts at sulfur purging and improving adhesion by repeated oxidation/polishing were not successful, in contrast to previous studies on NiCrAl

  8. Cell Concepts of Metal-Sulfur Batteries (Metal = Li, Na, K, Mg): Strategies for Using Sulfur in Energy Storage Applications.

    Science.gov (United States)

    Medenbach, Lukas; Adelhelm, Philipp

    2017-09-29

    There is great interest in using sulfur as active component in rechargeable batteries thanks to its low cost and high specific charge (1672 mAh/g). The electrochemistry of sulfur, however, is complex and cell concepts are required, which differ from conventional designs. This review summarizes different strategies for utilizing sulfur in rechargeable batteries among membrane concepts, polysulfide concepts, all-solid-state concepts as well as high-temperature systems. Among the more popular lithium-sulfur and sodium-sulfur batteries, we also comment on recent results on potassium-sulfur and magnesium-sulfur batteries. Moreover, specific properties related to the type of light metal are discussed.

  9. Oxidation under electron bombardment. A tool for studying the initial states of silicon oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Carriere, B.; Deville, J.P.; El Maachi, A.

    1987-06-01

    The exciting beam of an Auger electron spectrometer has been used to monitor the oxidation of silicon single crystals at room temperature and very low pressures of oxygen (approx. 10/sup -7/ Torr). This process allows us to build ultra-thin layers of silica on silicon (down to 30 A) but it is mostly used to investigate the mechanisms of the initial stages of oxidation. Auger spectra recorded continuously during the oxidation process provide information on (1) the nature of the silicon-oxygen chemical bonds which are interpreted through fine structure in the Auger peak, and (2) the kinetics of oxide formation which are deduced from curves of Auger signal versus time. An account is given of the contribution of these Auger studies to the description of the intermediate oxide layer during the reaction between silicon and oxygen and the influence of surface structural disorder, induced mainly by argon-ion bombardment, is discussed in terms of reactivity and oxide coverage.

  10. Capital cost: high and low sulfur coal plants-1200 MWe. [High sulfur coal

    Energy Technology Data Exchange (ETDEWEB)

    1977-01-01

    This Commercial Electric Power Cost Study for 1200 MWe (Nominal) high and low sulfur coal plants consists of three volumes. The high sulfur coal plant is described in Volumes I and II, while Volume III describes the low sulfur coal plant. The design basis and cost estimate for the 1232 MWe high sulfur coal plant is presented in Volume I, and the drawings, equipment list and site description are contained in Volume II. The reference design includes a lime flue gas desulfurization system. A regenerative sulfur dioxide removal system using magnesium oxide is also presented as an alternate in Section 7 Volume II. The design basis, drawings and summary cost estimate for a 1243 MWe low sulfur coal plant are presented in Volume III. This information was developed by redesigning the high sulfur coal plant for burning low sulfur sub-bituminous coal. These coal plants utilize a mechanical draft (wet) cooling tower system for condenser heat removal. Costs of alternate cooling systems are provided in Report No. 7 in this series of studies of costs of commercial electrical power plants.

  11. Technologies for the treatment of the sulfur dioxide and nitrogen oxides generated by the combustion in open chamber; Tecnologias para el tratamiento de dioxido de azufre y oxidos de nitrogeno generados por la combustion en camara abierta

    Energy Technology Data Exchange (ETDEWEB)

    Salazar Villalpando, Maria Dolores [Instituto Mexicano del Petroleo, Mexico, D. F. (Mexico)

    1993-12-31

    In general terms, there are only three ways of avoiding the sulfur dioxide and the nitrogen oxides, generated by the combustion in open chamber, from contaminating the air; the first one is utilizing low sulfur and nitrogen content fuels, the second one is by controlling the parameters that affect the combustion and the third one to treat and/or clean the gases before exhausting them to the air. In this document, some of the treatments for diminishing the pollutant emissions generated by the combustion in open chamber, are presented. [Espanol] En terminos generales, solo existen 3 maneras de evitar que el dioxido de azufre y oxidos de nitrogeno generados por la combustion en camara abierta sigan contaminando el aire, la primera es utilizar un combustible de bajo contenido de azufre y nitrogeno, la segunda es controlar los parametros que afectan la combustion, y la tercera es tratar y/o limpiar los gases antes de emitirlos a la atmosfera. En este documento se presentan algunos tratamientos para disminuir las emisiones de contaminantes generados por la combustion en camara abierta.

  12. Technologies for the treatment of the sulfur dioxide and nitrogen oxides generated by the combustion in open chamber; Tecnologias para el tratamiento de dioxido de azufre y oxidos de nitrogeno generados por la combustion en camara abierta

    Energy Technology Data Exchange (ETDEWEB)

    Salazar Villalpando, Maria Dolores [Instituto Mexicano del Petroleo, Mexico, D. F. (Mexico)

    1992-12-31

    In general terms, there are only three ways of avoiding the sulfur dioxide and the nitrogen oxides, generated by the combustion in open chamber, from contaminating the air; the first one is utilizing low sulfur and nitrogen content fuels, the second one is by controlling the parameters that affect the combustion and the third one to treat and/or clean the gases before exhausting them to the air. In this document, some of the treatments for diminishing the pollutant emissions generated by the combustion in open chamber, are presented. [Espanol] En terminos generales, solo existen 3 maneras de evitar que el dioxido de azufre y oxidos de nitrogeno generados por la combustion en camara abierta sigan contaminando el aire, la primera es utilizar un combustible de bajo contenido de azufre y nitrogeno, la segunda es controlar los parametros que afectan la combustion, y la tercera es tratar y/o limpiar los gases antes de emitirlos a la atmosfera. En este documento se presentan algunos tratamientos para disminuir las emisiones de contaminantes generados por la combustion en camara abierta.

  13. Ab initio investigation of sulfur monofluoride and its singly charged cation and anion in their ground electronic state

    International Nuclear Information System (INIS)

    Li Song; Chen Shan-Jun; Chen Yan; Chen Peng

    2016-01-01

    The SF radical and its singly charged cation and anion, SF + and SF − , have been investigated on the MRCI/aug-cc-pVXZ (X = Q, 5, 6) levels of theory with Davidson correction. Both the core–valence correlation and the relativistic effect are considered. The extrapolating to the complete basis set (CBS) limit is adopted to remove the basis set truncation error. Geometrical parameters, potential energy curves (PECs), vibrational energy levels, spectroscopic constants, ionization potentials, and electron affinities of the ground electronic state for all these species are obtained. The information with respect to molecular characteristics of the SF n (n = −1, 0, +1) systems derived in this work will help to extend our knowledge and to guide further experimental or theoretical researches. (paper)

  14. Interface Controlled Oxidation States in Layered Cobalt Oxide Nanoislands on Gold

    DEFF Research Database (Denmark)

    Walton, Alexander; Fester, Jakob; Bajdich, Michal

    2015-01-01

    Layered cobalt oxides have been shown to be highly active catalysts for the oxygen evolution reaction (OER; half of the catalytic “water splitting” reaction), particularly when promoted with gold. However, the surface chemistry of cobalt oxides and in particular the nature of the synergistic effect...

  15. Experimental and theoretical studies of the reactions of ground-state sulfur atoms with hydrogen and deuterium

    Science.gov (United States)

    Thompson, Kristopher M.; Gao, Yide; Marshall, Paul; Wang, Han; Zhou, Linsen; Li, Yongle; Guo, Hua

    2017-10-01

    The gas-phase kinetics of S(3P) atoms with H2 and D2 have been studied via the laser flash photolysis—resonance fluorescence technique. S atoms were generated by pulsed photolysis of CS2 at 193 nm and monitored by time-resolved fluorescence at 181 nm. The rate coefficients for H2 (k1) and D2 (k2), respectively, are summarized as k1(600-1110 K) = 3.0 × 10-9 exp(-1.317/×105-2.703 ×107K /T 8.314 T /K ) cm3 molecule-1 s-1 and k2(770-1110 K) = 2.2 × 10-14 (T/298 K)3.55 exp(-5420 K/T) cm3 molecule-1 s-1. Error limits are discussed in the text. The rate coefficients for formation of SH(SD) + H(D) on a newly developed triplet potential energy surface were characterized via ring polymer molecular dynamics and canonical variational transition-state theory. There is excellent agreement above about 1000 K between theory and experiment. At lower temperatures, the experimental rate coefficient is substantially larger than the results computed for the adiabatic reaction, suggesting a significant role for intersystem crossing to the singlet potential energy surface at lower temperatures.

