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Sample records for phosphine oxides sulfides

  1. Phosphine oxide surfactants revisited.

    PubMed

    Stubenrauch, Cosima; Preisig, Natalie; Laughlin, Robert G

    2016-04-01

    This review summarizes everything we currently know about the nonionic surfactants alkyl dimethyl (C(n)DMPO) and alkyl diethyl (C(n)DEPO) phosphine oxide (PO surfactants). The review starts with the synthesis and the general properties (Section 2) of these compounds and continues with their interfacial properties (Section 3) such as surface tension, surface rheology, interfacial tension and adsorption at solid surfaces. We discuss studies on thin liquid films and foams stabilized by PO surfactants (Section 4) as well as studies on their self-assembly into lyotropic liquid crystals and microemulsions, respectively (Section 5). We aim at encouraging colleagues from both academia and industry to take on board PO surfactants whenever possible and feasible because of their broad variety of excellent properties.

  2. Oxidative alkoxylation of phosphine in alcohol solutions of copper halides

    NASA Astrophysics Data System (ADS)

    Polimbetova, G. S.; Borangazieva, A. K.; Ibraimova, Zh. U.; Bugubaeva, G. O.; Keynbay, S.

    2016-08-01

    The phosphine oxidation reaction with oxygen in alcohol solutions of copper (I, II) halides is studied. Kinetic parameters, intermediates, and by-products are studied by means of NMR 31P-, IR-, UV-, and ESR- spectroscopy; and by magnetic susceptibility, redox potentiometry, gas chromatography, and elemental analysis. A reaction mechanism is proposed, and the optimum conditions are found for the reaction of oxidative alkoxylation phosphine.

  3. Enantioselective Cu-Catalyzed Arylation of Secondary Phosphine Oxides with Diaryliodonium Salts toward the Synthesis of P-Chiral Phosphines.

    PubMed

    Beaud, Rodolphe; Phipps, Robert J; Gaunt, Matthew J

    2016-10-12

    Catalytic synthesis of nonracemic P-chiral phosphine derivatives remains a significant challenge. Here we report Cu-catalyzed enantioselective arylation of secondary phosphine oxides with diaryliodonium salts for the synthesis of tertiary phosphine oxides with high enantiomeric excess. The new process is demonstrated on a wide range of substrates and leads to products that are well-established P-chiral catalysts and ligands.

  4. Enantioselective Cu-Catalyzed Arylation of Secondary Phosphine Oxides with Diaryliodonium Salts toward the Synthesis of P-Chiral Phosphines

    PubMed Central

    2016-01-01

    Catalytic synthesis of nonracemic P-chiral phosphine derivatives remains a significant challenge. Here we report Cu-catalyzed enantioselective arylation of secondary phosphine oxides with diaryliodonium salts for the synthesis of tertiary phosphine oxides with high enantiomeric excess. The new process is demonstrated on a wide range of substrates and leads to products that are well-established P-chiral catalysts and ligands. PMID:27689432

  5. Phosphine

    Integrated Risk Information System (IRIS)

    Phosphine ; CASRN 7803 - 51 - 2 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Effect

  6. Synthesis, characterization, and activity of yttrium(III) nitrate complexes bearing tripodal phosphine oxide and mixed phosphine-phosphine oxide ligands.

    PubMed

    Sues, Peter E; Lough, Alan J; Morris, Robert H

    2012-09-03

    A series of four tripodal phosphine oxide ligands, (OPR(2))(2)CHCH(2)POR(2) (1a-1d), and four mixed phosphine-phosphine oxide ligands, (OPR(2))(2)CHCH(2)PR(2) (3a-3d), were synthesized and coordinated to yttrium to produce Y(NO(3))(3)[(OPR(2))(2)CHCH(2)POR(2)] (2a-2d) and Y(NO(3))(3)[(OPR(2))(2)CHCH(2)PR(2)](OPPh(3)) (4a-4d) complexes. The previously reported ligand 1a and unknown phosphine oxide ligands 1b-1d were generated in an unprecedented trisubstitution reaction of bromoacetaldehyde diethyl acetal, while the novel partially reduced ligands 3a-3d were synthesized from 1a-1d according to a known literature protocol for the selective monoreduction of bisphosphine oxides. The neutral yttrium complexes 2a-2d are nine-coordinate and display a tricapped trigonal-prismatic geometry. Complexes 4a-4d are also neutral, nine-coordinate species and have a pendant phosphine functionality, which provides the potential to form bimetallic early-late transition-metal complexes. Additionally, yttrium complexes 2a-2d were activated with base and tested for the ring-opening polymerization of ε-caprolactone, but the results showed that base by itself was significantly more effective than the yttrium species investigated.

  7. A superior method for the reduction of secondary phosphine oxides.

    PubMed

    Busacca, Carl A; Lorenz, Jon C; Grinberg, Nelu; Haddad, Nizar; Hrapchak, Matt; Latli, Bachir; Lee, Heewon; Sabila, Paul; Saha, Anjan; Sarvestani, Max; Shen, Sherry; Varsolona, Richard; Wei, Xudong; Senanayake, Chris H

    2005-09-15

    [reaction: see text] Diisobutylaluminum hydride (DIBAL-H) and triisobutylaluminum have been found to be outstanding reductants for secondary phosphine oxides (SPOs). All classes of SPOs can be readily reduced, including diaryl, arylalkyl, and dialkyl members. Many SPOs can now be reduced at cryogenic temperatures, and conditions for preservation of reducible functional groups have been found. Even the most electron-rich and sterically hindered phosphine oxides can be reduced in a few hours at 50-70 degrees C. This new reduction has distinct advantages over existing technologies.

  8. A high-throughput hydrophilic interaction liquid chromatography coupled with a charged aerosol detector method to assess trisulfides in IgG1 monoclonal antibodies using tris(2-carboxyethyl)phosphine reaction products: Tris(2-carboxyethyl)phosphine-oxide and tris(2-carboxyethyl)phosphine-sulfide.

    PubMed

    Cornell, Christopher; Karanjit, Amish; Chen, Yan; Jacobson, Fredric

    2016-07-29

    A robust, high-throughput method using hydrophilic interaction liquid chromatography (HILIC) coupled with a charged aerosol detector (CAD) is reported as a novel approach for trisulfide quantitation in monoclonal antibodies (mAbs). The products of mAb reduction using tris(2-carboxyethyl)phosphine (TCEP) include a species (TCEP(S)) that is stoichiometrically produced from trisulfides. The TCEP reaction products are chromatographically separated, detected, and quantified by the HILICCAD method. The method was qualified to quantify trisulfides across a range of 1-40% (mol trisulfide/mol mAb). In all tested matrix components, assay linearity and intermediate precision were established with correlation coefficients (R(2))>0.99, and relative standard deviations (RSD)<10%. A method comparability study was performed using peptide mapping LC-MS as an orthogonal measurement. For the range of 1-40% trisulfides, the analysis demonstrates that, on average, HILICCAD reads between 0.95 and 1.10 times the value of LC-MS with 95% confidence. Applications of the HILICCAD method include trisulfide determination in purified mAbs to be used in the production of cysteine-linked antibody-drug conjugates, and in cell culture development studies to understand sources of, and strategies for control of, trisulfides.

  9. Sulfides and oxides in comets

    NASA Technical Reports Server (NTRS)

    Rietmeijer, Frans J. M.

    1988-01-01

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

  10. Experimental and theoretical investigations of the stereoselective synthesis of p-stereogenic phosphine oxides.

    PubMed

    Copey, Laurent; Jean-Gérard, Ludivine; Framery, Eric; Pilet, Guillaume; Robert, Vincent; Andrioletti, Bruno

    2015-06-15

    An efficient enantioselective strategy for the synthesis of variously substituted phosphine oxides has been developed, incorporating the use of (1S,2S)-2-aminocyclohexanol as the chiral auxiliary. The method relies on three key steps: 1) Highly diastereoselective formation of P(V) oxazaphospholidine, rationalized by a theoretical study; 2) highly diastereoselective ring-opening of the oxazaphospholidine oxide with organometallic reagents that takes place with inversion of configuration at the P atom; 3) enantioselective synthesis of phosphine oxides by cleavage of the remaining P-O bond. Interestingly, the use of a P(III) phosphine precursor afforded a P-epimer oxazaphospholidine. Hence, the two enantiomeric phosphine oxides can be synthesized starting from either a P(V) or a P(III) phosphine precursor, which constitutes a clear advantage for the stereoselective synthesis of sterically hindered phosphine oxides.

  11. Polyimides Containing Pendent Phosphine Oxide Groups for Space Applications

    NASA Technical Reports Server (NTRS)

    Thompson, C. M.; Smith, J. G., Jr.; Watson, K. A.; Connell, J. W.

    2002-01-01

    As part of an ongoing materials development activity to produce high performance polymers that are durable to the space environment, phosphine oxide containing polyimides have been under investigation. A novel dianhydride was prepared from 2,5-dihydroxyphenyldiphenylphosphine oxide in good yield. The dianhydride was reacted with commercially available diamines, and a previously reported diamine was reacted with commercially available dianhydrides to prepare isomeric polyimides. The physical and mechanical properties, particularly thermal and optical properties, of the polymers were determined. One material exhibited a high glass transition temperature, high tensile properties, and low solar absorptivity. The chemistry, physical, and mechanical properties of these resins will be discussed.

  12. Chiral magnesium BINOL phosphate-catalyzed phosphination of imines: access to enantioenriched α-amino phosphine oxides.

    PubMed

    Ingle, Gajendrasingh K; Liang, Yuxue; Mormino, Michael G; Li, Guilong; Fronczek, Frank R; Antilla, Jon C

    2011-04-15

    A new method to synthesize chiral α-amino phosphine oxides is reported. The reaction combines N-substituted imines and diphenylphosphine oxide and is catalyzed by a chiral magnesium phosphate salt. A wide variety of aliphatic and aromatic aldimines substituted by electron-neutral benzhydryl or dibenzocycloheptene groups were excellent substrates for the addition reaction. The dibenzocycloheptene protected imines afforded improved enantioselectivity in the resulting products. Substituted diphenylphosphine oxide nucleophiles also showed good reactivity.

  13. Prevention of sulfide oxidation in sulfide-rich waste rock

    NASA Astrophysics Data System (ADS)

    Nyström, Elsa; Alakangas, Lena

    2015-04-01

    The ability to reduce sulfide oxidation in waste rock after mine closure is a widely researched area, but to reduce and/or inhibit the oxidation during operation is less common. Sulfide-rich (ca 30 % sulfur) waste rock, partially oxidized, was leached during unsaturated laboratory condition. Trace elements such as As and Sb were relatively high in the waste rock while other sulfide-associated elements such as Cu, Pb and Zn were low compared to common sulfide-rich waste rock. Leaching of unsaturated waste rock lowered the pH, from around six down to two, resulting in continuously increasing element concentrations during the leaching period of 272 days. The concentrations of As (65 mg/L), Cu (6.9 mg/L), Sb (1.2 mg/L), Zn (149 mg/L) and S (43 g/L) were strongly elevated at the end of the leaching period. Different alkaline industrial residues such as slag, lime kiln dust and cement kiln dust were added as solid or as liquid to the waste rock in an attempt to inhibit sulfide oxidation through neo-formed phases on sulfide surfaces in order to decrease the mobility of metals and metalloids over longer time scale. This will result in a lower cost and efforts of measures after mine closure. Results from the experiments will be presented.

  14. Copper-catalyzed tandem phosphination-decarboxylation-oxidation of alkynyl acids with H-phosphine oxides: a facile synthesis of β-ketophosphine oxides.

    PubMed

    Zhang, Pengbo; Zhang, Liangliang; Gao, Yuzhen; Xu, Jian; Fang, Hua; Tang, Guo; Zhao, Yufen

    2015-05-07

    The general method for the tandem phosphination-decarboxylation-oxidation of alkynyl acids under aerobic conditions has been developed. In the presence of CuSO4·5H2O and TBHP, the reactions provide a novel access to β-ketophosphine oxides in good to excellent yields. This transformation allows the direct formation of a P-C bond and the construction of a keto group in one reaction.

  15. Copper-catalyzed asymmetric oxidation of sulfides.

    PubMed

    O'Mahony, Graham E; Ford, Alan; Maguire, Anita R

    2012-04-06

    Copper-catalyzed asymmetric sulfoxidation of aryl benzyl and aryl alkyl sulfides, using aqueous hydrogen peroxide as the oxidant, has been investigated. A relationship between the steric effects of the sulfide substituents and the enantioselectivity of the oxidation has been observed, with up to 93% ee for 2-naphthylmethyl phenyl sulfoxide, in modest yield in this instance (up to 30%). The influence of variation of solvent and ligand structure was examined, and the optimized conditions were then used to oxidize a number of aryl alkyl and aryl benzyl sulfides, producing sulfoxides in excellent yields in most cases (up to 92%), and good enantiopurities in certain cases (up to 84% ee).

  16. Catalyst and process for oxidizing hydrogen sulfide

    SciTech Connect

    Hass, R.H.; Ward, J.W.

    1984-04-24

    Catalysts comprising bismuth and vanadium components are highly active and stable, especially in the presence of water vapor, for oxidizing hydrogen sulfide to sulfur or SO/sub 2/. Such catalysts have been found to be especially active for the conversion of hydrogen sulfide to sulfur by reaction with oxygen or SO/sub 2/.

  17. Ab initio post-hartree-fock study of molecular structures and vibrational spectra of phosphine oxide, phosphinous acid, and their thio analogs

    SciTech Connect

    Kwiatkowski, J.S.; Leszczynski, J.

    1992-08-06

    This paper discusses how MP2 theory is used to predict the vibrational IR spectra and molecular parameters of phosphine oxide, phosphinous acid, and their thio analogs. This spectral data agrees well with experimental data, and might be applied to identification of the sulfur species. The calculations also correctly predict the observed shifts of the IR wavenumbers upon isotopic substitution of the molecules. 17 refs., 5 tabs.

  18. Nitrate-reducing, sulfide-oxidizing bacteria as microbial oxidants for rapid biological sulfide removal.

    PubMed

    De Gusseme, Bart; De Schryver, Peter; De Cooman, Michaël; Verbeken, Kim; Boeckx, Pascal; Verstraete, Willy; Boon, Nico

    2009-01-01

    The emission of hydrogen sulfide into the atmosphere of sewer systems induces the biological production of sulfuric acid, causing severe concrete corrosion. As a possible preventive solution, a microbial consortium of nitrate-reducing, sulfide-oxidizing bacteria (NR-SOB) was enriched in a continuously stirred tank reactor in order to develop a biological technique for the removal of dissolved sulfide. The consortium, dominated by Arcobacter sp., was capable of removing 99% of sulfide. Stable isotope fractioning of the sulfide indicated that the oxidation was a biological process. The capacity of the NR-SOB consortium for rapid removal of sulfide was demonstrated by using it as an inoculum in synthetic and real sewage. Removal rates up to 52 mg sulfide-S g VSS(-1) h(-1) were achieved, to our knowledge the highest removal rate reported so far for freshwater species in the absence of molecular oxygen. Further long-term incubation experiments revealed the capacity of the bacteria to oxidize sulfide without the presence of nitrate, suggesting that an oxidized redox reserve is present in the culture.

  19. Phosphine gas in the upper troposphere

    NASA Astrophysics Data System (ADS)

    Glindemann, Dietmar; Edwards, Marc; Kuschk, Peter

    The gas phosphine (PH 3) is a part of an atmospheric link of the phosphorus cycle on earth. Phosphine was reported elsewhere to be found worldwide in remote air samples in the lower troposphere in the low ng/m 3 range during the night, when oxidation is inhibited. But much less phosphine (pg/m 3 range) was found during daylight around noon in this reactive contaminated atmosphere. Here we found for the first time gaseous phosphine in remote air samples (0.39-2.45 ng/m 3, 16 locations) in the high troposphere above the North-Atlantic in November 1995 during daylight around noontime. The maximum concentration was measured at the highest altitude of 12,500 m. No night measurements could be conducted to compare day and night values. The finding of the reactive phosphine under the sunlight in the high troposphere far from possible terrestric sources is strange. A model experiment shows that phosphine could possibly survive the daylight much longer at high altitudes because of a lack of UV-induced oxidants in the clean and dry air. Additional model experiments indicate that phosphine can easier sustain its mobile gaseous state in the atmosphere compared to gases like hydrogen sulfide and ammonia which stick easier to aerosol and are subject to faster washout and return to Earth's surface. However, the ultimate fate of phosphine is the oxidation to form phosphoric acid as a low pH agent and as possible condensation nuclei for clouds at very high altitudes. The potent sources and atmospheric chemistry which allow phosphine to accumulate in the upper troposphere are still to be discovered.

  20. A novel tridentate bis(phosphinic acid)phosphine oxide based europium(III)-selective Nafion membrane luminescent sensor.

    PubMed

    Sainz-Gonzalo, F J; Popovici, C; Casimiro, M; Raya-Barón, A; López-Ortiz, F; Fernández, I; Fernández-Sánchez, J F; Fernández-Gutiérrez, A

    2013-10-21

    A new europium(III) membrane luminescent sensor based on a new tridentate bis(phosphinic acid)phosphine oxide (3) system has been developed. The synthesis of this new ligand is described and its full characterization by NMR, IR and elemental analyses is provided. The luminescent complex formed between europium(III) chloride and ligand 3 was evaluated in solution, observing that its spectroscopic and chemical characteristics are excellent for measuring in polymer inclusion membranes. Included in a Nafion membrane, all the parameters (ligand and ionic additives) that can affect the sensitivity and selectivity of the sensing membrane as well as the instrumental conditions were carefully optimized. The best luminescence signal (λexc = 229.06 nm and λem = 616.02 nm) was exhibited by the sensing film having a Nafion : ligand composition of 262.3 : 0.6 mg mL(-1). The membrane sensor showed a short response time (t95 = 5.0 ± 0.2 min) and an optimum working pH of 5.0 (25 mM acetate buffer solution). The membrane sensor manifested a good selectivity toward europium(III) ions with respect to other trivalent metals (iron, chromium and aluminium) and lanthanide(III) ions (lanthanum, samarium, terbium and ytterbium), although a small positive interference of terbium(III) ions was observed. It provided a linear range from 1.9 × 10(-8) to 5.0 × 10(-6) M with a very low detection limit (5.8 × 10(-9) M) and sensitivity (8.57 × 10(-7) a.u. per M). The applicability of this sensing film has been demonstrated by analyzing different kinds of spiked water samples obtaining recovery percentages of 95-97%.

  1. Method for inhibiting oxidation of metal sulfide-containing material

    DOEpatents

    Elsetinow, Alicia; Borda, Michael J.; Schoonen, Martin A.; Strongin, Daniel R.

    2006-12-26

    The present invention provides means for inhibiting the oxidation of a metal sulfide-containing material, such as ore mine waste rock or metal sulfide taiulings, by coating the metal sulfide-containing material with an oxidation-inhibiting two-tail lipid coating (12) thereon, thereby inhibiting oxidation of the metal sulfide-containing material in acid mine drainage conditions. The lipids may be selected from phospholipids, sphingolipids, glycolipids and combinations thereof.

  2. Synthesis and Lanthanide Coordination Chemistry of Phosphine Oxide Decorated Dibenzothiophene and Dibenzothiophene Sulfone Platforms

    SciTech Connect

    Rosario-Amorin, Daniel; Ouizem, Sabrina; Dickie, D. A.; Paine, Robert T.; Cramer, Roger E.; Hay, Benjamin; Podair, Julien; Delmau, Laetitia Helene

    2014-01-01

    Syntheses for new ligands based upon dibenzothiophene and dibenzothiophene sulfone platforms, decorated with phosphine oxide and methylphosphine oxide donor groups, are described. Coordination chem. of 4, 6- bis(diphenylphosphinoylmethyl) dibenzothiophene (8) , 4, 6- bis(diphenylphosphinoylmethyl) dibenzothiophene- 5, 5- dioxide (9) and 4, 6- bis(diphenylphosphinoyl) dibenzothiophene- 5, 5- dioxide (10) with lanthanide nitrates, Ln(NO3) 3 (H2O) n is outlined, and crystal structure detns. reveal a range of chelation interactions on Ln(III) ions. The HNO3 dependence of the solvent extn. performance of 9 and 10 in 1, 2- dichloroethane for Eu(III) and Am(III) is described and compared against the extn. behavior of related dibenzofuran ligands (2, 3; R = Ph) and n- octyl(phenyl) - N, N- diisobutylcarbamoylmethyl phosphine oxide (4) measured under identical conditions.

  3. Syntheses and properties of phosphine-substituted ruthenium(II) polypyridine complexes with nitrogen oxides.

    PubMed

    Nakamura, Go; Kondo, Mio; Crisalli, Meredith; Lee, Sze Koon; Shibata, Akane; Ford, Peter C; Masaoka, Shigeyuki

    2015-10-21

    Four novel phosphine-substituted ruthenium(ii) polypyridine complexes with nitrogen oxides-trans(P,NO2)-[Ru(trpy)(Pqn)(NO2)]PF6 (trans-NO2), cis(P,NO2)-[Ru(trpy)(Pqn)(NO2)]PF6 (cis-NO2), [Ru(trpy)(dppbz)(NO2)]PF6 (PP-NO2), and cis(P,NO)-[Ru(trpy)(Pqn)(NO)](PF6)3 (cis-NO)-were synthesised (trpy = 2,2':6',2''-terpyridine, Pqn = 8-(diphenylphosphanyl)quinoline, and dppbz = 1,2-bis(diphenylphosphanyl)benzene). The influence of the number and position of the phosphine group(s) on the electronic structure of these complexes was investigated using single-crystal X-ray structural analysis, UV-vis absorption spectroscopy, and electrochemical measurements. The substitution lability of the nitrogen oxide ligand of each complex is discussed in comparison with that of the corresponding acetonitrile complexes.

  4. Computer-Aided Molecular Design of Bis-phosphine Oxide Lanthanide Extractants

    DOE PAGES

    McCann, Billy W.; Silva, Nuwan De; Windus, Theresa L.; ...

    2016-02-17

    Computer-aided molecular design and high-throughput screening of viable host architectures can significantly reduce the efforts in the design of novel ligands for efficient extraction of rare earth elements. This paper presents a computational approach to the deliberate design of bis-phosphine oxide host architectures that are structurally organized for complexation of trivalent lanthanides. Molecule building software, HostDesigner, was interfaced with molecular mechanics software, PCModel, providing a tool for generating and screening millions of potential R2(O)P-link-P(O)R2 ligand geometries. The molecular mechanics ranking of ligand structures is consistent with both the solution-phase free energies of complexation obtained with density functional theory and themore » performance of known bis-phosphine oxide extractants. For the case where link is -CH2-, evaluation of the ligand geometry provides the first characterization of a steric origin for the ‘anomalous aryl strengthening’ effect. The design approach has identified a number of novel bis-phosphine oxide ligands that are better organized for lanthanide complexation than previously studied examples.« less

  5. Computer-Aided Molecular Design of Bis-phosphine Oxide Lanthanide Extractants

    SciTech Connect

    McCann, Billy W.; Silva, Nuwan De; Windus, Theresa L.; Gordon, Mark S.; Moyer, Bruce A.; Bryantsev, Vyacheslav S.; Hay, Benjamin P.

    2016-02-17

    Computer-aided molecular design and high-throughput screening of viable host architectures can significantly reduce the efforts in the design of novel ligands for efficient extraction of rare earth elements. This paper presents a computational approach to the deliberate design of bis-phosphine oxide host architectures that are structurally organized for complexation of trivalent lanthanides. Molecule building software, HostDesigner, was interfaced with molecular mechanics software, PCModel, providing a tool for generating and screening millions of potential R2(O)P-link-P(O)R2 ligand geometries. The molecular mechanics ranking of ligand structures is consistent with both the solution-phase free energies of complexation obtained with density functional theory and the performance of known bis-phosphine oxide extractants. For the case where link is -CH2-, evaluation of the ligand geometry provides the first characterization of a steric origin for the ‘anomalous aryl strengthening’ effect. The design approach has identified a number of novel bis-phosphine oxide ligands that are better organized for lanthanide complexation than previously studied examples.

  6. Simple phosphinate ligands access zinc clusters identified in the synthesis of zinc oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Pike, Sebastian D.; White, Edward R.; Shaffer, Milo S. P.; Williams, Charlotte K.

    2016-10-01

    The bottom-up synthesis of ligand-stabilized functional nanoparticles from molecular precursors is widely applied but is difficult to study mechanistically. Here we use 31P NMR spectroscopy to follow the trajectory of phosphinate ligands during the synthesis of a range of ligated zinc oxo clusters, containing 4, 6 and 11 zinc atoms. Using an organometallic route, the clusters interconvert rapidly and self-assemble in solution based on thermodynamic equilibria rather than nucleation kinetics. These clusters are also identified in situ during the synthesis of phosphinate-capped zinc oxide nanoparticles. Unexpectedly, the ligand is sequestered to a stable Zn11 cluster during the majority of the synthesis and only becomes coordinated to the nanoparticle surface, in the final step. In addition to a versatile and accessible route to (optionally doped) zinc clusters, the findings provide an understanding of the role of well-defined molecular precursors during the synthesis of small (2-4 nm) nanoparticles.

  7. Oxidation of hydrogen sulfide by human liver mitochondria.

    PubMed

    Helmy, Nada; Prip-Buus, Carina; Vons, Corinne; Lenoir, Véronique; Abou-Hamdan, Abbas; Guedouari-Bounihi, Hala; Lombès, Anne; Bouillaud, Frédéric

    2014-09-15

    Hydrogen sulfide (H2S) is the third gasotransmitter discovered. Sulfide shares with the two others (NO and CO) the same inhibiting properties towards mitochondrial respiration. However, in contrast with NO or CO, sulfide at concentrations lower than the toxic (μM) level is an hydrogen donor and a substrate for mitochondrial respiration. This is due to the activity of a sulfide quinone reductase found in a large majority of mitochondria. An ongoing study of the metabolic state of liver in obese patients allowed us to evaluate the sulfide oxidation capacity with twelve preparations of human liver mitochondria. The results indicate relatively high rates of sulfide oxidation with a large variability between individuals. These observations made with isolated mitochondria appear in agreement with the main characteristics of sulfide oxidation as established before with the help of cellular models.

  8. Hydrogen sulfide induces oxidative damage to RNA and DNA in a sulfide-tolerant marine invertebrate.

    PubMed

    Joyner-Matos, Joanna; Predmore, Benjamin L; Stein, Jenny R; Leeuwenburgh, Christiaan; Julian, David

    2010-01-01

    Hydrogen sulfide acts as an environmental toxin across a range of concentrations and as a cellular signaling molecule at very low concentrations. Despite its toxicity, many animals, including the mudflat polychaete Glycera dibranchiata, are periodically or continuously exposed to sulfide in their environment. We tested the hypothesis that a broad range of ecologically relevant sulfide concentrations induces oxidative stress and oxidative damage to RNA and DNA in G. dibranchiata. Coelomocytes exposed in vitro to sulfide (0-3 mmol L(-1) for 1 h) showed dose-dependent increases in oxidative stress (as 2',7'-dichlorofluorescein fluorescence) and superoxide production (as dihydroethidine fluorescence). Coelomocytes exposed in vitro to sulfide (up to 0.73 mmol L(-1) for 2 h) also acquired increased oxidative damage to RNA (detected as 8-oxo-7,8-dihydroguanosine) and DNA (detected as 8-oxo-7,8-dihydro-2'-deoxyguanosine). Worms exposed in vivo to sulfide (0-10 mmol L(-1) for 24 h) acquired elevated oxidative damage to RNA and DNA in both coelomocytes and body wall tissue. While the consequences of RNA and DNA oxidative damage are poorly understood, oxidatively damaged deoxyguanosine bases preferentially bind thymine, causing G-T transversions and potentially causing heritable point mutations. This suggests that sulfide can be an environmental mutagen in sulfide-tolerant invertebrates.

  9. Transient Kinetic Analysis of Hydrogen Sulfide Oxidation Catalyzed by Human Sulfide Quinone Oxidoreductase.

    PubMed

    Mishanina, Tatiana V; Yadav, Pramod K; Ballou, David P; Banerjee, Ruma

    2015-10-09

    The first step in the mitochondrial sulfide oxidation pathway is catalyzed by sulfide quinone oxidoreductase (SQR), which belongs to the family of flavoprotein disulfide oxidoreductases. During the catalytic cycle, the flavin cofactor is intermittently reduced by sulfide and oxidized by ubiquinone, linking H2S oxidation to the electron transfer chain and to energy metabolism. Human SQR can use multiple thiophilic acceptors, including sulfide, sulfite, and glutathione, to form as products, hydrodisulfide, thiosulfate, and glutathione persulfide, respectively. In this study, we have used transient kinetics to examine the mechanism of the flavin reductive half-reaction and have determined the redox potential of the bound flavin to be -123 ± 7 mV. We observe formation of an unusually intense charge-transfer (CT) complex when the enzyme is exposed to sulfide and unexpectedly, when it is exposed to sulfite. In the canonical reaction, sulfide serves as the sulfur donor and sulfite serves as the acceptor, forming thiosulfate. We show that thiosulfate is also formed when sulfide is added to the sulfite-induced CT intermediate, representing a new mechanism for thiosulfate formation. The CT complex is formed at a kinetically competent rate by reaction with sulfide but not with sulfite. Our study indicates that sulfide addition to the active site disulfide is preferred under normal turnover conditions. However, under pathological conditions when sulfite concentrations are high, sulfite could compete with sulfide for addition to the active site disulfide, leading to attenuation of SQR activity and to an alternate route for thiosulfate formation.

  10. Analogues of acyclic nucleosides derived from tris-(hydroxymethyl)phosphine oxide or bis-(hydroxymethyl)phosphinic acid coupled to DNA nucleobases.

    PubMed

    Nawrot, Barbara; Michalak, Olga; De Clercq, Erik; Stec, Wojciech J

    2004-11-01

    A series of novel acyclic nucleoside analogues containing bis-(hydroxymethyl)phosphinic acid (BHPA) or tris(hydroxymethyl)phosphine oxide (THPO) coupled with DNA nucleobases or with 5-fluorouracil were prepared and their antiviral activity was studied against cytomegalovirus (CMV), varicella-zoster virus (VZV), parainfluenza-virus type 3, reovirus-type 1, sindbis, coxsackie B4, punta toro, vesicular stomatitis and respiratory syncytial virus, herpes simplex virus-type 1 (KOS) and type 2 (G), vaccinia virus and herpes simplex virus-1 (TK- KOS ACVr). No specific antiviral effects were noted for any of test compounds against viruses evaluated, except thymine, cytosine and adenine derivatives of BHPA exerting borderline activity against respiratory syncytial virus at the 80 mg/ml concentration.

  11. Organization of the human mitochondrial hydrogen sulfide oxidation pathway.

    PubMed

    Libiad, Marouane; Yadav, Pramod Kumar; Vitvitsky, Victor; Martinov, Michael; Banerjee, Ruma

    2014-11-07

    Sulfide oxidation is expected to play an important role in cellular switching between low steady-state intracellular hydrogen sulfide levels and the higher concentrations where the physiological effects are elicited. Yet despite its significance, fundamental questions regarding how the sulfide oxidation pathway is wired remain unanswered, and competing proposals exist that diverge at the very first step catalyzed by sulfide quinone oxidoreductase (SQR). We demonstrate that, in addition to sulfite, glutathione functions as a persulfide acceptor for human SQR and that rhodanese preferentially synthesizes rather than utilizes thiosulfate. The kinetic behavior of these enzymes provides compelling evidence for the flow of sulfide via SQR to glutathione persulfide, which is then partitioned to thiosulfate or sulfite. Kinetic simulations at physiologically relevant metabolite concentrations provide additional support for the organizational logic of the sulfide oxidation pathway in which glutathione persulfide is the first intermediate formed.

  12. Hydrogen sulfide oxidation is coupled to oxidative phosphorylation in mitochondria of Solemya reidi

    SciTech Connect

    Powell, M.A.; Somero, G.N.

    1986-08-01

    Solemya reidi, a gutless clam found in sulfide-rich habitats, contains within its gills bacterial symbionts thought to oxidize sulfur compounds and provide a reduced carbon food source to the clam. However, the initial step or steps in sulfide oxidation occur in the animal tissue, and mitochondria isolated from both gill and symbiont-free foot tissue of the clam coupled the oxidation of sulfide to oxidative phosphorylation (adenosine triphosphate (ATP) synthesis). The ability of Solemya reidi to exploit directly the energy in sulfide for ATP synthesis is unprecedented, and suggests that sulfide-habitat animals that lack bacterial symbionts may also use sulfide as an inorganic energy source.

  13. Sulfide oxidation as a process for the formation of copper-rich magmatic sulfides

    NASA Astrophysics Data System (ADS)

    Wohlgemuth-Ueberwasser, Cora C.; Fonseca, Raúl O. C.; Ballhaus, Chris; Berndt, Jasper

    2013-01-01

    Typical magmatic sulfides are dominated by pyrrhotite and pentlandite with minor chalcopyrite, and the bulk atomic Cu/Fe ratio of these sulfides is typically less than unity. However, there are rare magmatic sulfide occurrences that are dominated by Cu-rich sulfides (e.g., bornite, digenite, and chalcopyrite, sometimes coexisting with metallic Cu) with atomic Cu/Fe as high as 5. Typically, these types of sulfide assemblages occur in the upper parts of moderately to highly fractionated layered mafic-ultramafic intrusions, a well-known example being the Pd/Au reef in the Upper Middle Zone of the Skaergaard intrusion. Processes proposed to explain why these sulfides are so unusually rich in Cu include fractional crystallization of Fe/(Ni) monosulfide and infiltration of postmagmatic Cu-rich fluids. In this contribution, we explore and experimentally evaluate a third possibility: that Cu-rich magmatic sulfides may be the result of magmatic oxidation. FeS-dominated Ni/Cu-bearing sulfides were equilibrated at variable oxygen fugacities in both open and closed system. Our results show that the Cu/Fe ratio of the sulfide melt increases as a function of oxygen fugacity due to the preferential conversion of FeS into FeO and FeO1.5, and the resistance of Cu2S to being converted into an oxide component even at oxygen fugacities characteristic of the sulfide/sulfate transition (above FMQ + 1). This phenomenon will lead to an increase in the metal/S ratio of a sulfide liquid and will also depress its liquidus temperature. As such, any modeling of the sulfide liquid line of descent in magmatic sulfide complexes needs to address this issue.

  14. Investigation on laboratory and pilot-scale airlift sulfide oxidation reactor under varying sulfide loading rate.

    PubMed

    Pokasoowan, Chanya; Kanitchaidecha, Wilawan; K C, Bal Krishna; Annachhatre, Ajit P

    2009-01-01

    Airlift bioreactor was established for recovering sulfur from synthetic sulfide wastewater under controlled dissolved oxygen condition. The maximum recovered sulfur was 14.49 g/day when sulfide loading rate, dissolved oxygen (DO) and pH values were 2.97 kgHS(-)/m(3)-day, 0.2-1.0 mg/L and 7.2-7.8, respectively. On the other hand, the increase in recovered sulfur reduced the contact surface of sulfide oxidizing bacteria which affects the recovery process. This effect caused to reduce the conversion of sulfide to sulfur. More recovered sulfur was produced at high sulfide loading rate due to the change of metabolic pathway of sulfide-oxidizing bacteria which prevented the toxicity of sulfide in the culture. The maximum activity in this system was recorded to be about 3.28 kgS/kgVSS-day. The recovered sulfur contained organic compounds which were confirmed by the results from XRD and CHN analyzer. Afterwards, by annealing the recovered sulfur at 120 degrees C for 24 hrs under ambient Argon, the percentage of carbon reduced from 4.44% to 0.30%. Furthermore, the percentage of nitrogen and hydrogen decreased from 0.79% and 0.48% to 0.00% and 0.14%, respectively. This result showed the success in increasing the purity of recovered sulfur by using the annealing technique. The pilot-scale biological sulfide oxidation process was carried out using real wastewater from Thai Rayon Industry in Thailand. The airlift reactor successfully removed sulfide more than 90% of the influent sulfide at DO concentration of less than 0.1 mg/L, whereas the elementary sulfur production was 2.37 kgS/m(3)-day at sulfide loading rate of 2.14 kgHS(-)/m(3)-day. The sulfur production was still increasing as the reactor had not yet reached its maximum sulfide loading rate.

  15. Photochemical dimerization and functionalization of alkanes, ethers, primary and secondary alcohols, phosphine oxides and silanes

    DOEpatents

    Crabtree, R.H.; Brown, S.H.

    1989-10-17

    The space-time yield and/or the selectivity of the photochemical dimerization of alkanes, ethers, primary and secondary alcohols, phosphine oxides and primary, secondary and tertiary silanes with Hg and U.V. light is enhanced by refluxing the substrate in the irradiated reaction zone at a temperature at which the dimer product condenses and remains condensed promptly upon its formation. Cross-dimerization of the alkanes, ethers and silanes with primary alcohols is disclosed, as is the functionalization to aldehydes of the alkanes with carbon monoxide.

  16. Photochemical dimerization and functionalization of alkanes, ethers, primary and secondary alcohols, phosphine oxides and silanes

    DOEpatents

    Crabtree, Robert H.; Brown, Stephen H.

    1989-01-01

    The space-time yield and/or the selectivity of the photochemical dimerization of alkanes, ethers, primary and secondary alcohols, phosphine oxides and primary, secondary and tertiary silanes with Hg and U.V. light is enhanced by refluxing the substrate in the irradiated reaction zone at a temperature at which the dimer product condenses and remains condensed promptly upon its formation. Cross-dimerization of the alkanes, ethers and silanes with primary alcohols is disclosed, as is the functionalization to aldehydes of the alkanes with carbon monoxide.

  17. Metal sulfide initiators for metal oxide sorbent regeneration

    DOEpatents

    Turk, Brian S.; Gupta, Raghubir P.

    2001-01-01

    A process of regenerating a sulfided sorbent is provided. According to the process of the invention, a substantial portion of the energy necessary to initiate the regeneration reaction is provided by the combustion of a particulate metal sulfide additive. In using the particulate metal sulfide additive, the oxygen-containing gas used to regenerate the sulfided sorbent can be fed to the regeneration zone without heating or at a lower temperature than used in conventional processes wherein the regeneration reaction is initiated only by heating the oxygen-containing gas. The particulate metal sulfide additive is preferably an inexpensive mineral ore such as iron pyrite which does not adversely affect the regeneration or corresponding desulfurization reactions. The invention further includes a sorbent composition comprising the particulate metal sulfide additive in admixture with an active metal oxide sorbent capable of removing one or more sulfur compounds from a sulfur-containing gas stream.

  18. Metal sulfide initiators for metal oxide sorbent regeneration

    DOEpatents

    Turk, Brian S.; Gupta, Raghubir P.

    1999-01-01

    A process of regenerating a sulfided sorbent is provided. According to the process of the invention, a substantial portion of the energy necessary to initiate the regeneration reaction is provided by the combustion of a particulate metal sulfide additive. In using the particulate metal sulfide additive, the oxygen-containing gas used to regenerate the sulfided sorbent can be fed to the regeneration zone without heating or at a lower temperature than used in conventional processes wherein the regeneration reaction is initiated only by heating the oxygen-containing. The particulate metal sulfide additive is preferably an inexpensive mineral ore such as iron pyrite which does not adversely affect the regeneration or corresponding desulfurization reactions. The invention further includes a sorbent composition comprising the particulate metal sulfide additive in admixture with an active metal oxide sorbent capable of removing one or more sulfur compounds from a sulfur-containing gas stream.

  19. Metal sulfide initiators for metal oxide sorbent regeneration

    DOEpatents

    Turk, B.S.; Gupta, R.P.

    1999-06-22

    A process of regenerating a sulfided sorbent is provided. According to the process of the invention, a substantial portion of the energy necessary to initiate the regeneration reaction is provided by the combustion of a particulate metal sulfide additive. In using the particulate metal sulfide additive, the oxygen-containing gas used to regenerate the sulfided sorbent can be fed to the regeneration zone without heating or at a lower temperature than used in conventional processes wherein the regeneration reaction is initiated only by heating the oxygen-containing gas. The particulate metal sulfide additive is preferably an inexpensive mineral ore such as iron pyrite which does not adversely affect the regeneration or corresponding desulfurization reactions. The invention further includes a sorbent composition comprising the particulate metal sulfide additive in admixture with an active metal oxide sorbent capable of removing one or more sulfur compounds from a sulfur-containing gas stream. 1 fig.