  16. Ab initio investigation of sulfur monofluoride and its singly charged cation and anion in their ground electronic state

    Science.gov (United States)

    Song, Li; Shan-Jun, Chen; Yan, Chen; Peng, Chen

    2016-03-01

    The SF radical and its singly charged cation and anion, SF+ and SF-, have been investigated on the MRCI/aug-cc-pVXZ (X = Q, 5, 6) levels of theory with Davidson correction. Both the core-valence correlation and the relativistic effect are considered. The extrapolating to the complete basis set (CBS) limit is adopted to remove the basis set truncation error. Geometrical parameters, potential energy curves (PECs), vibrational energy levels, spectroscopic constants, ionization potentials, and electron affinities of the ground electronic state for all these species are obtained. The information with respect to molecular characteristics of the SFn (n = -1, 0, +1) systems derived in this work will help to extend our knowledge and to guide further experimental or theoretical researches. Project supported by the National Natural Science Foundation of China (Grant Nos. 11304023 and 11447172), the Young and Middle-Aged Talent of Education Burea of Hubei Province, China (Grant No. Q20151307), and the Yangtze Youth Talents Fund of Yangtze University, China (Grant No. 2015cqr21).

  17. Desulfurization of organic sulfur from a subbituminous coal by electron-transfer process with K{sub 4}(Fe(CN){sub 6})

    Energy Technology Data Exchange (ETDEWEB)

    Dipu Borah [Pragjyotika J College, Titabar (India). Department of Chemistry

    2006-02-01

    The desulfurization reaction involving direct electron transfer from potassium ferrocyanide, K{sub 4}(Fe(CN){sub 6}), successfully removed organic sulfur from a subbituminous coal. The temperature variation of desulfurization revealed that increase of temperature enhanced the level of sulfur removal. Moreover, the desulfurization reaction was found to be dependent on the concentration of K{sub 4}(Fe(CN){sub 6}). Gradual increase in the concentration of K{sub 4}(Fe(CN){sub 6}) raised the magnitude of desulfurization, but at higher concentration the variation was not significant. The removal of organic sulfur from unoxidized coal slightly increased with reduced particle size. Desulfurization from oxidized coals (prepared by aerial oxidation) revealed a higher level of sulfur removal in comparison to unoxidized coal. Highest desulfurization of 36.4 wt % was obtained at 90{sup o}C and 0.1 M concentration of K{sub 4}(Fe(CN){sub 6}) in the 100-mesh size oxidized coal prepared at 200{sup o}C. Model sulfur compound study revealed that aliphatic types of sulfur compounds are primarily responsible for desulfurization. Because of higher stability, thiophene and condensed thiophene-type of compounds perhaps remained unaffected by the electron-transfer agent. Infrared study revealed the formation of oxidized sulfur compounds (sulfoxide, sulfone, sulfonic acid, etc.) in the oxidized coals. The desulfurization reaction in different systems is well-represented by the pseudo-first-order kinetic model. Application of the transition state theory indicated that the desulfurization reaction proceeds with the absorption of heat (endothermic reaction) and is nonspontaneous in nature. 53 refs., 6 figs., 3 tabs.

  18. Origin of interface states and oxide charges generated by ionizing radiation

    International Nuclear Information System (INIS)

    Sah, C.T.

    1976-01-01

    The randomly located trivalent silicon atoms are shown to account for the thermally generated interface states at the SiO 2 -Si interface. The interface state density is greatly reduced in water containing ambients at low temperatures (450 0 C) by forming trivalent silicon hydroxide bonds. Interface states are regenerated when the /triple bond/Si-OH bonds are broken by ionizing radiation and the OH ions are drifted away. In the bulk of the oxide film, the trivalent silicon and the interstitial oxygen donor centers are shown to be responsible for the heat and radiation generated positive space charge build-up (oxide charge) in thermally grown silicon oxide

  19. Origin of sulfur and crustal recycling of copper in polymetallic (Cu-Au-Co-Bi-U ± Ag) iron-oxide-dominated systems of the Great Bear Magmatic Zone, NWT, Canada

    Science.gov (United States)

    Acosta-Góngora, P.; Gleeson, S. A.; Samson, I. M.; Corriveau, L.; Ootes, L.; Jackson, S. E.; Taylor, B. E.; Girard, I.

    2018-03-01

    The Great Bear Magmatic Zone, in northwest Canada, contains numerous polymetallic mineral occurrences, prospects, and deposits of the iron oxide copper-gold deposit (IOCG) family. The mineralization is hosted by the Treasure Lake Group and igneous rocks of the Great Bear arc and was deposited concomitantly with the arc magmatism (ca. 1.88 to 1.87 Ga). In situ δ 34S ( n = 48) and δ 65Cu ( n = 79) analyses were carried out on ore-related sulfides from a number of these systems. The δ 34S values mainly vary between 0 and +5‰, consistent with derivation of sulfur from the mantle. Lower δ 34S values (-7.7 to +1.4‰) from the Sue-Dianne breccia may indicate SO2 disproportionation of a magmatic hydrothermal fluid. The δ 65Cu values vary between -1.2 and -0.3‰, and are lower than the igneous δ 65Cu range of values (0.0 ± 0.27‰). The S and Cu isotopic data are decoupled, which suggests that Cu (and possibly some S) was dissolved and remobilized from supracrustal rocks during early stages of alteration (e.g., sodic alteration) and then precipitated by lower temperature, more oxidizing fluids (e.g., Ca-Fe-K alteration). A limited fluid inclusion dataset and δ 13C and δ 18O values are also presented. The δ 18Ofluid values are consistent with a magmatic origin or a host-rock equilibrated meteoric water source, whereas the δ 13Cfluid values support a marine carbonate source. Combined, the S and Cu isotopic data indicate that while the emplacement of the Great Bear magmatic bodies may have driven fluid convection and may be the source of fluids and sulfur, metals such as Cu could have been recycled from crustal sources.

  20. Sulfur polymer cement concrete

    International Nuclear Information System (INIS)

    Weber, H.H.; McBee, W.C.

    1990-01-01

    Sulfur-based composite materials formulated using sulfur polymer cement (SPC) and mineral aggregates are described and compared with conventional portland cement based materials. Materials characteristics presented include mechanical strength, chemical resistance, impact resistance, moisture permeation, and linear shrinkage during placement and curing. Examples of preparation and placement of sulfur polymer cement concrete (SC) are described using commercial scale equipment. SC applications presented are focused into hostile chemical environments where severe portland cement concrete (PCC) failure has occurred

  1. Estimation of sulfur in coal by fast neutron activation

    International Nuclear Information System (INIS)

    Das, G.C.; Bhattacharyya, P.K.

    1995-01-01

    A simple method is described for estimation of sulfur in coal using fast neutron activation of sulfur, i.e. 32 S(n,p) 32 P and subsequent measurement of 32 P β-activity (1.72 MeV) by a Geiger-Mueller counter. Since the sulfur content of Indian coal ranges from 0.25 to 3%, simulated samples of coal containing sulfur in the range from 0.25 to 3% and common impurities like oxides of aluminium, calcium, iron and silicon have been used to establish the method. (author). 6 refs., 2 figs., 1 tab

  2. Simultaneous determination of selenium and tellurium in native sulfur by atomic absorption spectrophotometry

    International Nuclear Information System (INIS)

    Arikawa, Yoshiko; Hirai, Shoji; Ozawa, Takejiro.

    1979-01-01

    A method for the determination of selenium and tellurium in native sulfur has been investigated by means of atomic absorption spectrophotometry. Native sulfur collected from around fumarole or volcanic crater is ground down into powder, a portion of which weighing 1 g is subjected to analysis. A 2.6% (w/v) sodium hydroxide solution is added by 10 ml to the sample in a teflon beaker, and the mixture is then heated on a hot plate. Sulfur is decomposed and dissolved in the form of disulfide and thiosulfate. A 30% hydrogenperoxide solution is added by 10 ml to oxidize them to sulfate. At the same time selenium and tellurium contained in the sulfur sample are also thought to be oxidized to Se(VI) and Te(VI) states. The solution is neutralized with hydrochloric acid and diluted with distilled water to 100 ml. The sample solution thus prepared is sprayed into the air-acetylene flame of the atomic absorption spectrophotometer. The absorbance is measured at 195.9 nm for selenium and 214.2 nm for tellurium. Calibration curve is prepared by measuring the absorbances of the solutions prepared as follows. One gram portions of pure sulfur (99.9999%) are decomposed as for the samples. After neutralization, standard solutions containing each same amount of selenium and tellurium (0 -- 1000 μg) are added to the sulfur solution and then diluted with water to 100 ml. The standard deviations were estimated to be 50.4 ppm for selenium at 756 ppm and 16.6 ppm for tellurium at 587 ppm. For the check of the reliability of the method, results were compared with those obtained by neutron activation analysis. Results obtained by both methods showed good agreement. (author)

  3. Influence of organics and silica on Fe(II) oxidation rates and cell-mineral aggregate formation by the green-sulfur Fe(II)-oxidizing bacterium Chlorobium ferrooxidans KoFox - Implications for Fe(II) oxidation in ancient oceans

    Science.gov (United States)

    Gauger, Tina; Byrne, James M.; Konhauser, Kurt O.; Obst, Martin; Crowe, Sean; Kappler, Andreas