  20. Nickel Phosphine Catalysts with Pendant Amines for Electrocatalytic Oxidation of Alcohols

    SciTech Connect

    Weiss, Charles J.; Wiedner, Eric S.; Roberts, John A.; Appel, Aaron M.

    2015-01-01

    Nickel phosphine complexes with pendant amines have been found to be electrocatalysts for the oxidation of primary and secondary alcohols, with turnover frequencies as high as 3.3 s-1. These complexes are the first electrocatalysts for alcohol oxidation based on non-precious metals, which will be critical for use in fuel cells. The research by CJW, ESW, and AMA was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. The research by JASR was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

  1. An Experiment in Autotrophic Fermentation: Microbial Oxidation of Hydrogen Sulfide.

    ERIC Educational Resources Information Center

    Sublette, Kerry L.

    1989-01-01

    Described is an experiment which uses an autotrophic bacterium to anaerobically oxidize hydrogen sulfide to sulfate in a batch-stirred tank reactor. Discusses background information, experimental procedure, and sample results of this activity. (CW)

  2. Nanostructured Metal Oxides and Sulfides for Lithium-Sulfur Batteries.

    PubMed

    Liu, Xue; Huang, Jia-Qi; Zhang, Qiang; Mai, Liqiang

    2017-02-03

    Lithium-sulfur (Li-S) batteries with high energy density and long cycle life are considered to be one of the most promising next-generation energy-storage systems beyond routine lithium-ion batteries. Various approaches have been proposed to break down technical barriers in Li-S battery systems. The use of nanostructured metal oxides and sulfides for high sulfur utilization and long life span of Li-S batteries is reviewed here. The relationships between the intrinsic properties of metal oxide/sulfide hosts and electrochemical performances of Li-S batteries are discussed. Nanostructured metal oxides/sulfides hosts used in solid sulfur cathodes, separators/interlayers, lithium-metal-anode protection, and lithium polysulfides batteries are discussed respectively. Prospects for the future developments of Li-S batteries with nanostructured metal oxides/sulfides are also discussed.

  3. Simple phosphinate ligands access zinc clusters identified in the synthesis of zinc oxide nanoparticles

    PubMed Central

    Pike, Sebastian D.; White, Edward R.; Shaffer, Milo S. P.; Williams, Charlotte K.

    2016-01-01

    The bottom-up synthesis of ligand-stabilized functional nanoparticles from molecular precursors is widely applied but is difficult to study mechanistically. Here we use 31P NMR spectroscopy to follow the trajectory of phosphinate ligands during the synthesis of a range of ligated zinc oxo clusters, containing 4, 6 and 11 zinc atoms. Using an organometallic route, the clusters interconvert rapidly and self-assemble in solution based on thermodynamic equilibria rather than nucleation kinetics. These clusters are also identified in situ during the synthesis of phosphinate-capped zinc oxide nanoparticles. Unexpectedly, the ligand is sequestered to a stable Zn11 cluster during the majority of the synthesis and only becomes coordinated to the nanoparticle surface, in the final step. In addition to a versatile and accessible route to (optionally doped) zinc clusters, the findings provide an understanding of the role of well-defined molecular precursors during the synthesis of small (2–4 nm) nanoparticles. PMID:27734828

  4. Synthesis and characterization of aryl phosphine oxide containing thermoplastic polyimides and thermosetting polyimides with controlled reactivity

    NASA Astrophysics Data System (ADS)

    Zhuang, Hong

    1998-11-01

    Phosphorus containing monomers, bis(3-aminophenyl)methyl phosphine oxide (m-DAMPO) and bis(3-aminophenyl)phenyl phosphine oxide (m-DAPPO), were synthesized and incorporated into a thermoplastic poly(arylene ether imide) based upon 2,2sp'-bis (4-(3,4-dicarboxyphenoxy)phenyl) propane dianhydride and 1,3-phenylene diamine, in order to study their influence on flame resistance and other properties. DAMPO or DAPPO were quantitatively incorporated in concentrations of 25, 50, 75 and 100 mole percent, using the "one pot" ester-acid method. The number average molecular weights of the prepared materials were controlled to 20,000g/mol by off-setting the stoichiometry and endcapping with phthalic anhydride. This strategy enabled one to distinguish the effects of the phosphine oxide incorporation from the influence of molecular weight. The resulting copolymers demonstrated a significant increase in char yield as a function of the phosphine oxide content, thus suggesting improved fire resistance. Glass transition temperatures similar to the control were determined by DSC analysis. Analysis of the mechanical behavior of the DAMPO system at room temperature showed that tensile strength and elongation at failure values were comparable to the control system, while the DAPPO containing copolymers were surprisingly brittle. The influence of the reactive endgroup on the synthesis, cure behavior and network properties of thermosetting polyetherimides was investigated. Reactive phenylacetylene, acetylene and maleimide terminated poly(ether imide) oligomers were prepared and characterized. Optimal reaction conditions were established to produce fully endcapped oligomers with imidized structures and controlled molecular weight. The phenylacetylene endcapped system was synthesized by a conventional ester-acid method. The acetylene endcapped system was prepared via modified ester-acid method and the maleimide endcapped system was fabricated utilizing an amic-acid route. It was determined

  5. Vegetation successfully prevents oxidization of sulfide minerals in mine tailings.

    PubMed

    Li, Yang; Sun, Qingye; Zhan, Jing; Yang, Yang; Wang, Dan

    2016-07-15

    The oxidization of metal sulfide in tailings causes acid mine drainage. However, it remains unclear whether vegetation prevents the oxidization of metal sulfides. The oxidization characteristics and microbial indices of the tailings in the presence of various plant species were investigated to explore the effects of vegetation on the oxidization of sulfide minerals in tailings. The pH, reducing sulfur, free iron oxides (Fed), chemical oxygen consumption (COC) and biological oxygen consumption (BOC) were measured. Key iron- and sulfur-oxidizing bacteria (Acidithiobacillus spp., Leptospirillum spp. and Thiobacillus spp.) were quantified using real-time PCR. The results indicate that vegetation growing on tailings can effectively prevent the oxidization of sulfide minerals in tailings. A higher pH and reducing-sulfur content and lower Fed were observed in the 0-30 cm depth interval in the presence of vegetation compared to bare tailings (BT). The COC gradually decreased with depth in all of the soil profiles; specifically, the COC rapidly decreased in the 10-20 cm interval in the presence of vegetation but gradually decreased in the BT profiles. Imperata cylindrica (IC) and Chrysopogon zizanoides (CZ) profiles contained the highest BOC in the 10-20 cm interval. The abundance of key iron- and sulfur-oxidizing bacteria in the vegetated tailings were significantly lower than in the BT; in particular, IC was associated with the lowest iron- and sulfur-oxidizing bacterial abundance. In conclusion, vegetation successfully prevented the oxidization of sulfide minerals in the tailings, and Imperata cylindrica is the most effective in reducing the number of iron- and sulfur-oxidizing bacteria and helped to prevent the oxidization of sulfide minerals in the long term.

  6. Sulfide oxidation in fluidized bed bioreactor using nylon support material.

    PubMed

    Midha, Varsha; Jha, M K; Dey, Apurba

    2012-01-01

    A continuous fluidized bed bioreactor (FBBR) with nylon support particles was used to treat synthetic sulfide wastewater at different hydraulic retention time of 25, 50 and 75 min and upflow velocity of 14, 17 and 20 m/hr. The effects of upflow velocity, hydraulic retention time and reactor operation time on sulfide oxidation rate were studied using statistical model. Mixed culture obtained from the activated sludge, taken from tannery effluent treatment plant, was used as a source for microorganisms. The diameter and density of the nylon particles were 2-3 mm and 1140 kg/m3, respectively. Experiments were carried out in the reactor at a temperature of (30 +/- 2) degrees C, at a fixed bed height of 16 cm after the formation of biofilm on the surface of support particles. Biofilm thickness reached (42 +/- 3) microm after 15 days from reactor start-up. The sulfide oxidation, sulfate and sulfur formation is examined at all hydraulic retention times and upflow velocities. The results indicated that almost 90%-92% sulfide oxidation was achieved at all hydraulic retention times. Statistical model could explain 94% of the variability and analysis of variance showed that upflow velocity and hydraulic retention time slightly affected the sulfide oxidation rate. The highest sulfide oxidation of 92% with 70% sulfur was obtained at hydraulic retention time of 75 min and upflow velocity of 14 m/hr.

  7. Preparation of cadmium selenide-polyolefin composites from functional phosphine oxides and ruthenium-based metathesis.

    PubMed

    Skaff, Habib; Ilker, M Firat; Coughlin, E Bryan; Emrick, Todd

    2002-05-22

    Cadmium selenide nanoparticles, prepared by known methods, were stabilized with functional phosphine oxide 1, then used to support the polymerization of cyclic olefins radially outward from the surface by ruthenium-catalyzed ring-opening metathesis polymerization (ROMP). The conversion of compound 1 into the new metathesis catalyst 3 by carbene exchange and the subsequent polymerization of cyclic olefins were observed spectroscopically by (1)H NMR to afford for example CdSe-polycyclooctene composite 6. Transmission electron micrographs on thin films of these composites showed good nanoparticle dispersion. This is in stark contrast to the substantial nanoparticle aggregation observed when similar polymerizations were performed in the presence of conventional TOPO-covered nanoparticles. The methods reported here to prepare composite product 6 are applicable to other cyclic olefins, and suggest that this chemistry will be useful for incorporating CdSe nanoparticles into a wide variety of polymer matrices.

  8. Synthesis and fuel cell characterization of blend membranes from phenyl phosphine oxide containing flourinated novel polymers

    NASA Astrophysics Data System (ADS)

    Gürtekin Seden, Merve; Baştürk, Emre; Inan, Tülay Y.; Kayaman Apohan, Nilhan; Güngör, Atilla

    2014-12-01

    Novel fluorinated poly(arylene ether)'s are synthesized from polycondensation of bis (p-hydroxy-tetrafluoro) phenyl) phenyl phosphine oxide (PFPPO-OH) with 4,4‧-dichlorodiphenyl sulfone (DCDPS) and 2,2-bis(4-hydroxyphenyl)propane (Bisfenol A) (Copolymer 1a) or 2,2-bis(4-hydroxyphenyl) hexafluoropropane (Bisphenol AF) (Copolymer 1b). The fluorinated copolymers have been blended with sulphonated poly(ether ether ketone)-SPEEK by solvent casting method. The water uptake and proton conductivity of the blend membranes decreases with the increase of copolymer content as expected, but proton conductivity values are still comparable to that of Nafion117® membrane. Addition of hydrophobic copolymer 1b to the SPEEK caused increase in water vapor transmission. Methanol permeability of the membranes is decreased to 8.2 × 10-8 cm2 s-1 and 1.3 × 10-9 cm2 s-1 by addition of Copolymer 1a and 1b, respectively and they are much lower than that of Nafion® 117 (1.21E-06 (cm2 s-1). The blend membranes endure up to 6.5 h before it starts to dissolve. Hydrogen and oxygen permeability of the blend membranes is one-hundredth of the Nafion®. Fluorinated polymer improved chemical, mechanical, and hydrolytic stability and also phenyl phosphine oxide structure in the ionomer increased the thermal stability, gas and methanol permeability and overcomed the drawbacks of the Nafion® type membranes.

  9. Synthesis, characterization, and crystal structure of mercury(II) complex containing new phosphine oxide salt

    NASA Astrophysics Data System (ADS)

    Samiee, Sepideh; Kooti, Nadieh; Gable, Robert W.

    2017-02-01

    The reaction of new phosphonium-phosphine oxide salt [P(O)Ph2(CH2)2PPh2CH2C(O)C6H4NO2]Br (1) with mercury(II) iodide in a methanolic solution yielded [P(O)Ph2(CH2)2PPh2CH2C(O)C6H4NO2]2[Hg2I5Br](2). These two compounds were fully characterized by elemental analysis, IR, 1H, 31P, and 13C NMR spectra. Crystal and molecular structure of 2 has been determined by means of X-ray diffraction. In mercury compound, the phosphine oxide salt is found as a counter ion letting the mercury(II) ion to bound halides to all four coordination sites and to give dimermercurate(II) ions as the structure-constructing species. The neighboring [P(O)Ph2(CH2)2PPh2CH2C(O)C6H4NO2]2+cations are joined together by intramolecular Csbnd H⋯O hydrogen bonds to give a 1-D chain structure along the crystallographic b-axis. The [Hg2I5Br]2-anions act as cross-linkers between neighbouring strands extending the supramolecular structure into 2D layers in (110) planes as well as balances the charge of the complex. The significant effects of Csbnd H⋯X (Xdbnd O, Br and I) and π⋯π aromatic interactions play a major role in the crystal packing of compound 2.

  10. Evidence supporting biologically mediated sulfide oxidation in hot spring ecosystems

    NASA Astrophysics Data System (ADS)

    Cox, A. D.; Shock, E.

    2011-12-01

    The sulfide concentration of fluids in hydrothermal ecosystems is one of several factors determining the transition to microbial photosynthesis (Cox et al., 2011, Chem. Geol. 280, 344-351). To investigate the loss of sulfide in Yellowstone hot spring systems, measurements of total dissolved sulfide with respect to time were made in incubation experiments conducted on 0.2-micron filtered (killed controls) vs. unfiltered hot spring water at locations with three different pH:sulfide combinations (pH 2.5 with 50 μM sulfide, 5.2 with 5.6 μM sulfide, and 8.3 with 86 μM sulfide). At the higher pH values, the experiments yielded similar rates of sulfide loss in filtered and unfiltered water of approximately 0.8 (pH 5.2) and 7.6 nmol sulfide L-1s-1 (pH 8.3). At the acidic spring, the unfiltered water lost sulfide at a rate 1.6 times that of the filtered water (8.2 vs. 5 nmol sulfide L-1s-1). These results suggest that the pelagic biomass at the pH 5.2 and 8.3 springs may not affect sulfide loss, whereas in the pH 2.5 spring there appears to be an effect. In addition, the incubation of filamentous biomass with unfiltered water increased the rate of sulfide loss by approximately two-fold at a pH of 2.5 (59 vs. 31 nmol L-1s-1; Cox et al., 2011), five-fold at a pH of 5.2 (3.9 vs. 0.8 nmol sulfide L-1s-1), and barely increased the rate of sulfide loss at a pH of 8.3 (9.1 vs. 8.4 nmol sulfide L-1s-1). Sulfide is predominately present as HS- at a pH of 8.3, which may not be taken up as easily by microorganisms as the H2S (aq) that dominates sulfide speciation at pH 2.5 and 5.2. That the loss of sulfide at acidic pH is due to biotic rather than abiotic factors is further supported by studies with whole mat samples that show greater sulfide consumption than killed controls (D'Imperio et al., 2008, AEM 74, 5802-5808). Taken together, the results of these experiments suggest that the majority of sulfide oxidation occurs in the filamentous biomass of hot spring ecosystems, although

  11. Catalytic Oxidation of Alcohol via Nickel Phosphine Complexes with Pendant Amines

    SciTech Connect

    Weiss, Charles J.; Das, Partha Pratim; Higgins, Deanna LM; Helm, Monte L.; Appel, Aaron M.

    2014-09-05

    Nickel complexes were prepared with diphosphine ligands that contain pendant amines, and these complexes catalytically oxidize primary and secondary alcohols to their respective aldehydes and ketones. Kinetic and mechanistic studies of these prospective electrocatalysts were performed to understand what influences the catalytic activity. For the oxidation of diphenylmethanol, the catalytic rates were determined to be dependent on the concentration of both the catalyst and the alcohol. The catalytic rates were found to be independent of the concentration of base and oxidant. The incorporation of pendant amines to the phosphine ligand results in substantial increases in the rate of alcohol oxidation with more electron-donating substituents on the pendant amine exhibiting the fastest rates. We thank Dr. John C. Linehan, Dr. Elliott B. Hulley, Dr. Jonathan M. Darmon, and Dr. Elizabeth L. Tyson for helpful discussions. Research by CJW, PD, DLM, and AMA was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Research by MLH was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle.

  12. Summary of GPC/DV results for space exposed poly(arylene ether phosphine oxide)s

    NASA Technical Reports Server (NTRS)

    Siochi, Emilie

    1995-01-01

    Gel Permeation Chromatography (GPC) was used to analyze poly(arylene ether phosphine oxide)s whose backbones were identical except for the ketone content and placement. These samples were exposed to low Earth orbit environment (predominantly atomic oxygen) on space shuttle flights. The materials and their unexposed controls were then characterized by GPC to investigate the effect of atomic oxygen on the molecular weight distributions. Analysis of the soluble portion of the samples revealed that there was significant loss of high molecular weight species. The presence of insoluble material also suggested that crosslinking was induced by the atomic oxygen exposure and that this very likely occurred at the high molecular weight portion of the molecular weight distribution.

  13. Respirometric characterization of aerobic sulfide, thiosulfate and elemental sulfur oxidation by S-oxidizing biomass.

    PubMed

    Mora, Mabel; López, Luis R; Lafuente, Javier; Pérez, Julio; Kleerebezem, Robbert; van Loosdrecht, Mark C M; Gamisans, Xavier; Gabriel, David

    2016-02-01

    Respirometry was used to reveal the mechanisms involved in aerobic biological sulfide oxidation and to characterize the kinetics and stoichiometry of a microbial culture obtained from a desulfurizing biotrickling filter. Physical-chemical processes such as stripping and chemical oxidation of hydrogen sulfide were characterized since they contributed significantly to the conversions observed in respirometric tests. Mass transfer coefficient for hydrogen sulfide and the kinetic parameters for chemical oxidation of sulfide with oxygen were estimated. The stoichiometry of the process was determined and the different steps in the sulfide oxidation process were identified. The conversion scheme proposed includes intermediate production of elemental sulfur and thiosulfate and the subsequent oxidation of both compounds to sulfate. A kinetic model describing each of the reactions observed during sulfide oxidation was calibrated and validated. The product selectivity was found to be independent of the dissolved oxygen to hydrogen sulfide concentration ratio in the medium at sulfide concentrations ranging from 3 to 30 mg S L(-1). Sulfide was preferentially consumed (SOURmax = 49.2 mg DO g(-1) VSS min(-1)) and oxidized to elemental sulfur at dissolved oxygen concentrations above 0.8 mg DO L(-1). Substrate inhibition of sulfide oxidation was observed (K(i,S(2-))= 42.4 mg S L(-1)). Intracellular sulfur accumulation also affected negatively the sulfide oxidation rate. The maximum fraction of elemental sulfur accumulated inside cells was estimated (25.6% w/w) and a shrinking particle equation was included in the kinetic model to describe elemental sulfur oxidation. The microbial diversity obtained through pyrosequencing analysis revealed that Thiothrix sp. was the main species present in the culture (>95%).

  14. High conducting oxide--sulfide composite lithium superionic conductor

    DOEpatents

    Liang, Chengdu; Rangasamy, Ezhiylmurugan; Dudney, Nancy J.; Keum, Jong Kahk; Rondinone, Adam Justin

    2017-01-17

    A solid electrolyte for a lithium-sulfur battery includes particles of a lithium ion conducting oxide composition embedded within a lithium ion conducting sulfide composition. The lithium ion conducting oxide composition can be Li.sub.7La.sub.3Zr.sub.2O.sub.12 (LLZO). The lithium ion conducting sulfide composition can be .beta.-Li.sub.3PS.sub.4 (LPS). A lithium ion battery and a method of making a solid electrolyte for a lithium ion battery are also disclosed.

  15. Laboratory SIP signatures associated with oxidation of disseminated metal sulfides.

    PubMed

    Placencia-Gómez, Edmundo; Slater, Lee; Ntarlagiannis, Dimitrios; Binley, Andrew

    2013-05-01

    Oxidation of metal sulfide minerals is responsible for the generation of acidic waters rich in sulfate and metals. When associated with the oxidation of sulfide ore mine waste deposits the resulting pore water is called acid mine drainage (AMD); AMD is a known environmental problem that affects surface and ground waters. Characterization of oxidation processes in-situ is challenging, particularly at the field scale. Geophysical techniques, spectral induced polarization (SIP) in particular, may provide a means of such investigation. We performed laboratory experiments to assess the sensitivity of the SIP method to the oxidation mechanisms of common sulfide minerals found in mine waste deposits, i.e., pyrite and pyrrhotite, when the primary oxidant agent is dissolved oxygen. We found that SIP parameters, e.g., phase shift, the imaginary component of electrical conductivity and total chargeability, decrease as the time of exposure to oxidation and oxidation degree increase. This observation suggests that dissolution-depletion of the mineral surface reduces the capacitive properties and polarizability of the sulfide minerals. However, small increases in the phase shift and imaginary conductivity do occur during oxidation. These transient increases appear to correlate with increases of soluble oxidizing products, e.g., Fe(2+) and Fe(3+) in solution; precipitation of secondary minerals and the formation of a passivating layer to oxidation coating the mineral surface may also contribute to these increases. In contrast, the real component of electrical conductivity associated with electrolytic, electronic and interfacial conductance is sensitive to changes in the pore fluid chemistry as a result of the soluble oxidation products released (Fe(2+) and Fe(3+)), particularly for the case of pyrrhotite minerals.

  16. Catalysts for the selective oxidation of hydrogen sulfide to sulfur

    DOEpatents

    Srinivas, Girish; Bai, Chuansheng

    2000-08-08

    This invention provides catalysts for the oxidation of hydrogen sulfide. In particular, the invention provides catalysts for the partial oxidation of hydrogen sulfide to elemental sulfur and water. The catalytically active component of the catalyst comprises a mixture of metal oxides containing titanium oxide and one or more metal oxides which can be selected from the group of metal oxides or mixtures of metal oxides of transition metals or lanthanide metals. Preferred metal oxides for combination with TiO.sub.2 in the catalysts of this invention include oxides of V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo, Tc, Ru, Rh, Hf, Ta, W, Au, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. Catalysts which comprise a homogeneous mixture of titanium oxide and niobium (Nb) oxide are also provided. A preferred method for preparing the precursor homogenous mixture of metal hydroxides is by coprecipitation of titanium hydroxide with one or more other selected metal hydroxides. Catalysts of this invention have improved activity and/or selectivity for elemental sulfur production. Further improvements of activity and/or selectivity can be obtained by introducing relatively low amounts (up to about 5 mol %)of a promoter metal oxide (preferably of metals other than titanium and that of the selected second metal oxide) into the homogeneous metal/titanium oxide catalysts of this invention.

  17. Diphen­yl[2-(2-pyridylamino­meth­yl)phen­yl]phosphine oxide

    PubMed Central

    Hernández-Ortega, Simón; Cuenu Cabeza, Fernando; Cabrera-Ortiz, Armando

    2010-01-01

    The title compound, C24H21N2OP, was obtained by reacting 2-amino­pyridine and 2-(diphenyl­phosphin­yl)benzaldehyde in ethanol. It crystallizes with two crystallographically independent mol­ecules in the asymmetric unit. The amino­pyridine units and the benzene ring bonded to the phosphine oxide P atom form dihedral angles of 88.58 (7) and 82.47 (9)° in the two mol­ecules. The crystal structure displays strong N—H⋯O and weak C—H⋯O hydrogen bonds along the b axis and C—H⋯π aromatic intra- and inter­molecular inter­actions. PMID:21579222

  18. Molecular determinants of Kv1.5 channel block by diphenyl phosphine oxide-1.

    PubMed

    Du, Yi-mei; Zhang, Xiao-xian; Tu, Dan-na; Zhao, Ning; Liu, Yan-jie; Xiao, Hua; Sanguinetti, Michael C; Zou, Anruo; Liao, Yu-hua

    2010-06-01

    Kv1.5 channels conduct the ultra-rapid delayed rectifier current (I(Kur)) that contributes to action potential repolarization of human atrial myocytes. Block of these channels has been proposed as a treatment for atrial arrhythmias. Diphenyl phosphine oxide-1 (DPO-1) is a novel and potent inhibitor of Kv1.5 potassium channels. The present study was undertaken to characterize the mechanisms and molecular determinants of channel block by DPO-1. Experiments were carried out on wild-type and mutant Kv1.5 channels expressed in Xenopus laevis oocytes using the standard two microelectrode voltage clamp technique. DPO-1 blocked Kv1.5 current in oocytes with an IC(50) of 0.78+/-0.12 microM at +40 mV. Block was enhanced by higher rates of stimulation, consistent with preferential binding of the drug to the open state of the channel. Ala-scanning mutagenesis of the pore domain of Kv1.5 identified the residues Thr480, Leu499, Leu506, Ile508, Leu510 and Val514 as components of the putative binding site for DPO-1, partially overlapping the site previously defined for the Kv1.5 channel blockers AVE0118 and S0100176. Block of Kv1.5 by DPO-1 was significantly reduced in the presence of Kvbeta1.3.

  19. Wet oxidation of oil-bearing sulfide wastes

    SciTech Connect

    Miller, R.L.; Hotz, N.J.

    1991-01-01

    Oil-bearing metal sulfide sludges produced in treatment of an industrial wastewater, which includes plating wastes, have yielded to treatment by electrooxidation and hydrogen peroxide processes. The oxidation can be controlled to be mild enough to avoid decomposition of the organic phase while oxidizing the sulfides to sulfates. The pH is controlled to near neutral conditions where iron, aluminum and chromium(III) precipitate as hydrous oxides. Other metals, such as lead and barium, may be present as sulfate precipitates with limited solubility, while metals such as nickel and cadmium would be present as complexed ions in a sulfate solution. The oxidations were found to proceed smoothly, without vigorous reaction; heat liberation was minimal. 2 refs., 12 figs.

  20. Synthesis of actinide nitrides, phosphides, sulfides and oxides

    DOEpatents

    Van Der Sluys, William G.; Burns, Carol J.; Smith, David C.

    1992-01-01

    A process of preparing an actinide compound of the formula An.sub.x Z.sub.y wherein An is an actinide metal atom selected from the group consisting of thorium, uranium, plutonium, neptunium, and americium, x is selected from the group consisting of one, two or three, Z is a main group element atom selected from the group consisting of nitrogen, phosphorus, oxygen and sulfur and y is selected from the group consisting of one, two, three or four, by admixing an actinide organometallic precursor wherein said actinide is selected from the group consisting of thorium, uranium, plutonium, neptunium, and americium, a suitable solvent and a protic Lewis base selected from the group consisting of ammonia, phosphine, hydrogen sulfide and water, at temperatures and for time sufficient to form an intermediate actinide complex, heating said intermediate actinide complex at temperatures and for time sufficient to form the actinide compound, and a process of depositing a thin film of such an actinide compound, e.g., uranium mononitride, by subliming an actinide organometallic precursor, e.g., a uranium amide precursor, in the presence of an effectgive amount of a protic Lewis base, e.g., ammonia, within a reactor at temperatures and for time sufficient to form a thin film of the actinide compound, are disclosed.

  1. Interactions among sulfide-oxidizing bacteria

    NASA Technical Reports Server (NTRS)

    Poplawski, R.

    1985-01-01

    The responses of different phototrophic bacteria in a competitive experimental system are studied, one in which primary factors such as H2S or light limited photometabolism. Two different types of bacteria shared one limited source of sulfide under specific conditions of light. The selection of a purple and a green sulfur bacteria and the cyanobacterium was based on their physiological similarity and also on the fact that they occur together in microbial mats. They all share anoxygenic photosynthesis, and are thus probably part of an evolutionary continuum of phototrophic organisms that runs from, strictly anaerobic physiology to the ability of some cyanobacteria to shift between anoxygenic bacterial style photosynthesis and the oxygenic kind typical of eukaryotes.

  2. [Oxidation of sulfide minerals by Thiobacillus ferrooxidans].

    PubMed

    Malakhova, P T; Chebotarev, G M; Kovalenko, E V; Volkov, Iu A

    1981-01-01

    Samples of natural pyrites and sphalerites were subjected to the action of the mineral medium 9K with 1 g of Fe3+ per litre in the presence and in the absence of Thiobacillus ferrooxidans, and incubated at 28 degrees C under the stationary conditions for 30 days. The chemical composition of the solutions was studied after leaching as well as changes of the surfaces of monoliths. The deepest etching of surfaces with the formation of crusts and films of jarosite, limonite and goslarite occurs upon the combined action of bacteria and Fe3+ in regions of a fine-zonal structure enriched with an isomorphous arsenic admixture which are characterized by a defective weak structure. The pyrite and sphalerite from Charmitan with a higher arsenic and iron content were leached more than the pyrite and sphalerite from Kurgashincan. This was also corroborated by chemical analyses of leaching solutions and by monometric studies of crushed sulfide samples.

  3. Thermal and thermal-oxidative stability of trichloroethanol sulfide

    SciTech Connect

    Kalyavina, S.I.; Borshchevskii, S.B.; Medvedovskaya, I.I.; Stepanova, O.N.; Veselovskaya, L.F.; Zorina, E.F.

    1984-03-01

    This article reports on an investigation of the thermal and thermal-oxidative stability of bis(2,2,2-trichloro-1-hydroxyethyl) sulfide CCl/sub 3/-CHOHO-S-CHOH-CCl/sub 3/, which contains trichloromethyl and sulfide groups. The antiscoring effectiveness of this compound in TSp-14.5 oil is considerably better than that given by oils with the presently used commercial additives. The thermal stabilities of the sulfide additive and the IS-45 oil were tested in a stream of nitrogen at 100-150/sup 0/C, analyzing the reaction products by iodometric and mercurimetric titration to determine the quantities of sulfur and chlorine ions and the degree to which the additive had been converted to these ions. The thermal decomposition of the additive begins at 118/sup 0/C and increases with increasing temperature, whether it is tested by itself or in a 1.25% solution in IS-45 oil. The additive and the hydrocarbon oil with and without the additive were oxidized with atmospheric oxygen in a thin layer in a series of sealed ampuls, which were removed sequentially from the thermostat at predetermined time intervals for analysis of the gas phase by gas chromatography. It is concluded that the sulfide, which was studied as an extreme-pressure additive, when blended in IS-45 oil, has a lower thermal stability but a higher thermaloxidative stability in comparison with the straight hydrocarbon oil IS-45.

  4. (2,4,6-Trimethyl­phen­yl)boronic acid–triphenyl­phosphine oxide (1/1)

    PubMed Central

    Roşca, Sorin; Olaru, Marian; Raţ, Ciprian I.

    2012-01-01

    In the crystal structure of the title compound, C9H13BO2·C18H15OP, there are O—H⋯O hydrogen bonds between the O atom of triphenyl­phosphine oxide and one hy­droxy group of the boronic acid. Boronic acid mol­ecules form inversion-related hydrogen-bonded dimers in an R 2 2(8) motif. The structure is consolidated by inter­molecular C—H⋯O bonds and C—H⋯π inter­actions. PMID:22259536

  5. Apparatus for purifying arsine, phosphine, ammonia, and inert gases to remove Lewis acid and oxidant impurities therefrom

    DOEpatents

    Tom, Glenn M.; Brown, Duncan W.

    1991-01-08

    An apparatus for purifying a gaseous mixture comprising arsine, phosphine, ammonia, and/or inert gases, to remove Lewis acid and/or oxidant impurities therefrom, comprising a vessel containing a bed of a scavenger, the scavenger including a support having associated therewith an anion which is effective to remove such impurities, such anion being selected from one or more members of the group consisting of: (i) carbanions whose corresponding protonated compounds have a pK.sub.a value of from about 22 to about 36; and (ii) anions formed by reaction of such carbanions with the primary component of the mixture.

  6. IR and Raman study of Pt(II) and Pd(II) complexes of amino substituted phosphine oxides. Normal coordinate analysis

    NASA Astrophysics Data System (ADS)

    Trendafilova, N.; Georgieva, I.; Bauer, G.; Varbanov, S.; Dodoff, N.

    1997-06-01

    IR and Raman spectra of Pt(dapo) 2Cl 2 and Pd(dapo) 2Cl 2 (dapo=dimethyl(aminomethyl)phosphine oxide) have been measured in the 200-4000 cm -1 frequency range. Both the IR and Raman spectra show that dimethyl(aminomethyl)phosphine oxide ligands are monodentate coordinate. The results from the normal coordinate analysis calculations confirm the monodentate coordination of the ligands in agreement with some literature data. For Pd(dapo) 2Cl 2 complex the possibility for bidentate coordination of one dapo ligand is also considered.

  7. Inhibition of Sulfide Mineral Oxidation by Surface Coating Agents: Batch

    NASA Astrophysics Data System (ADS)

    Choi, J.; Ji, M. K.; Yun, H. S.; Park, Y. T.; Gee, E. D.; Lee, W. R.; Jeon, B.-H.

    2012-04-01

    Mining activities and mineral industries have impacted on rapid oxidation of sulfide minerals such as pyrite (FeS2) which leads to Acid Mine Drainage (AMD) formation. Some of the abandoned mines discharge polluted water without proper environmental remediation treatments, largely because of financial constraints in treating AMD. Magnitude of the problem is considerable, especially in countries with a long history of mining. As metal sulfides become oxidized during mining activities, the aqueous environment becomes acid and rich in many metals, including iron, lead, mercury, arsenic and many others. The toxic heavy metals are responsible for the environmental deterioration of stream, groundwater and soils. Several strategies to remediate AMD contaminated sites have been proposed. Among the source inhibition and prevention technologies, microencapsulation (coating) has been considered as a promising technology. The encapsulation is based on inhibition of O2 diffusion by surface coating agent and is expected to control the oxidation of pyrite for a long time. Potential of several surface coating agents for preventing oxidation of metal sulfide minerals from both Young-Dong coal mine and Il-Gwang gold mine were examined by conducting batch experiments and field tests. Powdered pyrite as a standard sulfide mineral and rock samples from two mine outcrops were mixed with six coating agents (KH2PO4, MgO and KMnO4 as chemical agents, and apatite, cement and manganite as mineral agents) and incubated with oxidizing agents (H2O2 or NaClO). Batch experiments with Young-Dong coal mine samples showed least SO42- production in presence of KMnO4 (16% sulfate production compared to no surface coating agents) or cement (4%) within 8 days. In the case of Il-Gwang mine samples, least SO42- production was observed in presence of KH2PO4 (8%) or cement (2%) within 8 days. Field-scale pilot tests at Il-Gwang site also showed that addition of KH2PO4 decreased sulfate production from 200 to

  8. Behavior of iron aluminides in oxidizing and sulfidizing environments

    SciTech Connect

    Tortorelli, P.F.; DeVan, J.H.; DiStefano, J.R.

    1989-01-01

    To date, use of iron aluminides based on Fe/sub 3/Al (less than or equal to30 at. % Al) or FeAl (30--50 at. % Al) for structural applications has been limited by their low ductility and poor fracture toughness at room temperature and inadequate strength above 600/degree/C. However, in recent years, a renewed effort has been devoted to the development of ductile iron aluminides with increased strength, particularly in view of their good potential for use in hostile environments. While it is expected that such aluminides will be able to form oxide scales for corrosion protection in oxidizing high temperature environments, resistance to degradation in oxidizing salt or oxidizing/sulfidizing gas environments has not been adequately addressed as a function of compositional and microstructural changes. This paper reviews and extends results for iron aluminides exposed to an oxidizing/sulfidizing gas and presents the first data for corrosion of this class of materials by an aggressive oxidizing molten nitrate salt of 48.5NaNO/sub 3/--50.5KNO/sub 3/--1Na/sub 2/O/sub 2/. 14 refs., 11 figs.

  9. Modeling of hydrogen sulfide oxidation in concrete corrosion products from sewer pipes.

    PubMed

    Jensen, Henriette Stokbro; Nielsen, Asbjørn Haaning; Hvitved-Jacobsen, Thorkild; Vollertsen, Jes

    2009-04-01

    Abiotic and biotic oxidation of hydrogen sulfide related to concrete corrosion was studied in corrosion products originating from a sewer manhole. The concrete corrosion products were suspended in an acidic solution, mimicking the conditions in the pore water of corroded concrete. The removal of hydrogen sulfide and dissolved oxygen was measured in parallel in the suspension, upon which the suspension was sterilized and the measurement repeated. The results revealed the biotic oxidation to be fast compared with the abiotic oxidation. The stoichiometry of the hydrogen sulfide oxidation was evaluated using the ratio between oxygen and hydrogen sulfide uptake. The ratio for the biotic oxidation pointed in the direction of elemental sulfur being formed as an intermediate in the oxidation of hydrogen sulfide to sulfuric acid. The experimental results were applied to suggest a hypothesis and a mathematical model describing the hydrogen sulfide oxidation pathway in a matrix of corroded concrete.

  10. Preparation of methylenediphosphine oxides and carbamoylmethyl-phosphines oxides from trimethylsilyl phosphinites

    SciTech Connect

    Chauzov, V.A.; Studnev, Yu.N.; Iznoskova, M.G.; Fokin, A.V.

    1987-06-20

    The conversion of diorganophosphonous acids to trimethylsilyl esters by the action of trimethylchlorosilane and trimethylamine and subsequent alkylation of the esters obtained by chloromethyldiorganophosphine oxides or N,N-dialkylamides of chloroacetic acid is shown to be a simple and effective method for the preparation of tetraorganomethylenediphosphine oxides and N,N-dialkylcarbamoylmethylphosphine oxides from diorganophosphinous acids. A full analysis of hydrogen 1 and phosphorus 31 NMR spectral data, performed in a number of deuterated solvents, is included.

  11. 'Low-acid' sulfide oxidation using nitrate-enriched groundwater

    NASA Astrophysics Data System (ADS)

    Donn, Michael; Boxall, Naomi; Reid, Nathan; Meakin, Rebecca; Gray, David; Kaksonen, Anna; Robson, Thomas; Shiers, Denis

    2016-04-01

    Acid drainage (AMD/ARD) is undoubtedly one of the largest environmental, legislative and economic challenges facing the mining industry. In Australia alone, at least 60m is spent on AMD related issues annually, and the global cost is estimated to be in the order of tens of billions US. Furthermore, the challenge of safely and economically storing or treating sulfidic wastes will likely intensify because of the trend towards larger mines that process increasingly higher volumes of lower grade ores and the associated sulfidic wastes and lower profit margins. While the challenge of managing potentially acid forming (PAF) wastes will likely intensify, the industrial approaches to preventing acid production or ameliorating the effects has stagnated for decades. Conventionally, PAF waste is segregated and encapsulated in non-PAF tips to limit access to atmospheric oxygen. Two key limitations of the 'cap and cover' approach are: 1) the hazard (PAF) is not actually removed; only the pollutant linkage is severed; and, 2) these engineered structures are susceptible to physical failure in short-to-medium term, potentially re-establishing that pollutant linkage. In an effort to address these concerns, CSIRO is investigating a passive, 'low-acid' oxidation mechanism for sulfide treatment, which can potentially produce one quarter as much acidity compared with pyrite oxidation under atmospheric oxygen. This 'low-acid' mechanism relies on nitrate, rather than oxygen, as the primary electron accepter and the activity of specifically cultured chemolithoautotrophic bacteria and archaea communities. This research was prompted by the observation that, in deeply weathered terrains of Australia, shallow (oxic to sub-oxic) groundwater contacting weathering sulfides are commonly inconsistent with the geochemical conditions produced by ARD. One key characteristic of these aquifers is the natural abundance of nitrate on a regional scale, which becomes depleted around the sulfide bodies, and

  12. Discovery of Brigatinib (AP26113), a Phosphine Oxide-Containing, Potent, Orally Active Inhibitor of Anaplastic Lymphoma Kinase.

    PubMed

    Huang, Wei-Sheng; Liu, Shuangying; Zou, Dong; Thomas, Mathew; Wang, Yihan; Zhou, Tianjun; Romero, Jan; Kohlmann, Anna; Li, Feng; Qi, Jiwei; Cai, Lisi; Dwight, Timothy A; Xu, Yongjin; Xu, Rongsong; Dodd, Rory; Toms, Angela; Parillon, Lois; Lu, Xiaohui; Anjum, Rana; Zhang, Sen; Wang, Frank; Keats, Jeffrey; Wardwell, Scott D; Ning, Yaoyu; Xu, Qihong; Moran, Lauren E; Mohemmad, Qurish K; Jang, Hyun Gyung; Clackson, Tim; Narasimhan, Narayana I; Rivera, Victor M; Zhu, Xiaotian; Dalgarno, David; Shakespeare, William C

    2016-05-26

    In the treatment of echinoderm microtubule-associated protein-like 4 (EML4)-anaplastic lymphoma kinase positive (ALK+) non-small-cell lung cancer (NSCLC), secondary mutations within the ALK kinase domain have emerged as a major resistance mechanism to both first- and second-generation ALK inhibitors. This report describes the design and synthesis of a series of 2,4-diarylaminopyrimidine-based potent and selective ALK inhibitors culminating in identification of the investigational clinical candidate brigatinib. A unique structural feature of brigatinib is a phosphine oxide, an overlooked but novel hydrogen-bond acceptor that drives potency and selectivity in addition to favorable ADME properties. Brigatinib displayed low nanomolar IC50s against native ALK and all tested clinically relevant ALK mutants in both enzyme-based biochemical and cell-based viability assays and demonstrated efficacy in multiple ALK+ xenografts in mice, including Karpas-299 (anaplastic large-cell lymphomas [ALCL]) and H3122 (NSCLC). Brigatinib represents the most clinically advanced phosphine oxide-containing drug candidate to date and is currently being evaluated in a global phase 2 registration trial.

  13. Mechanism of heterogeneous reaction of carbonyl sulfide on magnesium oxide.

    PubMed

    Liu, Yongchun; He, Hong; Xu, Wenqing; Yu, Yunbo

    2007-05-24

    Heterogeneous reaction of carbonyl sulfide (OCS) on magnesium oxide (MgO) under ambient conditions was investigated by in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), quadrupole mass spectrometer (QMS), and density functional theory (DFT) calculations. It reveals that OCS can be catalytically hydrolyzed by surface hydroxyl on MgO to produce carbon dioxide (CO2) and hydrogen sulfide (H2S), and then H2S can be further catalytically oxidized by surface oxygen or gaseous oxygen on MgO to form sulfite (SO3(2-)) and sulfate (SO4(2-)). Hydrogen thiocarbonate (HSCO2-) was found to be the crucial intermediate. Surface hydrogen sulfide (HS), sulfur dioxide (SO2), and surface sulfite (SO3(2-)) were also found to be intermediates for the formation of sulfate. Furthermore, the surface hydroxyl contributes not only to the formation of HSCO2- but also to HSCO2- decomposition. On the basis of experimental results, the heterogeneous reaction mechanism of OCS on MgO was discussed.

  14. High temperature hydrogen sulfide removal with tin oxide

    SciTech Connect

    Karpuk, M.E.; Copeland, R.J.; Feinberg, D.; Wickham, D.; Windecker, B.; Yu, J.

    1993-09-01

    The system is based on the absorption of hydrogen sulfide (H{sub 2}S) by stannic (tin) oxide. Two sorbents are required, the first sorbent is tin oxide and the second sorbent is a zinc oxide based material (i.e., zinc ferrite or zinc titanate) which is regenerated by air producing SO{sub 2}. TDA`s process carries out a modified Claus reaction to reduce the SO{sub 2} from the second sorbent generation to elemental sulfur. In this case the sulfided stannic oxide forms stannous sulfide (SnS) which reduces the SO{sub 2}. The absorption by SnO{sub 2} could remove over 90% of the H{sub 2}S from typical coal gas streams, but we use zinc ferrite (or zinc titanate), (a) to reduce H{sub 2}S to less than 20 ppM and (b) as a source of SO{sub 2} in regeneration. Due to stoichiometry of regeneration we want to remove half of the H{sub 2}S by SnO{sub 2} and the remainder by the second sorbent. The reactions with stannic oxide minimize the heat released during H{sub 2}S removal and regeneration. The absorption by SnO{sub 2} is slightly endothermic and cools the gas stream by less that 5{degrees}F (2.8{degrees}C) during absorption. Regeneration with SO{sub 2} is exothermic but releases only 11% of the heat that is liberated in regenerating the ZnO. For a nominal 6.5:1 steam to air the regeneration of ZnO increases the temperature by {approx_equal}400{degrees}F. The regeneration of SnO{sub 2} increases the temperature by less than 50{degrees}F (28{degrees}C) in the same gas flow.

  15. Phototrophic sulfide oxidation: environmental insights and a method for kinetic analysis

    PubMed Central

    Hanson, Thomas E.; Luther, George W.; Findlay, Alyssa J.; MacDonald, Daniel J.; Hess, Daniel

    2013-01-01

    Previously, we presented data that indicated microbial sulfide oxidation would out-compete strictly chemical, abiotic sulfide oxidation reactions under nearly all conditions relevant to extant ecosystems (Luther et al., 2011). In particular, we showed how anaerobic microbial sulfide oxidation rates were several orders of magnitude higher than even metal catalyzed aerobic sulfide oxidation processes. The fact that biotic anaerobic sulfide oxidation is kinetically superior to abiotic reactions implies that nearly all anaerobic and sulfidic environments should host microbial populations that oxidize sulfide at appreciable rates. This was likely an important biogeochemical process during long stretches of euxinia in the oceans suggested by the geologic record. In particular, phototrophic sulfide oxidation allows the utilization of carbon dioxide as the electron acceptor suggesting that this process should be particularly widespread rather than relying on the presence of other chemical oxidants. Using the Chesapeake Bay as an example, we argue that phototrophic sulfide oxidation may be more important in many environments than is currently appreciated. Finally, we present methodological considerations to assist other groups that wish to study this process. PMID:24391629

  16. Biogenesis of reactive sulfur species for signaling by hydrogen sulfide oxidation pathways.

    PubMed

    Mishanina, Tatiana V; Libiad, Marouane; Banerjee, Ruma

    2015-07-01

    The chemical species involved in H2S signaling remain elusive despite the profound and pleiotropic physiological effects elicited by this molecule. The dominant candidate mechanism for sulfide signaling is persulfidation of target proteins. However, the relatively poor reactivity of H2S toward oxidized thiols, such as disulfides, the low concentration of disulfides in the reducing milieu of the cell and the low steady-state concentration of H2S raise questions about the plausibility of persulfide formation via reaction between an oxidized thiol and a sulfide anion or a reduced thiol and oxidized hydrogen disulfide. In contrast, sulfide oxidation pathways, considered to be primarily mechanisms for disposing of excess sulfide, generate a series of reactive sulfur species, including persulfides, polysulfides and thiosulfate, that could modify target proteins. We posit that sulfide oxidation pathways mediate sulfide signaling and that sulfurtransferases ensure target specificity.

  17. Biogenesis of reactive sulfur species for signaling by hydrogen sulfide oxidation pathways

    PubMed Central

    Mishanina, Tatiana V; Libiad, Marouane; Banerjee, Ruma

    2016-01-01

    The chemical species involved in H2S signaling remain elusive despite the profound and pleiotropic physiological effects elicited by this molecule. The dominant candidate mechanism for sulfide signaling is persulfidation of target proteins. However, the relatively poor reactivity of H2S toward oxidized thiols, such as disulfides, the low concentration of disulfides in the reducing milieu of the cell and the low steady-state concentration of H2S raise questions about the plausibility of persulfide formation via reaction between an oxidized thiol and a sulfide anion or a reduced thiol and oxidized hydrogen disulfide. In contrast, sulfide oxidation pathways, considered to be primarily mechanisms for disposing of excess sulfide, generate a series of reactive sulfur species, including persulfides, polysulfides and thiosulfate, that could modify target proteins. We posit that sulfide oxidation pathways mediate sulfide signaling and that sulfurtransferases ensure target specificity. PMID:26083070

  18. Synthesis of Nanoporous Metals, Oxides, Carbides, and Sulfides: Beyond Nanocasting.

    PubMed

    Luc, Wesley; Jiao, Feng

    2016-07-19

    metal oxides with bimodal pore size distributions can be obtained. Combining nanocasting with chemical etching, a cobalt oxide with a hierarchical porous structure was synthesized, which possessed a surface area up to 250 m(2) g(-1), representing the highest surface area reported to date for nanoporous cobalt oxides. Lastly, this Account also covers the syntheses of nanoporous metal carbides and sulfides. The combination of in situ carburization and nanocasting enabled the syntheses of two ordered nanoporous metal carbides, Mo2C and W2C. For nanoporous metal sulfides, an "oxide-to-sulfide" synthetic strategy was proposed to address the large volume change issue of converting metal nitrate precursors to metal sulfide products in nanocasting. The successful syntheses of ordered nanoporous FeS2, CoS2, and NiS2 demonstrated the feasibility of the "oxide-to-sulfide" method. Concluding remarks include a summary of recent advances in the syntheses of nanoporous metal-based solids and a brief discussion of future opportunities in the hope of stimulating new interests and ideas.

  19. Oxidation sulfidation resistance of Fe-Cr-Ni alloys

    DOEpatents

    Natesan, Ken; Baxter, David J.

    1984-01-01

    High temperature resistance of Fe-Cr-Ni alloy compositions to oxidative and/or sulfidative conditions is provided by the incorporation of about 1-8 wt. % of Zr or Nb and results in a two-phase composition having an alloy matrix as the first phase and a fine grained intermetallic composition as the second phase. The presence and location of the intermetallic composition between grains of the matrix provides mechanical strength, enhanced surface scale adhesion, and resistance to corrosive attack between grains of the alloy matrix at temperatures of 500.degree.-1000.degree. C.

  20. Improved oxidation sulfidation resistance of Fe-Cr-Ni alloys

    DOEpatents

    Natesan, K.; Baxter, D.J.

    1983-07-26

    High temperature resistance of Fe-Cr-Ni alloy compositions to oxidative and/or sulfidative conditions is provided by the incorporation of about 1 to 8 wt % of Zr or Nb and results in a two-phase composition having an alloy matrix as the first phase and a fine grained intermetallic composition as the second phase. The presence and location of the intermetallic composition between grains of the matrix provides mechanical strength, enhanced surface scale adhesion, and resistance to corrosive attack between grains of the alloy matrix at temperatures of 500 to 1000/sup 0/C.

  1. Sulfidation mechanism for zinc oxide nanoparticles and the effect of sulfidation on their solubility.

    PubMed

    Ma, Rui; Levard, Clément; Michel, F Marc; Brown, Gordon E; Lowry, Gregory V

    2013-03-19

    Environmental transformations of nanoparticles (NPs) affect their properties and toxicity potential. Sulfidation is an important transformation process affecting the fate of NPs containing metal cations with an affinity for sulfide. Here, the extent and mechanism of sulfidation of ZnO NPs were investigated, and the properties of resulting products were carefully characterized. Synchrotron X-ray absorption spectroscopy and X-ray diffraction analysis reveal that transformation of ZnO to ZnS occurs readily at ambient temperature in the presence of inorganic sulfide. The extent of sulfidation depends on sulfide concentration, and close to 100% conversion can be obtained in 5 days given sufficient addition of sulfide. X-ray diffraction and transmission electron microscopy showed formation of primarily ZnS NPs smaller than 5 nm, indicating that sulfidation of ZnO NPs occurs by a dissolution and reprecipitation mechanism. The solubility of partially sulfidized ZnO NPs is controlled by the remaining ZnO core and not quenched by a ZnS shell formed as was observed for partially sulfidized Ag NPs. Sulfidation also led to NP aggregation and a decrease of surface charge. These changes suggest that sulfidation of ZnO NPs alters the behavior, fate, and toxicity of ZnO NPs in the environment. The reactivity and fate of the resulting <5 nm ZnS particles remains to be determined.

  2. Corrosion of concrete sewers--the kinetics of hydrogen sulfide oxidation.

    PubMed

    Vollertsen, Jes; Nielsen, Asbjørn Haaning; Jensen, Henriette Stokbro; Wium-Andersen, Tove; Hvitved-Jacobsen, Thorkild

    2008-05-01

    Hydrogen sulfide absorption and oxidation by corroding concrete surfaces was quantified in a test rig consisting of 6 concrete pipes operated under sewer conditions. The test rig was placed in an underground sewer monitoring station with access to fresh wastewater. Hydrogen sulfide gas was injected into the pipe every 2nd hour to peak concentrations around 1000 ppm. After some months of operation, the hydrogen sulfide became rapidly oxidized by the corroding concrete surfaces. At hydrogen sulfide concentrations of 1000 ppm, oxidation rates as high as 1 mg S m(-2) s(-1) were observed. The oxidation process followed simple nth order kinetics with a process order of 0.45-0.75. Extrapolating the results to gravity sewer systems showed that hydrogen sulfide oxidation by corroding concrete is a fast process compared to the release of hydrogen sulfide from the bulk water, resulting in low gas concentrations compared with equilibrium. Balancing hydrogen sulfide release with hydrogen sulfide oxidation at steady state conditions demonstrated that significant corrosion rates--several millimeters of concrete per year--can potentially occur at hydrogen sulfide gas phase concentrations well below 5-10 ppm. The results obtained in the study advances the knowledge on prediction of sewer concrete corrosion and the extent of odor problems.

  3. High temperature hydrogen sulfide removal with tin oxide

    SciTech Connect

    Copeland, R.J.; Feinberg, D.; Wickham, D.; Windecker, B.; Yu, J.

    1993-06-01

    This Phase II SBIR contract is developing a sorbent and process which removes H{sub 2}S from hot gasified coal and generates sulfur during regeneration of the sorbent. The process can be used with any type of reactor (e.g., fixed or moving bed) and any gasifier (e.g., KRW or Texaco) and shows lower costs that competing H{sub 2}S removal processes. TDA Research`s (TDA) process uses a regenerable stannic oxide-based (SnO{sub 2}) sorbent as the first sorbent and zinc ferrite (or zinc titanate) as a second sorbent to remove H{sub 2}S to very low concentrations. The process converts the sulfides from both sorbents to elemental sulfur, a commercial product which is easy to store and transport. The object of this phase is to develop chemically active, high sulfur loadings, and durable stannic oxide sorbents and to demonstrate the process at the bench scale.

  4. Three enzymatic activities catalyze the oxidation of sulfide to thiosulfate in mammalian and invertebrate mitochondria.

    PubMed

    Hildebrandt, Tatjana M; Grieshaber, Manfred K

    2008-07-01

    Hydrogen sulfide is a potent toxin of aerobic respiration, but also has physiological functions as a signalling molecule and as a substrate for ATP production. A mitochondrial pathway catalyzing sulfide oxidation to thiosulfate in three consecutive reactions has been identified in rat liver as well as in the body-wall tissue of the lugworm, Arenicola marina. A membrane-bound sulfide : quinone oxidoreductase converts sulfide to persulfides and transfers the electrons to the ubiquinone pool. Subsequently, a putative sulfur dioxygenase in the mitochondrial matrix oxidizes one persulfide molecule to sulfite, consuming molecular oxygen. The final reaction is catalyzed by a sulfur transferase, which adds a second persulfide from the sulfide : quinone oxidoreductase to sulfite, resulting in the final product thiosulfate. This role in sulfide oxidation is an additional physiological function of the mitochondrial sulfur transferase, rhodanese.

  5. Complete oxidation of solid phase sulfides by manganese and bacteria in anoxic marine sediments

    SciTech Connect

    Aller, R.C.; Rude, P.D. )

    1988-03-01

    During the physical or biological reworking of surficial marine sediments, metal oxides are often brought into contact with both solid and dissolved sulfides. Experiments simulating these mixing processes demonstrate that in natural sediments Mn-oxides can completely oxidize solid phase sulfides to SO{sup =}{sub 4} under anoxic conditions. The major source of sulfur is probably acid volatile sulfide. Minerals containing Mn{sup +4} are apparently more effective than Mn{sup +3} in driving the oxidation. There is slight or no evidence for complete sulfide oxidation by Fe-oxides under similar conditions. The reaction is inhibited by DNP (dinitrophenol) and Azide, implying biological mediation by a group of chemolithotrophic bacteria such as the thiobacilli, having a well-organized cytochrome system, oxidative phosphorylation coupled with sulfide oxidation, and possibly autotrophic CO{sub 2} fixation. Lack of sensitivity to chlorate suggests that a NO{sup {minus}}{sub 3} reductase complex is not involved. Because of metal reduction and the overall stoichiometry of reaction, this sulfide oxidation causes a rise in pH in contrast to oxidation by O{sub 2}. Alkalinity is also simultaneously depleted by Mn, Ca carbonate precipitation. Both manganoan kutnahorite and manganoan calcite are observed to form rapidly (days) during Mn reduction. The oxidation of sulfides by Mn-oxides is likely to be important, but highly variable, in organic-rich shelf sediments and environments such as hydrothermal vents where sulfidic plumes contact oxidized metals. A substantial proportion of sedimentary sulfide may be oxidized and Mn reduced by this pathway, particularly in bioturbated sediments. The relative roles of lithotrophic (S) and heterotrophic (C) Mn-reduction in marine sediments are presently unknown.

  6. Heterogeneous oxidation of carbonyl sulfide on atmospheric particles and alumina.

    PubMed

    He, Hong; Liu, Junfeng; Mu, Yujing; Yu, Yunbo; Chen, Meixue

    2005-12-15

    Heterogeneous oxidation of carbonyl sulfide (OCS) on atmospheric particles and alumina (Al2O3) was investigated in a closed system and a flowed system using in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). At room temperature, OCS could be catalytically oxidized on the surface of atmospheric particles and Al2O3 to form gas-phase CO2 and surface sulfate (SO4(2-)), sulfite (HSO3-), and hydrogen carbonate (HCO3-) species. The real atmospheric particles were characterized using X-ray fluorescence (XRF) and the Brunauer-Emmett-Teller (BET) method. As a simplified model, Al2O3 was used to study the reaction mechanism of heterogeneous oxidation of OCS. The hydrogen thiocarbonate surface (HSCO2-) species, an intermediate formed in the reaction of OCS with surface hydroxyl (OH), could only be observed on the prereduced Al2O3 sample. The experimental results also indicate that surface oxygen containing species on the atmospheric particle sample and the Al2O3 sample might be the key reactant for OCS oxidation. A reaction mechanism of heterogeneous oxidation of OCS on Al2O3 surface is discussed.

  7. Evaluation of long-term sulfide oxidation processes within pyrrhotite-rich tailings, Lynn Lake, Manitoba

    NASA Astrophysics Data System (ADS)

    Gunsinger, M. R.; Ptacek, C. J.; Blowes, D. W.; Jambor, J. L.

    2006-02-01

    Oxidation reactions have depleted sulfide minerals in the shallow tailings and have generated sulfate- and metal-rich pore water throughout the East Tailings Management Area (ETMA) at Lynn Lake, Manitoba, Canada. Information concerning the tailings geochemistry and mineralogy suggest the sulfide oxidation processes have reached an advanced stage in the area proximal to the point of tailings discharge. In contrast, the distal tailings, or slimes area, have a higher moisture content close to the impoundment surface, thereby impeding the ingress of oxygen and limiting sulfide oxidation. Numerical modelling of sulfide oxidation indicates the maximum rate of release for sulfate, Fe, and Ni occurred shortly after tailings deposition ceased. Although the sulfide minerals have been depleted in the very shallow tailings, the modelling suggests that sulfide oxidation will continue for hundreds and possibly thousands of years. The combination of sulfide minerals, principally pyrrhotite, that is susceptible to weathering processes and the relatively dry, coarse-grained nature of the tailings have resulted in the formation of a massive-hardpan layer in the proximal area of the ETMA. Because extensive accumulations of secondary oxyhydroxides of ferric iron are already present, remediation strategies for the ETMA should focus on mitigating the release of sulfide oxidation products rather than on preventing further oxidation.

  8. Arsenic Bioremediation by Biogenic Iron Oxides and Sulfides

    PubMed Central

    Couture, Raoul-Marie; Van Cappellen, Philippe; Corkhill, Claire L.; Charnock, John M.; Polya, David A.; Vaughan, David; Vanbroekhoven, Karolien; Lloyd, Jonathan R.

    2013-01-01

    Microcosms containing sediment from an aquifer in Cambodia with naturally elevated levels of arsenic in the associated groundwater were used to evaluate the effectiveness of microbially mediated production of iron minerals for in situ As remediation. The microcosms were first incubated without amendments for 28 days, and the release of As and other geogenic chemicals from the sediments into the aqueous phase was monitored. Nitrate or a mixture of sulfate and lactate was then added to stimulate biological Fe(II) oxidation or sulfate reduction, respectively. Without treatment, soluble As concentrations reached 3.9 ± 0.9 μM at the end of the 143-day experiment. However, in the nitrate- and sulfate-plus-lactate-amended microcosms, soluble As levels decreased to 0.01 and 0.41 ± 0.13 μM, respectively, by the end of the experiment. Analyses using a range of biogeochemical and mineralogical tools indicated that sorption onto freshly formed hydrous ferric oxide (HFO) and iron sulfide mineral phases are the likely mechanisms for As removal in the respective treatments. Incorporation of the experimental results into a one-dimensional transport-reaction model suggests that, under conditions representative of the Cambodian aquifer, the in situ precipitation of HFO would be effective in bringing groundwater into compliance with the World Health Organization (WHO) provisional guideline value for As (10 ppb or 0.13 μM), although soluble Mn release accompanying microbial Fe(II) oxidation presents a potential health concern. In contrast, production of biogenic iron sulfide minerals would not remediate the groundwater As concentration below the recommended WHO limit. PMID:23666325

  9. Oxidation kinetics of zinc sulfide: determination of intrinsic rate constant

    SciTech Connect

    Prabhu, G.M.

    1983-06-01

    An initial reaction rate study was done with the help of a thermogravimetric technique. Energy dispersive x-ray analyses on partially oxidized zinc sulfide pellets with a sintered porosity of 72.4% indicated flat sulfur intensity profiles within pellets reacted below 560/sup 0/C, which suggested a homogeneous reaction mechanism. Therefore, reaction temperatures below 600/sup 0/C were chosen for the reaction rate studies. Initial reaction rate studies on 72.4, 58.2, and 34.0% porous, cylindrical zinc sulfide pellets and the corresponding Arrhenius plot suggested chemical control in the temperature range from 480 to 565/sup 0/C. The corresponding intrinsic rate constant is correlated as k = 3.45 x 10/sup 17/ exp (- 86051/RT) cm/s. The variation in sulfur intensity within sintered pellets having a porosity of 72.4% that were reacted at temperatures above 560/sup 0/C indicated that the pore diffusion resistance gradually became comparable to the chemical reaction resistance leading to a mixed control mechanism above 570/sup 0/C. The critical temperature at which this shift occurred, increased with pellet porosity.

  10. Growth kinetics of hydrogen sulfide oxidizing bacteria in corroded concrete from sewers.

    PubMed

    Jensen, Henriette Stokbro; Lens, Piet N L; Nielsen, Jeppe L; Bester, Kai; Nielsen, Asbjørn Haaning; Hvitved-Jacobsen, Thorkild; Vollertsen, Jes

    2011-05-30

    Hydrogen sulfide oxidation by microbes present on concrete surfaces of sewer pipes is a key process in sewer corrosion. The growth of aerobic sulfur oxidizing bacteria from corroded concrete surfaces was studied in a batch reactor. Samples of corrosion products, containing sulfur oxidizing bacteria, were suspended in aqueous solution at pH similar to that of corroded concrete. Hydrogen sulfide was supplied to the reactor to provide the source of reduced sulfur. The removal of hydrogen sulfide and oxygen was monitored. The utilization rates of both hydrogen sulfide and oxygen suggested exponential bacterial growth with median growth rates of 1.25 d(-1) and 1.33 d(-1) as determined from the utilization rates of hydrogen sulfide and oxygen, respectively. Elemental sulfur was found to be the immediate product of the hydrogen sulfide oxidation. When exponential growth had been achieved, the addition of hydrogen sulfide was terminated leading to elemental sulfur oxidation. The ratio of consumed sulfur to consumed oxygen suggested that sulfuric acid was the ultimate oxidation product. To the knowledge of the authors, this is the first study to determine the growth rate of bacteria involved in concrete corrosion with hydrogen sulfide as source of reduced sulfur.

  11. Hydrogen Sulfide, Oxidative Stress and Periodontal Diseases: A Concise Review

    PubMed Central

    Greabu, Maria; Totan, Alexandra; Miricescu, Daniela; Radulescu, Radu; Virlan, Justina; Calenic, Bogdan

    2016-01-01

    In the past years, biomedical research has recognized hydrogen sulfide (H2S) not only as an environmental pollutant but also, along with nitric oxide and carbon monoxide, as an important biological gastransmitter with paramount roles in health and disease. Current research focuses on several aspects of H2S biology such as the biochemical pathways that generate the compound and its functions in human pathology or drug synthesis that block or stimulate its biosynthesis. The present work addresses the knowledge we have to date on H2S production and its biological roles in the general human environment with a special focus on the oral cavity and its involvement in the initiation and development of periodontal diseases. PMID:26805896

  12. Working with nitric oxide and hydrogen sulfide in biological systems

    PubMed Central

    Yuan, Shuai; Kevil, Christopher G.

    2014-01-01

    Nitric oxide (NO) and hydrogen sulfide (H2S) are gasotransmitter molecules important in numerous physiological and pathological processes. Although these molecules were first known as environmental toxicants, it is now evident that that they are intricately involved in diverse cellular functions with impact on numerous physiological and pathogenic processes. NO and H2S share some common characteristics but also have unique chemical properties that suggest potential complementary interactions between the two in affecting cellular biochemistry and metabolism. Central among these is the interactions between NO, H2S, and thiols that constitute new ways to regulate protein function, signaling, and cellular responses. In this review, we discuss fundamental biochemical principals, molecular functions, measurement methods, and the pathophysiological relevance of NO and H2S. PMID:25550314

  13. Luminescent sulfides and solution-deposited oxide thin films

    NASA Astrophysics Data System (ADS)

    Anderson, Jeremy T.

    Solid state luminescent sulfides are prepared as powders in order to elucidate the relationship between structure and light emission. While the sulfides studied in this dissertation are known phosphors, materials are investigated in a variety of new ways. Elementary properties and structures of MgS are reviewed, and preparation of MgS is described with sufficient detail that it may be reproduced in laboratories worldwide. Luminescence of MgS:Eu is evaluated, primarily by interpretation of published work. Solid pellets of MgS:Eu are created for the purpose of depositing thin-film layers by physical vapor deposition, and incorporating the phosphor layer within ACTFEL structures. Fabricated devices are found to exhibit bright ACTFEL luminescence--the brightest known for MgS. Similarly, MgS films are doped with a variety of lanthanide atoms to investigate the hot-electron distribution in MgS layers during device operation. The system BaGa2S4--SrGa 2S4 is evaluated for mutual solid phase solubility. Addition of Eu2+ causes each of these phases to photoluminescence. The emission energies (and therefore colors) are adjusted according to composition. Thin-film oxides are deposited from solution sources. Solution-deposited ZnO serves as the semiconductor layer in transparent thin-film transistor devices. A new class of dielectric material is also developed by solution methods. HafSOx and ZircSOx films, and derivative compositions, are evaluated in simple capacitor structures and demonstrated in functioning transistor devices. High-resolution nanolaminate structures are also constructed from this class of materials. From the knowledge and experience of developing oxide thin-films, more general chemical strategies are expressed.

  14. Sulfur isotope effects during sulfide oxidation to sulfate: model meets reality

    NASA Astrophysics Data System (ADS)

    Abdulrahman Beiruti, Zainab; Brunner, Benjamin; Hubert, Casey; Ferdelman, Timothy

    2010-05-01

    The combination of laboratory experiments and numerical models in the study of stable sulfur isotope fractionation is a useful tool that contributes to a better understanding of sulfur transformations in the environment. Because sulfur isotope fractionation during oxidative sulfur cycling is expected to yield much smaller isotope fractionation than sulfate reduction, sulfur isotope effects during sulfide oxidation have not received much attention. Nevertheless, in situations where sulfide oxidation dominates over other sulfur transformations, the imprint of these small isotope effects is preserved. These isotope imprints provide crucial information about the biogeochemical conditions under which sulfide oxidation occurred. Unlike sulfate reduction, where sulfur intermediates are hardly accumulated and rarely released to the environment, sulfide oxidation to sulfate often involves accumulation of intra- and extracellular elemental sulfur as an intermediate, which may be accessed later for oxidation to sulfate by the same or different organisms. The accumulation and consumption of a pool of elemental sulfur complicates the interpretation of sulfur isotope effects during sulfide oxidation, as kinetic sulfur isotope effects from oxidation of sulfide to elemental sulfur are superimposed by sulfur isotope exchange between sulfide and elemental sulfur, a pool that is simultaneously altered by isotope effects related to the oxidation of elemental sulfur to sulfate. We derived a numerical isotope mass balance model that combines the rates for sulfur isotope exchange between sulfide and elemental sulfur, oxidation of sulfide to elemental sulfur and oxidation of elemental sulfur to sulfate with the respective isotope effects. With this model, we can predict the evolution of the isotope composition of sulfide, elemental sulfur, and sulfate during a sulfide oxidation experiment. Sensitivity tests show that these isotope trends not only strongly depend on the size of isotope

  15. Sulfide oxidation by a noncanonical pathway in red blood cells generates thiosulfate and polysulfides.

    PubMed

    Vitvitsky, Victor; Yadav, Pramod K; Kurthen, Angelika; Banerjee, Ruma

    2015-03-27

    A cardioprotectant at low concentrations, H2S is a toxin at high concentrations and inhibits cytochrome c oxidase. A conundrum in H2S homeostasis is its fate in red blood cells (RBCs), which produce H2S but lack the canonical mitochondrial sulfide oxidation pathway for its clearance. The sheer abundance of RBCs in circulation enhances the metabolic significance of their clearance strategy for H2S, necessary to avoid systemic toxicity. In this study, we demonstrate that H2S generation by RBCs is catalyzed by mercaptopyruvate sulfurtransferase. Furthermore, we have discovered the locus of sulfide oxidation in RBCs and describe a new role for an old protein, hemoglobin, which in the ferric or methemoglobin state binds H2S and oxidizes it to a mixture of thiosulfate and hydropolysulfides. Our study reveals a previously undescribed route for the biogenesis of hydropolysulfides, which are increasingly considered important for H2S-based signaling, but their origin in mammalian cells is unknown. An NADPH/flavoprotein oxidoreductase system restores polysulfide-carrying hemoglobin derivatives to ferrous hemoglobin, thus completing the methemoglobin-dependent sulfide oxidation cycle. Methemoglobin-dependent sulfide oxidation in mammals is complex and has similarities to chemistry reported for the dissolution of iron oxides in sulfidic waters and during bioleaching of metal sulfides. The catalytic oxidation of H2S by hemoglobin explains how RBCs maintain low steady-state H2S levels in circulation, and suggests that additional hemeproteins might be involved in sulfide homeostasis in other tissues.

  16. Microbial oxidation of soluble sulfide in produced water from the Bakkeen Sands

    SciTech Connect

    Gevertz, D.; Zimmerman, S.; Jenneman, G.E.

    1995-12-31

    The presence of soluble sulfide in produced water results in problems for the petroleum industry due to its toxicity, odor, corrosive nature, and potential for wellbore plugging. Sulfide oxidation by indigenous nitrate-reducing bacteria (NRB) present in brine collected from wells at the Coleville Unit (CVU) in Saskatchewan, Canada, was investigated. Sulfide oxidation took place readily when nitrate and phosphate were added to brine enrichment cultures, resulting in a decrease in sulfide levels of 99-165 ppm to nondetectable levels (< 3.3 ppm). Produced water collected from a number of producing wells was screened to determine the time required for complete sulfide oxidation, in order to select candidate wells for treatment. Three wells were chosen, based on sulfide removal in 48 hours or less. These wells were treated down the backside of the annulus with a solution containing 10 mM KNO{sub 3} and 100 {mu}M NaH{sub 2}PO{sub 4}. Following a 24- to 72-hour shut-in, reductions in pretreatment sulfide levels of greater than 90% were observed for two of the wells, as well as sustained sulfide reductions of 50% for at least two days following startup. NRB populations in the produced brine were observed to increase significantly following treatment, but no significant increases in sulfate-reducing bacteria were observed. These results demonstrate the technical feasibility of stimulating indigenous populations of NRB to remediate and control sulfide in produced brine.

  17. Selective Catalytic Oxidation of Hydrogen Sulfide--IGCC Applications

    SciTech Connect

    Alvin, M.A.; Stevens, R.W.; Newby, R.A.; Keairns, D.L.

    2006-09-01

    Selective catalytic oxidation of hydrogen sulfide (SCOHS) to elemental sulfur using activated carbon and NETL-processed metal oxide catalyst systems has been investigated under bench-scale, simulated pressurized IGCC conditions for use in dry and humid gas cleaning process applications. For this technology to be successful, a 20% cost effective advantage and 1 percentage-point plant efficiency gain over current commercial technology, and <10-15 ppm total gas phase sulfur release into the effluent gas stream must be demonstrated. The results of our bench-scale catalyst/sorbent desulfurization and regeneration efforts for both bulk and polishing sulfur removal indicate that direct selective catalytic oxidation of H2S to elemental sulfur utilizing current activated carbon systems occurs only under conditions of low syngas temperature (<150°C), and in syngas effluent streams containing a low water and CO content. Thus the SCOHS desulfurization process is considered to be only potentially feasible for use in dry gas cleaning conditions for IGCC applications where syngas-CO is shifted to CO2, and regeneration of the catalyst occurs through heating in warm CO2, with simultaneous CO2 sequestration. SCOHS is not considered as a candidate desulfurization approach for use in humid IGCC gas cleaning applications.

  18. Catalytic Enantioselective Carbon-Oxygen Bond Formation: Phosphine-Catalyzed Synthesis of Benzylic Ethers via the Oxidation of Benzylic C-H Bonds.

    PubMed

    Ziegler, Daniel T; Fu, Gregory C

    2016-09-21

    Benzylic alcohols and ethers are common subunits in bioactive molecules, as well as useful intermediates in organic chemistry. In this Communication, we describe a new approach to the enantioselective synthesis of benzylic ethers through the chiral phosphine-catalyzed coupling of two readily available partners, γ-aryl-substituted alkynoates and alcohols, under mild conditions. In this process, the alkynoate partner undergoes an internal redox reaction. Specifically, the benzylic position is oxidized with good enantioselectivity, and the alkyne is reduced to the alkene.

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

    NASA Technical Reports Server (NTRS)

    Fry, B.; Ruf, W.; Gest, H.; Hayes, J. M.

    1988-01-01

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

  20. Joint Recovery of f-Elements Using Solvent Based on Carbamoyl-phosphine Oxides Heading Toward ORGA-Process

    SciTech Connect

    Ozawa, M.; Babain, V.; Shadrin, A.; Strelkov, S.; Kiseleva, R.; Murzin, A.

    2007-07-01

    Development of the recovery system which allows realizing joint recovery of all the actinides from the HLW is one of the relevant questions in radiochemistry. Carbamoyl-phosphine oxides (CMPO) were proposed and studied as extractant for rare-earth and transplutonium elements (RE and TPE) recovery from HLW with high acidity, for example TRUEX- and SETFICS-process. Organic system CMPO with TBP in kerosene is usually used as a solvent. However, low solubility of actinide adducts with CMPO results in third phase formation when the actinides concentration in organic phase is high. Application of fluorinated polar diluents increases the solubility of CMPO adducts with actinides in organic phase. It was shown that solvent based on carbamoyl-phosphonate in fluorinated polar diluents allows to recover both uranium and minor actinides concurrently, and there was no precipitation or third phase formation even at high uranium concentration in organic phase. The f-elements joint recovery process based on this solvent was proposed. Solvent containing octyl-phenyl-N,N-di-isobutyl-carbamoyl-methylene-phosphine oxide (O{phi}D[iB]CMPO) in polar diluent meta-nitro-benzo-trifluoride (fluoro-pole-732) was screened out for these studies. And, combined use of them with TBP modifier allows to provide uranium and europium (americium) high recovery characteristics concurrently with an opportunity of attainment of f-elements high concentration in organic phase. As it was indicated, precipitates or third phase was absent even when uranium content in organic phase was 100 g/l. Recovery efficiency to europium remained sufficiently high for its effective recovery. Organic phase saturation about 100% from theoretical attains in europium recovery with this system. Increasing of (O{phi}D[iB]CMPO) concentration in recovery system from 0.2 to 0.8 M results in europium content increasing in organic phase, but no third phase formation is observed. The highest possible europium content in organic phase

  1. Potential biological chemistry of hydrogen sulfide (H2S) with the nitrogen oxides.

    PubMed

    Bruce King, S

    2013-02-01

    Hydrogen sulfide, an important gaseous signaling agent generated in numerous biological tissues, influences many physiological processes. This biological profile seems reminiscent of nitric oxide, another important endogenously synthesized gaseous signaling molecule. Hydrogen sulfide reacts with nitric oxide or oxidized forms of nitric oxide and nitric oxide donors in vitro to form species that display distinct biology compared to both hydrogen sulfide and NO. The products of these interesting reactions may include small-molecule S-nitrosothiols or nitroxyl, the one-electron-reduced form of nitric oxide. In addition, thionitrous acid or thionitrite, compounds structurally analogous to nitrous acid and nitrite, may constitute a portion of the reaction products. Both the chemistry and the biology of thionitrous acid and thionitrite, compared to nitric oxide or hydrogen sulfide, remain poorly defined. General mechanisms for the formation of S-nitrosothiols, nitroxyl, and thionitrous acid based upon the ability of hydrogen sulfide to act as a nucleophile and a reducing agent with reactive nitric oxide-based intermediates are proposed. Hydrogen sulfide reactivity seems extensive and could have an impact on numerous areas of redox-controlled biology and chemistry, warranting more work in this exciting and developing area.

  2. Silylated Phosphines and Phosphoranimines.

    DTIC Science & Technology

    1986-10-10

    react smoothly with both substrates. Cyclopentadlene, for example, affords a .. ,. Diels - Alder adduct in each case. - *..:*. V.., 7., 7 NSiNe 3 PhPC1 2... condensation with ELECTEm LU ractie phsphies.Some new 2,2-addition and --J oxidation reactions of the P-C systems. Nf-HR.O 2318 LA... R NP(-NR)=CHR...groups, transilylation, and condensation with .. reactive phosphines. Some new 1,2-addition and oxidation reactions of the P=C systems, R2 NP=CHR,R NP(=NR

  3. Sulfur speciation and sulfide oxidation in the water column of the Black Sea

    NASA Astrophysics Data System (ADS)

    Luther, George W., III; Church, Thomas M.; Powell, David

    We have applied sulfur speciation techniques to understand the chemistry and cycling of sulfur in Black Sea waters. The only reduced dissolved inorganic sulfur species detected (above the low minimum detection limits of the voltammetric methods employed) in the water column was hydrogen sulfide. The maximum concentration of sulfide (423 μM) is similar to previous reports. Using a cathodic stripping square wave voltammetry (CSSWV) method for nanomolar levels of sulfide, we determined the precise boundary between the "free" hydrogen sulfide (sulfidic) zone and the upper (oxic/suboxic) water column at the two stations studied. This boundary has apparently moved up by about 50 m in the past 20 years. Our results help demonstrate three chemically distinct zones of water in the central basin of the Black Sea: (1) the oxic [0-65 m], (2) the anoxic/nonsulfidic [65-100 m] and (3) the sulfidic [>100 m]. Sulfide bound to metals ("complexed" sulfide) is observed in both the oxic and anoxic/nonsulfidic zones of the water column. This supports previous studies on metal sulfide forms. From the electrochemical data, it is possible to estimate the strength of the complexation of sulfide to metals (log K = 10 to 11). Thiosulfate and sulfite were below our minimum detectable limit (MDL) of 50 nM using CSSWV. Elemental sulfur (MDL 5 nM) was detected below the onset of the hydrogen sulfide zone (90-100 m) with a maximum of 30-60 nM near 120 m. The sulfur speciation results for the Black Sea are lower by one order of magnitude or more than other marine systems such as the Cariaco Trench and salt marshes. New HPLC techniques were applied to detect thiols at submicromolar levels. The presence of thiols (2-mercaptoethylamine, 2-mercaptoethanol, N-acetylcysteine and glutathione) is correlated with the remineralization of organic matter at the oxic and anoxic/nonsulfidic interface. Water samples collected from the upper 50 m of the sulfidic zone showed significant sulfide oxidation on

  4. CATALYTIC OXIDATION OF DIMETHYL SULFIDE WITH OZONE: EFFECT OF PROMOTER AND PHYSICO-CHEMICAL PROPERTIES OF METAL OXIDE CATALYSTS

    EPA Science Inventory

    This study reports improved catalytic activities and stabilities for the oxidation of dimethyl sulfide (DMS), a major pollutant of pulp and paper mills. Ozone was used as an oxidant and Cu, Mo, V, Cr and Mn metal oxides, and mixed metal oxides support on y-alumina as catalysts ov...