    2016-06-01

    Most studies on microbial phototrophic Fe(II) oxidation (photoferrotrophy) have focused on purple bacteria, but recent evidence points to the importance of green-sulfur bacteria (GSB). Their recovery from modern ferruginous environments suggests that these photoferrotrophs can offer insights into how their ancient counterparts grew in Archean oceans at the time of banded iron formation (BIF) deposition. It is unknown, however, how Fe(II) oxidation rates, cell-mineral aggregate formation, and Fe-mineralogy vary under environmental conditions reminiscent of the geological past. To address this, we studied the Fe(II)-oxidizer Chlorobium ferrooxidans KoFox, a GSB living in co-culture with the heterotrophic Geospirillum strain KoFum. We investigated the mineralogy of Fe(III) metabolic products at low/high light intensity, and in the presence of dissolved silica and/or fumarate. Silica and fumarate influenced the crystallinity and particle size of the produced Fe(III) minerals. The presence of silica also enhanced Fe(II) oxidation rates, especially at high light intensities, potentially by lowering Fe(II)-toxicity to the cells. Electron microscopic imaging showed no encrustation of either KoFox or KoFum cells with Fe(III)-minerals, though weak associations were observed suggesting co-sedimentation of Fe(III) with at least some biomass via these aggregates, which could support diagenetic Fe(III)-reduction. Given that GSB are presumably one of the most ancient photosynthetic organisms, and pre-date cyanobacteria, our findings, on the one hand, strengthen arguments for photoferrotrophic activity as a likely mechanism for BIF deposition on a predominantly anoxic early Earth, but, on the other hand, also suggest that preservation of remnants of Fe(II)-oxidizing GSB as microfossils in the rock record is unlikely.

  4. Towards a Predictive Thermodynamic Model of Oxidation States of Uranium Incorporated in Fe (hydr) oxides

    Energy Technology Data Exchange (ETDEWEB)

    Bagus, Paul S. [Univ. of North Texas, Denton, TX (United States)

    2013-01-01

    -Level Excited States: Consequences For X-Ray Absorption Spectroscopy”, J. Elec. Spectros. and Related Phenom., 200, 174 (2015) describes our first application of these methods. As well as applications to problems and materials of direct interest for our PNNL colleagues, we have pursued applications of fundamental theoretical significance for the analysis and interpretation of XPS and XAS spectra. These studies are important for the development of the fields of core-level spectroscopies as well as to advance our capabilities for applications of interest to our PNNL colleagues. An excellent example is our study of the surface core-level shifts, SCLS, for the surface and bulk atoms of an oxide that provides a new approach to understanding how the surface electronic of oxides differs from that in the bulk of the material. This work has the potential to lead to a new key to understanding the reactivity of oxide surfaces. Our theoretical studies use cluster models with finite numbers of atoms to describe the properties of condensed phases and crystals. This approach has allowed us to focus on the local atomistic, chemical interactions. For these clusters, we obtain orbitals and spinors through the solution of the Hartree-Fock, HF, and the fully relativistic Dirac HF equations. These orbitals are used to form configuration mixing wavefunctions which treat the many-body effects responsible for the open shell angular momentum coupling and for the satellites of the core-level spectra. Our efforts have been in two complementary directions. As well as the applications described above, we have placed major emphasis on the enhancement and extension of our theoretical and computational capabilities so that we can treat complex systems with a greater range of many-body effects. Noteworthy accomplishments in terms of method development and enhancement have included: (1) An improvement in our treatment of the large matrices that must be handled when many-body effects are treated. (2

  5. Ion bombardment effects on surface states in selected oxide systems: rutile and alkaline earth titanates

    International Nuclear Information System (INIS)

    Gruen, D.M.

    1978-01-01

    In this paper, the nature of the surface states of n-type TiO 2 and SrTiO 3 is discussed and the role of ion bombardment in modifying the properties of these states is elucidated. Insofar as possible, the interrelationships between oxide nonstoichiometry, surface states, ion bombardment effects and photoelectrolysis are explored

  6. Physiology and application of sulfur-reducing microorganisms from acidic environments

    NARCIS (Netherlands)

    Florentino, Anna Patrícya

    2017-01-01

    Sulfur cycle is one of the main geochemical cycles on Earth. Oxidation and reduction reactions of sulfur are mostly biotic and performed by microorganisms. In anaerobic conditions – marine and some freshwater systems, dissimilatory sulfur- and sulfate-reducing bacteria and archaea are key players

  7. Oxidation Kinetics of Copper: An Experiment in Solid State Chemistry.

    Science.gov (United States)

    Ebisuzaki, Y.; Sanborn, W. B.

    1985-01-01

    Oxidation kinetics in metals and the role defects play in diffusion-controlled reactions are discussed as background for a junior/senior-level experiment in the physical or inorganic chemistry laboratory. Procedures used and typical data obtained are provided for the experiment. (JN)

  8. The Protective and Therapeutic Roles of Hexamethylenetetramine and N-Acetyl-Cysteine on Sulfur Mustard-Induced Oxidative Stress in Rat Serum

    Directory of Open Access Journals (Sweden)

    M Jafari

    2016-04-01

    Conclusion: The study findings revealed that SM induces oxidative stress in rat serum. HMT and NAC can ameliorate SM-induced oxidative stress by altering antioxidant defense system in serum. The protective effect of HMT against the toxicity of SM is higher than NAC.

  9. A Tire-Sulfur Hybrid Adsorption Denitrification (T-SHAD) process for decentralized wastewater treatment.

    Science.gov (United States)

    Krayzelova, Lucie; Lynn, Thomas J; Banihani, Qais; Bartacek, Jan; Jenicek, Pavel; Ergas, Sarina J

    2014-09-15

    Nitrogen discharges from decentralized wastewater treatment (DWT) systems contribute to surface and groundwater contamination. However, the high variability in loading rates, long idle periods and lack of regular maintenance presents a challenge for biological nitrogen removal in DWT. A Tire-Sulfur Hybrid Adsorption Denitrification (T-SHAD) process was developed that combines nitrate (NO3(-)) adsorption to scrap tire chips with sulfur-oxidizing denitrification. This allows the tire chips to adsorb NO3(-) when the influent loading exceeds the denitrification capacity of the biofilm and release it when NO3(-) loading rates are low (e.g. at night). Three waste products, scrap tire chips, elemental sulfur pellets and crushed oyster shells, were used as a medium in adsorption, leaching, microcosm and up-flow packed bed bioreactor studies of NO3(-) removal from synthetic nitrified DWT wastewater. Adsorption isotherms showed that scrap tire chips have an adsorption capacity of 0.66 g NO3(-)-N kg(-1) of scrap tires. Leaching and microcosm studies showed that scrap tires leach bioavailable organic carbon that can support mixotrophic metabolism, resulting in lower effluent SO4(2-) concentrations than sulfur oxidizing denitrification alone. In column studies, the T-SHAD process achieved high NO3(-)-N removal efficiencies under steady state (90%), variable flow (89%) and variable concentration (94%) conditions. Copyright © 2014 Elsevier Ltd. All rights reserved.

  10. Plutonium uptake by Scenedesmus obliquus as a function of isotope and oxidation state

    International Nuclear Information System (INIS)

    Tkacik, M.F.; Giesy, J.P.; Wilhite, E.L.; Corey, J.C.

    1979-01-01

    Uptake of 238 Pu 4+ , 238 Pu 6+ , 239 Pu 4+ and 239 Pu 6+ by the green alga Scenedesmus obliquus (Turp) Kutz was studied to determine whether isotope or oxidation state differences affect Pu uptake from aqueous medium by algal cells. At equivalent 238 Pu and 239 PU concentrations, even when initial oxidation states differed, accumulations of these isotopes by S.obliquus were not significantly (p>0.05) different. Plutonium accumulation by S.obliquus was log-linear. (author)

  11. Effects of sulfur dioxide on vegetation

    Energy Technology Data Exchange (ETDEWEB)

    Whitby, G S

    1939-11-11

    A discussion is presented on the effects of sulfur dioxide on vegetation as observed at Trail, British Columbia. The investigation was carried out over a period of eight years, 1929 to 1937. The concentration of sulfur dioxide at the United States border was carefully determined throughout the crop season at a point 16 miles from the source of sulfur dioxide. Maximum and average concentrations in part per million are given. The sulfur content of vegetation was determined and was found to diminish as the distance from the smelter increased. It was determined that the sulfur content may rise to four times the normal amount without injurious effect. This is particularly so with prolonged low concentration. The effect on the soil was determined by measuring soluble sulfate, pH and exchangeable bases. The soil near the plant was affected, but this fell off rapidly with increase in distance so that eight miles from the smelter the soil was substantially normal. No effect on water supplies was found. An appreciable retardation in growth, as determined by annular rings, was noted for trees exposed to the sulfur dioxide. This effect was lost following installation of sulfur dioxide control at Trail. Conifers were found more susceptible during periods of active growth than when dormant. Also, transplanted conifers were more severly affected than native trees. Seedlings were less resistant that older trees.

  12. Gangue minerals reactivity in oxidative leaching of uraninite with dilute sulfuric acid from low-grade ores. An approach for better leach liquor purity

    International Nuclear Information System (INIS)

    Madakkaruppan, V.; Chanchal Sarbajna; Pius, Anitha; Sreenivas, T.