  5. CATALYTIC OXIDATION OF DIMETHYL SULFIDE WITH OZONE: EFFECTS OF PROMOTER AND PHYSICO-CHEMICAL PROPERTIES OF METAL OXIDE CATALYSTS

    EPA Science Inventory

    This study reports improved catalytic activities and stabilities for the oxidation of dimethyl sulfide (DMS), a major pollutant of pulp and paper mills. Ozone was used as an oxidant and activities of Cu, Mo, Cr and Mn oxides, and mixed metal oxides supported on -alumina, were tes...

  6. Selective oxidation of glycosyl sulfides to sulfoxides using magnesium monoperoxyphthalate and microwave irradiation.

    PubMed

    Chen, Ming-Yi; Patkar, Laxmikant Narhari; Lin, Chun-Cheng

    2004-04-16

    A protocol that uses moist magnesium monoperoxyphthalate (MMPP) as an oxidant under microwave irradiation rapidly yields a variety of glycosyl sulfoxides from corresponding sulfides in high yields with high selectivity.

  7. Investigation of the radiation-stimulated oxidation of sulfide by molecular oxygen

    SciTech Connect

    Muratbekov, M.B.; Beremzhanov, B.A.; Koroleva, G.Y.

    1986-07-01

    In order to determine the possibility of radiation stimulation of the oxidation of dissolved sulfide by molecular oxygen and to consider the mechanism from the standpoint of radiation chemical concepts, the authors investigated the radiation-stimulated oxidation of sulfide by molecular oxygen at pH 13. The kinetics were studied according to the decrease in oxygen with the aid of a gasometric set up.

  8. Probing the Ag, Au, and Cu electrode/pyridine-α-hydroxymethyl biphenyl phosphine oxide isomer interface with SERS

    NASA Astrophysics Data System (ADS)

    Pięta, Ewa; Proniewicz, Edyta; Boduszek, Bogdan; Olszewski, Tomasz K.; Nattich-Rak, Małgorzata; Kim, Younkyoo

    2015-04-01

    The potential-dependent surface enhanced Raman scattering (SERS) and generalized two-dimensional correlation analysis (G2DCA) methods were used to characterize three pyridine-α-hydroxymethyl biphenyl phosphine oxide isomers: (diphenylphosphoryl)(pyridine-2-yl)methanol (α-Py), (diphenylphosphoryl)(pyridine-3-yl)methanol (β-Py), and (diphenylphosphoryl)(pyridine-4-yl)methanol (γ-Py). The aforementioned compounds were deposited onto Ag, Au, and Cu electrode surfaces under different applied electrode potentials in an aqueous solution at physiological pH. On the basis of the enhancement, broadening, and shift in wavenumbers of individual bands, the geometry of the investigated molecules and influence of substituent position on the adsorption mode (in the α-(2-), β-(3-), and γ-(4-) positions), electrode type, and applied electrode potential were examined. It was found that the SERS spectra are dominated by bands assigned to phenyl (Ph) and pyridine (Py) ring vibrations. However, some differences in the arrangement of the aforementioned fragments were observed with changes to the type of the metal surface and the applied electrode potential.

  9. Kinetics and mechanism of the oxidation of organic sulfides by N-bromobenzamide

    SciTech Connect

    Chowdhury, K.; Banerji, K.K. )

    1990-09-14

    Kinetics of oxidation of 34 organic sulfides by N-bromobenzamide (NBB), to yield the corresponding sulfoxides, have been studied. The reaction is first-order with respect to the sulfide, NBB, and hydrogen ions. There is no effect of added benzamide. Protonated NBB has been postulated as the reactive oxidizing species. Reactivity of the sulfides toward NBB was subjected to correlation analysis by using multiparametric equations. The polar reaction constants are negative. Steric effects play a minor inhibitory role. A mechanism involving formulation of a halogenosulfonium cation, in the rate-determining step, has been proposed.

  10. Stable sulfur and oxygen isotope fractionation of anoxic sulfide oxidation by two different enzymatic pathways.

    PubMed

    Poser, Alexander; Vogt, Carsten; Knöller, Kay; Ahlheim, Jörg; Weiss, Holger; Kleinsteuber, Sabine; Richnow, Hans-H

    2014-08-19

    The microbial oxidation of sulfide is a key reaction of the microbial sulfur cycle, recycling sulfur in its most reduced valence state back to more oxidized forms usable as electron acceptors. Under anoxic conditions, nitrate is a preferential electron acceptor for this process. Two enzymatic pathways have been proposed for sulfide oxidation under nitrate reducing conditions, the sulfide:quinone oxidoreductase (SQR) pathway and the Sox (sulfur oxidation) system. In experiments with the model strains Thiobacillus denitrificans and Sulfurimonas denitrificans, both pathways resulted in a similar small sulfur and oxygen isotope fractionation of -2.4 to -3.6‰ for (34)S and -2.4 to -3.4‰ for (18)O. A similar pattern was detected during the oxidation of sulfide in a column percolated with sulfidic, nitrate amended groundwater. In experiments with (18)O-labeled water, a strong oxygen isotope fractionation was observed for T. denitrificans and S. denitrificans, indicating a preferential incorporation of (18)O-depleted oxygen released as water by nitrate reduction to nitrogen. The study indicates that nitrate-dependent sulfide oxidation might be monitored in the environment by analysis of (18)O-depleted sulfate.

  11. Spontaneous electrochemical treatment for sulfur recovery by a sulfide oxidation/vanadium(V) reduction galvanic cell.

    PubMed

    Kijjanapanich, Pimluck; Kijjanapanich, Pairoje; Annachhatre, Ajit P; Esposito, Giovanni; Lens, Piet N L

    2015-02-01

    Sulfide is the product of the biological sulfate reduction process which gives toxicity and odor problems. Wastewaters or bioreactor effluents containing sulfide can cause severe environmental impacts. Electrochemical treatment can be an alternative approach for sulfide removal and sulfur recovery from such sulfide rich solutions. This study aims to develop a spontaneous electrochemical sulfide oxidation/vanadium(V) reduction cell with a graphite electrode system to recover sulfide as elemental sulfur. The effects of the internal and external resistance on the sulfide removal efficiency and electrical current produced were investigated at different pH. A high surface area of the graphite electrode is required in order to have as less internal resistance as possible. In this study, graphite powder was added (contact area >633 cm(2)) in order to reduce the internal resistance. A sulfide removal efficiency up to 91% and electrical charge of more than 400 C were achieved when using five graphite rods supplemented with graphite powder as the electrode at an external resistance of 30 Ω and a sulfide concentration of 250 mg L(-1).

  12. New nitric oxide or hydrogen sulfide releasing aspirins.

    PubMed

    Lazzarato, Loretta; Chegaev, Konstantin; Marini, Elisabetta; Rolando, Barbara; Borretto, Emily; Guglielmo, Stefano; Joseph, Sony; Di Stilo, Antonella; Fruttero, Roberta; Gasco, Alberto

    2011-08-11

    A new series of (((R-oxy)carbonyl)oxy)methyl esters of aspirin (ASA), bearing nitric oxide (NO) or hydrogen sulfide (H(2)S) releasing groups, was synthesized, and the compounds were evaluated as new ASA co-drugs. All the products were quite stable in buffered solution at pH 1 and 7.4. Conversely, they were all rapidly metabolized, producing ASA and the NO/H(2)S releasing moiety used for their preparation. Consequent on ASA release, the compounds were capable of inhibiting collagen-induced platelet aggregation of human platelet-rich plasma (PRP). The simple NO/H(2)S donor substructures were able to relax contracted rat aorta strips, with a NO- and H(2)S-dependent mechanism, respectively, but they either did not trigger antiaggregatory activity or displayed antiplatelet potency markedly below that of the related co-drug. The new products might provide a safer and improved alternative to the use of ASA principally in its anti-inflammatory and antithrombotic applications.

  13. Polysulfides as Intermediates in the Oxidation of Sulfide to Sulfate by Beggiatoa spp.

    PubMed Central

    Schwedt, Anne; Kreutzmann, Anne-Christin; Kuypers, Marcel M. M.; Milucka, Jana

    2014-01-01

    Zero-valent sulfur is a key intermediate in the microbial oxidation of sulfide to sulfate. Many sulfide-oxidizing bacteria produce and store large amounts of sulfur intra- or extracellularly. It is still not understood how the stored sulfur is metabolized, as the most stable form of S0 under standard biological conditions, orthorhombic α-sulfur, is most likely inaccessible to bacterial enzymes. Here we analyzed the speciation of sulfur in single cells of living sulfide-oxidizing bacteria via Raman spectroscopy. Our results showed that under various ecological and physiological conditions, all three investigated Beggiatoa strains stored sulfur as a combination of cyclooctasulfur (S8) and inorganic polysulfides (Sn2−). Linear sulfur chains were detected during both the oxidation and reduction of stored sulfur, suggesting that Sn2− species represent a universal pool of bioavailable sulfur. Formation of polysulfides due to the cleavage of sulfur rings could occur biologically by thiol-containing enzymes or chemically by the strong nucleophile HS− as Beggiatoa migrates vertically between oxic and sulfidic zones in the environment. Most Beggiatoa spp. thus far studied can oxidize sulfur further to sulfate. Our results suggest that the ratio of produced sulfur and sulfate varies depending on the sulfide flux. Almost all of the sulfide was oxidized directly to sulfate under low-sulfide-flux conditions, whereas only 50% was oxidized to sulfate under high-sulfide-flux conditions leading to S0 deposition. With Raman spectroscopy we could show that sulfate accumulated in Beggiatoa filaments, reaching intracellular concentrations of 0.72 to 1.73 M. PMID:24212585

  14. Survival of hydrogen sulfide oxidizing bacteria on corroded concrete surfaces of sewer systems.

    PubMed

    Jensen, H S; Nielsen, A H; Hvitved-Jacobsen, T; Vollertsen, J

    2008-01-01

    The activity of hydrogen sulfide oxidizing bacteria within corroded concrete from a sewer manhole was investigated. The bacteria were exposed to hydrogen sulfide starvation for up till 18 months, upon which their hydrogen sulfide oxidizing activity was measured. It was tested whether the observed reduction in biological activity was caused by a biological lag phase or by decay of the bacteria. The results showed that the bacterial activity declined with approximately 40% pr. month during the first two months of hydrogen sulfide starvation. After 2-3 months of starvation, the activity stabilized. Even after 6 months of starvation, exposure to hydrogen sulfide for 6 hours a day on three successive days could restore the bacteriological activity to about 80% of the initial activity. After 12 months of starvation, the activity could, however, not be restored, and after 18 months the biological activity approached zero. The long-term survival aspect of concrete corroding bacteria has implications for predicting hydrogen sulfide corrosion in sewer systems subject to irregular hydrogen sulfide loadings, e.g. as they occur in temperate climates where hydrogen sulfide often is a summer-problem only.

  15. Sulfide oxidation coupled to arsenate reduction by a diverse microbial community in a soda lake.

    PubMed

    Hollibaugh, James T; Budinoff, Charles; Hollibaugh, Ryan A; Ransom, Briana; Bano, Nasreen

    2006-03-01

    We characterized the arsenate-reducing, sulfide-oxidizing population of Mono Lake, California, by analyzing the distribution and diversity of rrnA, cbbL, and dissimilatory arsenate reductase (arrA) genes in environmental DNA, arsenate-plus sulfide-amended lake water, mixed cultures, and isolates. The arsenate-reducing community was diverse. An organism represented by an rrnA sequence previously retrieved from Mono Lake and affiliated with the Desulfobulbaceae (Deltaproteobacteria) appears to be an important member of the arsenate-reducing, sulfide-oxidizing community. Sulfide oxidation coupled with arsenate reduction appears to proceed via a two-electron transfer, resulting in the production of arsenite and an intermediate S compound that is subsequently disproportionated. A realgar-like As/S mineral was formed in some experiments.

  16. Electric coupling between distant nitrate reduction and sulfide oxidation in marine sediment.

    PubMed

    Marzocchi, Ugo; Trojan, Daniela; Larsen, Steffen; Meyer, Rikke Louise; Revsbech, Niels Peter; Schramm, Andreas; Nielsen, Lars Peter; Risgaard-Petersen, Nils

    2014-08-01

    Filamentous bacteria of the Desulfobulbaceae family can conduct electrons over centimeter-long distances thereby coupling oxygen reduction at the surface of marine sediment to sulfide oxidation in deeper anoxic layers. The ability of these cable bacteria to use alternative electron acceptors is currently unknown. Here we show that these organisms can use also nitrate or nitrite as an electron acceptor thereby coupling the reduction of nitrate to distant oxidation of sulfide. Sulfidic marine sediment was incubated with overlying nitrate-amended anoxic seawater. Within 2 months, electric coupling of spatially segregated nitrate reduction and sulfide oxidation was evident from: (1) the formation of a 4-6-mm-deep zone separating sulfide oxidation from the associated nitrate reduction, and (2) the presence of pH signatures consistent with proton consumption by cathodic nitrate reduction, and proton production by anodic sulfide oxidation. Filamentous Desulfobulbaceae with the longitudinal structures characteristic of cable bacteria were detected in anoxic, nitrate-amended incubations but not in anoxic, nitrate-free controls. Nitrate reduction by cable bacteria using long-distance electron transport to get privileged access to distant electron donors is a hitherto unknown mechanism in nitrogen and sulfur transformations, and the quantitative importance for elements cycling remains to be addressed.

  17. Microbial communities involved in electricity generation from sulfide oxidation in a microbial fuel cell.

    PubMed

    Sun, Min; Tong, Zhong-Hua; Sheng, Guo-Ping; Chen, Yong-Zhen; Zhang, Feng; Mu, Zhe-Xuan; Wang, Hua-Lin; Zeng, Raymond J; Liu, Xian-Wei; Yu, Han-Qing; Wei, Li; Ma, Fang

    2010-10-15

    Simultaneous electricity generation and sulfide removal can be achieved in a microbial fuel cell (MFC). In electricity harvesting from sulfide oxidation in such an MFC, various microbial communities are involved. It is essential to elucidate the microbial communities and their roles in the sulfide conversion and electricity generation. In this work, an MFC was constructed to enrich a microbial consortium, which could harvest electricity from sulfide oxidation. Electrochemical analysis demonstrated that microbial catalysis was involved in electricity output in the sulfide-fed MFC. The anode-attached and planktonic communities could perform catalysis independently, and synergistic interactions occurred when the two communities worked together. A 16S rRNA clone library analysis was employed to characterize the microbial communities in the MFC. The anode-attached and planktonic communities shared similar richness and diversity, while the LIBSHUFF analysis revealed that the two community structures were significantly different. The exoelectrogenic, sulfur-oxidizing and sulfate-reducing bacteria were found in the MFC anodic chamber. The discovery of these bacteria was consistent with the community characteristics for electricity generation from sulfide oxidation. The exoelectrogenic bacteria were found both on the anode and in the solution. The sulfur-oxidizing bacteria were present in greater abundance on the anode than in the solution, while the sulfate-reducing bacteria preferably lived in the solution.

  18. Online oxygen control for sulfide oxidation in anaerobic treatment of high-sulfate wastewater.

    PubMed

    Khanal, Samir Kumar; Huang, Ju-Chang

    2006-04-01

    A new technique for sulfide control was investigated in an upflow-anaerobic filter (UAF) treating high-strength, sulfate-rich wastewater. The technique used periodic oxygen injection using oxidation-reduction potential (ORP) as a controlling parameter to regulate oxygen injection. The UAF was operated at a constant influent total-organic carbon of 6740 mg/L but with different influent sulfates of 1000, 3000, and 6000 mg/L. At 1000 and 3000 mg/L influent sulfates, the produced sulfide did not impose any inhibition to methane-producing bacteria (MPB). However, at 6000 mg/L influent sulfate, the produced dissolved sulfide of 804 mg S/L (free sulfide = 280 mg S/L) severely inhibited the methanogenesis, but not the sulfidogenesis. Upon oxygen injection at elevated ORP of -265 mV, sulfides were almost completely eliminated with a concomitant improvement in methane yield by 46%. If oxygenation was excessive because of an oversetting of ORP, the excess oxygen could be used rapidly by facultative heterotrophs, thereby protecting the MPB from oxygen stress. Regarding online sulfide oxidation, it was found that the biogas and injected oxygen needed to pass through an aqueous layer containing trace metals, which were found to have a significant catalytic effect on abiotic sulfide oxidation.

  19. Oxidative Weathering of Archean Sulfides: Implications for the Great Oxidation Event

    NASA Astrophysics Data System (ADS)

    Johnson, A.; Romaniello, S. J.; Reinhard, C.; Garcia-Robledo, E.; Revsbech, N. P.; Canfield, D. E.; Lyons, T. W.; Anbar, A. D.

    2015-12-01

    The first widely accepted evidence for oxidation of Earth's atmosphere and oceans occurs ~2.45 Ga immediately prior to the Great Oxidation Event (GOE). A major line of evidence for this transition includes the abundances and isotopic variations of redox-sensitive transition metals in marine sediments (e.g., Fe, Mo, Re, Cr, and U). It is often assumed that oxidative weathering is required to liberate these redox-sensitive elements from sulfide minerals in the crust, and hence that their presence in early Archean marine sediments signifies that oxidative weathering was stimulated by small and/or transient "whiffs" of O2 in the environment.1 However, studies of crustal sulfide reactivity have not been conducted at O2 concentrations as low as those that would have prevailed when O2 began its rise during the late Archean (estimated at <10-5 present atmospheric O2).2 As a result, it is difficult to quantify O2 concentrations implied by observed trace metal variations. As a first step toward providing more quantitative constraints on late Archean pO2, we conducted laboratory studies of pyrite and molybdenite oxidation kinetics at the nanomolar O2 concentrations that are relevant to late Archean environments. These measurements were made using recently developed, highly sensitive optical O2 sensors to monitor the rates at which the powdered minerals consumed dissolved O2 in a range of pH-buffered solutions.3Our data extend the range of experimental pyrite oxidation rates in the literature by three orders of magnitude from ~10-3 present atmospheric O2 to ~10-6. We find that molybdenite and pyrite oxidation continues to <1 nM O2 (4 x 10-6 present atmospheric O2). This implies that oxidative weathering of sulfides could occur under conditions which preserve MIF S fractionation. Furthermore, our results indicate that the rate law and reaction order of pyrite oxidation kinetics change significantly at nanomolar concentrations of O2 when compared to previous compilations.2 Our

  20. Kinetics of Indigenous Nitrate Reducing Sulfide Oxidizing Activity in Microaerophilic Wastewater Biofilms.

    PubMed

    Villahermosa, Desirée; Corzo, Alfonso; Garcia-Robledo, Emilio; González, Juan M; Papaspyrou, Sokratis

    2016-01-01

    Nitrate decreases sulfide release in wastewater treatment plants (WWTP), but little is known on how it affects the microzonation and kinetics of related microbial processes within the biofilm. The effect of nitrate addition on these properties for sulfate reduction, sulfide oxidation, and oxygen respiration were studied with the use of microelectrodes in microaerophilic wastewater biofilms. Mass balance calaculations and community composition analysis were also performed. At basal WWTP conditions, the biofilm presented a double-layer system. The upper microaerophilic layer (~300 μm) showed low sulfide production (0.31 μmol cm-3 h-1) and oxygen consumption rates (0.01 μmol cm-3 h-1). The anoxic lower layer showed high sulfide production (2.7 μmol cm-3 h-1). Nitrate addition decreased net sulfide production rates, caused by an increase in sulfide oxidation rates (SOR) in the upper layer, rather than an inhibition of sulfate reducing bacteria (SRB). This suggests that the indigenous nitrate reducing-sulfide oxidizing bacteria (NR-SOB) were immediately activated by nitrate. The functional vertical structure of the biofilm changed to a triple-layer system, where the previously upper sulfide-producing layer in the absence of nitrate split into two new layers: 1) an upper sulfide-consuming layer, whose thickness is probably determined by the nitrate penetration depth within the biofilm, and 2) a middle layer producing sulfide at an even higher rate than in the absence of nitrate in some cases. Below these layers, the lower net sulfide-producing layer remained unaffected. Net SOR varied from 0.05 to 0.72 μmol cm-3 h-1 depending on nitrate and sulfate availability. Addition of low nitrate concentrations likely increased sulfate availability within the biofilm and resulted in an increase of both net sulfate reduction and net sulfide oxidation by overcoming sulfate diffusional limitation from the water phase and the strong coupling between SRB and NR-SOB syntrophic

  1. Kinetics of Indigenous Nitrate Reducing Sulfide Oxidizing Activity in Microaerophilic Wastewater Biofilms

    PubMed Central

    Villahermosa, Desirée; Corzo, Alfonso; Garcia-Robledo, Emilio; González, Juan M.; Papaspyrou, Sokratis

    2016-01-01

    Nitrate decreases sulfide release in wastewater treatment plants (WWTP), but little is known on how it affects the microzonation and kinetics of related microbial processes within the biofilm. The effect of nitrate addition on these properties for sulfate reduction, sulfide oxidation, and oxygen respiration were studied with the use of microelectrodes in microaerophilic wastewater biofilms. Mass balance calaculations and community composition analysis were also performed. At basal WWTP conditions, the biofilm presented a double-layer system. The upper microaerophilic layer (~300 μm) showed low sulfide production (0.31 μmol cm-3 h-1) and oxygen consumption rates (0.01 μmol cm-3 h-1). The anoxic lower layer showed high sulfide production (2.7 μmol cm-3 h-1). Nitrate addition decreased net sulfide production rates, caused by an increase in sulfide oxidation rates (SOR) in the upper layer, rather than an inhibition of sulfate reducing bacteria (SRB). This suggests that the indigenous nitrate reducing-sulfide oxidizing bacteria (NR-SOB) were immediately activated by nitrate. The functional vertical structure of the biofilm changed to a triple-layer system, where the previously upper sulfide-producing layer in the absence of nitrate split into two new layers: 1) an upper sulfide-consuming layer, whose thickness is probably determined by the nitrate penetration depth within the biofilm, and 2) a middle layer producing sulfide at an even higher rate than in the absence of nitrate in some cases. Below these layers, the lower net sulfide-producing layer remained unaffected. Net SOR varied from 0.05 to 0.72 μmol cm-3 h-1 depending on nitrate and sulfate availability. Addition of low nitrate concentrations likely increased sulfate availability within the biofilm and resulted in an increase of both net sulfate reduction and net sulfide oxidation by overcoming sulfate diffusional limitation from the water phase and the strong coupling between SRB and NR-SOB syntrophic

  2. High-efficiency turquoise-blue electrophosphorescence from a Pt(II)-pyridyltriazolate complex in phosphine oxide host

    SciTech Connect

    Bhansali, Unnat S; Polikarpov, Evgueni; Swensen, James S; Chen, Wei; Jia, Huiping; Gaspar, Daniel J; Gnade, Bruce E; Padmaperuma, Asanga B; Omary, Mohammad A

    2009-12-10

    We have demonstrated high-efficiency turquoise-blue electrophosphorescence from the complex Pt(ptp)2 = bis[3,5–bis(2–pyridyl)–1,2,4–triazolato]platinum(II) doped in the wide band-gap, ambipolar phosphine oxide host HM-A1 = 4-(diphenylphosphoryl)-N,N-diphenylaniline. For devices with 5% Pt(ptp)2 doping in HM-A1, we have achieved a peak external quantum efficiency and power efficiency of (11.8 ± 0.6) % and (61.2 ± 5.9) lm/W with high-pixel values of 13.1 % and 70.6 lm/W, respectively. These parameters maintained (10.6 ± 0.2) % and (40.3 ± 1.2) lm/W at a brightness of 1000 cd/m2 with high-pixel values of 10.8 % and 41.6 lm/W. Examination of several device structures suggests that the high performance is due to improved charge transport and exciton confinement in the emissive region. Devices with 1-10% doping concentration exhibit turquoise-blue emissions (λmax ~ 480 nm) with a monotonic decrease in monomer/excimer intensity ratio upon increasing the doping concentration. Devices with 5% doping exhibit sufficient blue contribution to attain white light upon combination with highly-doped or neat emissive layers of the same phosphor; the work herein represents a significant backdrop toward optimizing such white OLEDs given the performance metrics above, which to our knowledge represent the highest performance for OLEDs that exhibit blue emission maxima.

  3. PCN pincer palladium(II) complex catalyzed enantioselective hydrophosphination of enones: synthesis of pyridine-functionalized chiral phosphine oxides as NC(sp(3))O pincer preligands.

    PubMed

    Hao, Xin-Qi; Huang, Juan-Juan; Wang, Tao; Lv, Jing; Gong, Jun-Fang; Song, Mao-Ping

    2014-10-17

    A series of chiral PCN pincer Pd(II) complexes VI-XIII with aryl-based aminophosphine-imidazoline or phosphinite-imidazoline ligands were synthesized and characterized. They were examined as enantioselective catalysts for the hydrophosphination of enones. Among them, complex IX, which features a Ph2PO donor as well as an imidazoline donor with (4S)-phenyl and N-Tol-p groups, was found to be the optimal catalyst. Thus, in the presence of 2-5 mol % of complex IX a wide variety of enones reacted smoothly with diarylphosphines to give the corresponding chiral phosphine derivatives in high yields with enantioselectivities of up to 98% ee. In particular, heteroaryl species such as 2-thienyl-, 2-furyl-, and 2-pyridinyl-containing enones that have a strong coordination ability to the Pd center were also appropriate substrates for the current catalytic system. For example, hydrophosphination of 2-alkenoylpyridines with diphenylphosphine followed by oxidation with H2O2 afforded the corresponding pyridine-functionalized chiral phosphine oxides in good yields with good to excellent enantioselectivities (10 examples, up to 95% ee). Furthermore, it had been demonstrated that the obtained pyridine-containing phosphine oxide acted as a tridentate ligand in the reaction with PdCl2 to form an intriguing NCsp(3)O pincer Pd(II) complex via Csp(3)-H bond activation, which to our knowledge is the first example of a chiral DCsp(3)D' Pd pincer (D ≠ D'; D and D' denote donor atoms such as P, N, etc.).

  4. Sulfide-oxidizing activity and bacterial community structure in a fluidized bed reactor from a zero-discharge mariculture system.

    PubMed

    Cytryn, Eddie; Minz, Dror; Gelfand, Ilya; Neori, Amir; Gieseke, Armin; De Beer, Dirk; Van Rijn, Jaap

    2005-03-15

    In the present work we describe a comprehensive analysis of sulfide oxidation in a fluidized bed reactor (FBR) from an environmentally sustainable, zero-discharge mariculture system. The FBR received oxygen-depleted effluent from a digestion basin (DB) that is responsible for gasification of organic matter and nitrogen. The FBR is a crucial component in this recirculating system because it safeguards the fish from the toxic sulfide produced in the DB. Microscale sulfide oxidation potential and bacterial community composition within FBR biofilms were correlated to biofilter performance by integrating bulk chemical, microsensor (O2, pH, and H2S), and molecular microbial community analyses. The FBR consistently oxidized sulfide during two years of continuous operation, with an estimated average sulfide removal rate of 1.3 g of sulfide-S L(FBR)(-1) d(-1). Maximum sulfide oxidation rates within the FBR biofilms were 0.36 and 0.21 mg of sulfide-S cm(-3) h(-1) in the oxic and anoxic layers, respectively, indicating that both oxygen and nitrate serve as electron acceptors for sulfide oxidation. The estimated anoxic sulfide removal rate, as extrapolated from bench scale, autotrophic, nitrate-amended experiments, was 0.7 g of sulfide-S L(FBR)(-1) d(-1), which is approximately 50% of the total estimated sulfide removal in the FBR. Community composition analyses using denaturing gradient gel electrophoresis (DGGE) of bacterial 16S rRNA gene fragments from FBR samples taken at six-month intervals revealed several sequences that were closely affiliated with sulfide-oxidizing bacteria. These included the denitrifying, sulfide-oxidizing bacteria Thiomicrospira denitrificans, members of the filamentous Thiothrix genus, and sulfide-oxidizing symbionts from the Gammaproteobacteria. In addition, marine Alphaproteobacteria and Bacteroidetes species were present in all of the DGGE profiles examined. DGGE analyses showed significant shifts in the bacterial community composition between

  5. Pathways of sulfide oxidation by haloalkaliphilic bacteria in limited-oxygen gas lift bioreactors.

    PubMed

    Klok, Johannes B M; van den Bosch, Pim L F; Buisman, Cees J N; Stams, Alfons J M; Keesman, Karel J; Janssen, Albert J H

    2012-07-17

    Physicochemical processes, such as the Lo-cat and Amine-Claus process, are commonly used to remove hydrogen sulfide from hydrocarbon gas streams such as landfill gas, natural gas, and synthesis gas. Biodesulfurization offers environmental advantages, but still requires optimization and more insight in the reaction pathways and kinetics. We carried out experiments with gas lift bioreactors inoculated with haloalkaliphilic sulfide-oxidizing bacteria. At oxygen-limiting levels, that is, below an O(2)/H(2)S mole ratio of 1, sulfide was oxidized to elemental sulfur and sulfate. We propose that the bacteria reduce NAD(+) without direct transfer of electrons to oxygen and that this is most likely the main route for oxidizing sulfide to elemental sulfur which is subsequently oxidized to sulfate in oxygen-limited bioreactors. We call this pathway the limited oxygen route (LOR). Biomass growth under these conditions is significantly lower than at higher oxygen levels. These findings emphasize the importance of accurate process control. This work also identifies a need for studies exploring similar pathways in other sulfide oxidizers such as Thiobacillus bacteria.

  6. Metal oxide and mercuric sulfide nanoparticles synthesis and characterization

    NASA Astrophysics Data System (ADS)

    Xu, Xin

    Commercially available and laboratory-synthesized metal based nanoparticles (NPs), iron oxide (Fe2O3), copper oxide (CuO), titanium dioxide (TiO2), zinc oxide (ZnO) and mercuric sulfide (HgS) were studied by comprehensive characterizations methods. The general synthesis process was modified sol-gel method. The size and morphology of NPs could be influenced by temperature, sonication, calcination, precursor concentration, pH and types of reaction media. All types of the laboratory-synthesized or commercially available NPs were characterized by physical and chemical processes. One characteristic of NP that can lead to ambiguous toxicity test results was the effect of agglomeration of primary nano-sized particles. Laser light scattering was used to measure the aggregated and particle size distribution. Aggregation effects were apparent and often extensive in some synthesis approaches. Electron microscopy (SEM and TEM) gave the images of those laboratory-synthesized particles and aggregation. The average single particle was about 5-20 nm of ZnO; 20-40 nm of CuO; 10-20 nm of TiO2; 20-35 nm of Fe2O3; 10-15 nm of HgS, while the aggregate size was in the range of a hundred nanometers or more. These five types of NPs were obtained with spherical and oblong formation and the agglomeration of ZnO, CuO, HgS and TiO2 was random, but Fe2O3 has web-like aggregation. Other measurements performed on the particles and aggregates include bandgap energies, surface composition, surface area, hydrodynamic radius, and particle surface charge. In aqueous environment, NPs are subject to processes such as solubilization and aggregation. These processes can be controlling factors in the fate of nanomaterials in environmental settings, including bioavailability to organisms. This study has focused primarily on measurement of the solubility in aqueous media of varying composition (pH, ionic strength, and organic carbon), sedimentation and stability. The aggregate size distribution was

  7. Characterization of a newly isolated strain Pseudomonas sp. C27 for sulfide oxidation: Reaction kinetics and stoichiometry

    PubMed Central

    Xu, Xi-Jun; Chen, Chuan; Guo, Hong-liang; Wang, Ai-jie; Ren, Nan-qi; Lee, Duu-Jong

    2016-01-01

    Sulfide biooxidation by the novel sulfide-oxidizing bacteria Pseudomonas sp. C27, which could perform autotrophic and heterotrophic denitrification in mixotrophic medium, was studied in batch and continuous systems. Pseudomonas sp. C27 was able to oxidize sulfide at concentrations as high as 17.66 mM. Sulfide biooxidation occurred in two distinct stages, one resulting in the formation of sulfur with nitrate reduction to nitrite, followed by thiosulfate formation with nitrite reduction to N2. The composition of end-products was greatly impacted by the ratio of sulfide to nitrate initial concentrations. At a ratio of 0.23, thiosulfate represented 100% of the reaction products, while only 30% with a ratio of 1.17. In the continuous bioreactor, complete removal of sulfide was observed at sulfide concentration as high as 9.38 mM. Overall sulfide removal efficiency decreased continuously upon further increases in influent sulfide concentrations. Based on the experimental data kinetic parameter values were determined. The value of maximum specific growth rate, half saturation constant, decay coefficient, maintenance coefficient and yield were to be 0.11 h−1, 0.68 mM sulfide, 0.11 h−1, 0.21 mg sulfide/mg biomass h and 0.43 mg biomass/mg sulfide, respectively, which were close to or comparable with those reported in literature by other researches. PMID:26864216

  8. Alternatives to Sulfide Dehairing: Use of Oxidative Agents

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The dehairing of cattle hides with sodium sulfate generates large quantities of waste that are of environmental concern as they have a large biological and chemical oxygen demand. Additionally, sodium sulfide is a potential workplace hazard. We had worked with industry to develop a rapid dehairing...

  9. Hydrogen sulfide poisoning in solid oxide fuel cells under accelerated testing conditions

    NASA Astrophysics Data System (ADS)

    Li, Ting Shuai; Wang, Wei Guo; Chen, Tao; Miao, He; Xu, Cheng

    This study investigates the 0.2% hydrogen sulfide poisoning of Ni/YSZ anode-supported solid oxide fuel cells (SOFCs). The deterioration degrees and recovery extents of the cell current density, cell voltage and operation temperature are monitored. The results of impedance spectroscopy analysis show that hydrogen sulfide poisoning behavior may affect oxygen ion migration and gas diffusion and conversion on the anode side. Microstructural inspection reveals sulfur or sulfide formed on the anode-active area, which accounts for the immediate and severe cell power drop upon the injection of H 2S. The nickel sulfide in the anodic functional layer cannot be completely removed after long-term regeneration and thus may be a key factor in the permanent degradation of the cell.

  10. The sulfide ore looping oxidation process: An alternative to current roasting and smelting practice

    NASA Astrophysics Data System (ADS)

    McHugh, Larry F.; Balliett, Robert; Mozolic, Jean A.

    2008-07-01

    This novel method utilizes the reactions of metal sulfides and metal oxides. It is applicable to single-metal systems such as Mo, Cu, Co, Ni, Fe, and Zn individual sulfides and to mixed sulfides such as chalcopyrite and Mo/Fe. In addition to primary ores, waste stream products such as spent catalysts can be effectively processed. The benchmark work done on MoS2/MoO3 resulted in an MoO2 product with less than 0.095 wt.% sulfur. Other sulfide concentrate materials showed similar results. In the first stage of the looping process, a highly concentrated SO2 off-gas stream is produced that could be directed to an acid plant or converted to liquid. The products from the first process step can be directed down line for further processing or can be used as is. In the second step of looping oxidation, the product is oxidized back to its fully oxidized state and is mainly looped back to drive the oxidation process in the first reaction. There are also several opportunities for energy recovery and conversion, making looping oxidation an energy-efficient process.

  11. Electron and Hole Transport in a Wide Bandgap Organic Phosphine Oxide for Blue Electrophosphorecsence

    SciTech Connect

    Cai, Xiuyu; Padmaperuma, Asanga B.; Sapochak, Linda S.; Vecchi, Paul A.; Burrows, Paul E.

    2008-02-28

    We report blue phosphorescent organic light-emitting devices (OLEDs) using an ambipolar host, N-(4-diphenylphosphoryl phenyl) carbazole (MPO12), doped with iridium (III) bis[4,6-difluorophenyl)-pyridinato-N,C2´]picolinate (FIrpic). The external quantum efficiency and operating voltage is 9.1±0.1% and 4.8 V, respectively, measured at a brightness of 800 cd/m2 with no outcoupling enhancement. By varying the layer structure of the OLEDs, we show that MPO12 is capable of transporting both electrons and holes, in contrast to previous demonstrations using diphosphine oxides, which only transported electrons. The improved hole transport results in improved device efficiency.

  12. Inhibition of microbiological sulfide oxidation by methanethiol and dimethyl polysulfides at natron-alkaline conditions.

    PubMed

    van den Bosch, Pim L F; de Graaff, Marco; Fortuny-Picornell, Marc; van Leerdam, Robin C; Janssen, Albert J H

    2009-06-01

    To avoid problems related to the discharge of sulfidic spent caustics, a biotechnological process is developed for the treatment of gases containing both hydrogen sulfide and methanethiol. The process operates at natron-alkaline conditions (>1 mol L(-1) of sodium- and potassium carbonates and a pH of 8.5-10) to enable the treatment of gases with a high partial CO(2) pressure. In the process, methanethiol reacts with biologically produced sulfur particles to form a complex mixture predominantly consisting of inorganic polysulfides, dimethyl disulfide (DMDS), and dimethyl trisulfide (DMTS). The effect of these organic sulfur compounds on the biological oxidation of sulfide to elemental sulfur was studied with natron-alkaliphilic bacteria belonging to the genus Thioalkalivibrio. Biological oxidation rates were reduced by 50% at 0.05 mM methanethiol, while for DMDS and DMTS, this was estimated to occur at 1.5 and 1.0 mM, respectively. The inhibiting effect of methanethiol on biological sulfide oxidation diminished due to its reaction with biologically produced sulfur particles. This reaction increases the feasibility of biotechnological treatment of gases containing both hydrogen sulfide and methanethiol at natron-alkaline conditions.

  13. Kinetic Constants for Biological Ammonium and Nitrite Oxidation Processes Under Sulfide Inhibition.

    PubMed

    Bejarano-Ortiz, Diego Iván; Huerta-Ochoa, Sergio; Thalasso, Frédéric; Cuervo-López, Flor de María; Texier, Anne-Claire

    2015-12-01

    Inhibition of nitrification by sulfide was assessed using sludge obtained from a steady-state nitrifying reactor. Independent batch activity assays were performed with ammonium and nitrite as substrate, in order to discriminate the effect of sulfide on ammonium and nitrite oxidation. In the absence of sulfide, substrate affinity constants (K S,NH4  = 2.41 ± 0.11 mg N/L; K s, NO2  = 0.74 ± 0.03 mg N/L) and maximum specific rates (q max,NH4  = 0.086 ± 0.008 mg N/mg microbial protein h; q max,NO2  = 0.124 ± 0.001 mg N/mg microbial protein h) were determined. Inhibition of ammonium oxidation was no-competitive (inhibition constant (K i , NH4 ) of 2.54 ± 0.12 mg HS(-)-S/L) while inhibition of nitrite oxidation was mixed (competitive inhibition constant (K' i , NO2 ) of 0.22 ± 0.03 mg HS(-)-S/L and no-competitive inhibition constant (K i , NO2 ) of 1.03 ± 0.06 mg HS(-)-S/L). Sulfide has greater inhibitory effect on nitrite oxidation than ammonium oxidation, and its presence in nitrification systems should be avoided to prevent accumulation of nitrite. By simulating the effect of sulfide addition in a continuous nitrifying reactor under steady-state operation, it was shown that the maximum sulfide concentration that the sludge can tolerate without affecting the ammonium consumption efficiency and nitrate yield is 1 mg HS(-)-S/L.

  14. Oxygen and sulfur isotope fractionation during sulfide oxidation by anoxygenic phototrophic bacteria

    NASA Astrophysics Data System (ADS)

    Brabec, Michelle Y.; Lyons, Timothy W.; Mandernack, Kevin W.