    2016-01-01

    This paper presents results of sulfuric acid leaching studies carried out on a low-grade uranium ore with emphasis on attaining maximum uranium leachability with minimum content of detrimental ions like Si, Al, Fe, Mg and P, which originate from reactive gangue minerals like chlorite, biotite and apatite. A 'two-stage leaching' scheme was developed wherein the total reaction time and the pH of the slurry were split such that the initial phase consists of higher acidity with shorter reaction period and the later phase involves reduced acidity and longer reaction time. This modification gives leach liquor of higher purity with good uranium leachability at relatively lower acid consumption. (author)

  13. EXTRACTION AND QUANTITATIVE ANALYSIS OF ELEMENTAL SULFUR FROM SULFIDE MINERAL SURFACES BY HIGH-PERFORMANCE LIQUID CHROMATOGRAPHY. (R826189)

    Science.gov (United States)

    A simple method for the quantitative determination of elemental sulfur on oxidized sulfide minerals is described. Extraction of elemental sulfur in perchloroethylene and subsequent analysis with high-performance liquid chromatography were used to ascertain the total elemental ...

  14. Sulfur metabolism in the extreme acidophile Acidithiobacillus caldus

    Directory of Open Access Journals (Sweden)

    Stefanie eMangold

    2011-02-01

    Full Text Available Given the challenges to life at low pH, an analysis of inorganic sulfur compound oxidation was initiated in the chemolithoautotrophic extremophile Acidithiobacillus caldus. A. caldus is able to metabolize elemental sulfur and a broad range of inorganic sulfur compounds. It has been implicated in the production of environmentally damaging acidic solutions as well as participating in industrial bioleaching operations where it forms part of microbial consortia used for the recovery of metal ions. Based upon the recently published A. caldus type strain genome sequence, a bioinformatic reconstruction of elemental sulfur and inorganic sulfur compound metabolism predicted genes included: sulfide quinone reductase (sqr, tetrathionate hydrolase (tth, two sox gene clusters potentially involved in thiosulfate oxidation (soxABXYZ, sulfur oxygenase reductase (sor, and various electron transport components. RNA transcript profiles by semi-quantitative reverse transcription PCR suggested up-regulation of sox genes in the presence of tetrathionate. Extensive gel based proteomic comparisons of total soluble and membrane enriched protein fractions during growth on elemental sulfur and tetrathionate identified differential protein levels from the two Sox clusters as well as several chaperone and stress proteins up-regulated in the presence of elemental sulfur. Proteomics results also suggested the involvement of heterodisulfide reductase (HdrABC in A. caldus inorganic sulfur compound metabolism. A putative new function of Hdr in acidophiles is discussed. Additional proteomic analysis evaluated protein expression differences between cells grown attached to solid, elemental sulfur versus planktonic cells. This study has provided insights into sulfur metabolism of this acidophilic chemolithotroph and gene expression during attachment to solid elemental sulfur.

  15. Generalized molybdenum oxide surface chemical state XPS determination via informed amorphous sample model

    Energy Technology Data Exchange (ETDEWEB)

    Baltrusaitis, Jonas, E-mail: job314@lehigh.edu [Department of Chemical Engineering, Lehigh University, B336 Iacocca Hall, 111 Research Drive, Bethlehem, PA 18015 (United States); PhotoCatalytic Synthesis group, MESA+ Institute for Nanotechnology, Faculty of Science and Technology, University of Twente, Meander 229, P.O. Box 217, 7500 AE Enschede (Netherlands); Mendoza-Sanchez, Beatriz [CRANN, Chemistry School, Trinity College Dublin, Dublin (Ireland); Fernandez, Vincent [Institut des Matériaux Jean Rouxel, 2 rue de la Houssinière, BP 32229, F-44322 Nantes Cedex 3 (France); Veenstra, Rick [PhotoCatalytic Synthesis group, MESA+ Institute for Nanotechnology, Faculty of Science and Technology, University of Twente, Meander 229, P.O. Box 217, 7500 AE Enschede (Netherlands); Dukstiene, Nijole [Department of Physical and Inorganic Chemistry, Kaunas University of Technology, Radvilenu pl. 19, LT-50254 Kaunas (Lithuania); Roberts, Adam [Kratos Analytical Ltd, Trafford Wharf Road, Wharfside, Manchester, M17 1GP (United Kingdom); Fairley, Neal [Casa Software Ltd, Bay House, 5 Grosvenor Terrace, Teignmouth, Devon TQ14 8NE (United Kingdom)

    2015-01-30

    Highlights: • We analyzed and modeled spectral envelopes of complex molybdenum oxides. • Molybdenum oxide films of varying valence and crystallinity were synthesized. • MoO{sub 3} and MoO{sub 2} line shapes from experimental data were created. • Informed amorphous sample model (IASM) developed. • Amorphous molybdenum oxide XPS envelopes were interpreted. - Abstract: Accurate elemental oxidation state determination for the outer surface of a complex material is of crucial importance in many science and engineering disciplines, including chemistry, fundamental and applied surface science, catalysis, semiconductors and many others. X-ray photoelectron spectroscopy (XPS) is the primary tool used for this purpose. The spectral data obtained, however, is often very complex and can be subject to incorrect interpretation. Unlike traditional XPS spectra fitting procedures using purely synthetic spectral components, here we develop and present an XPS data processing method based on vector analysis that allows creating XPS spectral components by incorporating key information, obtained experimentally. XPS spectral data, obtained from series of molybdenum oxide samples with varying oxidation states and degree of crystallinity, were processed using this method and the corresponding oxidation states present, as well as their relative distribution was elucidated. It was shown that monitoring the evolution of the chemistry and crystal structure of a molybdenum oxide sample due to an invasive X-ray probe could be used to infer solutions to complex spectral envelopes.

  16. SOLID STATE ENERGY CONVERSION ALLIANCE DELPHI SOLID OXIDE FUEL CELL

    Energy Technology Data Exchange (ETDEWEB)

    Steven Shaffer; Sean Kelly; Subhasish Mukerjee; David Schumann; Gail Geiger; Kevin Keegan; John Noetzel; Larry Chick

    2003-12-08

    The objective of Phase I under this project is to develop a 5 kW Solid Oxide Fuel Cell power system for a range of fuels and applications. During Phase I, the following will be accomplished: Develop and demonstrate technology transfer efforts on a 5 kW stationary distributed power generation system that incorporates steam reforming of natural gas with the option of piped-in water (Demonstration System A). Initiate development of a 5 kW system for later mass-market automotive auxiliary power unit application, which will incorporate Catalytic Partial Oxidation (CPO) reforming of gasoline, with anode exhaust gas injected into an ultra-lean burn internal combustion engine. This technical progress report covers work performed by Delphi from January 1, 2003 to June 30, 2003, under Department of Energy Cooperative Agreement DE-FC-02NT41246. This report highlights technical results of the work performed under the following tasks: Task 1 System Design and Integration; Task 2 Solid Oxide Fuel Cell Stack Developments; Task 3 Reformer Developments; Task 4 Development of Balance of Plant (BOP) Components; Task 5 Manufacturing Development (Privately Funded); Task 6 System Fabrication; Task 7 System Testing; Task 8 Program Management; and Task 9 Stack Testing with Coal-Based Reformate.

  17. Nanostructured sulfur cathodes

    KAUST Repository

    Yang, Yuan

    2013-01-01

    Rechargeable Li/S batteries have attracted significant attention lately due to their high specific energy and low cost. They are promising candidates for applications, including portable electronics, electric vehicles and grid-level energy storage. However, poor cycle life and low power capability are major technical obstacles. Various nanostructured sulfur cathodes have been developed to address these issues, as they provide greater resistance to pulverization, faster reaction kinetics and better trapping of soluble polysulfides. In this review, recent developments on nanostructured sulfur cathodes and mechanisms behind their operation are presented and discussed. Moreover, progress on novel characterization of sulfur cathodes is also summarized, as it has deepened the understanding of sulfur cathodes and will guide further rational design of sulfur electrodes. © 2013 The Royal Society of Chemistry.

  18. Ultrasound-assisted oxidative desulfurization of bitumen

    Science.gov (United States)

    Kamal, Wan Mohamad Ikhwan bin Wan; Okawa, Hirokazu; Kato, Takahiro; Sugawara, Katsuyasu

    2017-07-01

    Bitumen contains a high percentage of sulfur (about 4.6 wt %). A hydrodesulfurization method is used to remove sulfur from bitumen. The drawback of this method is the requirement for a high temperature of >300 °C. Most of the sulfur in bitumen exists as thiophene. Oxidative desulfurization (ODS), involving oxidizing sulfur using H2O2, then removing it using NaOH, allows the removal of sulfur in thiophene at low temperatures. We removed sulfur from bitumen using ODS treatment under ultrasound irradiation, and 52% of sulfur was successfully removed. Additionally, the physical action of ultrasound assisted the desulfurization of bitumen, even at low H2O2 concentrations.

  19. The life sulfuric: microbial ecology of sulfur cycling in marine sediments.

    Science.gov (United States)

    Wasmund, Kenneth; Mußmann, Marc; Loy, Alexander

    2017-08-01

    Almost the entire seafloor is covered with sediments that can be more than 10 000 m thick and represent a vast microbial ecosystem that is a major component of Earth's element and energy cycles. Notably, a significant proportion of microbial life in marine sediments can exploit energy conserved during transformations of sulfur compounds among different redox states. Sulfur cycling, which is primarily driven by sulfate reduction, is tightly interwoven with other important element cycles (carbon, nitrogen, iron, manganese) and therefore has profound implications for both cellular- and ecosystem-level processes. Sulfur-transforming microorganisms have evolved diverse genetic, metabolic, and in some cases, peculiar phenotypic features to fill an array of ecological niches in marine sediments. Here, we review recent and selected findings on the microbial guilds that are involved in the transformation of different sulfur compounds in marine sediments and emphasise how these are interlinked and have a major influence on ecology and biogeochemistry in the seafloor. Extraordinary discoveries have increased our knowledge on microbial sulfur cycling, mainly in sulfate-rich surface sediments, yet many questions remain regarding how sulfur redox processes may sustain the deep-subsurface biosphere and the impact of organic sulfur compounds on the marine sulfur cycle. © 2017 The Authors. Environmental Microbiology published by Society for Applied Microbiology and John Wiley & Sons Ltd.

  20. Gamma radiolysis of aliphatic sulfur compounds in aqueous solutions. A study to contribute to the analysis of the end products of the OH radical-induced oxidation of aliphatic mercaptanes, sulfides, and disulfides

    International Nuclear Information System (INIS)

    Weiss, J.

    1982-01-01

    By identifying and determining numerous hitherto unknown end products, the study in hand contributes to a better insight into the radiation chemical processes occurring in OH radical-induced oxidation of aliphatic sulfur compounds. An extraction method has been developed for the qualitative and quantitative analysis of end products in aqueous solution in order to determine these compounds down to the level of trace amounts. Separation of endproducts is achieved by means of gas chromatography and high-pressure liquid chromatography, subsequent identification by GC-MS analysis. Aliphatic mercaptanes are oxidized by OH radicals to thiyl radicals which after combination can be detected as disulfide. At high radiation doses, secondary reactions will lead to polysulfides of which the homologues could first be prepared as the pure substance. The end products of the γ-radiolysis of aliphatic thioethers are determined to be dithia compounds, symmetrical or asymmetrical disulfides, or polysulfides, depending on the thioethers. With some end products, the radiation chemical yield is found to be a function of the absorbed dose so that material balances are impossible. Intermediate thiyl, α-alkyl mercaptoalkyl or alkyl radicals can be captured by tetramethyl ethylene, cyclohexene or p-benzoquinone, and can then be identified as the relevant adducts. (orig./RB) [de

  1. Extraction of sulfuric acid with TOPO

    International Nuclear Information System (INIS)

    Shuyun, Xue; Yonghui, Yang; Yanzhao, Yang; Sixiu, Sun; Borong, Bao

    1998-01-01

    A study on solvent extraction of sulfuric acid by tri-octylphosphine oxide (TOPO) in n-heptane has been made. Extraction coefficients of H 2 SO 4 as a function of H 2 SO 4 concentration in aqueous phase, and extractant concentrations in organic phase have been studied. The composition of extracted species, equilibrium constants of extraction reaction have been evaluated. These results are important for interpreting extraction equilibrium data of uranium(VI) or other metal ions with TOPO in sulfuric acid media. (author)

  2. Efficient Electrolytes for Lithium–Sulfur Batteries

    International Nuclear Information System (INIS)

    Angulakshmi, Natarajan; Stephan, Arul Manuel

    2015-01-01

    This review article mainly encompasses on the state-of-the-art electrolytes for lithium–sulfur batteries. Different strategies have been employed to address the issues of lithium–sulfur batteries across the world. One among them is identification of electrolytes and optimization of their properties for the applications in lithium–sulfur batteries. The electrolytes for lithium–sulfur batteries are broadly classified as (i) non-aqueous liquid electrolytes, (ii) ionic liquids, (iii) solid polymer, and (iv) glass-ceramic electrolytes. This article presents the properties, advantages, and limitations of each type of electrolytes. Also, the importance of electrolyte additives on the electrochemical performance of Li–S cells is discussed.

  3. Efficient Electrolytes for Lithium-Sulfur Batteries

    Directory of Open Access Journals (Sweden)

    Natarajan eAngulakshmi

    2015-05-01

    Full Text Available This review article mainly encompasses on the state-of-the-art electrolytes for lithium–sulfur batteries. Different strategies have been employed to address the issues of lithium-sulfur batteries across the world. One among them is identification of electrolytes and optimization of their properties for the applications in lithium-sulfur batteries. The electrolytes for lithium-sulfur batteries are broadly classified as (i non-aqueous liquid electrolytes, (ii ionic liquids, (iii solid polymer and (iv glass-ceramic electrolytes. This article presents the properties, advantages and limitations of each type of electrolytes. Also the importance of electrolyte additives on the electrochemical performance of Li-S cells is discussed.

  4. Efficient Electrolytes for Lithium–Sulfur Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Angulakshmi, Natarajan [Department of Materials Science and Engineering, Politecnico di Torino, Turin (Italy); Stephan, Arul Manuel, E-mail: arulmanuel@gmail.com [Central Electrochemical Research Institute (CSIR-CECRI), Karaikudi (India)

    2015-05-21

    This review article mainly encompasses on the state-of-the-art electrolytes for lithium–sulfur batteries. Different strategies have been employed to address the issues of lithium–sulfur batteries across the world. One among them is identification of electrolytes and optimization of their properties for the applications in lithium–sulfur batteries. The electrolytes for lithium–sulfur batteries are broadly classified as (i) non-aqueous liquid electrolytes, (ii) ionic liquids, (iii) solid polymer, and (iv) glass-ceramic electrolytes. This article presents the properties, advantages, and limitations of each type of electrolytes. Also, the importance of electrolyte additives on the electrochemical performance of Li–S cells is discussed.

  5. SOLID STATE ENERGY CONVERSION ALLIANCE DELPHI SOLID OXIDE FUEL CELL

    Energy Technology Data Exchange (ETDEWEB)

    Steven Shaffer; Sean Kelly; Subhasish Mukerjee; David Schumann; Gail Geiger; Kevin Keegan; Larry Chick

    2004-05-07

    The objective of this project is to develop a 5 kW Solid Oxide Fuel Cell power system for a range of fuels and applications. During Phase I, the following will be accomplished: Develop and demonstrate technology transfer efforts on a 5 kW stationary distributed power generation system that incorporates steam reforming of natural gas with the option of piped-in water (Demonstration System A). Initiate development of a 5 kW system for later mass-market automotive auxiliary power unit application, which will incorporate Catalytic Partial Oxidation (CPO) reforming of gasoline, with anode exhaust gas injected into an ultra-lean burn internal combustion engine. This technical progress report covers work performed by Delphi from July 1, 2003 to December 31, 2003, under Department of Energy Cooperative Agreement DE-FC-02NT41246. This report highlights technical results of the work performed under the following tasks: Task 1 System Design and Integration; Task 2 Solid Oxide Fuel Cell Stack Developments; Task 3 Reformer Developments; Task 4 Development of Balance of Plant (BOP) Components; Task 5 Manufacturing Development (Privately Funded); Task 6 System Fabrication; Task 7 System Testing; Task 8 Program Management; Task 9 Stack Testing with Coal-Based Reformate; and Task 10 Technology Transfer from SECA CORE Technology Program. In this reporting period, unless otherwise noted Task 6--System Fabrication and Task 7--System Testing will be reported within Task 1 System Design and Integration. Task 8--Program Management, Task 9--Stack Testing with Coal Based Reformate, and Task 10--Technology Transfer from SECA CORE Technology Program will be reported on in the Executive Summary section of this report.

  6. Reduction Rates for Higher Americium Oxidation States in Nitric Acid

    Energy Technology Data Exchange (ETDEWEB)

    Grimes, Travis Shane [Idaho National Lab. (INL), Idaho Falls, ID (United States); Mincher, Bruce Jay [Idaho National Lab. (INL), Idaho Falls, ID (United States); Schmitt, Nicholas C [Idaho National Lab. (INL), Idaho Falls, ID (United States)

    2015-09-30

    The stability of hexavalent americium was measured using multiple americium concentrations and nitric acid concentrations after contact with the strong oxidant sodium bismuthate. Contrary to our hypotheses Am(VI) was not reduced faster at higher americium concentrations, and the reduction was only zero-order at short time scales. Attempts to model the reduction kinetics using zero order kinetic models showed Am(VI) reduction in nitric acid is more complex than the autoreduction processes reported by others in perchloric acid. The classical zero-order reduction of Am(VI) was found here only for short times on the order of a few hours. We did show that the rate of Am(V) production was less than the rate of Am(VI) reduction, indicating that some Am(VI) undergoes two electron-reduction to Am(IV). We also monitored the Am(VI) reduction in contact with the organic diluent dodecane. A direct comparison of these results with those in the absence of the organic diluent showed the reduction rates for Am(VI) were not statistically different for both systems. Additional americium oxidations conducted in the presence of Ce(IV)/Ce(III) ions showed that Am(VI) is reduced without the typical growth of Am(V) observed in the systems sans Ce ion. This was an interesting result which suggests a potential new reduction/oxidation pathway for Am in the presence of Ce; however, these results were very preliminary, and will require additional experiments to understand the mechanism by which this occurs. Overall, these studies have shown that hexavalent americium is fundamentally stable enough in nitric acid to run a separations process. However, the complicated nature of the reduction pathways based on the system components is far from being rigorously understood.