    2012-04-01

    Sulfide-mediated anoxygenic photosynthesis (SMAP) carried out by anaerobic phototrophic bacteria may have played an important role in sulfur cycling, formation of sulfate, and, perhaps, primary production in the Earth’s early oceans. Determination of ε34SSO4-Sulfide- and ε18OSO4-H2O values for bacterial sulfide oxidation will permit more refined interpretation of the δ34S and δ18OSO4 values measured in modern anoxic environments, such as meromictic lakes where sulfide commonly extends into the photic zone, and in the ancient rock record, particularly during periods of the Precambrian when anoxic and sulfidic (euxinic) conditions were believed to be more pervasive than today. Laboratory experiments with anaerobic purple and green sulfur phototrophs, Allochromatium vinosum and Chlorobaculum tepidum, respectively, were conducted to determine the sulfur and oxygen isotope fractionation during the oxidation of sulfide to sulfate. Replicate experiments were conducted at 25 °C for A. vinosum and 45 °C for C. tepidum, and in duplicate at three different starting oxygen isotope values for water to determine sulfate-water oxygen isotope fractionations accurately (ε18OSO4-H2O). ε18OSO4-H2O values of 5.6 ± 0.2‰ and 5.4 ± 0.1‰ were obtained for A. vinosum and C. tepidum, respectively. Temperature had no apparent effect on the ε18OSO4-H2O values. By combining all data from both cultures, an average ε18OSO4-H2O value of 5.6 ± 0.3‰ was obtained for SMAP. This value falls between those previously reported for bacterial oxidation of sphalerite and elemental sulfur (7-9‰) and abiotic and biotic oxidation of pyrite and chalcopyrite (2-4‰). Sulfur isotope fractionation between sulfide and sulfate formed by A.vinosum was negligible (0.1 ± 0.2‰) during all experiments. For C. tepidum an apparent fractionation of -2.3 ± 0.5‰ was observed during the earlier stages of oxidation based on bulk δ34S measurements of sulfate and sulfide and became smaller (-0.7

  15. In Situ Gene Expression Responsible for Sulfide Oxidation and CO2 Fixation of an Uncultured Large Sausage-Shaped Aquificae Bacterium in a Sulfidic Hot Spring

    PubMed Central

    Tamazawa, Satoshi; Yamamoto, Kyosuke; Takasaki, Kazuto; Mitani, Yasuo; Hanada, Satoshi; Kamagata, Yoichi; Tamaki, Hideyuki

    2016-01-01

    We investigated the in situ gene expression profile of sulfur-turf microbial mats dominated by an uncultured large sausage-shaped Aquificae bacterium, a key metabolic player in sulfur-turfs in sulfidic hot springs. A reverse transcription-PCR analysis revealed that the genes responsible for sulfide, sulfite, and thiosulfate oxidation and carbon fixation via the reductive TCA cycle were continuously expressed in sulfur-turf mats taken at different sampling points, seasons, and years. These results suggest that the uncultured large sausage-shaped bacterium has the ability to grow chemolithoautotrophically and plays key roles as a primary producer in the sulfidic hot spring ecosystem in situ. PMID:27297893

  16. In Situ Gene Expression Responsible for Sulfide Oxidation and CO2 Fixation of an Uncultured Large Sausage-Shaped Aquificae Bacterium in a Sulfidic Hot Spring.

    PubMed

    Tamazawa, Satoshi; Yamamoto, Kyosuke; Takasaki, Kazuto; Mitani, Yasuo; Hanada, Satoshi; Kamagata, Yoichi; Tamaki, Hideyuki

    2016-06-25

    We investigated the in situ gene expression profile of sulfur-turf microbial mats dominated by an uncultured large sausage-shaped Aquificae bacterium, a key metabolic player in sulfur-turfs in sulfidic hot springs. A reverse transcription-PCR analysis revealed that the genes responsible for sulfide, sulfite, and thiosulfate oxidation and carbon fixation via the reductive TCA cycle were continuously expressed in sulfur-turf mats taken at different sampling points, seasons, and years. These results suggest that the uncultured large sausage-shaped bacterium has the ability to grow chemolithoautotrophically and plays key roles as a primary producer in the sulfidic hot spring ecosystem in situ.

  17. Contact doping of silicon wafers and nanostructures with phosphine oxide monolayers.

    PubMed

    Hazut, Ori; Agarwala, Arunava; Amit, Iddo; Subramani, Thangavel; Zaidiner, Seva; Rosenwaks, Yossi; Yerushalmi, Roie

    2012-11-27

    Contact doping method for the controlled surface doping of silicon wafers and nanometer scale structures is presented. The method, monolayer contact doping (MLCD), utilizes the formation of a dopant-containing monolayer on a donor substrate that is brought to contact and annealed with the interface or structure intended for doping. A unique feature of the MLCD method is that the monolayer used for doping is formed on a separate substrate (termed donor substrate), which is distinct from the interface intended for doping (termed acceptor substrate). The doping process is controlled by anneal conditions, details of the interface, and molecular precursor used for the formation of the dopant-containing monolayer. The MLCD process does not involve formation and removal of SiO(2) capping layer, allowing utilization of surface chemistry details for tuning and simplifying the doping process. Surface contact doping of intrinsic Si wafers (i-Si) and intrinsic silicon nanowires (i-SiNWs) is demonstrated and characterized. Nanowire devices were formed using the i-SiNW channel and contact doped using the MLCD process, yielding highly doped SiNWs. Kelvin probe force microscopy (KPFM) was used to measure the longitudinal dopant distribution of the SiNWs and demonstrated highly uniform distribution in comparison with in situ doped wires. The MLCD process was studied for i-Si substrates with native oxide and H-terminated surface for three types of phosphorus-containing molecules. Sheet resistance measurements reveal the dependency of the doping process on the details of the surface chemistry used and relation to the different chemical environments of the P═O group. Characterization of the thermal decomposition of several monolayer types formed on SiO(2) nanoparticles (NPs) using TGA and XPS provides insight regarding the role of phosphorus surface chemistry at the SiO(2) interface in the overall MLCD process. The new MLCD process presented here for controlled surface doping

  18. [Oxidation Process of Dissolvable Sulfide by Manganite and Its Influencing Factors].

    PubMed

    Luo, Yao; Li, Shan; Tan, Wen-feng; Liu, Fan; Cai, Chong-fa; Qiu, Guo-hong

    2016-04-15

    As one of the manganese oxides, which are easily generated and widely distributed in supergene environment, manganite participates in the oxidation of dissolvable sulfide (S²⁻), and affects the migration, transformation, and the fate of sulfides. In the present work, the redox mechanism was studied by determining the intermediates, and the influence of initial pH and oxygen atmosphere on the processes were studied. The chemical composition, crystal structures and micromorphologies were characterized by XRD, FTIR and TEM. The concentration of S²⁻ and its oxidation products were analyzed using spectrophotometer, high performance liquid chromatograph and ion chromatograph. The results indicated that elemental sulfur was formed as the major oxidation product of S²⁻ oxidation, and decreased pH could accelerate the oxidation rate of S²⁻ in the initial stage, however, there was no significant influence on final products. Elemental S could be further oxidized to S₂O₃²⁻ when the reaction system was bubbled with oxygen, and manganite exhibited excellent catalytic performance and chemical stability during the oxidation of dissolvable sulfide by oxygen. After reaction of more than 10 h, the crystal structure of manganite remained stable.

  19. Progress in bioleaching: fundamentals and mechanisms of bacterial metal sulfide oxidation--part A.

    PubMed

    Vera, Mario; Schippers, Axel; Sand, Wolfgang

    2013-09-01

    Bioleaching of metal sulfides is performed by a diverse group of microorganisms. The dissolution chemistry of metal sulfides follows two pathways, which are determined by the mineralogy and the acid solubility of the metal sulfides: the thiosulfate and the polysulfide pathways. Bacterial cells can effect this metal sulfide dissolution via iron(II) ion and sulfur compound oxidation. Thereby, iron(III) ions and protons, the metal sulfide-attacking agents, are available. Cells can be active either in planktonic state or in forming biofilms on the mineral surface; however, the latter is much more efficient in terms of bioleaching kinetics. In the case of Acidithiobacillus ferrooxidans, bacterial exopolymers contain iron(III) ions, each complexed by two uronic acid residues. The resulting positive charge allows an electrostatic attachment to the negatively charged pyrite. Thus, the first function of complexed iron(III) ions is the mediation of cell attachment, while their second function is oxidative dissolution of the metal sulfide, similar to the role of free iron(III) ions in non-contact leaching. In both cases, the electrons extracted from the metal sulfide reduce molecular oxygen via a redox chain forming a supercomplex spanning the periplasmic space and connecting both outer and inner membranes. In this review, we summarize some recent discoveries relevant to leaching bacteria which contribute to a better understanding of these fascinating microorganisms. These include surface science, biochemistry of iron and sulfur metabolism, anaerobic metabolism, and biofilm formation. The study of microbial interactions among multispecies leaching consortia, including cell-to-cell communication mechanisms, must be considered in order to reveal more insights into the biology of bioleaching microorganisms and their potential biotechnological use.

  20. Microbially mediated re-oxidation of sulfide during dissimilatory sulfate reduction by Desulfobacter latus

    NASA Astrophysics Data System (ADS)

    Eckert, T.; Brunner, B.; Edwards, E. A.; Wortmann, U. G.

    2011-06-01

    Enzymatic reactions during dissimilatory sulfate reduction (DSR) are often treated as unidirectional with respect to dissolved sulfide. However, quantitative models describing kinetic sulfur isotope fractionations during DSR consider the individual enzymatic reactions as reversible ( Rees, 1973). Brunner and Bernasconi (2005) extended this line of thought, and suggested that as long as cell external sulfide (CES) concentrations are high enough, CES may diffuse back across the cytoplasmic cell membrane and may subsequently be re-oxidized to sulfate. Here, we test this hypothesis by measuring the time evolution of the δ34S-sulfate signal during DSR in closed system experiments under different levels of sulfide stress (0-20 mM and 0-40 mM total dissolved sulfide). Our results show that the measured δ34S-sulfate signal is markedly different in the latter case and that the observed sulfate S-isotope time-evolution is incompatible with a Rayleigh type fractionation model. In contrast, our results are consistent with a sulfate reduction and fractionation model that allows for a cell internal oxidation of dissolved sulfide by a sulfate reducer.

  1. Temperature dependence of the oxidative stability of corn oil and polyalphaolefin in the presence of sulfides

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The effect of sulfide-modified corn oil (SMCO) and ditertiary dodecyl pentasulfide (PS) additives on the oxidative stability of corn (CO) and polyalphaolefin (PAO) oils was investigated using pressurized differential scanning calorimetry in dynamic (DDSC) and isothermal (IDSC) modes. DDSC showed a ...

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

    EPA Science Inventory

    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...

  3. Transformation and destabilization of graphene oxide in reducing aqueous solutions containing sulfide.

    PubMed

    Fu, Heyun; Qu, Xiaolei; Chen, Wei; Zhu, Dongqiang

    2014-12-01

    The colloidal stability of carbon nanomaterials is a key factor controlling their fate and bioavailability in natural aquatic systems. The authors report that graphene oxide nanoparticles could be destabilized in reducing aqueous solutions containing a low concentration (0.5 mM) of sulfide, a naturally occurring reductant. Spectroscopic characterization using combined X-ray photoelectron, Fourier-transform infrared, X-ray diffraction, and Raman analyses revealed that the surface oxygen-containing groups (mainly epoxy groups) of graphene oxide were significantly reduced after reacting with sodium sulfide. The destabilization of graphene oxide was likely caused by the enhanced surface hydrophobicity of the reduced graphene oxide, whereas electrostatic repulsion played a minimal role. Solution pH was found to affect both the deoxygenation process and the aggregation behavior of graphene oxide. Coexisting humic acid reduced the reaction efficiency and stabilized graphene oxide through steric hindrance. These findings suggest for the first time that the colloidal behavior of carbon nanomaterials might change drastically when they enter natural reducing environments containing sulfide such as anaerobic aquifers and sediments.

  4. Oxidative Remobilization of Technetium Sequestered by Sulfide-Transformed Nano Zerovalent Iron

    SciTech Connect

    Fan, Dimin; Anitori, Roberto; Tebo, Bradley M.; Tratnyek, P. G.; Lezama Pacheco, Juan S.; Kukkadapu, Ravi K.; Kovarik, Libor; Engelhard, Mark H.; Bowden, Mark E.

    2014-06-02

    The dissolution of Tc(IV) sulfide and concurrent transformation of sulfidated ZVI during 2 oxidation were examined. Kinetic data obtained with 10 mL batch reactors showed that Tc(VII) 3 reduced by sulfidated nZVI has significantly slower reoxidation rates than Tc(VII) reduced by 4 nZVI only. In a 50 mL batch reactor, initial inhibition of Tc(IV) dissolution was apparent and 5 lasted until 120 hours at S/Fe = 0.112, presumably due to the redox buffer capacity of FeS. This 6 is evidenced by the parallel trends in oxidation-reduction potentials (ORP) and Tc dissolution 7 kinetics. Mӧssbauer spectra and micro X-ray diffraction of S/Fe = 0.112 suggested the 8 persistence of FeS after 24-h oxidation although X-ray photoelectron spectroscopy indicated 9 substantial surface oxidation. After 120-h oxidation, all characterizations showed complete 10 oxidation of FeS, which further indicates that FeS inhibits Tc oxidation. X-ray absorption 11 spectroscopy for S/Fe = 0.011 showed significantly increasing percentage of TcS2 in the solid 12 phase after 24-h oxidation, indicating TcS2 is more resistant to oxidation than TcO2. At S/Fe = 13 0.112, the XAS results revealed significant transformation of Tc speciation from TcS2 to TcO2 14 after 120-h oxidation at S/Fe = 0.112. Given that no apparent Tc dissolution occurred during this 15 period, the speciation transformation might play a secondary role in hindering Tc oxidation, 16 especially as redox buffer capacity approached depletion.

  5. Kinetic investigation of sulfidizing annealing of scorodite in processing of refractory oxidized gold-containing ores

    NASA Astrophysics Data System (ADS)

    Boboev, I. R.; Strizhko, L. S.; Bobozoda, Sh.; Gorbunov, E. P.

    2016-03-01

    The results of kinetic studies on the removal of arsenic from scorodite using sulfidizing annealing are presented. The reaction order with respect to the reactant and the activation energy are established from the experimental data. The rate-determining step of the sulfidizing annealing process is determined. The main reactions that occur during the sulfidizing of arsenic in scorodite are proposed on the basis of the obtained results and confirmed by thermodynamic calculations and chemical analyses. The major results of testing this technology, as applied to the refractory oxidized ores in which arsenic is mainly concentrated in scorodite, are presented. Arsenic removal from this ore is confirmed by chemical and quantitative X-ray diffraction analyses and by qualitative phase analysis. Industrial use of this technology provides safe and efficient processing of refractory gold-containing ores, where arsenic is mainly concentrated in scorodite.

  6. Method of removing hydrogen sulfide from gases utilizing a zinc oxide sorbent and regenerating the sorbent

    DOEpatents

    Jalan, Vinod M.; Frost, David G.

    1984-01-01

    A spent solid sorbent resulting from the removal of hydrogen sulfide from a fuel gas flow is regenerated with a steam-air mixture. The mixture of steam and air may also include additional nitrogen or carbon dioxide. The gas mixture contacts the spent sorbent containing metal sulfide at a temperature above 500.degree. C. to regenerate the sulfide to metal oxide or carbonate. Various metal species including the period four transition metals and the lanthanides are suitable sorbents that may be regenerated by this method. In addition, the introduction of carbon dioxide gas permits carbonates such as those of strontium, barium and calcium to be regenerated. The steam permits regeneration of spent sorbent without formation of metal sulfate. Moreover, the regeneration will proceed with low oxygen concentrations and will occur without the increase in temperature to minimize the risk of sintering and densification of the sorbent.

  7. Reduced graphene oxide based silver sulfide hybrid films formed at a liquid/liquid interface

    SciTech Connect

    Bramhaiah, K. John, Neena S.

    2014-04-24

    Free-standing, ultra-thin films of silver sulfide and reduced graphene oxide (RGO) based silver sulfide hybrids are prepared at a liquid/liquid interface employing in situ chemical reaction strategy. Ag{sub 2}S and RGO−Ag{sub 2}S hybrid films are characterized by various techniques such as UV-visible and photo luminescence spectroscopy, X-ray diffraction and scanning electron microscopy. The morphology of hybrid films consists of Ag{sub 2}S nanocrystals on RGO surface while Ag{sub 2}S films contains branched network of dendritic structures. RGO−Ag{sub 2}S exhibit interesting optical and electrical properties. The hybrid films absorb in the region 500–650 nm and show emission in the red region. A higher conductance is observed for the hybrid films arising from the RGO component. This simple low cost method can be extended to prepare other RGO based metal sulfides.

  8. Role of biogenic sulfide in attenuating zinc oxide and copper nanoparticle toxicity to acetoclastic methanogenesis.

    PubMed

    Gonzalez-Estrella, Jorge; Puyol, Daniel; Sierra-Alvarez, Reyes; Field, Jim A

    2015-01-01

    Soluble ions released by zinc oxide (ZnO) and copper (Cu(0)) nanoparticles (NPs) have been associated with toxicity to methanogens. This study evaluated the role of biogenic sulfide in attenuating ZnO and Cu(0) NP toxicity to methanogens. Short- and long-term batch experiments were conducted to explore ZnO and Cu(0) NPs toxicity to acetoclastic methanogens in sulfate-containing (0.4mM) and sulfate-free conditions. ZnO and Cu(0) were respectively 14 and 7-fold less toxic in sulfate-containing than in sulfate-free assays as indicated by inhibitory constants (Ki). The Ki with respect to residual soluble metal indicated that soluble metal was well correlated with toxicity irrespective of the metal ion source or presence of biogenic sulfide. Long-term assays indicated that ZnO and Cu(0) NPs caused different effects on methanogens. ZnO NPs without protection of sulfide caused a chronic effect, whereas Cu(0) NPs caused an acute effect and recovered. This study confirms that biogenic sulfide effectively attenuates ZnO and Cu(0) NPs toxicity to methanogens by the formation of metal sulfides.

  9. Third phase formation in the extraction of Nd(III) by octyl(phenyl)-N,N-diisobutyl carbamoyl methyl phosphine oxide (O{Phi}CMPO)

    SciTech Connect

    Suresh, A.; Brahmmananda Rao, C.V.S.; Sabharwal, K.N.; Srinivasan, T.G.; Vasudeva Rao, P.R.

    1999-01-01

    Third phase formation in the extraction of Nd(III) by 0.2 M Octyl(Phenyl)-N,N-Diisobutyl Carbamoyl methyl phosphine oxide (O{Phi}CMPO) in n-dodecane has been studied with tri-n-butyl phosphate (TBP) and tri-n-amyl phosphate (TAP) as modifiers to provide a comparison between these two modifier systems. The effect of concentration of TAP as modifier for the extraction of Nd(III) by 0.2 M O{Phi}CMPO has been studied. The extraction of Nd(III) by TAP/n-dodecane in the absence of O{Phi}CMPO has also been studied and the results are reported here.

  10. Extraction of Am(III), Eu(III) and U(VI) from perchloric acid and mixtures of acids by dialkyl-(diaryl) [diethylcarbamoylmethyl] phosphine oxides

    SciTech Connect

    Chmutova, M.K.; Litvina, M.N.; Nesterova, N.P.; Myasoedov, B.F.; Kabachnik, M.I.

    1992-07-01

    Extraction of Am(III), and Eu(III) and U(VI) from perchloric acid solutions by dialkyl(diaryl) [diethyl-carbamoylmethyl] phosphine oxides (CMPO) has been investigated. It has been shown that elements are extracted more effectively from perchloric acid solutions than from nitric acid. An `anomalous aryl effect` increases sufficiently in perchloric media as compared with nitric media. Solvate numbers of elements also increase in perchloric acid, they being extremely high for aryl-substituted reagents and not so high for alkyl-substituted compounds. It has been shown that in HNO{sub 3} and HClO{sub 4} solutions the value of `anomalous aryl effect` directly depends on the difference in values of element solvate numbers in complexes with aryl- and alkyl-substituted CMPO. Am(III), Eu(III) and U(VI) are not practically extracted from phosphoric and sulphuric acids by CMPO solutions. 16 refs., 7 figs., 3 tabs.

  11. Mechanism study on the sulfidation of ZnO with sulfur and iron oxide at high temperature

    PubMed Central

    Han, Junwei; Liu, Wei; Zhang, Tianfu; Xue, Kai; Li, Wenhua; Jiao, Fen; Qin, Wenqing

    2017-01-01

    The mechanism of ZnO sulfidation with sulfur and iron oxide at high temperatures was studied. The thermodynamic analysis, sulfidation behavior of zinc, phase transformations, morphology changes, and surface properties were investigated by HSC 5.0 combined with FactSage 7.0, ICP, XRD, optical microscopy coupled with SEM-EDS, and XPS. The results indicate that increasing temperature and adding iron oxide can not only improve the sulfidation of ZnO but also promote the formation and growth of ZnS crystals. Fe2O3 captured the sulfur in the initial sulfidation process as iron sulfides, which then acted as the sulfurizing agent in the late period, thus reducing sulfur escape at high temperatures. The addition of carbon can not only enhance the sulfidation but increase sulfur utilization rate and eliminate the generation of SO2. The surfaces of marmatite and synthetic zinc sulfides contain high oxygen due to oxidation and oxygen adsorption. Hydroxyl easily absorbs on the surface of iron-bearing zinc sulfide (Zn1−xFexS). The oxidation of synthetic Zn1−xFexS is easier than marmatite in air. PMID:28186156

  12. Mechanism study on the sulfidation of ZnO with sulfur and iron oxide at high temperature

    NASA Astrophysics Data System (ADS)

    Han, Junwei; Liu, Wei; Zhang, Tianfu; Xue, Kai; Li, Wenhua; Jiao, Fen; Qin, Wenqing

    2017-02-01

    The mechanism of ZnO sulfidation with sulfur and iron oxide at high temperatures was studied. The thermodynamic analysis, sulfidation behavior of zinc, phase transformations, morphology changes, and surface properties were investigated by HSC 5.0 combined with FactSage 7.0, ICP, XRD, optical microscopy coupled with SEM-EDS, and XPS. The results indicate that increasing temperature and adding iron oxide can not only improve the sulfidation of ZnO but also promote the formation and growth of ZnS crystals. Fe2O3 captured the sulfur in the initial sulfidation process as iron sulfides, which then acted as the sulfurizing agent in the late period, thus reducing sulfur escape at high temperatures. The addition of carbon can not only enhance the sulfidation but increase sulfur utilization rate and eliminate the generation of SO2. The surfaces of marmatite and synthetic zinc sulfides contain high oxygen due to oxidation and oxygen adsorption. Hydroxyl easily absorbs on the surface of iron-bearing zinc sulfide (Zn1‑xFexS). The oxidation of synthetic Zn1‑xFexS is easier than marmatite in air.

  13. Sulfidogenic biotreatment of synthetic acid mine drainage and sulfide oxidation in anaerobic baffled reactor.

    PubMed

    Bekmezci, Ozan K; Ucar, Deniz; Kaksonen, Anna H; Sahinkaya, Erkan

    2011-05-30

    The treatment of synthetic acid mine drainage (AMD) water (pH 3.0-6.5) containing sulfate (3.0-3.5 g L(-1)) and various metals (Co, Cu, Fe, Mn, Ni, and Zn) was studied in an ethanol-fed sulfate-reducing 4-compartment anaerobic baffled reactor (ABR) at 32°C. The reactor was operated for 160 days at different chemical oxygen demand (COD)/sulfate ratios, hydraulic retention times (HRT), pH, and metal concentrations to study the robustness of the process. The last compartment of the reactor was aerated at different rates to study the bio-oxidation of sulfide to elemental sulfur. The highest sulfate reduction efficiency (88%) was obtained with a feed sulfate concentration of 3.5 g L(-1), COD/sulfate mass ratio of 0.737, feed pH of 3.0 and HRT of 2 days without aeration in the 4th compartment. The corresponding COD removal efficiency was about 92%. The alkalinity produced in the sulfidogenic ethanol oxidation neutralized the acidic mine water from pH 3.0-4.5 to pH 7.0-8.0. Effluent soluble and total heavy metal concentrations were substantially reduced with removal efficiencies generally higher than 99%, except for Mn (25-77%). Limited aeration in the 4th compartment of ABR promoted incomplete oxidation of sulfide to elemental sulfur rather than complete oxidation to sulfate. Depending on the aeration rate and HRT, 32-74% of produced sulfide was oxidized to elemental sulfur. This study demonstrates that by optimizing operating conditions, sulfate reduction, metal removal, alkalinity generation, and excess sulfide oxidation can be achieved in a single ABR treating AMD.

  14. Characterization of an autotrophic sulfide-oxidizing marine Arcobacter sp. that produces filamentous sulfur.

    PubMed

    Wirsen, C O; Sievert, S M; Cavanaugh, C M; Molyneaux, S J; Ahmad, A; Taylor, L T; DeLong, E F; Taylor, C D

    2002-01-01

    A coastal marine sulfide-oxidizing autotrophic bacterium produces hydrophilic filamentous sulfur as a novel metabolic end product. Phylogenetic analysis placed the organism in the genus Arcobacter in the epsilon subdivision of the Proteobacteria. This motile vibrioid organism can be considered difficult to grow, preferring to grow under microaerophilic conditions in flowing systems in which a sulfide-oxygen gradient has been established. Purified cell cultures were maintained by using this approach. Essentially all 4',6-diamidino-2-phenylindole dihydrochloride-stained cells in a flowing reactor system hybridized with Arcobacter-specific probes as well as with a probe specific for the sequence obtained from reactor-grown cells. The proposed provisional name for the coastal isolate is "Candidatus Arcobacter sulfidicus." For cells cultured in a flowing reactor system, the sulfide optimum was higher than and the CO(2) fixation activity was as high as or higher than those reported for other sulfur oxidizers, such as Thiomicrospira spp. Cells associated with filamentous sulfur material demonstrated nitrogen fixation capability. No ribulose 1,5-bisphosphate carboxylase/oxygenase could be detected on the basis of radioisotopic activity or by Western blotting techniques, suggesting an alternative pathway of CO(2) fixation. The process of microbial filamentous sulfur formation has been documented in a number of marine environments where both sulfide and oxygen are available. Filamentous sulfur formation by "Candidatus Arcobacter sulfidicus" or similar strains may be an ecologically important process, contributing significantly to primary production in such environments.

  15. Oxidative remobilization of technetium sequestered by sulfide-transformed nano zerovalent iron.

    PubMed

    Fan, Dimin; Anitori, Roberto P; Tebo, Bradley M; Tratnyek, Paul G; Lezama Pacheco, Juan S; Kukkadapu, Ravi K; Kovarik, Libor; Engelhard, Mark H; Bowden, Mark E

    2014-07-01

    Our previous study showed that formation of TcS2-like phases is favored over TcO2 under sulfidic conditions stimulated by nano zerovalent iron. This study further investigates the stability of Tc(IV) sulfide upon reoxidation by solution chemistry, solid phase characterization, and X-ray absorption spectroscopy. Tc dissolution data showed that Tc(VII) reduced by sulfide-transformed nZVI has substantially slower reoxidation kinetics than Tc(VII) reduced by nZVI only. The initial inhibition of Tc(IV) dissolution at S/Fe = 0.112 is due to the redox buffer capacity of FeS, which is evidenced by the parallel trends in oxidation-reduction potentials (ORP) and Tc dissolution kinetics. The role of FeS in inhibiting Tc oxidation is further supported by the Mössbauer spectroscopy and micro X-ray diffraction data at S/Fe = 0.112, showing persistence of FeS after 24-h oxidation but complete oxidation after 120-h oxidation. X-ray absorption spectroscopy data for S/Fe = 0.011 showed significantly increasing percentages of TcS2 in the solid phase after 24-h oxidation, indicating stronger resistance of TcS2 to oxidation. At S/Fe = 0.112, the XAS results revealed significant transformation of Tc speciation from TcS2 to TcO2 after 120-h oxidation. Given that no apparent Tc dissolution occurred during this period, the speciation transformation might play a secondary role in hindering Tc oxidation. Collectively, the results indicate that sequestrating Tc as TcS2 under stimulated sulfate reduction is a promising strategy to improve the long-term stability of reduced Tc in subsurface remediation.

  16. Synthesis of bacteria promoted reduced graphene oxide-nickel sulfide networks for advanced supercapacitors.

    PubMed

    Zhang, Haiming; Yu, Xinzhi; Guo, Di; Qu, Baihua; Zhang, Ming; Li, Qiuhong; Wang, Taihong

    2013-08-14

    Supercapacitors with potential high power are useful and have attracted much attention recently. Graphene-based composites have been demonstrated to be promising electrode materials for supercapacitors with enhanced properties. To improve the performance of graphene-based composites further and realize their synthesis with large scale, we report a green approach to synthesize bacteria-reduced graphene oxide-nickel sulfide (BGNS) networks. By using Bacillus subtilis as spacers, we deposited reduced graphene oxide/Ni3S2 nanoparticle composites with submillimeter pores directly onto substrate by a binder-free electrostatic spray approach to form BGNS networks. Their electrochemical capacitor performance was evaluated. Compared with stacked reduced graphene oxide-nickel sulfide (GNS) prepared without the aid of bacteria, BGNS with unique nm-μm structure exhibited a higher specific capacitance of about 1424 F g(-1) at a current density of 0.75 A g(-1). About 67.5% of the capacitance was retained as the current density increased from 0.75 to 15 A g(-1). At a current density of 75 A g(-1), a specific capacitance of 406 F g(-1) could still remain. The results indicate that the reduced graphene oxide-nickel sulfide network promoted by bacteria is a promising electrode material for supercapacitors.

  17. High-temperature oxidation/sulfidation resistance of iron-aluminide coatings

    SciTech Connect

    Tortorelli, P.F.; Wright, I.G.; Goodwin, G.M.; Howell, M.

    1996-04-01

    Iron aluminides containing > 20-25 at. % Al have oxidation and sulfidation resistance at temperatures well above those at which these alloys have adequate mechanical strength. Accordingly, these alloys may find application as coatings or claddings on more conventional higher-strength materials which are generally less corrosion-resistant at high temperatures. To this end, iron-aluminide coatings were prepared by gas tungsten arc and gas metal arc weld-overlay techniques. Specimens were cut from weld deposits and exposed to a highly aggressive oxidizing-sulfidizing (H2S-H2-H2O-Ar) environment at 800 C. All the weld overlayers showed good corrosion behavior under isothermal conditions, including a gas metal arc-produced deposit with only 21 at. % Al. Rapid degradation in corrosion resistance was observed under thermal cycling conditions when the initally grown scales spalled and the rate of reaction was then not controlled by formation of slowly growing Al oxide. Higher starting Al concentrations (> {approximately} 25 at. %) are needed to assure overall oxidation-sulfidation resistance of the weld overlays, but hydrogen cracking susceptibility must be minimized in order to physically separate the corrosive species from the reactive substrate material.

  18. Inhibition of a biological sulfide oxidation under haloalkaline conditions by thiols and diorgano polysulfanes.

    PubMed

    Roman, Pawel; Lipińska, Joanna; Bijmans, Martijn F M; Sorokin, Dimitry Y; Keesman, Karel J; Janssen, Albert J H

    2016-09-15

    A novel approach has been developed for the simultaneous description of reaction kinetics to describe the formation of polysulfide and sulfate anions from the biological oxidation of hydrogen sulfide (H2S) using a quick, sulfide-dependent respiration test. Next to H2S, thiols are commonly present in sour gas streams. We investigated the inhibition mode and the corresponding inhibition constants of six thiols and the corresponding diorgano polysulfanes on the biological oxidation of H2S. A linear relationship was found between the calculated IC50 values and the lipophilicity of the inhibitors. Moreover, a mathematical model was proposed to estimate the biomass activity in the absence and presence of sulfurous inhibitors. The biomass used in the respiration tests originated from a full-scale biodesulfurization reactor. A microbial community analysis of this biomass revealed that two groups of microorganism are abundant, viz. Ectothiorhodospiraceae and Piscirickettsiaceae.

  19. Oxidation, carburization and/or sulfidation resistant iron aluminide alloy

    DOEpatents

    Sikka, Vinod K.; Deevi, Seetharama C.; Fleischhauer, Grier S.; Hajaligol, Mohammad R.; Lilly, Jr., A. Clifton

    2003-08-19

    The invention relates generally to aluminum containing iron-base alloys useful as electrical resistance heating elements. The aluminum containing iron-base alloys have improved room temperature ductility, electrical resistivity, cyclic fatigue resistance, high temperature oxidation resistance, low and high temperature strength, and/or resistance to high temperature sagging. The alloy has an entirely ferritic microstructure which is free of austenite and includes, in weight %, over 4% Al, .ltoreq.1% Cr and either .gtoreq.0.05% Zr or Zro.sub.2 stringers extending perpendicular to an exposed surface of the heating element or .gtoreq.0.1% oxide dispersoid particles. The alloy can contain 14-32% Al, .ltoreq.2% Ti, .ltoreq.2% Mo, .ltoreq.1% Zr, .ltoreq.1% C, .ltoreq.0.1% B. .ltoreq.30% oxide dispersoid and/or electrically insulating or electrically conductive covalent ceramic particles, .ltoreq.1% rare earth metal, .ltoreq.1% oxygen, .ltoreq.3% Cu, balance Fe.

  20. Alteration of Mantle Sulfides: the Effects of Oxidation and Melt Infiltration in a Kilbourne Hole Harzburgite Xenolith

    NASA Astrophysics Data System (ADS)

    Barrett, T. J.; Harvey, J.; Warren, J. M.; Klein, F.; Walshaw, R.

    2013-12-01

    Sulfides, while commonly present in volumetrically minor amounts (< 0.1 modal %; e.g.[1]) in the mantle, impart a strong control over many of the highly siderophile and strongly chalcophile elements. The mass balance of some elements, such as Os, are almost completely controlled by heterogeneously distributed sulfide grains[2][3]. Hence, processes that re-distribute sulfides and / or alter their composition can have profound effects on the information preserved within them regarding primary mantle processes. Different generations of interstitial sulfide may partly or completely re-equilibrate with one another or may be exposed to open-system processes that mobilize and / or precipitate sulfides[4]. In mantle xenoliths in particular, supergene weathering at the Earth's surface can oxidize sulfide to soluble sulfate, and its removal affects highly siderophile and strongly chalcophile element abundances [6]. Here we present the initial results from a study of interstitial mantle sulfides (n = 24) recovered from a single harzburgitic xenolith from Kilbourne Hole, NM. Large compositional differences are observed in the sulfides even at the scale of a single xenolith. Mono-sulfide solid solution has exsolved into two Fe-Ni-rich phases, one with a significantly larger Ni content for a given Fe abundance. Occurrences of Cu-rich sulfides are rare, but where present Cu can account for up to 22 weight % of the sulfide. Critically, no fresh, unaltered sulfides were recovered and in all of the sulfides there is evidence for at least two secondary processes. EDS mapping of the sulfides reveals pervasive, but incomplete, oxidation in all of the grains; Raman spectroscopy reveals this oxide to be goethite. In addition, there is also evidence for the interaction of many of the sulfides with a volatile-rich silicate melt. Silicate melt veins cross-cut the original sulfide mineralogy in some areas of the sulfide grain, while leaving other areas virtually untouched. The degree of

  1. Frustrated Lewis pair modification by 1,1-carboboration: disclosure of a phosphine oxide triggered nitrogen monoxide addition to an intramolecular P/B frustrated Lewis pair.

    PubMed

    Liedtke, René; Scheidt, Felix; Ren, Jinjun; Schirmer, Birgitta; Cardenas, Allan Jay P; Daniliuc, Constantin G; Eckert, Hellmut; Warren, Timothy H; Grimme, Stefan; Kehr, Gerald; Erker, Gerhard

    2014-06-25

    The vicinal frustrated Lewis pair (FLP) mes2P-CH2CH2-B(C6F5)2 (3) reacts with phenyl(trimethylsilyl)acetylene by 1,1-carboboration to give the extended C3-bridged FLP 6 featuring a substituted vinylborane subunit. The FLP 6 actively cleaves dihydrogen. The FLP 3 also undergoes a 1,1-carboboration reaction with diphenylphosphino(trimethylsilyl)acetylene to give the P/B/P FLP 11 that features a central unsaturated four-membered heterocyclic P/B FLP and a pendant CH2CH2-Pmes2 functional group. Compound 11 reacts with nitric oxide (NO) by oxidation of the pendant Pmes2 unit to the P(O)mes2 phosphine oxide and N,N-addition of the P/B FLP unit to NO to yield the persistent P/B/PO FLPNO aminoxyl radical 14. This reaction is initiated by P(O)mes2 formation and opening of the central Ph2P···B(C6F5)2 linkage triggered by the pendant CH2CH2-P(O)mes2 group.

  2. Iron sulfide oxidation as influenced by calcium carbonate application.

    PubMed

    Hossner, L R; Doolittle, J J

    2003-01-01

    Two overburden materials, with different FeS2 contents (1.9 and 4.1%) and low acid neutralization potential, were limed with CaCO3 at rates of 0, 25, 50, 75, 100, and 125% based on the amount of CaCO3 needed to provide an acid-base account deficit (A/Ba) of zero (A/Ba = neutralization potential--potential acidity--exchangeable acidity). The limed overburden materials were inoculated with Thiobacillus ferrooxidans and leached weekly with deionized water. Residual FeS2 and CaCO3 were determined in samples over a 378-d period. Oxidation followed zero-order kinetics with respect to FeS2 concentration at pH values greater than 4 and first-order kinetics at pH values less than 4. Zero-order oxidation rates ranged from 0.01 to 0.46 micromol g(-1) d(-1) in the overburden with 1.9% FeS2 and from 0.01 to 0.22 micromol g(-1) d(-1) in the overburden with 4.1% FeS2. Oxidation following the first-order rate law had a first-order rate constant of 0.03 d(-1) in the 1.9% FeS2 overburden and 0.01 d(-1) in the 4.1% FeS2 overburden. The calculated half-life was 23 d for the 1.9% FeS2 overburden and 69 d for the 4.1% FeS2 overburden. Additions of CaCO3 affected FeS2 oxidation by controlling the pH of the system. Liming to greater than 50% of the acid-base account deficit did not significantly affect the zero-order oxidation rate. Dissolution of the applied CaCO3 was found to be faster than the oxidation of FeS2 at pH values greater than 4. It was projected that at lime rates up to 125%, the CaCO3 would dissolve and leach out of the system before all the FeS2 oxidized, leaving the potential for acid minesoil formation.

  3. Oxidation of dimethyl sulfide to dimethyl sulfoxide by phototrophic purple bacteria

    SciTech Connect

    Zeyer, J.; Eicher, P.; Wakeham, S.G.; Schwarzenbach, R.P.

    1987-09-01

    Enrichment cultures of phototrophic purple bacteria rapidly oxidized up to 10 mM dimethyl sulfide (DMS) to dimethyl sulfoxide (DMSO). DMSO was qualitatively identified by proton nuclear magnetic resonance. By using a biological assay, DMSO was always quantitatively recovered from the culture media. DMS oxidation was not detected in cultures incubated in the dark, and it was slow in cultures exposed to full daylight. Under optimal conditions, the second-order rate constant for DMS oxidation was 6 day/sup -1/ mg of protein/sup -1/ ml/sup -1/. The rate constant was reduced in the presence of high concentration of sulfide (>1 mM), but was not affected by the addition of acetate. DMS was also oxidized to DMSO by a pure strain (tentatively identified as a Thiocystis sp.) isolated from the enrichment cultures. DMS supported growth of the enrichment cultures and of the pure strain by serving as an electron source for photosynthesis. A determination of the amount of protein produced in the cultures and an estimation of the electron balance suggested that the two electrons liberated during the oxidation of DMS to DMSO were quantitatively used to reduce carbon dioxide to biomass. The oxidation of DMS by phototrophic purple bacteria may be an important source of DMSO detected in anaerobic ponds and marshes.

  4. Predicting the Release of Sulfide Oxidation Products at Mine Waste Sites

    NASA Astrophysics Data System (ADS)

    Blowes, D. W.; Ptacek, C. J.; Mayer, K. U.; Bain, J. G.; Moncur, M. C.; Jambor, J. L.

    2004-05-01

    Reactive solute transport models provide sophisticated tools for predicting the magnitude and duration of acid generation and metal release in mine waste disposal facilities. Over the past decade, these models have become increasingly advanced. The ability of reactive solute transport models to simulate integrated biogeochemical and hydrological processes now challenges our ability to characterize these systems on the field and laboratory scale. Application of reactive solute transport models relies on the development of an accurate conceptual model and specification of the chemical, physical and hydrological characteristics of the waste materials. Release of acidic water and dissolved metals from mine waste disposal facilities is controlled by a complex combination of physical, chemical, and biological processes. The oxidation of sulfide minerals is ultimately controlled by the availability of oxygen, which is usually transported in its gaseous form. The reaction between oxygen and sulfide minerals is catalyzed by chemolithotrophic bacteria. The oxidation of individual sulfide minerals occurs at differing rates. Sulfide oxidation reactions release acid, sulfate and dissolved metals. The acid released may be neutralized by reaction with carbonate, hydroxide and aluminosilicate minerals. The metals released may be attenuated by precipitation of secondary minerals, by coprecipitation or by adsorption reactions. Thorough characterization of the waste properties which control gas transport and water flow through the waste materials is required. In addition, a thorough knowledge of the initial composition and mineralogy is required to develop representative estimates of the environmental effects of the waste materials. When sufficient information is available, the results of reactive solute transport simulations show close agreement to measurements made at field sites and in laboratory experiments.

  5. High temperature hydrogen sulfide removal with stannic oxide

    SciTech Connect

    Karpuk, M.E.; Copeland, R.J.; Feinberg, D.; Wickham, D.; Windecker, B.; Yu, J.

    1994-10-01

    This contract focuses on the development of sorbents and processes for removal of H{sub 2}S from hot coal gas with the product of sorbent regeneration being elemental sulfur. TDA Research`s process uses a regenerable tin(IV) oxide-based (SnO{sub 2}) sorbent as the first sorbent and zinc ferrite (or zinc titanate) as a second sorbent.

  6. The impact of electrogenic sulfide oxidation on elemental cycling and solute fluxes in coastal sediment

    NASA Astrophysics Data System (ADS)

    Rao, Alexandra M. F.; Malkin, Sairah Y.; Hidalgo-Martinez, Silvia; Meysman, Filip J. R.

    2016-01-01

    Filamentous sulfide oxidizing cable bacteria are capable of linking the oxidation of free sulfide in deep anoxic layers of marine sediments to the reduction of oxygen or nitrate in surface sediments by conducting electrons over centimeter-scale distances. Previous studies have shown that this newly discovered microbial process, referred to as electrogenic sulfide oxidation (e-SOx), may alter elemental cycling in sediments, but the nature and rates of the resulting biogeochemical transformations and their influence on benthic-pelagic coupling remain largely unknown. Here we quantify changes in sediment geochemistry and solute fluxes at the sediment-water interface as e-SOx develops and declines over time in laboratory incubations of organic-rich sediments from a seasonally hypoxic coastal basin (Marine Lake Grevelingen, The Netherlands). Our results show that e-SOx enhanced sediment O2 consumption and acidified subsurface sediment, resulting in the dissolution of calcium carbonate and iron sulfide minerals in deeper sediment horizons and the associated accumulation of dissolved iron, manganese, and calcium in porewater. Remobilized Fe diffusing upward was reoxidized at the sediment-water interface, producing an amorphous Fe oxide crust, while dissolved Fe diffusing downward was reprecipitated in the form of FeS as it encountered the free sulfide horizon. The development of e-SOx enhanced the diffusive release of dissolved Mn at the sediment-water interface, capped the phosphate efflux, generated a buildup of organic matter in surface sediments, and strongly stimulated the release of alkalinity from the sediment. About 75% of this alkalinity production was associated with net CaCO3 dissolution, while the remaining 25% was attributed to a pumping mechanism that transfers alkalinity from anodic H2S oxidation (an alkalinity sink) in deeper sediments to cathodic O2 reduction (an alkalinity source) near the sediment-water interface. The resulting sediment alkalinity

  7. Kinetic and stoichiometric characterization of anoxic sulfide oxidation by SO-NR mixed cultures from anoxic biotrickling filters.

    PubMed

    Mora, Mabel; Fernández, Maikel; Gómez, José Manuel; Cantero, Domingo; Lafuente, Javier; Gamisans, Xavier; Gabriel, David

    2015-01-01

    Monitoring the biological activity in biotrickling filters is difficult since it implies estimating biomass concentration and its growth yield, which can hardly be measured in immobilized biomass systems. In this study, the characterization of a sulfide-oxidizing nitrate-reducing biomass obtained from an anoxic biotrickling filter was performed through the application of respirometric and titrimetric techniques. Previously, the biomass was maintained in a continuous stirred tank reactor under steady-state conditions resulting in a growth yield of 0.328 ± 0.045 g VSS/g S. To properly assess biological activity in respirometric tests, abiotic assays were conducted to characterize the stripping of CO2 and sulfide. The global mass transfer coefficient for both processes was estimated. Subsequently, different respirometric tests were performed: (1) to solve the stoichiometry related to the autotrophic denitrification of sulfide using either nitrate or nitrite as electron acceptors, (2) to evaluate the inhibition caused by nitrite and sulfide on sulfide oxidation, and (3) to propose, calibrate, and validate a kinetic model considering both electron acceptors in the overall anoxic biodesulfurization process. The kinetic model considered a Haldane-type equation to describe sulfide and nitrite inhibitions, a non-competitive inhibition to reflect the effect of sulfide on the elemental sulfur oxidation besides single-step denitrification since no nitrite was produced during the biological assays.

  8. Persistency-field Eh-pH diagrams for sulfides and their application to supergene oxidation and enrichment of sulfide ore bodies

    USGS Publications Warehouse

    Sato, M.

    1992-01-01

    At temperatures prevailing near the Earth's surface, metastable co-existence of chemical substances is common because chemical reactions that would directly lead to the attainment of thermody-namically most stable equilibria are often blocked by high activation energy barriers. The persistency of a metastable assemblage is then governed by alternative reaction paths that provide lower activation energy barriers. Comparison of observed mineral assemblages in the supergene oxidized and enriched sulfide ores with corresponding stability Eh-pH diagrams reveals that the supergene assemblages are mostly metastable due primarily to the persistency of sulfide minerals beyond stability boundaries. A new set of diagrams called persistency-field Eh-pH diagrams has been constructed for binary metal sulfides on the basis of electrochemical and other experimental data. Each diagram delineates the persistency field, which is a combined field of thermodynamic stability and reaction path-controlled metastability, for a specific sulfide mineral. When applied to the supergene assemblages, these new diagrams show much better correspondence to the field observations. Although there may still be room for further refinement, the new diagrams appear to provide a strong visual aid to the understanding of the behavior of sulfide minerals in the supergene conditions. ?? 1992.

  9. Parameterization of phosphine ligands reveals mechanistic pathways and predicts reaction outcomes

    NASA Astrophysics Data System (ADS)

    Niemeyer, Zachary L.; Milo, Anat; Hickey, David P.; Sigman, Matthew S.

    2016-06-01

    The mechanistic foundation behind the identity of a phosphine ligand that best promotes a desired reaction outcome is often non-intuitive, and thus has been addressed in numerous experimental and theoretical studies. In this work, multivariate correlations of reaction outcomes using 38 different phosphine ligands were combined with classic potentiometric analyses to study a Suzuki reaction, for which the site selectivity of oxidative addition is highly dependent on the nature of the phosphine. These studies shed light on the generality of hypotheses regarding the structural influence of different classes of phosphine ligands on the reaction mechanism(s), and deliver a methodology that should prove useful in future studies of phosphine ligands.

  10. Effect of bioturbation on metal-sulfide oxidation in surficial freshwater sediments

    SciTech Connect

    Peterson, G.S.; Ankley, G.T.; Leonard, E.N.

    1996-12-01

    Recent studies have demonstrated the role of acid-volatile sulfide (AVS) in controlling the bioavailability of several cationic metals in anoxic sediments. However, metal-sulfide complexes can be relatively labile with respect to oxidation associated with factors such as seasonal changes in rates of oxidation/production of AVS. Another potentially important mechanism of AVS oxidation in surficial sediments is bioturbation. The authors used different densities of the burrowing oligochaete Lumbriculus variegatus in a series of laboratory experiments to evaluate the effect of bioturbation on oxidation of AVS and subsequent bioavailability of cadmium and zinc spiked into freshwater sediments. Metal bioavailability was determined directly by bioaccumulation in the test organisms and indirectly through analysis of interstitial (pore) water metal concentrations. In the studies, horizon-specific sediment analyses were conducted to assess spatial differences in AVS and pore-water metal concentrations specifically related to organism activity. Burrowing activity of the oligochaete significantly reduced AVS concentrations in surficial sediments in a density-dependent manner and resulted in elevated interstitial water concentrations of cadmium but not zinc. Concentrations of cadmium in pore water from deeper horizons were consistently lower than those in the surficial sediments. The bioaccumulation of cadmium, but not zinc, but the oligochaetes. Overall, the results indicate that bioturbation can enhance the bioavailability of some cationic metals in surficial sediments, via oxidation of AVS, and demonstrate the importance of analyzing surficial sediments when assessing bioavailability of metals in sediments.

  11. Community Shift from Phototrophic to Chemotrophic Sulfide Oxidation following Anoxic Holomixis in a Stratified Seawater Lake

    PubMed Central

    Korlević, Marino; Berg, Jasmine S.; Bura-Nakić, Elvira; Ciglenečki, Irena; Amann, Rudolf; Orlić, Sandi

    2014-01-01

    Most stratified sulfidic holomictic lakes become oxygenated after annual turnover. In contrast, Lake Rogoznica, on the eastern Adriatic coast, has been observed to undergo a period of water column anoxia after water layer mixing and establishment of holomictic conditions. Although Lake Rogoznica's chemistry and hydrography have been studied extensively, it is unclear how the microbial communities typically inhabiting the oxic epilimnion and a sulfidic hypolimnion respond to such a drastic shift in redox conditions. We investigated the impact of anoxic holomixis on microbial diversity and microbially mediated sulfur cycling in Lake Rogoznica with an array of culture-independent microbiological methods. Our data suggest a tight coupling between the lake's chemistry and occurring microorganisms. During stratification, anoxygenic phototrophic sulfur bacteria were dominant at the chemocline and in the hypolimnion. After an anoxic mixing event, the anoxygenic phototrophic sulfur bacteria entirely disappeared, and the homogeneous, anoxic water column was dominated by a bloom of gammaproteobacterial sulfur oxidizers related to the GSO/SUP05 clade. This study is the first report of a community shift from phototrophic to chemotrophic sulfide oxidizers as a response to anoxic holomictic conditions in a seasonally stratified seawater lake. PMID:25344237

  12. Spontaneous ignition limits of silane and phosphine

    SciTech Connect

    Kondo, Shigeo; Tokuhashi, Kazuaki; Nagai, Hidekazu; Iwasaka, Masaji; Kaise, Masahiro

    1995-04-01

    Spontaneous ignition limits of silane and phosphine have been investigated at relatively low concentrations. For silane, the spontaneous ignition occurs if the mixture concentration is such that the silane/oxygen ratio is higher than a certain threshold limit value. In other words, the mixture is not stable if the ratio is higher than a certain value. On the other hand. in the case of phosphine the threshold limit line has been found to be a little curved, though the reason for the fact is not clear. At any rate, it is concluded that the spontaneous ignition of both silane and phosphine occurs as a result of a competition of chain branching and chain breaking reactions, in a way that is qualitatively similar to that in hydrogen oxidation.

  13. Identification of bacteria potentially responsible for oxic and anoxic sulfide oxidation in biofilters of a recirculating mariculture system.

    PubMed

    Cytryn, Eddie; van Rijn, Jaap; Schramm, Andreas; Gieseke, Armin; de Beer, Dirk; Minz, Dror

    2005-10-01

    Bacteria presumably involved in oxygen- or nitrate-dependent sulfide oxidation in the biofilters of a recirculating marine aquaculture system were identified using a new application of reverse transcription-PCR denaturing gradient gel electrophoresis (DGGE) analysis termed differential-transcription (DT)-DGGE. Biofilter samples were incubated in various concentrations of sulfide or thiosulfate (0 to 5 mM) with either oxygen or nitrate as the sole electron acceptor. Before and after short-term incubations (10 to 20 h), total DNA and RNA were extracted, and a 550-bp fragment of the 16S rRNA genes was PCR amplified either directly or after reverse transcription. DGGE analysis of DNA showed no significant change of the original microbial consortia upon incubation. In contrast, DGGE of cDNA revealed several phylotypes whose relative band intensities markedly increased or decreased in response to certain incubation conditions, indicating enhanced or suppressed rRNA transcription and thus implying metabolic activity under these conditions. Specifically, species of the gammaproteobacterial genus Thiomicrospira and phylotypes related to symbiotic sulfide oxidizers could be linked to oxygen-dependent sulfide oxidation, while members of the Rhodobacteraceae (genera Roseobacter, Rhodobacter, and Rhodobium) were putatively active in anoxic, nitrate-dependent sulfide oxidation. For all these organisms, the physiology of their closest cultured relatives matches their DT-DGGE-inferred function. In addition, higher band intensities following exposure to 5 mM sulfide and nitrate were observed for Thauera-, Hydrogenophaga-, and Dethiosulfovibrio-like phylotypes. For these genera, nitrate-dependent sulfide oxidation has not been documented previously and therefore DT-DGGE might indicate a higher relative tolerance to high sulfide concentrations than that of other community members. We anticipate that DT-DGGE will be of general use in tracing functionally equivalent yet

  14. Alternative waste residue materials for passive in situ prevention of sulfide-mine tailings oxidation: A field evaluation

    USGS Publications Warehouse

    Nason, Peter; Johnson, Raymond H.; Neuschutz, Clara; Alakangas, Lena; Ohlander, Bjorn

    2014-01-01

    Novel solutions for sulfide-mine tailings remediation were evaluated in field-scale experiments on a former tailings repository in northern Sweden. Uncovered sulfide-tailings were compared to sewage-sludge biosolid amended tailings over 2 years. An application of a 0.2 m single-layer sewage-sludge amendment was unsuccessful at preventing oxygen ingress to underlying tailings. It merely slowed the sulfide-oxidation rate by 20%. In addition, sludge-derived metals (Cu, Ni, Fe, and Zn) migrated and precipitated at the tailings-to-sludge interface. By using an additional 0.6 m thick fly-ash sealing layer underlying the sewage sludge layer, a solution to mitigate oxygen transport to the underlying tailings and minimize sulfide-oxidation was found. The fly-ash acted as a hardened physical barrier that prevented oxygen diffusion and provided a trap for sludge-borne metals. Nevertheless, the biosolid application hampered the application, despite the advances in the effectiveness of the fly-ash layer, as sludge-borne nitrate leached through the cover system into the underlying tailings, oxidizing pyrite. This created a 0.3 m deep oxidized zone in 6-years. This study highlights that using sewage sludge in unconventional cover systems is not always a practical solution for the remediation of sulfide-bearing mine tailings to mitigate against sulfide weathering and acid rock drainage formation.

  15. Oxidation of sulfides and rapid weathering in recent landslides

    NASA Astrophysics Data System (ADS)

    Emberson, Robert; Hovius, Niels; Galy, Albert; Marc, Odin

    2016-09-01

    Linking together the processes of rapid physical erosion and the resultant chemical dissolution of rock is a crucial step in building an overall deterministic understanding of weathering in mountain belts. Landslides, which are the most volumetrically important geomorphic process at these high rates of erosion, can generate extremely high rates of very localised weathering. To elucidate how this process works we have taken advantage of uniquely intense landsliding, resulting from Typhoon Morakot, in the T'aimali River and surrounds in southern Taiwan. Combining detailed analysis of landslide seepage chemistry with estimates of catchment-by-catchment landslide volumes, we demonstrate that in this setting the primary role of landslides is to introduce fresh, highly labile mineral phases into the surface weathering environment. There, rapid weathering is driven by the oxidation of pyrite and the resultant sulfuric-acid-driven dissolution of primarily carbonate rock. The total dissolved load correlates well with dissolved sulfate - the chief product of this style of weathering - in both landslides and streams draining the area (R2 = 0.841 and 0.929 respectively; p < 0.001 in both cases), with solute chemistry in seepage from landslides and catchments affected by significant landsliding governed by the same weathering reactions. The predominance of coupled carbonate-sulfuric-acid-driven weathering is the key difference between these sites and previously studied landslides in New Zealand (Emberson et al., 2016), but in both settings increasing volumes of landslides drive greater overall solute concentrations in streams. Bedrock landslides, by excavating deep below saprolite-rock interfaces, create conditions for weathering in which all mineral phases in a lithology are initially unweathered within landslide deposits. As a result, the most labile phases dominate the weathering immediately after mobilisation and during a transient period of depletion. This mode of

  16. Microbial Diversity and Population Structure of Extremely Acidic Sulfur-Oxidizing Biofilms From Sulfidic Caves

    NASA Astrophysics Data System (ADS)

    Jones, D.; Stoffer, T.; Lyon, E. H.; Macalady, J. L.

    2005-12-01

    Extremely acidic (pH 0-1) microbial biofilms called snottites form on the walls of sulfidic caves where gypsum replacement crusts isolate sulfur-oxidizing microorganisms from the buffering action of limestone host rock. We investigated the phylogeny and population structure of snottites from sulfidic caves in central Italy using full cycle rRNA methods. A small subunit rRNA bacterial clone library from a Frasassi cave complex snottite sample contained a single sequence group (>60 clones) similar to Acidithiobacillus thiooxidans. Bacterial and universal rRNA clone libraries from other Frasassi snottites were only slightly more diverse, containing a maximum of 4 bacterial species and probably 2 archaeal species. Fluorescence in situ hybridization (FISH) of snottites from Frasassi and from the much warmer Rio Garrafo cave complex revealed that all of the communities are simple (low-diversity) and dominated by Acidithiobacillus and/or Ferroplasma species, with smaller populations of an Acidimicrobium species, filamentous fungi, and protists. Our results suggest that sulfidic cave snottites will be excellent model microbial ecosystems suited for ecological and metagenomic studies aimed at elucidating geochemical and ecological controls on microbial diversity, and at mapping the spatial history of microbial evolutionary events such as adaptations, recombinations and gene transfers.

  17. Chemical denudation and the role of sulfide oxidation at Werenskioldbreen, Svalbard

    NASA Astrophysics Data System (ADS)

    Stachnik, Łukasz; Majchrowska, Elżbieta; Yde, Jacob C.; Nawrot, Adam P.; Cichała-Kamrowska, Katarzyna; Ignatiuk, Dariusz; Piechota, Agnieszka

    2016-07-01

    This study aims to determine the rate of chemical denudation and the relationships between dominant geochemical reactions operating in the proglacial and subglacial environments of the polythermal glacier Werenskioldbreen (SW Svalbard) during an entire ablation season. Water sampling for major ion chemistry was performed at a proglacial hydrometric station and from subglacial outflows from May to September 2011. These data were combined with measurements of discharge and supraglacial ablation rates. The slopes and intercepts in best-fit regressions of [*Ca2+ + *Mg2+ vs. *SO42-] and [HCO3- vs. *SO42-] in meltwater from ice-marginal subglacial channels were close to the stoichiometric parameters of sulfide oxidation and simple hydrolysis coupled to carbonate dissolution (*concentrations corrected for input of sea-salt). This shows that these relationships predominates the meltwater chemistry. Our findings also show that sulfide oxidation is a better indicator of the configuration of subglacial drainage systems than, for instance, Na+ and K+. In the proglacial area and in sub-artesian outflows, the ion associations represent sulfide oxidation but other processes such as ion exchange and dissolution of Ca and Mg efflorescent salts may also contribute to the solute variations. These processes may cause enhanced fluxes of Ca2+ and HCO3- from glacierized basins during the early ablation and peak flow seasons as the proglacial salts re-dissolve. The overall chemical denudation rate in the basin for 2011 (ranging from 1601 to 1762 meq m-2 yr-1 (121.9 to 132.2 t km-2 yr-1)) was very high when compared to other Svalbard valley glaciers suggesting that the high rate of chemical denudation was mostly caused by the high rates of discharge and ablation. Chemical weathering intensities (876 and 964 meq m-3 yr-1) exceeded previously reported intensities in Svalbard.

  18. First principles search for n-type oxide, nitride, and sulfide thermoelectrics

    PubMed Central

    Garrity, Kevin F.

    2016-01-01

    Oxides have many potentially desirable characteristics for thermoelectric applications, including low cost and stability at high temperatures, but thus far there are few known high zT n-type oxide thermoelectrics. In this work, we use high-throughput first principles calculations to screen transition metal oxides, nitrides, and sulfides for candidate materials with high power factors and low thermal conductivity. We find a variety of promising materials, and we investigate these materials in detail in order to understand the mechanisms that cause them to have high power factors. These materials all combine a high density of states near the Fermi level with dispersive bands, reducing the trade-off between the Seebeck coefficient and the electrical conductivity, but they do so for several different reasons. In addition, our calculations indicate that many of our candidate materials have low thermal conductivity. PMID:27885361

  19. First principles search for n-type oxide, nitride, and sulfide thermoelectrics.

    PubMed

    Garrity, Kevin F

    2016-07-15

    Oxides have many potentially desirable characteristics for thermoelectric applications, including low cost and stability at high temperatures, but thus far there are few known high zT n-type oxide thermoelectrics. In this work, we use high-throughput first principles calculations to screen transition metal oxides, nitrides, and sulfides for candidate materials with high power factors and low thermal conductivity. We find a variety of promising materials, and we investigate these materials in detail in order to understand the mechanisms that cause them to have high power factors. These materials all combine a high density of states near the Fermi level with dispersive bands, reducing the trade-off between the Seebeck coefficient and the electrical conductivity, but they do so for several different reasons. In addition, our calculations indicate that many of our candidate materials have low thermal conductivity.

  20. First-principles search for n -type oxide, nitride, and sulfide thermoelectrics

    NASA Astrophysics Data System (ADS)

    Garrity, Kevin F.

    2016-07-01

    Oxides have many potentially desirable characteristics for thermoelectric applications, including low cost and stability at high temperatures, but thus far there are few known high z T n -type oxide thermoelectrics. In this work, we use high-throughput first-principles calculations to screen transition metal oxides, nitrides, and sulfides for candidate materials with high power factors and low thermal conductivity. We find a variety of promising materials, and we investigate these materials in detail in order to understand the mechanisms that cause them to have high power factors. These materials all combine a high density of states near the Fermi level with dispersive bands, reducing the trade-off between the Seebeck coefficient and the electrical conductivity, but they do so for several different reasons. In addition, our calculations indicate that many of our candidate materials have low thermal conductivity.

  1. Microbial Ecology Assessment of Mixed Copper Oxide/Sulfide Dump Leach Operation

    SciTech Connect

    Bruhn, D F; Thompson, D N; Noah, K S

    1999-06-01

    Microbial consortia composed of complex mixtures of autotrophic and heterotrophic bacteria are responsible for the dissolution of metals from sulfide minerals. Thus, an efficient copper bioleaching operation depends on the microbial ecology of the system. A microbial ecology study of a mixed oxide/sulfide copper leaching operation was conducted using an "overlay" plating technique to differentiate and identify various bacterial consortium members of the genera Thiobacillus, Leptospirillum, Ferromicrobium, and Acidiphilium. Two temperatures (30C and 45C) were used to select for mesophilic and moderately thermophilic bacteria. Cell numbers varied from 0-106 cells/g dry ore, depending on the sample location and depth. After acid curing for oxide leaching, no viable bacteria were recovered, although inoculation of cells from raffinate re-established a microbial population after three months. Due to the low pH of the operation, very few non-iron-oxidizing acidophilic heterotrophs were recovered. Moderate thermophiles were isolated from the ore samples. Pregnant liquor solutions (PLS) and raffinate both contained a diversity of bacteria. In addition, an intermittently applied waste stream that contained high levels of arsenic and fluoride was tested for toxicity. Twenty vol% waste stream in PLS killed 100% of the cells in 48 hours, indicating substantial toxicity and/or growth inhibition. The data indicate that bacteria populations can recover after acid curing, and that application of the waste stream to the dump should be avoided. Monitoring the microbial ecology of the leaching operation provided significant information that improved copper recovery.

  2. Matrix metalloproteinases in atherosclerosis: role of nitric oxide, hydrogen sulfide, homocysteine, and polymorphisms

    PubMed Central

    Vacek, Thomas P; Rehman, Shahnaz; Neamtu, Diana; Yu, Shipeng; Givimani, Srikanth; Tyagi, Suresh C

    2015-01-01

    Atherosclerosis is an inflammatory process that involves activation of matrix metalloproteinases (MMPs); MMPs degrade collagen and allow for smooth-muscle cell migration within a vessel. Moreover, this begets an accumulation of other cellular material, resulting in occlusion of the vessel and ischemic events to tissues in need of nutrients. Homocysteine has been shown to activate MMPs via an increase in oxidative stress and acting as a signaling molecule on receptors like the peroxisome proliferator activated receptor-γ and N-methyl-D-aspartate receptor. Nitric oxide has been shown to be beneficial in some cases of deactivating MMPs. However, in other cases, it has been shown to be harmful. Further studies are warranted on the scenarios that are beneficial versus destructive. Hydrogen sulfide (H2S) has been shown to decrease MMP activities in all cases in the literature by acting as an antioxidant and vasodilator. Various MMP-knockout and gene-silencing models have been used to determine the function of the many different MMPs. This has allowed us to discern the role that each MMP has in promoting or alleviating pathological conditions. Furthermore, there has been some study into the MMP polymorphisms that exist in the population. The purpose of this review is to examine the role of MMPs and their polymorphisms on the development of atherosclerosis, with emphasis placed on pathways that involve nitric oxide, hydrogen sulfide, and homocysteine. PMID:25767394

  3. Hollow nanoparticles of metal oxides and sulfides: fast preparation via laser ablation in liquid.

    PubMed

    Niu, K Y; Yang, J; Kulinich, S A; Sun, J; Du, X W

    2010-11-16

    In this work, diverse hollow nanoparticles of metal oxides and sulfides were prepared by simply laser ablating metal targets in properly chosen liquids. The Kirkendall voiding and the selective heating with an infrared laser were shown to work as two independent mechanisms for the formation of such hollow nanoparticles in only one- or two-step synthesis approaches. One of the prepared materials, ZnS hollow nanoparticles, showed high performance in gas sensing. The simple, fast, inexpensive technique that is proposed demonstrates very promising perspectives.

  4. Pressure-induced luminescence quenching of terbium-coped oxide sulfides

    SciTech Connect

    Gleason, J.K.; Offen, H.W. ); Turley, W.D. )

    1993-03-03

    The photoluminescence of Tb[sup 3+]- and Eu[sup 3+]-doped rare earth oxide sulfides has been studied as a function of pressure. The luminescence intensity and lifetime of the [sup 5]D[sub 3] level of Tb[sup 3+] is quenched by pressure as a result of the pressure-induced red shift of the interconfigurational 4f[sup 7]5d band, in agreement with the energy gap law of radiationless transitions. 33 refs., 7 figs.

  5. Sulfide-oxidizing bacteria establishment in an innovative microaerobic reactor with an internal silicone membrane for sulfur recovery from wastewater.

    PubMed

    Valdés, F; Camiloti, P R; Rodriguez, R P; Delforno, T P; Carrillo-Reyes, J; Zaiat, M; Jeison, D

    2016-06-01

    A novel bioreactor, employing a silicone membrane for microaeration, was studied for partial sulfide oxidation to elemental sulfur. The objective of this study was to assess the feasibility of using an internal silicone membrane reactor (ISMR) to treat dissolved sulfide and to characterize its microbial community. The ISMR is an effective system to eliminate sulfide produced in anaerobic reactors. Sulfide removal efficiencies reached 96 % in a combined anaerobic/microaerobic reactor and significant sulfate production did not occur. The oxygen transfer was strongly influenced by air pressure and flow. Pyrosequencing analysis indicated various sulfide-oxidizing bacteria (SOB) affiliated to the species Acidithiobacillus thiooxidans, Sulfuricurvum kujiense and Pseudomonas stutzeri attached to the membrane and also indicated similarity between the biomass deposited on the membrane wall and the biomass drawn from the material support, supported the establishment of SOB in an anaerobic sludge under microaerobic conditions. Furthermore, these results showed that the reactor configuration can develop SOB under microaerobic conditions and can improve and reestablish the sulfide conversion to elemental sulfur.

  6. Light-Dependent Sulfide Oxidation in the Anoxic Zone of the Chesapeake Bay Can Be Explained by Small Populations of Phototrophic Bacteria

    PubMed Central

    Bennett, Alexa J.; Hanson, Thomas E.; Luther, George W.

    2015-01-01

    Microbial sulfide oxidation in aquatic environments is an important ecosystem process, as sulfide is potently toxic to aerobic organisms. Sulfide oxidation in anoxic waters can prevent the efflux of sulfide to aerobic water masses, thus mitigating toxicity. The contribution of phototrophic sulfide-oxidizing bacteria to anaerobic sulfide oxidation in the Chesapeake Bay and the redox chemistry of the stratified water column were investigated in the summers of 2011 to 2014. In 2011 and 2013, phototrophic sulfide-oxidizing bacteria closely related to Prosthecochloris species of the phylum Chlorobi were cultivated from waters sampled at and below the oxic-anoxic interface, where measured light penetration was sufficient to support populations of low-light-adapted photosynthetic bacteria. In 2012, 2013, and 2014, light-dependent sulfide loss was observed in freshly collected water column samples. In these samples, extremely low light levels caused 2- to 10-fold increases in the sulfide uptake rate over the sulfide uptake rate under dark conditions. An enrichment, CB11, dominated by Prosthecochloris species, oxidized sulfide with a Ks value of 11 μM and a Vmax value of 51 μM min−1 (mg protein−1). Using these kinetic values with in situ sulfide concentrations and light fluxes, we calculated that a small population of Chlorobi similar to those in enrichment CB11 can account for the observed anaerobic light-dependent sulfide consumption activity in natural water samples. We conclude that Chlorobi play a far larger role in the Chesapeake Bay than currently appreciated. This result has potential implications for coastal anoxic waters and expanding oxygen-minimum zones as they begin to impinge on the photic zone. PMID:26296727

  7. Light-dependent sulfide oxidation in the anoxic zone of the Chesapeake Bay can be explained by small populations of phototrophic bacteria.

    PubMed

    Findlay, Alyssa J; Bennett, Alexa J; Hanson, Thomas E; Luther, George W

    2015-11-01

    Microbial sulfide oxidation in aquatic environments is an important ecosystem process, as sulfide is potently toxic to aerobic organisms. Sulfide oxidation in anoxic waters can prevent the efflux of sulfide to aerobic water masses, thus mitigating toxicity. The contribution of phototrophic sulfide-oxidizing bacteria to anaerobic sulfide oxidation in the Chesapeake Bay and the redox chemistry of the stratified water column were investigated in the summers of 2011 to 2014. In 2011 and 2013, phototrophic sulfide-oxidizing bacteria closely related to Prosthecochloris species of the phylum Chlorobi were cultivated from waters sampled at and below the oxic-anoxic interface, where measured light penetration was sufficient to support populations of low-light-adapted photosynthetic bacteria. In 2012, 2013, and 2014, light-dependent sulfide loss was observed in freshly collected water column samples. In these samples, extremely low light levels caused 2- to 10-fold increases in the sulfide uptake rate over the sulfide uptake rate under dark conditions. An enrichment, CB11, dominated by Prosthecochloris species, oxidized sulfide with a Ks value of 11 μM and a Vmax value of 51 μM min(-1) (mg protein(-1)). Using these kinetic values with in situ sulfide concentrations and light fluxes, we calculated that a small population of Chlorobi similar to those in enrichment CB11 can account for the observed anaerobic light-dependent sulfide consumption activity in natural water samples. We conclude that Chlorobi play a far larger role in the Chesapeake Bay than currently appreciated. This result has potential implications for coastal anoxic waters and expanding oxygen-minimum zones as they begin to impinge on the photic zone.

  8. INVESTIGATION ON DURABILITY AND REACTIVITY OF PROMISING METAL OXIDE SORBENTS DURING SULFIDATION AND REGENERATION. QUARTERLY AND FINAL REPORT

    SciTech Connect

    K.C. KWON

    1998-08-01

    Hot-gas desulfurization for the integrated gasification combined cycle (IGCC) process has been investigated by many researchers to remove effectively hydrogen sulfide with various metal oxide sorbents at high pressures and high temperatures. Metal oxides such as zinc titanate oxides, zinc ferrite oxide, copper oxide, manganese oxide and calcium oxide, were found to be promising sorbents in comparison with other removal methods such as membrane separations and reactive membrane separations. Some metal oxide sorbents exhibited the quite favorable performance in terms of attrition resistance and sulfur capacity. Experiments on removal reaction of H{sub 2}S from coal gas mixtures with formulated metal oxide sorbents were conducted in a batch reactor or a differential reactor. The objectives of this research project are to formulate promising metal oxide sorbents for removal of sulfur from coal gas mixtures, to find initial reaction kinetics for the metal oxide-hydrogen sulfide heterogeneous reaction system, to obtain effects of hydrogen, nitrogen and moisture on dynamic absorption and equilibrium absorption at various absorption temperatures. Promising durable metal oxide sorbents with high-sulfur-absorbing capacity were formulated by mixing active metal oxide powders with inert metal oxide powders, and calcining these powder mixtures. The Research Triangle Institute (RTI), a sub-contractor of this research project, will also prepare promising metal oxide sorbents for this research project, plan experiments on removal of sulfur compounds from coal gases with metal oxide, and review experimental results.

  9. Adsorption/oxidation of hydrogen sulfide on nitrogen-containing activated carbons

    SciTech Connect

    Adib, F.; Bagreev, A.; Bandosz, T.J.

    2000-02-22

    Wood-based activated carbon was modified by impregnation with urea and heat treatment at 450 and 950 C. The chemical and physical properties of materials were determined using acid/base titration, FTIR, thermal analysis, IGC, and sorption of nitrogen. The surface features were compared to those of a commercial urea-modified carbon. Then, the H{sub 2}S breakthrough capacity tests were carried out, and the sorption capacity was evaluated. The results showed that urea-modified sorbents have a capacity similar to that of the received material; however, the conversion of hydrogen sulfide to a water-soluble species is significantly higher. It happens due to a high dispersion of basic nitrogen compounds in the small pores of carbons, where oxidation of hydrogen sulfide ions to sulfur radicals followed by the creation of sulfur oxides and sulfuric acid occurs. It is proposed that the process proceeds gradually, from small pores to larger, and that the degree of microporosity is an important factor.

  10. Effects of methanethiol on the biological oxidation of sulfide at natron-alkaline conditions.

    PubMed

    van den Bosch, Pim L F; Fortuny-Picornell, Marc; Janssen, Albert J H

    2009-01-15

    The effects of methanethiol (MT) on biological sulfide oxidation were studied in a continuously operated bioreactor, in which chemolithoautotrophic bacteria belonging to the genus Thioalkalivibrio convert hydrogen sulfide (H2S) at natron-alkaline conditions. Previous bioreactor experiments have shown that always a fraction of the H2S is oxidized to sulfate and thiosulfate. This is unwanted, as it leads to caustic requirements for pH control and the formation of a bleed stream to discharge these compounds from the process. The current research shows that due to the addition of MT, sulfate formation is prevented. As a result, all supplied H2S is completely converted into elemental sulfur. Treatment of a continuous supply of 51.0 mM day(-1) H2S and 79 microM day(-1) MT was feasible for a prolonged period, with 99 mol% selectivity for sulfur formation. A part of the MT reacts with the freshly produced sulfur particles to form dimethyl disulfide (DMDS) and dimethyl trisulfide (DMTS). Results indicate that MT, DMDS, and DMTS partly adsorb onto the biosulfur particles. At concentrations above 10 microM, these volatile organic sulfur compounds induce biomass decay.

  11. Selection and Application of Sulfide Oxidizing Microorganisms Able to Withstand Thiols in Gas Biodesulfurization Systems.

    PubMed

    Roman, Pawel; Klok, Johannes B M; Sousa, João A B; Broman, Elias; Dopson, Mark; Van Zessen, Erik; Bijmans, Martijn F M; Sorokin, Dimitry Y; Janssen, Albert J H

    2016-12-06

    After the first commercial applications of a new biological process for the removal of hydrogen sulfide (H2S) from low pressure biogas, the need arose to broaden the operating window to also enable the removal of organosulfur compounds from high pressure sour gases. In this study we have selected microorganisms from a full-scale biodesulfurization system that are capable of withstanding the presence of thiols. This full-scale unit has been in stable operation for more than 10 years. We investigated the microbial community by using high-throughput sequencing of 16S rRNA gene amplicons which showed that methanethiol gave a competitive advantage to bacteria belonging to the genera Thioalkalibacter (Halothiobacillaceae family) and Alkalilimnicola (Ectothiorhosdospiraceae family). The sulfide-oxidizing potential of the acclimatized population was investigated under elevated thiol loading rates (4.5-9.1 mM d(-1)), consisting of a mix of methanethiol, ethanethiol, and propanethiol. With this biomass, it was possible to achieve a stable bioreactor operation at which 80% of the supplied H2S (61 mM d(-1)) was biologically oxidized to elemental sulfur. The remainder was chemically produced thiosulfate. Moreover, we found that a conventionally applied method for controlling the oxygen supply to the bioreactor, that is, by maintaining a redox potential set-point value, appeared to be ineffective in the presence of thiols.

  12. Cuprous Sulfide/Reduced Graphene Oxide Hybrid Nanomaterials: Solvothermal Synthesis and Enhanced Electrochemical Performance

    NASA Astrophysics Data System (ADS)

    He, Zhanjun; Zhu, Yabo; Xing, Zheng; Wang, Zhengyuan

    2016-01-01

    The cuprous sulfide nanoparticles (CuS NPs)-decorated reduced graphene oxide (rGO) nanocomposites have been successfully prepared via a facile and efficient solvothermal synthesis method. Scanning electron microscopy and transmission electron microscopy images demonstrated that CuS micronspheres composed of nanosheets and distributed on the rGO layer in well-monodispersed form. Fourier-transform infrared spectroscopy analyses and x-ray photoelectron spectroscopy showed that graphene oxide (GO) had been reduced to rGO. The electrochemical performances of CuS/rGO nanocomposites were investigated by cyclic voltammetry and charge/discharge techniques, which showed that the specific capacitance of CuS/rGO nanocomposites was enhanced because of the introduction of rGO.

  13. Selectivity of layered double hydroxides and their derivative mixed metal oxides as sorbents of hydrogen sulfide.

    PubMed

    Othman, Mohamed A; Zahid, Waleed M; Abasaeed, Ahmed E

    2013-06-15

    In the context of finding high efficient sorbent materials for removing hydrogen sulfide (H2S) from air stream, a screening study was performed to find the best combination of metals for the synthesis of layered double hydroxides (LDHs) and their derivative mixed metal oxides. Based on selectivity of 998 natural mineral species of sulfur-containing compounds, Cu(2+), Ni(2+) and Zn(2+) were selected as divalent metals, and Fe(3+), Al(3+) and Cr(3+) as trivalent metals to synthesis the LDHs sorbents. 10 LDHs materials and their calcined mixed metal oxides, Ni(0.66)Al(0.34), Cu(0.35)Ni(0.32)Al(0.33), Zn(0.66)Al(0.34), Cu(0.36)Zn(0.32)Al(0.32), Ni(0.64)Fe(0.36), Cu(0.35)Ni(0.31)Fe(0.34), Ni(0.66)Cr(0.34), Cu(0.35)Ni(0.31)Cr(0.34), Zn(0.66)Cr(0.34), Cu(0.33)Zn(0.32)Cr(0.35) were synthesized, characterized chemically and physically, and then tested using breakthrough test to determine their sulfur uptake. Ni(0.64)Fe(0.36) mixed metal oxides was found to have the best uptake of hydrogen sulfide (136 mg H₂S/g). Regeneration of spent Ni(0.64)Fe(0.36) mixed metal oxides was studied using two different mixture solutions, NaCl/NaOH and acetate-buffer/NaCl/NaOH. The latter mixture successfully desorbed the sulfur from the Ni0.64Fe0.36 sorbent for 2 cycles of regeneration/sorption.

  14. Enriching distinctive microbial communities from marine sediments via an electrochemical-sulfide-oxidizing process on carbon electrodes

    PubMed Central

    Li, Shiue-Lin; Nealson, Kenneth H.

    2015-01-01

    Sulfide is a common product of marine anaerobic respiration, and a potent reactant biologically and geochemically. Here we demonstrate the impact on microbial communities with the removal of sulfide via electrochemical methods. The use of differential pulse voltammetry revealed that the oxidation of soluble sulfide was seen at +30 mV (vs. SHE) at all pH ranges tested (from pH = 4 to 8), while non-ionized sulfide, which dominated at pH = 4 was poorly oxidized via this process. Two mixed cultures (CAT and LA) were enriched from two different marine sediments (from Catalina Island, CAT; from the Port of Los Angeles, LA) in serum bottles using a seawater medium supplemented with lactate, sulfate, and yeast extract, to obtain abundant biomass. Both CAT and LA cultures were inoculated in electrochemical cells (using yeast-extract-free seawater medium as an electrolyte) equipped with carbon-felt electrodes. In both cases, when potentials of +630 or +130 mV (vs. SHE) were applied, currents were consistently higher at +630 then at +130 mV, indicating more sulfide being oxidized at the higher potential. In addition, higher organic-acid and sulfate conversion rates were found at +630 mV with CAT, while no significant differences were found with LA at different potentials. The results of microbial-community analyses revealed a decrease in diversity for both CAT and LA after electrochemical incubation. In addition, some bacteria (e.g., Clostridium and Arcobacter) not well-known to be capable of extracellular electron transfer, were found to be dominant in the electrochemical cells. Thus, even though the different mixed cultures have different tolerances for sulfide, electrochemical-sulfide removal can lead to major population changes. PMID:25741331

  15. Polystyrene bound oxidovanadium(IV) and dioxidovanadium(V) complexes of histamine derived ligand for the oxidation of methyl phenyl sulfide, diphenyl sulfide and benzoin.