  7. Approaches to Determining the Oxidation State of Nitrogen and Carbon Atoms in Organic Compounds for High School Students

    Science.gov (United States)

    Jurowski, Kamil; Krzeczkowska, Malgorzata Krystyna; Jurowska, Anna

    2015-01-01

    The concept of oxidation state (or oxidation number) and related issues have always been difficult for students. In addition, there are misunderstandings and obscurities, which can cause improper balancing of the chemical equations (mostly in organic reactions). In particular, these problems are related to determination of the oxidation state of…

  8. Phase Behavior and Equations of State of the Actinide Oxides

    Science.gov (United States)

    Chidester, B.; Pardo, O. S.; Panero, W. R.; Fischer, R. A.; Thompson, E. C.; Heinz, D. L.; Prescher, C.; Prakapenka, V. B.; Campbell, A.

    2017-12-01

    The distribution of the long-lived heat-producing actinide elements U and Th in the deep Earth has important implications for the dynamics of the mantle and possibly the energy budget of Earth's core. The low shear velocities of the Large Low-Shear Velocity Provinces (LLSVPs) on the core-mantle boundary suggests that these regions are at least partially molten and may contain concentrated amounts of the radioactive elements, as well as other large cations such as the rare Earth elements. As such, by exploring the phase behavior of actinide-bearing minerals at extreme conditions, some insight into the mineralogy, formation, and geochemical and geodynamical effects of these regions can be gained. We have performed in situ high-pressure, high-temperature synchrotron X-ray diffraction experiments and calculations on two actinide oxide materials, UO2 and ThO2, to determine their phase behavior at the extreme conditions of the lower mantle. Experiments on ThO2 reached 60 GPa and 2500 K, and experiments on UO2 reached 95 GPa and 2500 K. We find that ThO2 exists in the fluorite-type structure to 20 GPa at high temperatures, at which point it transforms to the high-pressure cotunnite-type structure and remains thus up to 60 GPa. At room temperature, an anomalous expansion of the fluorite structure is observed prior to the transition, and may signal anion sub-lattice disorder. Similarly, UO2 exists in the fluorite-type structure at ambient conditions and up to 28 GPa at high temperatures. Above these pressures, we have observed a previously unidentified phase of UO2 with a tetragonal structure as the lower-temperature phase and the cotunnite-type phase at higher temperatures. Above 78 GPa, UO2 undergoes another transition or possible dissociation into two separate oxide phases. These phase diagrams suggest that the actinides could exist as oxides in solid solution with other analogous phases (e.g. ZrO2) in the cotunnite-type structure throughout much of Earth's lower mantle.

  9. On matrix stabilisation of d- and f-transition metal ions in unstable oxidation states

    Energy Technology Data Exchange (ETDEWEB)

    Kiselev, Yurii M [Department of Chemistry, M.V. Lomonosov Moscow State University, Moscow (Russian Federation)

    2009-01-31

    The state-of-the-art in matrix stabilisation of d- and f-transition metal ions in unstable oxidation states is analysed. Main aspects of this problem concerning the genealogy of appropriate matrix systems are classified. Relevant examples are given and the data that contradict the scheme proposed are discussed. The thermodynamics of the matrix stabilisation effect is considered using the concept of isomorphic miscibility. The influence of defects and non-equilibrium on the matrix stabilisation effect is discussed. The problem of identification of the oxidation states in matrix systems is examined and various types of matrix systems are considered.

  10. On matrix stabilisation of d- and f-transition metal ions in unstable oxidation states

    International Nuclear Information System (INIS)

    Kiselev, Yurii M

    2009-01-01

    The state-of-the-art in matrix stabilisation of d- and f-transition metal ions in unstable oxidation states is analysed. Main aspects of this problem concerning the genealogy of appropriate matrix systems are classified. Relevant examples are given and the data that contradict the scheme proposed are discussed. The thermodynamics of the matrix stabilisation effect is considered using the concept of isomorphic miscibility. The influence of defects and non-equilibrium on the matrix stabilisation effect is discussed. The problem of identification of the oxidation states in matrix systems is examined and various types of matrix systems are considered.

  11. Abiotic oxidation of pyrite by Fe(III) in acidic media and its implications for sulfur isotope measurements of lattice-bound sulfate in sediments

    Digital Repository Service at National Institute of Oceanography (India)

    Mazumdar, A.; Goldberg, T.; Strauss, H.

    (OH) 3 (Perez-Lopez et al., 2007) and hydrated iron sulfate (Lefticariu et al., 2006) havealsobeen reported. Someflaky material deposited in some of the reaction pits (Fig. 5C) in our experiment probably resembles ferric oxide/hydroxide (Perez-Lopez et al...–160. Perez-Lopez, R., Cama, J., Nieto, J.M., Ayora, C., 2007. The iron-coating role on the oxidation kinetics of a pyritic sludge doped with flyash. Geochim Cosmochim Acta. 71, 1921–1934. Piper, D.Z., Kolodny, Y.,1987. The stable isotopic composition of a...

  12. Adsorption properties versus oxidation states of rutile TiO2(110)

    DEFF Research Database (Denmark)

    Martinez, Umberto; Hammer, Bjørk

    2011-01-01

    Using density functional theory we have studied the adsorption properties of different atoms and molecules deposited on a stoichiometric, reduced, and oxidized rutile TiO2(110) surface. Depending on the oxidation state of the surface, electrons can flow from or to the substrate and, therefore...... of the charge flow depends on the oxidation state of the rutile surface and on the adsorption site. Generally, the charging effect leads to more stable complexes. However, the increase in the binding energy of the adsorbates is highly dependent on the electronic states of the surface prior to the adsorption...... event. In this work we have analyzed in details these mechanisms and we have also established a direct correlation between the enhanced binding energy of the adsorbates and the induced gap states...

  13. Microanalysis of iron oxidation state in iron oxides using X Ray Absorption Near Edge Structure (XANES)

    Science.gov (United States)

    Sutton, S. R.; Delaney, J.; Bajt, S.; Rivers, M. L.; Smith, J. V.

    1993-01-01

    An exploratory application of x ray absorption near edge structure (XANES) analysis using the synchrotron x ray microprobe was undertaken to obtain Fe XANES spectra on individual sub-millimeter grains in conventional polished sections. The experiments concentrated on determinations of Fe valence in a suite of iron oxide minerals for which independent estimates of the iron speciation could be made by electron microprobe analysis and x ray diffraction.

  14. Three-dimensional nitrogen and sulfur co-doped holey-reduced graphene oxide frameworks anchored with MoO2 nanodots for advanced rechargeable lithium-ion batteries

    Science.gov (United States)

    Pei, Jie; Geng, Hongbo; Ang, Huixiang; Zhang, Lingling; Wei, Huaixin; Cao, Xueqin; Zheng, Junwei; Gu, Hongwei

    2018-07-01

    In this manuscript, we synthesize a porous three-dimensional anode material consisting of molybdenum dioxide nanodots anchored on nitrogen (N)/sulfur (S) co-doped reduced graphene oxide (GO) (3D MoO2/NP-NSG) through hydrothermal, lyophilization and thermal treatment. First, the NP-NSG is formed via hydrothermal treatment using graphene oxide, hydrogen peroxide (H2O2), and thiourea as the co-dopant for N and S, followed by calcination of the N/S co-doped GO in the presence of ammonium molybdate tetrahydrate to obtain the 3D MoO2/NP-NSG product. This novel material exhibits a series of out-bound electrochemical performances, such as superior conductivity, high specific capacity, and excellent stability. As an anode for lithium-ion batteries (LIBs), the MoO2/NP-NSG electrode has a high initial specific capacity (1376 mAh g‑1), good cycling performance (1250 mAh g‑1 after 100 cycles at a current density of 0.2 A g‑1), and outstanding Coulombic efficiency (99% after 450 cycles at a current density of 1 A g‑1). Remarkably, the MoO2/NP-NSG battery exhibits exceedingly good rate capacities of 1021, 965, 891, 760, 649, 500 and 425 mAh g‑1 at different current densities of 200, 500, 1000, 2000, 3000, 4000 and 5000 mA g‑1, respectively. The superb electrochemical performance is owed to the high porosity of the 3D architecture, the synergistic effect contribution from N and S co-doped in the reduced graphene oxide (rGO), and the uniform distribution of MoO2 nanodots on the rGO surface.