    PubMed

    Maurya, Mannar R; Arya, Aarti; Kumar, Amit; Pessoa, João Costa

    2009-03-28

    Ligand Hsal-his (I) derived from salicylaldehyde and histamine has been covalently bound to chloromethylated polystyrene cross-linked with 5% divinylbenzene. Upon treatment with [VO(acac)(2)] in DMF, the polystyrene-bound ligand (abbreviated as PS-Hsal-his, II) gave the stable polystyrene-bound oxidovanadium(iv) complex PS-[V(IV)O(sal-his)(acac)] , which upon oxidation yielded the dioxidovanadium(v) PS-[V(V)O(2)(sal-his)] complex. The corresponding non polymer-bound complexes [V(IV)O(sal-his)(acac)] and [V(V)O(2)(sal-his)] have also been obtained. These complexes have been characterised by IR, electronic, (51)V NMR and EPR spectral studies, and thermal as well as scanning electron micrograph studies. Complexes and have been used as a catalyst for the oxidation of methyl phenyl sulfide, diphenyl sulfide and benzoin with 30% H(2)O(2) as oxidant. Under the optimised reaction conditions, a maximum of 93.8% conversion of methyl phenyl sulfide with 63.7% selectivity towards methyl phenyl sulfoxide and 36.3% towards methyl phenyl sulfone has been achieved in 2 h with 2 . Under similar conditions, diphenyl sulfide gave 83.4% conversion where selectivity of reaction products varied in the order: diphenyl sulfoxide (71.8%) > diphenyl sulfone (28.2%). A maximum of 91.2% conversion of benzoin has been achieved within 6 h, and the selectivities of reaction products are: methylbenzoate (37.0%) > benzil (30.5%) > benzaldehyde-dimethylacetal (22.5%) > benzoic acid (8.1%). The PS-bound complex, 1 exhibits very comparable catalytic potential. These polymer-anchored heterogeneous catalysts do not leach during catalytic action, are recyclable and show higher catalytic activity and turnover frequency than the corresponding non polymer-bound complexes. EPR and (51)V NMR spectroscopy was used to characterise methanolic solutions of 3 and 4 and to identify species formed upon addition of H(2)O(2) and/or acid and/or methyl phenyl sulfide.

  16. In-Situ Incubation of Iron-Sulfide Mineral in Seawater Reveals Colonization by Iron-Oxidizing Gammaproteobacteria and Zetaproteobacteria.

    NASA Astrophysics Data System (ADS)

    Barco, R. A.; Ramírez, G. A.; Sylvan, J. B.; Edwards, K. J.

    2015-12-01

    Sulfide mineral precipitation occurs at mid-ocean ridge (MOR) spreading centers, both in the form of plume particles and massive sulfide structures. A common constituent of MOR sulfide mineral is pyrrhotite (Fe1-xS). This mineral was chosen as a substrate for in-situ incubation studies in the shallow waters of Catalina Islands, CA to investigate the colonization of iron-oxidizing bacteria. Gammaproteobacteria and Alphaproteobacteria largely dominated the bacterial community on pyrrhotite samples incubated in the water column. Pyrrhotite samples incubated at the sediment/water column interface showed more even dominance by Gammaproteobacteria, Alphaproteobacteria, Deltaproteobacteria and Bacteroidetes. Cultivations that originated from these pyrrhotite samples resulted in the enrichment of Zetaproteobacteria with either twisted-stalks (Mariprofundus) or sheath structures. Additionally, a candidate novel Gammaproteobacterium was isolated and shown to grow autotrophically via the oxidation of iron.

  17. Air-Stable Gold Nanoparticles Ligated by Secondary Phosphine Oxides as Catalyst for the Chemoselective Hydrogenation of Substituted Aldehydes: a Remarkable Ligand Effect.

    PubMed

    Cano, Israel; Huertos, Miguel A; Chapman, Andrew M; Buntkowsky, Gerd; Gutmann, Torsten; Groszewicz, Pedro B; van Leeuwen, Piet W N M

    2015-06-24

    Air-stable and homogeneous gold nanoparticles (AuNPs, 1a-5a) ligated by various secondary phosphine oxides (SPOs), [R(1)R(2)P(O)H] (R(1) = Naph, R(2) = (t)Bu, L1; R(1) = R(2) = Ph, L2; R(1) = Ph, R(2) = Naph, L3; R(1) = R(2) = Et, L4; R(1) = R(2) = Cy, L5; R(1) = R(2) = (t)Bu, L6), with different electronic and steric properties were synthesized via NaBH4 reduction of the corresponding Au(I)-SPO complex. These easily accessible ligands allow the formation of well dispersed and small nanoparticles (size 1.2-2.2 nm), which were characterized by the use of a wide variety of techniques, such as transmission electron microscopy, thermogravimetric analysis, UV-vis, energy-dispersive X-ray, X-ray photoelectron spectroscopy (XPS), attenuated total reflectance Fourier transform infrared spectroscopy (ATR FT-IR), and cross polarization magic angle spinning (CP MAS) NMR spectroscopy. A pronounced ligand effect was found, and CP MAS NMR experiments enabled us to probe important differences in the polarity of the P-O bond of the SPOs coordinated to the nanoparticle surface depending on the type of substituents in the ligand. AuNPs containing aryl SPOs carry only SPO anions and are highly selective for aldehyde hydrogenation. AuNPs of similar size made with alkyl SPOs contain also SPOH, hydrogen bonded to SPO anions. As a consequence they contain less Au(I) and more Au(0), as is also evidenced by XPS. They are less selective and active in aldehyde hydrogenation and now show the typical activity of Au(0)NPs in nitro group hydrogenation.

  18. Microbial Ecology Assessment of Mixed Copper Oxide/Sulfide Dump Leach Operation

    SciTech Connect

    Bruhn, Debby Fox; Thompson, David Neal; Noah, Karl Scott

    1999-06-01

    Microbial consortia composed of complex mixtures of autotrophic and heterotrophic bacteria are responsible for the dissolution of metals from sulfide minerals. Thus, an efficient copper bioleaching operation depends on the microbial ecology of the system. A microbial ecology study of a mixed oxide/sulfide copper leaching operation was conducted using an "overlay" plating technique to differentiate and identify various bacterial consortium members of the genera Thiobacillus, “Leptospirillum”, “Ferromicrobium”, and Acidiphilium. Two temperatures (30°C and 45°C) were used to select for mesophilic and moderately thermophilic bacteria. Cell numbers varied from 0-106 cells/g dry ore, depending on the sample location and depth. After acid curing for oxide leaching, no viable bacteria were recovered, although inoculation of cells from raffinate re-established a microbial population after three months. Due to low the pH of the operation, very few non-iron-oxidizing acidophilic heterotrophs were recovered. Moderate thermophiles were isolated from the ore samples. Pregnant liquor solutions (PLS) and raffinate both contained a diversity of bacteria. In addition, an intermittently applied waste stream that contained high levels of arsenic and fluoride was tested for toxicity. Twenty vol% waste stream in PLS killed 100% of the cells in 48 hours, indicating substantial toxicity and/or growth inhibition. The data indicate that bacteria populations can recover after acid curing, and that application of the waste stream to the dump should be avoided. Monitoring the microbial ecology of the leaching operation provided significant information that improved copper recovery.

  19. Sulfate reduction and sulfide oxidation in extremely steep salinity gradients formed by freshwater springs emerging into the Dead Sea.

    PubMed

    Häusler, Stefan; Weber, Miriam; Siebert, Christian; Holtappels, Moritz; Noriega-Ortega, Beatriz E; De Beer, Dirk; Ionescu, Danny

    2014-12-01

    Abundant microbial mats, recently discovered in underwater freshwater springs in the hypersaline Dead Sea, are mostly dominated by sulfur-oxidizing bacteria. We investigated the source of sulfide and the activity of these communities. Isotopic analysis of sulfide and sulfate in the spring water showed a fractionation of 39-50‰ indicative of active sulfate reduction. Sulfate reduction rates (SRR) in the spring sediment (< 2.8 nmol cm(-3) day(-1)) are too low to account for the measured sulfide flux. Thus, sulfide from the springs, locally reduced salinity and O2 from the Dead Sea water are responsible for the abundant microbial biomass around the springs. The springs flow is highly variable and accordingly the local salinities. We speculate that the development of microbial mats dominated by either Sulfurimonas/Sulfurovum-like or Thiobacillus/Acidithiobacillus-like sulfide-oxidizing bacteria, results from different mean salinities in the microenvironment of the mats. SRR of up to 10 nmol cm(-3) day(-1) detected in the Dead Sea sediment are surprisingly higher than in the less saline springs. While this shows the presence of an extremely halophilic sulfate-reducing bacteria community in the Dead Sea sediments, it also suggests that extensive salinity fluctuations limit these communities in the springs due to increased energetic demands for osmoregulation.

  20. Reactive removal of 2-chloroethyl ethyl sulfide vapors under visible light irradiation by cerium oxide modified highly porous zirconium (hydr) oxide

    NASA Astrophysics Data System (ADS)

    Mitchell, Joshua K.; Arcibar-Orozco, Javier A.; Bandosz, Teresa J.

    2016-12-01

    Highly porous cerium oxide modified Zr(OH)4 samples were synthesized using a simple one stage urea precipitation method. The amorphicity level of zirconium hydroxide did not change upon addition of cerium oxide particles. A unique aspect of the cerium oxide-modified materials is the presence of both the oxide (CeO2) and hydroxide (Zr(OH)4) phases resulting in a unique microporous structure of the final material. Extensive characterization using various chemical and physical methods revealed significant differences in the surface features. All synthesized materials were microporous and small additions of cerium oxide affected the surface chemistry. These samples were found as effective catalysts for a decontamination of mustard gas surrogate, 2-chloroethyl ethyl sulfide (CEES). Cerium oxide addition significantly decreased the band gap of zirconium hydroxide. Ethyl vinyl sulfide and 1,2-bis (Ethyl thio) ethane were identified as surface reaction products.

  1. cis-Bis(nitrato-κ2 O,O′)bis­(triethyl­phosphine oxide-κO)nickel(II)

    PubMed Central

    Seidel, Rüdiger W.

    2009-01-01

    In the title compound, [Ni(NO3)2(C6H15OP)2], the NiII ion, lying on a crystallographic twofold axis, adopts a distorted octa­hedral coordination, consisting of O-donor atoms of two symmetry-related triethyl­phospine oxide and two bidentate nitrate ligands. PMID:21582983

  2. Selective Catalytic Oxidation of Hydrogen Sulfide--Systems Analysis for IGCC Applications

    SciTech Connect

    Newby, R.A.; Keairns, D.L.; Alvin, M.A.

    2006-09-01

    Selective catalytic oxidation of hydrogen sulfide (SCOHS) has been evaluated conceptually for IGCC applications, and the theoretical limits of reaction performance, process performance, and economic potential in IGCC have been estimated. Syngas conditions that have high partial pressures of total sulfur result in substantial liquid sulfur retention within the catalyst bed, with relatively complex processing being required. Applications that have much lower total sulfur partial pressure in the process gas might permit SCOHS operation under conditions where little liquid sulfur is retained in the catalyst, reducing the processing complexity and possibly improving the desulfurization performance. The results from our recent IGCC process evaluations using the SCOHS technology and conventional syngas cleaning are presented, and alternative SCOHS process configurations and applications that provide greater performance and cost potential are identified.

  3. Thermochemical, structural and electronic properties of amorphous oxides, nitrides and sulfides

    NASA Astrophysics Data System (ADS)

    Zawadzki, Pawel; Lany, Stephan

    2015-03-01

    Amorphous thin films materials become increasingly important components of many functional devices such as thin film displays, photovoltaic cells or thin film transistors. Due to lack of grain boundaries, they have superior uniformity and smoothest, flexibility and corrosion resistance. Amorphous thin films are typically prepared using physical vapor deposition (PVD) techniques at temperatures well below the melting point of deposited material (<0.2Tm). Computational models of amorphous structures, however, are almost elusively constructed from a high temperature equilibrated crystal melt using simulated annealing (SA) protocol. To account for low temperature growth conditions of amorphous thin films we recently developed a new simulation technique. The method, kinetically limited minimization (KLM), starts from a randomly initialized structure and minimizes the total energy in a number of local structural perturbation-relaxation events. We apply KLM to model amorphous structures of 20 binary oxides, nitrides and sulfides and compare their thermochemical, structural and electronic properties.

  4. Growth mechanisms of zinc oxide and zinc sulfide films by mist chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Uno, Kazuyuki; Yamasaki, Yuichiro; Tanaka, Ichiro

    2017-01-01

    The growth mechanisms of zinc oxide and zinc sulfide films by mist chemical vapor deposition (mist-CVD) were experimentally investigated from the viewpoint of mist behaviors and chemical reactions. The proper growth model, either vaporization or the Leidenfrost model, was studied by supplying two kinds of mists with different kinds of sources, such as H2 16O and H2 18O for ZnO growth and ZnCl2 and thiourea for ZnS growth. Moreover, the origin of the oxygen atoms of ZnO was investigated using a quantitative analysis. The role of chloro complex of zinc in the growth of ZnS from aqueous solutions was also examined by systematic studies.

  5. Coating and enhanced photocurrent of vertically aligned zinc oxide nanowire arrays with metal sulfide materials.

    PubMed

    Volokh, Michael; Diab, Mahmud; Magen, Osnat; Jen-La Plante, Ilan; Flomin, Kobi; Rukenstein, Pazit; Tessler, Nir; Mokari, Taleb

    2014-08-27

    Hybrid nanostructures combining zinc oxide (ZnO) and a metal sulfide (MS) semiconductor are highly important for energy-related applications. Controlled filling and coating of vertically aligned ZnO nanowire arrays with different MS materials was achieved via the thermal decomposition approach of single-source precursors in the gas phase by using a simple atmospheric-pressure chemical vapor deposition system. Using different precursors allowed us to synthesize multicomponent structures such as nanowires coated with alloy shell or multishell structures. Herein, we present the synthesis and structural characterization of the different structures, as well as an electrochemical characterization and a photovoltaic response of the ZnO-CdS system, in which the resulting photocurrent upon illumination indicates charge separation at the interface.

  6. Impact of isostatic land uplift and artificial drainage on oxidation of brackish-water sediments rich in metastable iron sulfide

    NASA Astrophysics Data System (ADS)

    Boman, Anton; Fröjdö, Sören; Backlund, Krister; Åström, Mats E.

    2010-02-01

    This study examines the dynamics of sulfur and trace elements (As, Co, Mo, Ni, Ti and Zn) when brackish-water sediments, unusually rich in metastable iron sulfide (probably a mixture of mackinawite and greigite), are brought into the oxidation zone by postglacial isostatic land uplift and farmland drainage. When subaqueous sediments approach the sea level, metastable iron sulfide is oxidized in the upmost layers and pyrite preserved and even accumulated concomitantly trapping Co, Ni and Zn but not As and Mo. When the land uplift has brought the sediments above sea level and natural drainage thus is initiated, the pyrite is oxidized and Co, Ni and Zn are released and transported down the profile. If this setting remained undisturbed, the slightly oxidized sediment (unripe soil) would become covered by peat and thus protected from further oxidation and metal translocation. Often these sediments are, however, artificially drained resulting in extensive oxidation and fast soil-profile development. The soil is an acid sulfate (AS) soil, characterized by low pH (<4), extensive leaching of metals and an abundance of disseminated brownish Fe(III) precipitates. We suggest that the fast soil development is due to initial oxidation of metastable iron sulfide, followed by pyrite oxidation. Drain bottom sediment, which in terms of chemistry and S-isotopes resembled that of the surfacing sea bottom strata, acted during the sampling period as a sink for metals. The abundant preservation of metastable iron sulfide below the groundwater table, even long periods after uplift above the sea level, is a puzzling feature. We suggest that it is the net result of sulfur starvation, an abundance of Fe(II) and strongly reducing conditions.

  7. Allenes in Asymmetric Catalysis. Asymmetric Ring-Opening of Meso-Epoxides Catalyzed by Allene-Containing Phosphine Oxides

    PubMed Central

    Pu, Xiaotao; Qi, Xiangbing; Ready, Joseph M.

    2009-01-01

    Unsymmetrically substituted allenes (1,2 dienes) are inherently chiral and can be prepared in optically pure form. Nonetheless, to date the allene framework has not been incorporated into ligands for asymmetric catalysis. Since allenes project functionality differently than either tetrahedral carbon or chiral biaryls, they may create complementary chiral environments. This study demonstrates that optically active C2 symmetric allene-containing bisphosphine oxides can catalyze the addition of SiCl4 to meso epoxides with high enantioselectivity. The epoxide-opening likely involves generation of a Lewis acidic, cationic (bisphosphine oxide)SiCl3 complex. The fact that high asymmetric induction is observed suggests that allenes may represent a new platform for the development of ligands and catalysts for asymmetric synthesis. PMID:19722613

  8. Influence of iron sulfides on abiotic oxidation of UO2 by nitrite and dissolved oxygen in natural sediments.

    PubMed

    Carpenter, Julian; Bi, Yuqiang; Hayes, Kim F

    2015-01-20

    Iron sulfide precipitates formed under sulfate reducing conditions may buffer U(IV) insoluble solid phases from reoxidation after oxidants re-enter the reducing zone. In this study, sediment column experiments were performed to quantify the effect of biogenic mackinawite on U(IV) stability in the presence of nitrite or dissolved oxygen (DO). Two columns, packed with sediment from an abandoned U contaminated mill tailings site near Rifle, CO, were biostimulated for 62 days with an electron donor (3 mM acetate) in the presence (BRS+) and absence (BRS−) of 7 mM sulfate. The bioreduced sediment was supplemented with synthetic uraninite (UO2(s)), sterilized by gamma-irradiation, and then subjected to a sequential oxidation by nitrite and DO. Biogenic iron sulfides produced in the BRS+ column, mostly as mackinawite, inhibited U(IV) reoxidation and mobilization by both nitrite and oxygen. Most of the influent nitrite (0.53 mM) exited the columns without oxidizing UO2, while a small amount of nitrite was consumed by iron sulfides precipitates. An additional 10-day supply of 0.25 mM DO influent resulted in the release of about 10% and 49% of total U in BRS+ and BRS– columns, respectively. Influent DO was effectively consumed by biogenic iron sulfides in the BRS+ column, while DO and a large U spike were detected after only a brief period in the effluent in the BRS– column.

  9. Thermodynamic modeling and experimental analysis of oxidation/sulfidation of nickel-chromium-aluminum model alloy coatings

    NASA Astrophysics Data System (ADS)

    Mueller, Erik M.

    With the current focus on finding future energy sources, land-based power gas turbines offer a desirable alternative to common coal-fired steam power generation. Ni-Cr-Al-X alloys are the material basis for producing overlay bond coats for the turbine blades used in sections of the turbine engine experiencing the most extreme environments. These overlay coatings are designed to provide environmental protection for the blades and vanes. While the oxidation of such alloys has been investigated and modeled in-depth, the concurrent sulfidation attack has not. This corrosion mode is now being heavily researched with the desire to use gasified coal, biomass, and other renewable fuel sources in gas turbines that often contain significant amounts of sulfur. The purpose of this dissertation was to use thermodynamic calculations to describe and predict the oxidation/sulfidation processes of two Ni-Cr-Al model alloys regarding phase evolution, composition, and component activities. These calculations, in the form of potential and phase fraction diagrams, combined with sulfidation experiments using kinetic measurements and materials characterization techniques, were able to describe and predict the simultaneous oxidation and sulfidation that occurred in these alloys.

  10. Biotreatment of refinery spent sulfidic caustics

    SciTech Connect

    Sublette, K.L.; Rajganesh, B.; Woolsey, M.; Plato, A.

    1995-12-31

    Caustics are used in petroleum refinering to remove hydrogen sulfide from various hydrocarbon streams. Spent sulfidic caustics from two Conoco refineries have been successfully biotreated on bench and pilot scale, resulting in neutralization and removal of active sulfides. Sulfides were completely oxidized to sulfate by Thiobacillus denitrificans. Microbial oxidation of sulfide produced acid, which at least partially neutralized the caustic.

  11. Continuous sulfidogenic wastewater treatment with iron sulfide sludge oxidation and recycle.

    PubMed

    Deng, Dongyang; Lin, Lian-Shin

    2017-05-01

    This study evaluated the technical feasibility of packed-bed sulfidogenic bioreactors dosed with ferrous chloride for continuous wastewater treatment over a 450-day period. In phase I, the bioreactors were operated under different combinations of carbon, iron, and sulfate mass loads without sludge recycling to identify optimal treatment conditions. A COD/sulfate mass ratio of 2 and a Fe/S molar ratio of 1 yielded the best treatment performance with COD oxidation rate of 786 ± 82 mg/(L⋅d), which resulted in 84 ± 9% COD removal, 94 ± 6% sulfate reduction, and good iron retention (99 ± 1%) under favorable pH conditions (6.2-7.0). In phase II, the bioreactors were operated under this chemical load combination over a 62-day period, during which 7 events of sludge collection, oxidation, and recycling were performed. The collected sludge materials contained both inorganic and organic matter with FeS and FeS2 as the main inorganic constituents. In each event, the sludge materials were oxidized in an oxidizing basin before recycling to mix with the wastewater influent. Sludge recycling yielded enhanced COD removal (90 ± 6% vs. 75 ± 7%), and better effluent quality in terms of pH (6.8 ± 0.1 vs. 6.5 ± 0.2), iron (0.7 ± 0.5 vs. 1.9 ± 1.7 mg/L), and sulfide-S (0.3 ± 0.1 vs. 0.4 ± 0.1 mg/L) removal compared to the baseline operation without sludge recycling during phase II. This process exhibited treatment stability with reasonable variations, and fairly consistent sludge content over long periods of operation under a range of COD/sulfate and Fe/S ratios without sludge recycling. The bioreactors were found to absorb recycling-induced changes efficiently without causing elevated suspended solids in the effluents.

  12. Niche differentiation among mat-forming, sulfide-oxidizing bacteria at cold seeps of the Nile Deep Sea Fan (Eastern Mediterranean Sea).

    PubMed

    Grünke, S; Felden, J; Lichtschlag, A; Girnth, A-C; De Beer, D; Wenzhöfer, F; Boetius, A

    2011-07-01

    Sulfidic muds of cold seeps on the Nile Deep Sea Fan (NDSF) are populated by different types of mat-forming sulfide-oxidizing bacteria. The predominant sulfide oxidizers of three different mats were identified by microscopic and phylogenetic analyses as (i) Arcobacter species producing cotton-ball-like sulfur precipitates, (ii) large filamentous sulfur bacteria including Beggiatoa species, and (iii) single, spherical Thiomargarita species. High resolution in situ microprofiles revealed different geochemical settings selecting for the different mat types. Arcobacter mats occurred where oxygen and sulfide overlapped above the seafloor in the bottom water interface. Filamentous sulfide oxidizers were associated with steep gradients of oxygen and sulfide in the sediment. A dense population of Thiomargarita was favored by temporarily changing supplies of oxygen and sulfide in the bottom water. These results indicate that the decisive factors in selecting for different mat-forming bacteria within one deep-sea province are spatial or temporal variations in energy supply. Furthermore, the occurrence of Arcobacter spp.-related 16S rRNA genes in the sediments below all three types of mats, as well as on top of brine lakes of the NDSF, indicates that this group of sulfide oxidizers can switch between different life modes depending on the geobiochemical habitat setting.

  13. Investigation on durability and reactivity of promising metal oxide sorbents during sulfidation and regeneration. Quarterly report, October--December 1994

    SciTech Connect

    Kwon, K.C.

    1995-01-01

    Hot-gas desulfurization for the integrated gasification combined cycle (IGCC) process has been investigated by many researchers to remove effectively hydrogen sulfide with various metal oxide sorbents at high pressures and high temperatures. Metal oxides such as zinc titanate oxides, zinc ferrite oxide, copper oxide, manganese oxide and calcium oxide, were found to be promising sorbents in comparison with other removal methods such as membrane separations and reactive membrane separations. Some metal oxide sorbents exhibited the quite favorable performance in terms of attrition resistance and sulfur capacity. Removal reaction of H{sub 2}S from coal gas mixtures with ZT-4 or other promising sorbents of fine solid particles, and regeneration reaction of sulfur-loaded sorbents will be carried on in a batch reactor or a continuous differential reactor. The objectives of this research project are to find intrinsic initial reaction kinetics for the metal oxide-hydrogen sulfide heterogeneous reaction system, to obtain effects of concentrations of coal gas components such as hydrogen, carbon monoxide, carbon dioxide, oxygen, nitrogen and moisture on equilibrium reaction rate constants of the reaction system at various reaction temperatures and pressures, to identify regeneration kinetics of sulfur-loaded metal oxide sorbents, and to formulate promising metal oxide sorbent for the removal of sulfur from coal gas mixtures. Promising durable metal oxide sorbents of high-sulfur-absorbing capacity will be formulated by mixing active metal oxide powders with inert metal oxide powders and calcining these powder mixtures, or impregnating active metal oxide sorbents on supporting metal oxide matrixes.

  14. Investigation on durability and reactivity of promising metal oxide sorbents during sulfidation and regeneration. Quarterly report, January--March 1995

    SciTech Connect

    Kwon, K.C.

    1995-03-01

    Hot-gas desulfurization for the integrated gasification combined cycle (IGCC) process has been investigated by many researchers to remove effectively hydrogen sulfide with various metal oxide sorbents at high pressures and high temperatures. Metal oxides such as zinc titanate oxides, zinc ferrite oxide, copper oxide, manganese oxide and calcium oxide, were found to be promising sorbents in comparison with other removal methods such as membrane separations and reactive membrane separations. Some metal oxide sorbents exhibited the quite favorable performance in terms of attrition resistance and sulfur capacity. Removal reaction of H{sub 2}S from coal gas mixtures with ZT-4 or other promising sorbents of fine solid particles, and regeneration reaction of sulfur-loaded sorbents will be carried on in a batch reactor or a continuous differential reactor. The objectives of this research project are to find intrinsic initial reaction kinetics for the metal oxide-hydrogen sulfide heterogeneous reaction system, to obtain effects of concentrations of coal gas components such as hydrogen, carbon monoxide, carbon dioxide, oxygen, nitrogen and moisture on equilibrium reaction rate constants of the reaction system at various reaction temperatures and pressures, to identify regeneration kinetics of sulfur-loaded metal oxide sorbents, and to formulate promising metal oxide sorbents for the removal of sulfur from coal gas mixtures. Promising durable metal oxide sorbents of high-sulfur-absorbing capacity will be formulated by mixing active metal oxide powders with inert metal oxide powders and calcining these powder mixtures, or impregnating active metal oxide sorbents on supporting metal oxide matrixes.

  15. Oxidation of gas mixtures containing dimethyl sulfide, hydrogen sulfide, and methanethiol using a two-stage biotrickling filter.

    PubMed

    Ruokojärvi, A; Ruuskanen, J; Martikainen, P J; Olkkonen, M

    2001-01-01

    A biofiltration technique was developed for removing a mixture of hydrogen sulfide (H2S), methanethiol (MeSH), and dimethyl sulfide (Me2S) from waste gases. Since H2S, especially at high concentrations, disturbs the removal of Me2S, two biotrickling filters with different microbes and operating pH levels were connected in series to create a two-stage system. Different loads of these gases were studied in order to determine their impact on the removal capacity of the system. The microbial consortia for these filters were enriched from the sludge of a Finnish refinery with bubbling H2S or Me2S. Acclimation for Me2S took 2 weeks, though no acclimation time was needed for the other gases. The first filter, at a pH of 2, removed most of the H2S and some of the MeSH and Me2S. The second filter, at a pH of approximately 6.5, removed the rest of the MeSH and most of the Me2S. The total maximum loads of the whole two-stage biotrickling filter were 1150 g/m3/day for H2S-S (suffix S indicates the results are counted as sulfur amounts), 879 g/m3/day for Me2S-S, and 66 g/m3/day for MeSH-S treated in a gas mixture. The average removal efficiencies for all gases tested were 99% or higher.

  16. Carbon monoxide, hydrogen sulfide, and nitric oxide as signaling molecules in the gastrointestinal tract.

    PubMed

    Farrugia, Gianrico; Szurszewski, Joseph H

    2014-08-01

    Carbon monoxide (CO) and hydrogen sulfide (H2S) used to be thought of simply as lethal and (for H2S) smelly gaseous molecules; now they are known to have important signaling functions in the gastrointestinal tract. CO and H2S, which are produced in the gastrointestinal tract by different enzymes, regulate smooth muscle membrane potential and tone, transmit signals from enteric nerves, and can regulate the immune system. The pathways that produce nitric oxide, H2S, and CO interact; each can inhibit and potentiate the level and activity of the other. However, there are significant differences between these molecules, such as in half-lives; CO is more stable and therefore able to have effects distal to the site of production, whereas nitric oxide and H2S are short lived and act only close to sites of production. We review their signaling functions in the luminal gastrointestinal tract and discuss how their pathways interact. We also describe other physiological functions of CO and H2S and how they might be used as therapeutic agents.

  17. Interaction of Hydrogen Sulfide with Nitric Oxide in the Cardiovascular System.

    PubMed

    Nagpure, B V; Bian, Jin-Song

    2016-01-01

    Historically acknowledged as toxic gases, hydrogen sulfide (H2S) and nitric oxide (NO) are now recognized as the predominant members of a new family of signaling molecules, "gasotransmitters" in mammals. While H2S is biosynthesized by three constitutively expressed enzymes (CBS, CSE, and 3-MST) from L-cysteine and homocysteine, NO is generated endogenously from L-arginine by the action of various isoforms of NOS. Both gases have been transpired as the key and independent regulators of many physiological functions in mammalian cardiovascular, nervous, gastrointestinal, respiratory, and immune systems. The analogy between these two gasotransmitters is evident not only from their paracrine mode of signaling, but also from the identical and/or shared signaling transduction pathways. With the plethora of research in the pathophysiological role of gasotransmitters in various systems, the existence of interplay between these gases is being widely accepted. Chemical interaction between NO and H2S may generate nitroxyl (HNO), which plays a specific effective role within the cardiovascular system. In this review article, we have attempted to provide current understanding of the individual and interactive roles of H2S and NO signaling in mammalian cardiovascular system, focusing particularly on heart contractility, cardioprotection, vascular tone, angiogenesis, and oxidative stress.

  18. Interaction of Hydrogen Sulfide with Nitric Oxide in the Cardiovascular System

    PubMed Central

    Nagpure, B. V.; Bian, Jin-Song

    2016-01-01

    Historically acknowledged as toxic gases, hydrogen sulfide (H2S) and nitric oxide (NO) are now recognized as the predominant members of a new family of signaling molecules, “gasotransmitters” in mammals. While H2S is biosynthesized by three constitutively expressed enzymes (CBS, CSE, and 3-MST) from L-cysteine and homocysteine, NO is generated endogenously from L-arginine by the action of various isoforms of NOS. Both gases have been transpired as the key and independent regulators of many physiological functions in mammalian cardiovascular, nervous, gastrointestinal, respiratory, and immune systems. The analogy between these two gasotransmitters is evident not only from their paracrine mode of signaling, but also from the identical and/or shared signaling transduction pathways. With the plethora of research in the pathophysiological role of gasotransmitters in various systems, the existence of interplay between these gases is being widely accepted. Chemical interaction between NO and H2S may generate nitroxyl (HNO), which plays a specific effective role within the cardiovascular system. In this review article, we have attempted to provide current understanding of the individual and interactive roles of H2S and NO signaling in mammalian cardiovascular system, focusing particularly on heart contractility, cardioprotection, vascular tone, angiogenesis, and oxidative stress. PMID:26640616

  19. Highly improved electroluminescence from a series of novel Eu(III) complexes with functional single-coordinate phosphine oxide ligands: tuning the intramolecular energy transfer, morphology, and carrier injection ability of the complexes.

    PubMed

    Xu, Hui; Yin, Kun; Huang, Wei

    2007-01-01

    The functional single-coordinate phosphine oxide ligands (4-diphenylaminophenyl)diphenylphosphine oxide (TAPO), (4-naphthalen-1-yl-phenylaminophenyl)diphenylphosphine oxide (NaDAPO), and 9-[4-(diphenylphosphinoyl)phenyl]-9H-carbazole (CPPO), as the direct combinations of hole-transporting moieties, and electron-transporting triphenylphosphine oxide (TPPO) were designed and synthesized (amines or carbazole), together with their Eu(III) complexes [Eu(tapo)(2)(tta)(3)] (1), [Eu(nadapo)(2)(tta)(3)] (2), and [Eu(cppo)(2)(tta)(3)] (3; TTA: 2-thenoyltrifluoroacetonate). The investigation indicated that by taking advantage of the modification inertia of the phosphine oxide ligands, the direct introduction of the hole-transport groups as chromophore made TAPO, NaDAPO, and CPPO obtain the most compact structure and mezzo S(1) and T(1) energy levels, which improved the intramolecular energy transfer in their Eu(III) complexes. The amorphous phase of 1-3 proved the weak intermolecular interaction, which resulted in extraordinarily low self-quenching of the complexes. The excellent double-carrier transport ability of the ligands was studied with Gaussian calculations, and the bipolar structure of TAPO and CPPO was proved. The great improvement of the double-carrier transport ability of 1-3 was shown by cyclic voltammetry. Their HOMO and LUMO energy levels of around 5.3 and 3.0 eV, respectively, are the best results for Eu(III) complexes reported so far. A single-layer organic light-emitting diode of 2 had the impressive brightness of 59 cd m(-2) which, to the best of our knowledge, is the highest reported so far. Both of the four-layer devices based on pure 1 and 2 had a maximum brightness of more than 1000 cd m(-2), turn-on voltages lower than 5 V, maximum external quantum yields of more than 3 % and excellent spectral stability.

  20. Photoinduced oxidation of H2S species: A sink for sulfide in seawater

    NASA Astrophysics Data System (ADS)

    Pos, Willer H.; Milne, Peter J.; Riemer, Daniel D.; Zika, Rod G.

    1997-06-01

    Photokinetic studies demonstrate that sulfide is consumed in seawater upon light exposure. The half-life (t1/2) of sulfide (10 μM) added to Biscayne Bay water and Gulf Stream water are 49(±15) and 147(±10) min, respectively. Both UV and visible radiation were shown to accelerate the photodecomposition of sulfide. However, due to a higher amount of radiation in the visible range reaching the sea surface, we predict that this portion of the light spectrum will be most important in inducing photoreaction of sufide in seawater. This as yet unaccounted sink of sulfide in seawater could be responsible for the sulfide daytime low and nighttime high concentration values observed by several investigators. This finding further unbalances the sulfide budget and reinforces the need for systematic research on the role of photochemical processes on sulfur species in seawater.

  1. Tracking photosynthetic sulfide oxidation in a meromictic lake using sulfate δ34S and δ18O

    NASA Astrophysics Data System (ADS)

    Gilhooly, W. P.; Reinhard, C.; Lyons, T. W.; Glass, J. B.

    2012-12-01

    Phototrophic sulfur bacteria oxidize sulfide and fix carbon dioxide in the presence of sunlight without producing oxygen. Environmental conditions in the Paleo- and Mesoproterozoic, when atmospheric oxygen concentrations were at low levels and portions of the oceans were anoxic and sulfidic (euxinic), were conducive to widespread carbon fixation by anoxygenic photosynthesis. This pathway may have helped sustain euxinic conditions in the Proterozoic water column. With limited organic biomarker and geochemical evidence for widespread production of anoxygenic phototrophs, however, additional proxies are needed to fingerprint paleoecological and biogeochemical signals associated with photic zone euxinia. Paired δ34S and δ18O from ancient sulfates (gypsum, barite, or CAS) may offer an added constraint on the history and ecological dominance of photosynthetic S-oxidation. Sulfate-oxygen can fractionate during sulfate reduction, but the extent of isotopic enrichment is controlled either by kinetic isotope effects imparted during intracellular enzymatic steps or equilibrium oxygen exchange with ambient water. An improved understanding of these processes can be gained from modern natural environments. Mahoney Lake is a density-stratified lake located within the White Lake Basin of British Columbia. The euxinic water column supports a dense plate of purple sulfur bacteria (Amoebobacter purpureus) that thrives where free sulfide intercepts the photic zone at ~7 m water depth. We analyzed the isotopic composition of sulfate (δ34SSO4 and δ18OSO4), sulfide (δ34SH2S), and water (δ18OH2O) to track the potentially coupled processes of dissimilatory sulfate reduction and phototrophic sulfide oxidation within this meromictic lake. Large isotopic offsets observed between sulfate and sulfide within the monimolimnion (δ34SSO4-H2S = 51‰) and within pore waters along the oxic margin (δ34SSO4-H2S >50‰) are consistent with sulfate reduction in both the sediments and the anoxic

  2. Sensitivity of Interfibrillar and Subsarcolemmal Mitochondria to Cobalt Chloride-induced Oxidative Stress and Hydrogen Sulfide Treatment

    PubMed Central

    Ayswarya, A.; Kurian, G. A.

    2016-01-01

    Oxidative stress plays a significant role not only in cardiovascular disease but also in non-communicable diseases, where it plays a significant role the mortality rate. Hydrogen sulfide, the biological gaseous signaling molecule that preserves mitochondria in its mode of action, is an effective cardioprotective drug. However, cardiac mitochondria comprise of two distinct populations, namely interfibrillar and subsarcolemmal mitochondria, which respond distinctly in cardiovascular disease. This study was designed to determine the direct impact of cobalt chloride-induced oxidative stress in isolated mitochondrial subpopulations with an intention to examine the efficacy of hydrogen sulfide in preserving interfibrillar and subsarcolemmal mitochondria functional activities when they were incubated as pretreated, co-treated and post-treated agent. Mitochondrial subpopulations were isolated from the heart of male Wistar rats and subjected to cobalt chloride treatment (500 μM) for 20 min, followed by incubation with 10 μM sodium hydrosulfide in three different ways (Pre, Co, and Post-cobalt chloride treatment). Mitochondrial oxidative stress was measured by the concentration of thiobarbituric acid reactive species, reduced glutathione and the activities of enzymes like superoxide dismutase, catalase and glutathione peroxidase. Mitochondrial membrane potential, swelling behavior and enzyme activities were measured to assess its function. The increased level of lipid peroxidation and the decreased level of reduced glutathione in cobalt chloride-induced group confirm the induction of oxidative stress and were more predominant in the subsarcolemmal mitochondria. Hydrogen sulfide treatment to interfibrillar and subsarcolemmal mitochondria preserved their functional activities, but the effect was prominent only with co-treated group. In conclusion, the present study demonstrated that subsarcolemmal mitochondria are more prone to oxidative stress and the co-treatment of the

  3. Sensitivity of Interfibrillar and Subsarcolemmal Mitochondria to Cobalt Chloride-induced Oxidative Stress and Hydrogen Sulfide Treatment.