  15. The oxidation states of elements in pure and Ca-doped BiCuSeO thermoelectric oxides

    International Nuclear Information System (INIS)

    Hsiao, Chun-Lung; Qi, Xiaoding

    2016-01-01

    Bi 1−x Ca x CuSeO (x = 0–0.3) was synthesized at 650 °C in an air-tight system flowing with pure argon. The Ca doping resulted in an increase in the thermoelectric figure of merit (ZT) as the consequence of increased carrier concentration. X-ray photoelectron spectroscopy (XPS) was carried out to check the oxidation states in Bi 1−x Ca x CuSeO. The results indicated that in addition to the expected Bi 3+ and Cu 1+ , there existed Bi 2+ and Cu 2+ in the undoped BiCuSeO, whereas in the Ca-doped BiCuSeO, Bi 4+ , Cu 3+ and Cu 2+ were observed. The Ca dopant was confirmed to be in the 2+ oxidation state. Two broad peaks centered at 54.22 and 58.59 eV were recorded in the vicinity around the binding energy of Se 3d. The former is often observed in the Se-containing intermetallics while the latter is often found in the Se-containing oxides, indicating that along with the expected Se–Cu bonding, a bonding between Se and O may also exist. Based on the XPS results, the charge compensation mechanisms were proposed for Bi 1−x Ca x CuSeO, which may shed some light on the origins of charge carriers. BiCuSeO based oxides have recently be discovered to have a large ZT comparable to the best alloys currently in use, because of the large Seebeck coefficient and small thermal conductivity. However, their electrical conductivity is lower compared to the best thermoelectrics. This work may provide some hints for the further improvement of ZT in BiCuSeO based oxides. - Graphical abstract: The oxidation states, charge compensation mechanisms, and origins of charge carriers in Bi 1−x Ca x CuSeO thermoelectrics. Display Omitted

  16. Characteristics and adaptability of iron- and sulfur-oxidizing microorganisms used for the recovery of metals from minerals and their concentrates

    Directory of Open Access Journals (Sweden)

    Rawlings Douglas E

    2005-05-01

    Full Text Available Abstract Microorganisms are used in large-scale heap or tank aeration processes for the commercial extraction of a variety of metals from their ores or concentrates. These include copper, cobalt, gold and, in the past, uranium. The metal solubilization processes are considered to be largely chemical with the microorganisms providing the chemicals and the space (exopolysaccharide layer where the mineral dissolution reactions occur. Temperatures at which these processes are carried out can vary from ambient to 80°C and the types of organisms present depends to a large extent on the process temperature used. Irrespective of the operation temperature, biomining microbes have several characteristics in common. One shared characteristic is their ability to produce the ferric iron and sulfuric acid required to degrade the mineral and facilitate metal recovery. Other characteristics are their ability to grow autotrophically, their acid-tolerance and their inherent metal resistance or ability to acquire metal resistance. Although the microorganisms that drive the process have the above properties in common, biomining microbes usually occur in consortia in which cross-feeding may occur such that a combination of microbes including some with heterotrophic tendencies may contribute to the efficiency of the process. The remarkable adaptability of these organisms is assisted by several of the processes being continuous-flow systems that enable the continual selection of microorganisms that are more efficient at mineral degradation. Adaptability is also assisted by the processes being open and non-sterile thereby permitting new organisms to enter. This openness allows for the possibility of new genes that improve cell fitness to be selected from the horizontal gene pool. Characteristics that biomining microorganisms have in common and examples of their remarkable adaptability are described.

  17. Ab initio molecular dynamics simulation of aqueous solution of nitric oxide in different formal oxidation states

    Science.gov (United States)

    Venâncio, Mateus F.; Rocha, Willian R.

    2015-10-01

    Ab initio molecular dynamics simulations were used to investigate the early chemical events involved in the dynamics of nitric oxide (NOrad), nitrosonium cation (NO+) and nitroxide anion (NO-) in aqueous solution. The NO+ ion is very reactive in aqueous solution having a lifetime of ∼4 × 10-13 s, which is shorter than the value of 3 × 10-10 s predicted experimentally. The NO+ reacts generating the nitrous acid as an intermediate and the NO2- ion as the final product. The dynamics of NOrad revealed the reversibly formation of a transient anion radical species HONOrad -.

  18. Sulfur deactivation of fatty ester hydrogenolysis catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Brands, D.S.; U-A-Sai, G.; Poels, E.K.; Bliek, A. [Univ. of Amsterdam (Netherlands). Dept. of Chemical Engineering

    1999-08-15

    Trace organosulfur compounds present as natural impurities in oleochemical feedstocks may lead to activation of copper-containing catalysts applied for hydrogenolysis of esters toward fatty alcohols. In this paper, the sulfur deactivation of Cu/SiO{sub 2} and Cu/ZnO/SiO{sub 2} catalysts was studied in the liquid-phase hydrogenolysis of methyl palmitate. The rate of deactivation is fast and increases as a function of the sulfur-containing compound present: octadecanethiol {approx} dihexadecyl disulfide < benzyl isothiocyanate < methyl p-toluene sulfonate < dihexadecyl sulfide < dibenzothiophene. The rapid deactivation is caused by the fact that sulfur is quantitatively removed from the reaction mixture and because mainly surface sulfides are formed under hydrogenolysis conditions. The life time of a zinc-promoted catalyst is up to two times higher than that of the Cu/SiO{sub 2} catalyst, most likely due to zinc surface sulfide formation. The maximum sulfur coverage obtained after full catalyst deactivation with dibenzothiophene and dihexadecyl sulfide--the sulfur compounds that cause the fastest deactivation--may be as low as 0.07. This is due to the fact that decomposition of these compounds as well as the hydrogenolysis reaction itself proceeds on ensembles of copper atoms. Catalyst regeneration studies reveal that activity cannot be regained by reduction or combined oxidation/reduction treatments. XRD, TPR, and TPO results confirm that no distinct bulk copper or zinc sulfide or sulfate phases are present.

  19. The analysis of thermoplastic characteristics of special polymer sulfur composite

    Science.gov (United States)

    Książek, Mariusz

    2017-01-01

    Specific chemical environments step out in the industry objects. Portland cement composites (concrete and mortar) were impregnated by using the special polymerized sulfur and technical soot as a filler (polymer sulfur composite). Sulfur and technical soot was applied as the industrial waste. Portland cement composites were made of the same aggregate, cement and water. The process of special polymer sulfur composite applied as the industrial waste is a thermal treatment process in the temperature of about 150-155°C. The result of such treatment is special polymer sulfur composite in a liquid state. This paper presents the plastic constants and coefficients of thermal expansion of special polymer sulfur composites, with isotropic porous matrix, reinforced by disoriented ellipsoidal inclusions with orthotropic symmetry of the thermoplastic properties. The investigations are based on the stochastic differential equations of solid mechanics. A model and algorithm for calculating the effective characteristics of special polymer sulfur composites are suggested. The effective thermoplastic characteristics of special polymer sulfur composites, with disoriented ellipsoidal inclusions, are calculated in two stages: First, the properties of materials with oriented inclusions are determined, and then effective constants of a composite with disoriented inclusions are determined on the basis of the Voigt or Rice scheme. A brief summary of new products related to special polymer sulfur composites is given as follows: Impregnation, repair, overlays and precast polymer concrete will be presented. Special polymer sulfur as polymer coating impregnation, which has received little attention in recent years, currently has some very interesting applications.

  20. Sulfur dioxide initiates global climate change in four ways

    International Nuclear Information System (INIS)

    Ward, Peter L.

    2009-01-01

    1980 anthropogenic sulfur emissions peaked and began to decrease because of major efforts especially in Japan, Europe, and the United States to reduce acid rain. Atmospheric concentrations of methane began decreasing in 1990 and have remained nearly constant since 2000, demonstrating an increase in oxidizing capacity. Global temperatures became roughly constant around 2000 and even decreased beginning in late 2007. Meanwhile atmospheric concentrations of carbon dioxide have continued to increase at the same rate that they have increased since 1970. Thus SO 2 is playing a far more active role in initiating and controlling global warming than recognized by the Intergovernmental Panel on Climate Change. Massive reduction of SO 2 should be a top priority in order to reduce both global warming and acid rain. But man is also adding two to three orders of magnitude more CO 2 per year to the climate than one 'large' volcanic eruption added in the past. Thus CO 2 , a greenhouse gas, is contributing to global warming and should be reduced. We have already significantly reduced SO 2 emissions in order to reduce acid rain. We know how to do it both technically and politically. In the past, sudden climate change was typically triggered by sudden increases in volcanic activity. Slow increases in greenhouse gases, therefore, do not appear as likely as currently thought to trigger tipping points where the climate suddenly changes. However we do need to start planning an appropriate human response to future major increases in volcanic activity.

  1. 99Tc and Re incorporated into metal oxide polyoxometalates: oxidation state stability elucidated by electrochemistry and theory.

    Science.gov (United States)

    McGregor, Donna; Burton-Pye, Benjamin P; Mbomekalle, Israel M; Aparicio, Pablo A; Romo, Susanna; López, Xavier; Poblet, Josep M; Francesconi, Lynn C

    2012-08-20

    The radioactive element technetium-99 ((99)Tc, half-life = 2.1 × 10(5) years, β(-) of 253 keV), is a major byproduct of (235)U fission in the nuclear fuel cycle. (99)Tc is also found in radioactive waste tanks and in the environment at National Lab sites and fuel reprocessing centers. Separation and storage of the long-lived (99)Tc in an appropriate and stable waste-form is an important issue that needs to be addressed. Considering metal oxide solid-state materials as potential storage matrixes for Tc, we are examining the redox speciation of Tc on the molecular level using polyoxometalates (POMs) as models. In this study we investigate the electrochemistry of Tc complexes of the monovacant Wells-Dawson isomers, α(1)-P(2)W(17)O(61)(10-) (α1) and α(2)-P(2)W(17)O(61)(10-) (α2) to identify features of metal oxide materials that can stabilize the immobile Tc(IV) oxidation state accessed from the synthesized Tc(V)O species and to interrogate other possible oxidation states available to Tc within these materials. The experimental results are consistent with density functional theory (DFT) calculations. Electrochemistry of K(7-n)H(n)[Tc(V)O(α(1)-P(2)W(17)O(61))] (Tc(V)O-α1), K(7-n)H(n)[Tc(V)O(α(2)-P(2)W(17)O(61))] (Tc(V)O-α2) and their rhenium analogues as a function of pH show that the Tc-containing derivatives are always more readily reduced than their Re analogues. Both Tc and Re are reduced more readily in the lacunary α1 site as compared to the α2 site. The DFT calculations elucidate that the highest oxidation state attainable for Re is VII while, under the same electrochemistry conditions, the highest oxidation state for Tc is VI. The M(V)→ M(IV) reduction processes for Tc(V)O-α1 are not pH dependent or only slightly pH dependent suggesting that protonation does not accompany reduction of this species unlike the M(V)O-α2 (M = (99)Tc, Re) and Re(V)O-α1 where M(V/IV) reduction process must occur hand in hand with protonation of the terminal M═O to

  2. Carbon oxidation state as a metric for describing the chemistry of atmospheric organic aerosol

    Energy Technology Data Exchange (ETDEWEB)

    Massachusetts Institute of Technology; Kroll, Jesse H.; Donahue, Neil M.; Jimenez, Jose L.; Kessler, Sean H.; Canagaratna, Manjula R.; Wilson, Kevin R.; Altieri, Katye E.; Mazzoleni, Lynn R.; Wozniak, Andrew S.; Bluhm, Hendrik; Mysak, Erin R.; Smith, Jared D.; Kolb, Charles E.; Worsnop, Douglas R.

    2010-11-05

    A detailed understanding of the sources, transformations, and fates of organic species in the environment is crucial because of the central roles that organics play in human health, biogeochemical cycles, and Earth's climate. However, such an understanding is hindered by the immense chemical complexity of environmental mixtures of organics; for example, atmospheric organic aerosol consists of at least thousands of individual compounds, all of which likely evolve chemically over their atmospheric lifetimes. Here we demonstrate the utility of describing organic aerosol (and other complex organic mixtures) in terms of average carbon oxidation state (OSC), a quantity that always increases with oxidation, and is readily measured using state-of-the-art analytical techniques. Field and laboratory measurements of OSC , using several such techniques, constrain the chemical properties of the organics and demonstrate that the formation and evolution of organic aerosol involves simultaneous changes to both carbon oxidation state and carbon number (nC).

  3. Oxidation state analyses of uranium with emphasis on chemical speciation in geological media

    International Nuclear Information System (INIS)

    Ervanne, H.

    2004-01-01

    This thesis focuses on chemical methods suitable for the determination of uranium redox species in geological materials. Nd-coprecipitation method was studied for the determination of uranium oxidation states in ground waters. This method is ideally suited for the separation of uranium oxidation states in the field, which means that problems associated with the instability of U(IV) during transport are avoided. An alternative method, such as ion exchange, is recommended for the analysis of high saline and calcium- and iron-rich ground waters. U(IV)/Utot was 2.8-7.2% in ground waters in oxidizing conditions and 60-93% in anoxic conditions. From thermodynamic model calculations applied to results from anoxic ground waters it was concluded that uranium can act as redox buffer in granitic ground waters. An ion exchange method was developed for the analysis of uranium oxidation states in different solid materials of geological origin. These included uranium minerals, uraniumbearing minerals, fracture coatings and bulk rock. U(IV)/Utot was 50-70% in uraninites, 5.8-8.7% in secondary uranium minerals, 15-49% in different fracture coatings and 64- 77% in samples from deep bedrock. In the uranium-bearing minerals, U(IV)/Utot was 33-43% (allanites), 5.9% (fergusonite) and 93% (monazite). Although the ion exchange method gave reliable results, there is a risk for the conversion of uranium oxidation states during analysis of heterogeneous samples due to the redox reactions that take place in the presence of some iron compounds. This risk was investigated in a study of several common iron-bearing minerals. The risk for conversion of uranium oxidation states can be screened by sample selection and minimized with use of a redox buffer compound such as polyacrylic acid (PAA). In studies of several carboxylic acids, PAA was found to be the most suitable for extending the application of the method. The stability of uranium oxidation states during analysis and the selectivity

  4. Single and multiple ionization of sulfur atoms by electron impact

    International Nuclear Information System (INIS)

    Ziegler, D.L.

    1982-01-01

    Laboratory measurements of the cross sections for single, double, triple, and quadruple ionization of sulfur atoms by electron impact are presented for collision energies from threshold to 500 eV. The cross sections for single ionization of sulfur are measured relative to those of several elements whose absolute cross sections for single ionization are known. Cross sections for each multiple ionization process are then measured relative to those for single ionization. The configuration and operation of the apparatus for these measurements are described. The possible effects of excited sulfur reactants are examined, and the reported cross sections are felt to be characteristic of ground state sulfur atoms

  5. Oxidation of extracellular cysteine/cystine redox state in bleomycin-induced lung fibrosis.

    Science.gov (United States)

    Iyer, Smita S; Ramirez, Allan M; Ritzenthaler, Jeffrey D; Torres-Gonzalez, Edilson; Roser-Page, Susanne; Mora, Ana L; Brigham, Kenneth L; Jones, Dean P; Roman, Jesse; Rojas, Mauricio

    2009-01-01

    Several lines of evidence indicate that depletion of glutathione (GSH), a critical thiol antioxidant, is associated with the pathogenesis of idiopathic pulmonary fibrosis (IPF). However, GSH synthesis depends on the amino acid cysteine (Cys), and relatively little is known about the regulation of Cys in fibrosis. Cys and its disulfide, cystine (CySS), constitute the most abundant low-molecular weight thiol/disulfide redox couple in the plasma, and the Cys/CySS redox state (E(h) Cys/CySS) is oxidized in association with age and smoking, known risk factors for IPF. Furthermore, oxidized E(h) Cys/CySS in the culture media of lung fibroblasts stimulates proliferation and expression of transitional matrix components. The present study was undertaken to determine whether bleomycin-induced lung fibrosis is associated with a decrease in Cys and/or an oxidation of the Cys/CySS redox state and to determine whether these changes were associated with changes in E(h) GSH/glutathione disulfide (GSSG). We observed distinct effects on plasma GSH and Cys redox systems during the progression of bleomycin-induced lung injury. Plasma E(h) GSH/GSSG was selectively oxidized during the proinflammatory phase, whereas oxidation of E(h) Cys/CySS occurred at the fibrotic phase. In the epithelial lining fluid, oxidation of E(h) Cys/CySS was due to decreased food intake. Thus the data show that decreased precursor availability and enhanced oxidation of Cys each contribute to the oxidation of extracellular Cys/CySS redox state in bleomycin-induced lung fibrosis.

  6. Conductive framework of inverse opal structure for sulfur cathode in lithium-sulfur batteries.

    Science.gov (United States)

    Jin, Lu; Huang, Xiaopeng; Zeng, Guobo; Wu, Hua; Morbidelli, Massimo

    2016-09-07

    As a promising cathode inheritor for lithium-ion batteries, the sulfur cathode exhibits very high theoretical volumetric capacity and energy density. In its practical applications, one has to solve the insulating properties of sulfur and the shuttle effect that deteriorates cycling stability. The state-of-the-art approaches are to confine sulfur in a conductive matrix. In this work, we utilize monodisperse polystyrene nanoparticles as sacrificial templates to build polypyrrole (PPy) framework of an inverse opal structure to accommodate (encapsulate) sulfur through a combined in situ polymerization and melting infiltration approach. In the design, the interconnected conductive PPy provides open channels for sulfur infiltration, improves electrical and ionic conductivity of the embedded sulfur, and reduces polysulfide dissolution in the electrolyte through physical and chemical adsorption. The flexibility of PPy and partial filling of the inverse opal structure endure possible expansion and deformation during long-term cycling. It is found that the long cycling stability of the cells using the prepared material as the cathode can be substantially improved. The result demonstrates the possibility of constructing a pure conductive polymer framework to accommodate insulate sulfur in ion battery applications.

  7. DetOx: a program for de