    PubMed

    Ayswarya, A; Kurian, G A

    2016-01-01

    Oxidative stress plays a significant role not only in cardiovascular disease but also in non-communicable diseases, where it plays a significant role the mortality rate. Hydrogen sulfide, the biological gaseous signaling molecule that preserves mitochondria in its mode of action, is an effective cardioprotective drug. However, cardiac mitochondria comprise of two distinct populations, namely interfibrillar and subsarcolemmal mitochondria, which respond distinctly in cardiovascular disease. This study was designed to determine the direct impact of cobalt chloride-induced oxidative stress in isolated mitochondrial subpopulations with an intention to examine the efficacy of hydrogen sulfide in preserving interfibrillar and subsarcolemmal mitochondria functional activities when they were incubated as pretreated, co-treated and post-treated agent. Mitochondrial subpopulations were isolated from the heart of male Wistar rats and subjected to cobalt chloride treatment (500 μM) for 20 min, followed by incubation with 10 μM sodium hydrosulfide in three different ways (Pre, Co, and Post-cobalt chloride treatment). Mitochondrial oxidative stress was measured by the concentration of thiobarbituric acid reactive species, reduced glutathione and the activities of enzymes like superoxide dismutase, catalase and glutathione peroxidase. Mitochondrial membrane potential, swelling behavior and enzyme activities were measured to assess its function. The increased level of lipid peroxidation and the decreased level of reduced glutathione in cobalt chloride-induced group confirm the induction of oxidative stress and were more predominant in the subsarcolemmal mitochondria. Hydrogen sulfide treatment to interfibrillar and subsarcolemmal mitochondria preserved their functional activities, but the effect was prominent only with co-treated group. In conclusion, the present study demonstrated that subsarcolemmal mitochondria are more prone to oxidative stress and the co-treatment of the

  4. Improving the efficiency of cadmium sulfide-sensitized titanium dioxide/indium tin oxide glass photoelectrodes using silver sulfide as an energy barrier layer and a light absorber

    NASA Astrophysics Data System (ADS)

    Chen, Chong; Zhai, Yong; Li, Chunxi; Li, Fumin

    2014-11-01

    Cadmium sulfide (CdS) and silver sulfide (Ag2S) nanocrystals are deposited on the titanium dioxide (TiO2) nanocrystalline film on indium tin oxide (ITO) substrate to prepare CdS/Ag2S/TiO2/ITO photoelectrodes through a new method known as the molecular precursor decomposition method. The Ag2S is interposed between the TiO2 nanocrystal film and CdS nanocrystals as an energy barrier layer and a light absorber. As a consequence, the energy conversion efficiency of the CdS/Ag2S/TiO2/ITO electrodes is significantly improved. Under AM 1.5 G sunlight irradiation, the maximum efficiency achieved for the CdS(4)/Ag2S/TiO2/ITO electrode is 3.46%, corresponding to an increase of about 150% as compared to the CdS(4)/TiO2/ITO electrode without the Ag2S layer. Our experimental results show that the improved efficiency is mainly due to the formation of Ag2S layer that may increase the light absorbance and reduce the recombination of photogenerated electrons with redox ions from the electrolyte.

  5. Improving the efficiency of cadmium sulfide-sensitized titanium dioxide/indium tin oxide glass photoelectrodes using silver sulfide as an energy barrier layer and a light absorber

    PubMed Central

    2014-01-01

    Cadmium sulfide (CdS) and silver sulfide (Ag2S) nanocrystals are deposited on the titanium dioxide (TiO2) nanocrystalline film on indium tin oxide (ITO) substrate to prepare CdS/Ag2S/TiO2/ITO photoelectrodes through a new method known as the molecular precursor decomposition method. The Ag2S is interposed between the TiO2 nanocrystal film and CdS nanocrystals as an energy barrier layer and a light absorber. As a consequence, the energy conversion efficiency of the CdS/Ag2S/TiO2/ITO electrodes is significantly improved. Under AM 1.5 G sunlight irradiation, the maximum efficiency achieved for the CdS(4)/Ag2S/TiO2/ITO electrode is 3.46%, corresponding to an increase of about 150% as compared to the CdS(4)/TiO2/ITO electrode without the Ag2S layer. Our experimental results show that the improved efficiency is mainly due to the formation of Ag2S layer that may increase the light absorbance and reduce the recombination of photogenerated electrons with redox ions from the electrolyte. PMID:25411566

  6. Improving the efficiency of cadmium sulfide-sensitized titanium dioxide/indium tin oxide glass photoelectrodes using silver sulfide as an energy barrier layer and a light absorber.

    PubMed

    Chen, Chong; Zhai, Yong; Li, Chunxi; Li, Fumin

    2014-01-01

    Cadmium sulfide (CdS) and silver sulfide (Ag2S) nanocrystals are deposited on the titanium dioxide (TiO2) nanocrystalline film on indium tin oxide (ITO) substrate to prepare CdS/Ag2S/TiO2/ITO photoelectrodes through a new method known as the molecular precursor decomposition method. The Ag2S is interposed between the TiO2 nanocrystal film and CdS nanocrystals as an energy barrier layer and a light absorber. As a consequence, the energy conversion efficiency of the CdS/Ag2S/TiO2/ITO electrodes is significantly improved. Under AM 1.5 G sunlight irradiation, the maximum efficiency achieved for the CdS(4)/Ag2S/TiO2/ITO electrode is 3.46%, corresponding to an increase of about 150% as compared to the CdS(4)/TiO2/ITO electrode without the Ag2S layer. Our experimental results show that the improved efficiency is mainly due to the formation of Ag2S layer that may increase the light absorbance and reduce the recombination of photogenerated electrons with redox ions from the electrolyte.

  7. Calculating the partitioning of the isotopes of Mo between oxidic and sulfidic species in aqueous solution

    NASA Astrophysics Data System (ADS)

    Tossell, J. A.

    2005-06-01

    The fractionation of the isotopes of Mo between different geological environments has recently been determined to high accuracy using mass spectrometry ( Barling et al., 2001). Fractionation is observed between Mo in seawater, where it exists primarily in the form of the Mo(VI) anion molybdate, MoO 4-2, and in oxic sediments, where the Mo is isotopically lighter than in sea water by ˜1.8‰ (in terms of the 97Mo, 95Mo isotope pair). EXAFS evidence exists for a five- or six-coordinate Mo environment in the Fe,Mn oxyhydroxides of ferromanganese nodules ( Kuhn et al., 2003). In sediment regimes which are anoxic and sulfidic (sometimes referred to as euxinic), where the Mo(VI) is expected to exist as a sulfide, no fractionation is observed compared to seawater. This is presumably because of the stoichiometric conversion of the Mo from MoO 4-2 to MoS 4-2 ( Erickson and Helz, 2000) and then to other sulfides. If the conversion is stoichiometrically complete, mass balance requires the same isotopic distribution in reactant and product. This is a result of the very high equilibrium constant for this reaction. Thus, to understand isotopic fractionation processes both the equilibrium constants for the isotopic fractionation reactions and the equilbrium constants for transformation of one chemical compound to another must be considered. We here present quantum mechanical calculations of the isotopic fractionation equilibrium constants for the isotopes 92Mo and 100Mo between MoO 4-2, MoO 3(OH) -, MoO 2(OH) 2, MoO 3, MoO 3(OH 2) 3, MoS 4-2 and a number of other oxidic and sulfidic complexes of Mo. The fractionation equilibrium constants are calculated directly from the computed vibrational, rotational and translational contributions to the free energy in the gas-phase using quantum methods. Calculated vibrational frequencies and ratios of frequencies for different isotopomers are first obtained using a number of different quantum methods and compared with available

  8. Oxidative stress-dependent conversion of hydrogen sulfide to sulfite by activated neutrophils.

    PubMed

    Mitsuhashi, Hideki; Yamashita, Shin; Ikeuchi, Hidekazu; Kuroiwa, Takashi; Kaneko, Yoriaki; Hiromura, Keiju; Ueki, Kazue; Nojima, Yoshihisa

    2005-12-01

    Sulfite, which is known as a major constituent of volcanic gas, is endogenously produced in mammals, and its concentration in serum is increased in patients with pneumonia. It has been reported that sulfite is produced by oxidation from hydrogen sulfide (H2S) as an intermediate in the mammalian body. The objective of this study was to investigate the ability of reactive oxygen species from neutrophils to produce sulfite from H2S. Sulfite production from activated neutrophils stimulated with N-formyl-methionyl-leucyl-phenylalanine gradually increased with an increased concentration of sodium hydrosulfide (NaHS) in the medium. The production of sulfite was markedly suppressed with an NADPH oxidase inhibitor, diphenyleneiodonium. When NaHS was added to the supernatant of activated neutrophils, a significant amount of sulfite was synthesized in the test tubes. Furthermore, when a medium containing NaHS was incubated with a water-soluble radical initiator, 2,2'-azobis-(amidinopropane) dihydrochloride, sulfite was formed in the solution and this increase was markedly suppressed by ascorbic acid. Finally, we determined serum concentrations of sulfite and H2S in an in vivo model of neutrophil activation induced by systemic injection of lipopolysaccharide (LPS) into rats. We found a significant increase in serum sulfite and H2S after LPS injection. Importantly, coadministration of ascorbic acid with LPS further increased serum H2S but suppressed sulfite levels. This finding implies that oxidative stress-dependent conversion of H2S to sulfite might occur in vivo. Thus, the oxidation of H2S is a novel sulfite production pathway in the inflammatory condition, and this chemical synthesis might be responsible for the upregulation of sulfite production in inflammatory conditions such as pneumonia.

  9. Inhibitory effect of hydrogen sulfide on ozone-induced airway inflammation, oxidative stress, and bronchial hyperresponsiveness.

    PubMed

    Zhang, Pengyu; Li, Feng; Wiegman, Coen H; Zhang, Min; Hong, Yan; Gong, Jicheng; Chang, Yan; Zhang, Junfeng Jim; Adcock, Ian; Chung, Kian Fan; Zhou, Xin

    2015-01-01

    Exposure to ozone has been associated with airway inflammation, oxidative stress, and bronchial hyperresponsiveness. The goal of this study was to examine whether these adverse effects of ozone could be prevented or reversed by hydrogen sulfide (H2S) as a reducing agent. The H2S donor sodium (NaHS) (2 mg/kg) or vehicle (PBS) was intraperitoneally injected into mice 1 hour before and after 3-hour ozone (2.5 ppm) or air exposure, and the mice were studied 24 hours later. Preventive and therapeutic treatment with NaHS reduced the ozone-induced increases in the total cells, including neutrophils and macrophages; this treatment also reduced levels of cytokines, including TNF-α, chemokine (C-X-C motif) ligand 1, IL-6, and IL-1β levels in bronchial alveolar lavage fluid; inhibited bronchial hyperresponsiveness; and attenuated ozone-induced increases in total malondialdehyde in bronchoalveolar lavage fluid and decreases in the ratio of reduced glutathione/oxidized glutathione in the lung. Ozone exposure led to decreases in the H2S production rate and in mRNA and protein levels of cystathionine-β-synthetase and cystathionine-γ-lyase in the lung. These effects were prevented and reversed by NaHS treatment. Furthermore, NaHS prevented and reversed the phosphorylation of p38 mitogen-activated protein kinase and heat shock protein 27. H2S may have preventive and therapeutic value in the treatment of airway diseases that have an oxidative stress basis.

  10. The role of Zr and Nb in oxidation/sulfidation behavior of Fe-Cr-Ni alloys

    SciTech Connect

    Natesan, K. ); Baxter, D.J. INCO Alloy Ltd., Hereford, England )

    1990-11-01

    05Structural Fe-Cr-Ni alloys may undergo rapid degradation at elevated temperatures unless protective surface oxide scales are formed and maintained. The ability of alloys to resist rapid degradation strongly depends on their Cr content and the chemistry of the exposure environment. Normally, 20 wt % Cr is required for service at temperatures up to 1000{degree}C; the presence of sulfur, however, inhibits formation of a protective surface oxide scale. The oxidation and sulfidation behavior of Fe-Cr-Ni alloys is examined over a wide temperature range (650 to 1000{degree}C), with particular emphasis on the effects of alloy Cr content and the radiation of reactive elements such as Nb and Zr. Both Nb and Zr are shown to promote protective oxidation behavior on the 12 wt % Cr alloy in oxidizing environments and to suppress sulfidation in mixed oxygen/sulfur environments. Additions of Nb and Zr at 3 wt % level resulted in stabilization of Cr{sub 2}O{sub 3} scale and led to a barrier layer of Nb- or Zr-rich oxide at the scale/metal interface, which acted to minimize the transport of base metal cations across the scale. Oxide scales were preformed in sulfur-free environments and subsequently exposed to oxygen/sulfur mixed-gas atmospheres. Preformed scales were found to delay the onset of breakaway corrosion. Corrosions test results obtained under isothermal and thermal cycling conditions are presented. 58 refs., 55 figs., 8 tabs.

  11. Photopromoted Ru-catalyzed asymmetric aerobic sulfide oxidation and epoxidation using water as a proton transfer mediator.

    PubMed

    Tanaka, Haruna; Nishikawa, Hiroaki; Uchida, Tatsuya; Katsuki, Tsutomu

    2010-09-01

    Ru(NO)-salen complexes were found to catalyze asymmetric aerobic oxygen atom transfer reactions such as sulfide oxidation and epoxidation in the presence of water under visible light irradiation at room temperature. Oxidation of sulfides including alkyl aryl sulfides and 2-substituted 1,3-dithianes using complex 2 as the catalyst proceeded with moderate to high enantioselectivity of up to 98% ee, and epoxidation of conjugated olefins using complex 3 as the catalyst proceeded with good to high enantioselectivity of 76-92% ee. Unlike biological oxygen atom transfer reactions that need a proton and electron transfer system, this aerobic oxygen atom transfer reaction requires neither such a system nor a sacrificial reductant. Although the mechanism of this oxidation has not been completely clarified, some experimental results support the notion that an aqua ligand coordinated with the ruthenium ion serves as a proton transfer agent for the oxygen activation process, and it is recycled and used as the proton transfer mediator during the process. Thus, we have achieved catalytic asymmetric oxygen atom transfer reaction using molecular oxygen that can be carried out under ambient conditions.

  12. Characterization and kinetics of sulfide-oxidizing autotrophic denitrification in batch reactors containing suspended and immobilized cells.

    PubMed

    Moraes, B S; Souza, T S O; Foresti, E

    2011-01-01

    Sulfide-oxidizing autotrophic denitrification is an advantageous alternative over heterotrophic denitrification, and may have potential for nitrogen removal of low-strength wastewaters, such as anaerobically pre-treated domestic sewage. This study evaluated the fundamentals and kinetics of this process in batch reactors containing suspended and immobilized cells. Batch tests were performed for different NOx-/S2- ratios and using nitrate and nitrite as electron acceptors. Autotrophic denitrification was observed for both electron acceptors, and NOx-/S2- ratios defined whether sulfide oxidation was complete or not. Kinetic parameter values obtained for nitrate were higher than for nitrite as electron acceptor. Zero-order models were better adjusted to profiles obtained for suspended cell reactors, whereas first-order models were more adequate for immobilized cell reactors. However, in the latter, mass transfer physical phenomena had a significant effect on kinetics based on biochemical reactions. Results showed that sulfide-oxidizing autotrophic denitrification can be successfully established for low-strength wastewaters and have potential for nitrogen removal from anaerobically pre-treated domestic sewage.

  13. Oxidative stress suppresses the cellular bioenergetic effect of the 3-mercaptopyruvate sulfurtransferase/hydrogen sulfide pathway

    SciTech Connect

    Módis, Katalin; Asimakopoulou, Antonia; Coletta, Ciro; Papapetropoulos, Andreas; Szabo, Csaba

    2013-04-19

    Highlights: •Oxidative stress impairs 3-MST-derived H{sub 2}S production in isolated enzyme and in isolated mitochondria. •This impairs the stimulatory bioenergetic effects of H{sub 2}S in hepatocytes. •This has implications for the pathophysiology of diseases with oxidative stress. -- Abstract: Recent data show that lower concentrations of hydrogen sulfide (H{sub 2}S), as well as endogenous, intramitochondrial production of H{sub 2}S by the 3-mercaptopyruvate (3-MP)/3-mercaptopyruvate sulfurtransferase (3-MST) pathway serves as an electron donor and inorganic source of energy to support mitochondrial electron transport and ATP generation in mammalian cells by donating electrons to Complex II. The aim of our study was to investigate the role of oxidative stress on the activity of the 3-MP/3-MST/H{sub 2}S pathway in vitro. Hydrogen peroxide (H{sub 2}O{sub 2}, 100–500 μM) caused a concentration-dependent decrease in the activity of recombinant mouse 3-MST enzyme. In mitochondria isolated from murine hepatoma cells, H{sub 2}O{sub 2} (50–500 μM) caused a concentration-dependent decrease in production of H{sub 2}S from 3-MP. In cultured murine hepatoma cells H{sub 2}O{sub 2}, (3–100 μM), did not result in overall cytotoxicity, but caused a partial decrease in basal oxygen consumption and respiratory reserve rapacity. The positive bioenergetic effect of 3-MP (100–300 nM) was completely abolished by pre-treatment of the cells with H{sub 2}O{sub 2} (50 μM). The current findings demonstrate that oxidative stress inhibits 3-MST activity and interferes with the positive bioenergetic role of the 3-MP/3-MST/H{sub 2}S pathway. These findings may have implications for the pathophysiology of various conditions associated with increased oxidative stress, such as various forms of critical illness, cardiovascular diseases, diabetes or physiological aging.

  14. The Role of Sulfur Oxidation in Carbonate Precipitation and Dissolution Within Sulfidic Hot Springs

    NASA Astrophysics Data System (ADS)

    Alford, S. E.; Kapitulčinová, D.; Kotrc, B.; Langerhuus, A. T.; Berelson, W.; Dawson, S.; Corsetti, F.; Hanselmann, K.; Johnson, H.; Spear, J.; Stevenson, B. S.; de La Torre, J.; 2008, G.

    2008-12-01

    Geothermal waters that have interacted with subsurface limestones often precipitate aragonite and calcite (travertine) upon cooling and degassing of CO2, forming terraced travertine deposits like those at Mammoth Hot Springs (MHS) in Yellowstone National Park. It has been shown that surfaces of filamentous microbial "Aquificales-dominated streamer communities" comprising the Apron and Channel Facies in these systems can act as nucleation sites for carbonate precipitation leading to the fine-scale tubular micro-structures consistently observed in travertine terraces, modern and ancient. The expected carbonate precipitates were found on streamer communities on the proximal Slope facies, however, ESEM imaging and EDX analysis revealed sulfur crystals, rather than carbonate precipitates, in association with Aquificales-dominated communities collected near the mouth of Narrow Gauge (pH 6.43, T 73.5°C), a sulfidic bicarbonate spring within the MHS system. Thermodynamic analysis of geochemical spring water datasets (data from Angel Terrace Spring applied to the Narrow Gauge site) demonstrates that lowering of the acid-neutralizing capacity (ANC) of spring waters can be achieved by sulfur oxidation. Although the first step of oxidation from H2S to S° cannot account for the lack of aragonite on the streamer biofilms, oxidation of even small amounts of S° to S2O32- and further to SO42- markedly decreases ANC. This microbially mediated reaction may lead to a shift in the local pH and a shift in the ion activity product (IAP) for Ca2+ x CO32- to below the solubility product (Ksp) of CaCO3. Our calculations suggest that this reaction, sulfur oxidation with oxygen to sulfate, can liberate sufficient protons to drive aragonite to undersaturation, if the initial sulfur concentration is 5 mM, and the [Ca] and [CO3] concentrations are initially 0.01 M and 1-10 uM, respectively. The potential importance of sulfur oxidation in hot springs, the molecular signatures of this process

  15. Geochemical, metagenomic and metaproteomic insights into trace metal utilization by methane-oxidizing microbial consortia in sulfidic marine sediments

    SciTech Connect

    Glass, DR. Jennifer; Yu, DR. Hang; Steele, Joshua; Dawson, Katherine; Sun, S; Chourey, Karuna; Hettich, Robert {Bob} L; Orphan, V

    2014-01-01

    Microbes have obligate requirements for trace metals in metalloenzymes that catalyze important biogeochemical reactions. In anoxic methane- and sulfide-rich environments, microbes may have unique adaptations for metal acquisition and utilization due to decreased bioavailability as a result of metal sulfide precipitation. However, micronutrient cycling is largely unexplored in cold ( 10 C) and sulfidic (>1 mM H2S) deep-sea methane seep ecosystems. We investigated trace metal geochemistry and microbial metal utilization in methane seeps offshore Oregon and California, USA, and report dissolved concentrations of nickel (0.5-270 nM), cobalt (0.5-6 nM), molybdenum (10-5,600 nM) and tungsten (0.3-8 nM) in Hydrate Ridge sediment porewaters. Despite low levels of cobalt and tungsten, metagenomic and metaproteomic data suggest that microbial consortia catalyzing anaerobic oxidation of methane utilize both scarce micronutrients in addition to nickel and molybdenum. Genetic machinery for cobalt-containing vitamin B12 biosynthesis was present in both anaerobic methanotrophic archaea (ANME) and sulfate-reducing bacteria (SRB). Proteins affiliated with the tungsten-containing form of formylmethanofuran dehydrogenase were expressed in ANME from two seep ecosystems, the first evidence for expression of a tungstoenzyme in psychrotolerant microorganisms. Finally, our data suggest that chemical speciation of metals in highly sulfidic porewaters may exert a stronger influence on microbial bioavailability than total concentration

  16. Roles of hydrogen sulfide and nitric oxide in the alleviation of cadmium-induced oxidative damage in alfalfa seedling roots.

    PubMed

    Li, Le; Wang, Yanqin; Shen, Wenbiao

    2012-06-01

    Despite hydrogen sulfide (H(2)S) and nitric oxide (NO) are important endogenous signals or bioregulators involved in many vital aspects of plant growth and responses against abiotic stresses, little information was known about their interaction. In the present study, we evaluated the effects of H(2)S and NO on alfalfa (Medicago sativa L.) plants exposed to cadmium (Cd) stress. Pretreatment with an H(2)S donor sodium hydrosulfide (NaHS) and well-known NO donor sodium nitroprusside (SNP) decreased the Cd toxicity. This conclusion was supported by the decreases of lipid peroxidation as well as the amelioration of seedling growth inhibition and Cd accumulation, in comparison with the Cd-stressed alone plants. Total activities and corresponding transcripts of antioxidant enzymes, including superoxide dismutase, peroxidase and ascorbate peroxidase were modulated differentially, thus leading to the alleviation of oxidative damage. Effects of H(2)S above were reversed by 2-(4-carboxyphenyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide potassium salt (cPTIO), the specific scavenger of NO. By using laser confocal scanning microscope combined with Greiss reagent method, further results showed that NO production increased significantly after the NaHS pretreatment regardless of whether Cd was applied or not, all of which were obviously inhibited by cPTIO. These decreases of NO production were consistent with the exaggerated syndromes associated with Cd toxicity. Together, above results suggested that NO was involved in the NaHS-induced alleviation of Cd toxicity in alfalfa seedlings, and also indicated that there exists a cross-talk between H(2)S and NO responsible for the increased abiotic stress tolerance.

  17. Middle-thermophilic sulfur-oxidizing bacteria Thiomonas sp. RAN5 strain for hydrogen sulfide removal.

    PubMed

    Asano, Ryoki; Hirooka, Kayako; Nakai, Yutaka

    2012-01-01

    Hydrogen sulfide (H2S) is one of the most toxic and offensively odorous gases and is generated in anaerobic bioreactors. A middle-thermophilic sulfur-oxidizing bacterium (SOB), Thiomonas sp. strain RAN5, was isolated and applied for H2S removal from both artificial and anaerobically digested gas. When a bioreactor containing medium inoculated with RAN5 was aerated continuously with artificial gas (containing 100 ppm H2S) at 45 degrees C for 156 hr, the H2S concentration in the vented gas was reduced by 99%. This was not affected by the presence of other microbes in the bioreactor The H2S removal efficiency of the RAN5 bioreactor for anaerobically digested gas was greater than 99% at influent H2S concentrations ranging from 2 to 1800 ppm; the efficiency decreased to 90% at influent H2S concentrations greater than 2000 ppm. Thiomonas sp. strain RAN5 cannot survive at room temperature, and thus its leakage from a wastewater treatment plant would not damage sewage systems. These data suggest that Thiomonas sp. strain RAN5 may be a useful microorganism for H2S removal.

  18. Carbon Monoxide, Hydrogen Sulfide, and Nitric Oxide as Signaling Molecules in the Gastrointestinal Tract

    PubMed Central

    Farrugia, Gianrico; Szurszewski, Joseph H.

    2014-01-01

    Carbon monoxide (CO) and hydrogen sulfide (H2S) used to be thought of simply as lethal and (for H2S) smelly gaseous molecules; now they are known to have important signaling functions in the gastrointestinal tract. CO and H2S, which are produced in the gastrointestinal tract by different enzymes, regulate smooth muscle membrane potential and tone, transmit signals from enteric nerves and can regulate the immune system. The pathways that produce nitric oxide (NO) H2S and CO interact—each can inhibit and potentiate the level and activity of the other. However, there are significant differences between these molecules, such as in half-lives; CO is more stable and therefore able to have effects distal to the site of production, whereas NO and H2S are short lived and act only close to sites of production. We review their signaling functions in the luminal gastrointestinal tract and discuss how their pathways interact. We also describe other physiologic functions of CO and H2S and how they might be used as therapeutic agents. PMID:24798417

  19. Cadmium sulfide quantum dots induce oxidative stress and behavioral impairments in the marine clam Scrobicularia plana.

    PubMed

    Buffet, Pierre-Emmanuel; Zalouk-Vergnoux, Aurore; Poirier, Laurence; Lopes, Christelle; Risso-de-Faverney, Christine; Guibbolini, Marielle; Gilliland, Douglas; Perrein-Ettajani, Hanane; Valsami-Jones, Eugenia; Mouneyrac, Catherine

    2015-07-01

    Cadmium sulfide (CdS) quantum dots have a number of current applications in electronics and solar cells and significant future potential in medicine. The aim of the present study was to examine the toxic effects of CdS quantum dots on the marine clam Scrobicularia plana exposed for 14 d to these nanomaterials (10 µg Cd L(-1) ) in natural seawater and to compare them with soluble Cd. Measurement of labile Cd released from CdS quantum dots showed that 52% of CdS quantum dots remained in the nanoparticulate form. Clams accumulated the same levels of Cd regardless of the form in which it was delivered (soluble Cd vs CdS quantum dots). However, significant changes in biochemical responses were observed in clams exposed to CdS quantum dots compared with soluble Cd. Increased activities of catalase and glutathione-S-transferase were significantly higher in clams exposed in seawater to Cd as the nanoparticulate versus the soluble form, suggesting a specific nano effect. The behavior of S. plana in sediment showed impairments of foot movements only in the case of exposure to CdS quantum dots. The results show that oxidative stress and behavior biomarkers are sensitive predictors of CdS quantum dots toxicity in S. plana. Such responses, appearing well before changes might occur at the population level, demonstrate the usefulness of this model species and type of biomarker in the assessment of nanoparticle contamination in estuarine ecosystems.

  20. Photocatalytic oxidation of gaseous 2-chloroethyl ethyl sulfide over TiO2.

    PubMed

    Martyanov, Igor N; Klabunde, Kenneth J

    2003-08-01

    Photocatalytic oxidation of gaseous 2-chloroethyl ethyl sulfide (2-CEES, ClCH2CH2SCH2CH3) over TiO2 illuminated with UV light and maintained at 25 or 80 degrees C in air has been investigated. 2-CEES was found to suffer progressive oxidation to yield ethylene (CH2CH2), chloroethylene (ClCHCH2), ethanol (CH3CH2OH), acetaldehyde (CH3C(O)H), chloroacetaldehyde (ClCH2C(O)H), diethyl disulfide (CH3CH2S2CH2CH3), 2-chloroethyl ethyl disulfide (ClCH2CH2S2CH2CH3), and bis(2-chloroethyl) disulfide (ClCH2CH2S2CH2CH2Cl) as the main primary intermediates, and water (H2O), carbon dioxide (CO2), sulfur dioxide (SO2), surface sulfate ions (SO4(2-)), and hydrogen chloride (HCl) as the final products. Trace concentrations of gaseous 2-chloroethanol (ClCH2CH2OH), ethanesulfonyl chloride (CH3CH2SO2Cl), ethyl thioacetate (CH3CH2SC(O)CH3), and considerable amounts of acetic acid (CH3C(O)OH), crotonaldehyde (CH3CHCHC(O)H), methyl acetate (CH3C(O)OCH3), and methyl formate (CH3OC(O)H) were also detected in the gas phase during the photooxidation conducted at 80 degrees C. Increase in temperature from 25 to 80 degrees C accelerates formation of gaseous ethanol, acetaldehyde, chloroacetaldehyde, diethyl disulfide, 2-chloroethyl ethyl disulfide, and bis(2-chloroethyl) disulfide but suppresses ethylene and chloroethylene production at initial stages of the process. Some aspects of the possible reaction mechanism leading to this wide array of intermediates and final products are discussed.

  1. Nitric oxide-releasing flurbiprofen reduces formation of proinflammatory hydrogen sulfide in lipopolysaccharide-treated rat.

    PubMed

    Anuar, Farhana; Whiteman, Matthew; Siau, Jia Ling; Kwong, Shing Erl; Bhatia, Madhav; Moore, Philip K

    2006-04-01

    The biosynthesis of both nitric oxide (NO) and hydrogen sulfide (H2S) is increased in lipopolysaccharide (LPS)-injected mice and rats but their interaction in these models is not known. In this study we examined the effect of the NO donor, nitroflurbiprofen (and the parent molecule flurbiprofen) on NO and H2S metabolism in tissues from LPS-pretreated rats. Administration of LPS (10 mg kg(-1), i.p.; 6 h) resulted in an increase (P<0.05) in plasma TNF-alpha, IL-1beta and nitrate/nitrite (NO(x)) concentrations, liver H2S synthesis (from added cysteine), CSE mRNA, inducible nitric oxide synthase (iNOS), myeloperoxidase (MPO) activity (marker for neutrophil infiltration) and nuclear factor-kappa B (NF-kappaB) activation. Nitroflurbiprofen (3-30 mg kg(-1), i.p.) administration resulted in a dose-dependent inhibition of the LPS-mediated increase in plasma TNF-alpha, IL-1beta and NO(x) concentration, liver H2S synthesis (55.00+/-0.95 nmole mg protein(-1), c.f. 62.38+/-0.47 nmole mg protein(-1), n = 5, P<0.05), CSE mRNA, iNOS, MPO activity and NF-kappaB activation. Flurbiprofen (21 mg kg(-1), i.p.) was without effect. These results show for the first time that nitroflurbiprofen downregulates the biosynthesis of proinflammatory H2S and suggest that such an effect may contribute to the augmented anti-inflammatory activity of this compound. These data also highlight the existence of 'crosstalk' between NO and H2S in this model of endotoxic shock.

  2. Surface modifications of steels to improve corrosion resistance in sulfidizing-oxidizing environments

    NASA Astrophysics Data System (ADS)

    Behrani, Vikas

    Industrial and power generation processes employ units like boilers and gasifiers to burn sulfur containing fuels to produce steam and syn gas (H 2 and CO), which can generate electricity using turbines and fuel cells. These units often operate under environments containing gases such as H 2S, SO2, O2 etc, which can attack the metallic structure and impose serious problems of corrosion. Corrosion control in high temperature sulfur bearing environments is a challenging problem requiring information on local gaseous species at the surface of alloy and mechanisms of degradation in these environments. Coatings have proved to be a better alternative for improving corrosion resistance without compromising the bulk mechanical properties. Changes in process conditions may result in thermal and/or environment cycling between oxidizing and sulfidizing environments at the alloy surface, which can damage the protective scale formed on the alloy surface, leading to increase in corrosion rates. Objective of this study was to understand the effect of fluctuating environments on corrosion kinetics of carbon steels and develop diffusion based coatings to mitigate the high temperatures corrosion under these conditions. More specifically, the focus was: (1) to characterize the local gaseous environments at the surface of alloys in boilers; (2) optimizing diffusion coatings parameters for carbon steel; (3) understand the underlying failure mechanisms in cyclic environments; (4) to improve aluminide coating behavior by co-deposition of reactive elements such as Yttrium and Hafnium; (5) to formulate a plausible mechanism of coating growth and effects of alloying elements on corrosion; and (6) to understand the spallation behavior of scale by measuring stresses in the scales. The understanding of coating mechanism and effects of fluctuating gaseous environments provides information for designing materials with more reliable performance. The study also investigates the mechanism behind

  3. Sulfide oxidation and distribution of metals near abandoned copper mines in coastal environments, Prince William Sound, Alaska, USA

    USGS Publications Warehouse

    Koski, R.A.; Munk, L.; Foster, A.L.; Shanks, Wayne C.; Stillings, L.L.

    2008-01-01

    The oxidation of sulfide-rich rocks, mostly leftover debris from Cu mining in the early 20th century, is contributing to metal contamination of local coastal environments in Prince William Sound, Alaska. Analyses of sulfide, water, sediment, precipitate and biological samples from the Beatson, Ellamar, and Threeman mine sites show that acidic surface waters generated from sulfide weathering are pathways for redistribution of environmentally important elements into and beyond the intertidal zone at each site. Volcanogenic massive sulfide deposits composed of pyrrhotite and (or) pyrite + chalcopyrite + sphalerite with subordinate galena, arsenopyrite, and cobaltite represent potent sources of Cu, Zn, Pb, As, Co, Cd, and Hg. The resistance to oxidation among the major sulfides increases in the order pyrrhotite ??? sphalerite < chalcopyrite ??? pyrite; thus, pyrrhotite-rich rocks are typically more oxidized than those dominated by pyrite. The pervasive alteration of pyrrhotite begins with rim replacement by marcasite followed by replacement of the core by sulfur, Fe sulfate, and Fe-Al sulfate. The oxidation of chalcopyrite and pyrite involves an encroachment by colloform Fe oxyhydroxides at grain margins and along crosscutting cracks that gradually consumes the entire grain. The complete oxidation of sulfide-rich samples results in a porous aggregate of goethite, lepidocrocite and amorphous Fe-oxyhydroxide enclosing hydrothermal and sedimentary silicates. An inverse correlation between pH and metal concentrations is evident in water data from all three sites. Among all waters sampled, pore waters from Ellamar beach gravels have the lowest pH (???3) and highest concentrations of base metals (to ???25,000 ??g/L), which result from oxidation of abundant sulfide-rich debris in the sediment. High levels of dissolved Hg (to 4100 ng/L) in the pore waters probably result from oxidation of sphalerite-rich rocks. The low-pH and high concentrations of dissolved Fe, Al, and SO4

  4. CONFIRMATION OF CIRCUMSTELLAR PHOSPHINE

    SciTech Connect

    Agúndez, M.; Cernicharo, J.; Encrenaz, P.; Teyssier, D.

    2014-08-01

    Phosphine (PH{sub 3}) was tentatively identified a few years ago in the carbon star envelopes IRC +10216 and CRL 2688 from observations of an emission line at 266.9 GHz attributable to the J = 1-0 rotational transition. We report the detection of the J = 2-1 rotational transition of PH{sub 3} in IRC +10216 using the HIFI instrument on board Herschel, which definitively confirms the identification of PH{sub 3}. Radiative transfer calculations indicate that infrared pumping in excited vibrational states plays an important role in the excitation of PH{sub 3} in the envelope of IRC +10216, and that the observed lines are consistent with phosphine being formed anywhere between the star and 100 R {sub *} from the star, with an abundance of 10{sup –8} relative to H{sub 2}. The detection of PH{sub 3} challenges chemical models, none of which offer a satisfactory formation scenario. Although PH{sub 3} holds just 2% of the total available phosphorus in IRC +10216, it is, together with HCP, one of the major gas phase carriers of phosphorus in the inner circumstellar layers, suggesting that it could also be an important phosphorus species in other astronomical environments. This is the first unambiguous detection of PH{sub 3} outside the solar system, and is a further step toward a better understanding of the chemistry of phosphorus in space.

  5. Theoretical spectroscopic constants for the low-lying states of the oxides and sulfides of Mo and Tc

    NASA Technical Reports Server (NTRS)

    Langhoff, Stephen R.; Bauschlicher, Charles W., Jr.; Pettersson, Lars G. M.; Siegbahn, Per E. M.

    1989-01-01

    Spectroscopic results were determined for the ground and low-lying states of the oxides and sulfides of Mo and Tc, using the single-reference-based modified coupled pair functional method of Ahlrichs et al. (1985) and Chong et al. (1986) and the multireference-based state-averaged CASSCF/MRCI method. Spectroscopic constants, dipole moments, Mulliken populations, and radiative lifetimes were calculated for selected low-lying states of these molecular systems. The spectroscopy of the MoS and TcS molecules was found to be quite analogous to the corresponding oxides.

  6. Effect of hydrogen sulfide on chemical looping combustion of coal-derived synthesis gas over bentonite-supported metal-oxide oxygen carriers

    SciTech Connect

    Tian, H.J.; Simonyi, T.; Poston, J.; Siriwardane, R.

    2009-09-15

    The effect of hydrogen sulfide (H{sub 2}S) on the chemical looping combustion of coal-derived synthesis gas with bentonite-supported metal oxides - such as iron oxide, nickel oxide, manganese oxide, and copper oxide - was investigated by thermogravimetric analysis, mass spectrometry, and X-ray photoelectron spectroscopy (XPS). During the reaction with synthesis gas containing H{sub 2}S, metal-oxide oxygen carriers were first reduced by carbon monoxide and hydrogen, and then interacted with H{sub 2}S to form metal sulfide, which resulted in a weight gain during the reduction/sulfidation step. The reduced/sulfurized compounds could be regenerated to form sulfur dioxide and oxides during the oxidation reaction with air. The reduction/oxidation capacities of iron oxide and nickel oxide were not affected by the presence of H{sub 2}S, but both manganese oxide and copper oxide showed decreased reduction/oxidation capacities. However, the rates of reduction and oxidation decreased in the presence of H{sub 2}S for all four metal oxides.

  7. Thermodynamic Modeling of Sulfide Capacity of Na2O-Containing Oxide Melts

    NASA Astrophysics Data System (ADS)

    Moosavi-Khoonsari, Elmira; Jung, In-Ho

    2016-10-01

    Thermodynamic modeling of the sulfide dissolution in the Na2O-FetO-CaO-MgO-MnO-Al2O3-SiO2 multicomponent slags was performed to investigate the desulfurization of hot metal using Na2O-containing fluxes. The dissolution behavior of sulfur in the melts was modeled using the modified quasi-chemical model in the quadruplet approximation. This model can take into account the short-range ordering and the reciprocal exchange reaction of cations and anions in oxy-sulfide slags. Experimental sulfide capacity data were well predicted from the model with only three model parameters.

  8. Enhancing the Performance of the Rechargeable Iron Electrode in Alkaline Batteries with Bismuth Oxide and Iron Sulfide Additives

    SciTech Connect

    Manohar, AK; Yang, CG; Malkhandi, S; Prakash, GKS; Narayanan, SR

    2013-09-07

    Iron-based alkaline rechargeable batteries have the potential of meeting the needs of large-scale electrical energy storage because of their low-cost, robustness and eco-friendliness. However, the widespread commercial deployment of iron-based batteries has been limited by the low charging efficiency and the poor discharge rate capability of the iron electrode. In this study, we have demonstrated iron electrodes containing bismuth oxide and iron sulfide with a charging efficiency of 92% and capable of being discharged at the 3C rate. Such a high value of charging efficiency combined with the ability to discharge at high rates is being reported for the first time. The bismuth oxide additive led to the in situ formation of elemental bismuth and a consequent increase in the overpotential for the hydrogen evolution reaction leading to an increase in the charging efficiency. We observed that the sulfide ions added to the electrolyte and iron sulfide added to the electrode mitigated-electrode passivation and allowed for continuous discharge at high rates. At the 3C discharge rate, a utilization of 0.2 Ah/g was achieved. The performance level of the rechargeable iron electrode demonstrated here is attractive for designing economically-viable large-scale energy storage systems based on alkaline nickel-iron and iron-air batteries. (C) 2013 The Electrochemical Society. All rights reserved.

  9. Zinc oxide nanocubes as a destructive nanoadsorbent for the neutralization chemistry of 2-chloroethyl phenyl sulfide: A sulfur mustard simulant.

    PubMed

    Kiani, Armin; Dastafkan, Kamran

    2016-09-15

    Zinc oxide nanocubes were surveyed for their destructive turn-over to decontaminate 2-chloro ethyl phenyl sulfide, a sulfur mustard simulant. Prior to the reaction, nanocubes were prepared through sol-gel method using monoethanolamine, diethylene glycol, and anhydrous citric acid as the stabilizing, cross linking/structure directing agents, respectively. The formation of nanoscale ZnO, the cubic morphology, crystalline structure, and chemical-adsorptive characteristics were certified by FESEM-EDS, TEM-SAED, XRD, FTIR, BET-BJH, H2-TPR, and ESR techniques. Adsorption and destruction reactions were tracked by GC-FID analysis in which the effects of polarity of the media, reaction time, and temperature on the destructive capability of the surface of nanocubes were investigated and discussed. Results demonstrated that maximum neutralization occurred in n-heptane solvent after 1/2h at 55°C. Kinetic study construed that the neutralization reaction followed the pseudo-second order model with a squared correlation coefficient and rate constant of 0.9904 and 0.00004gmg(-1)s(-1), respectively. Furthermore, GC-MS measurement confirmed the formation of 2-hydroxy ethyl phenyl sulfide (2-HEPS) and phenyl vinyl sulfide (PVS) as neutralization products that together with Bronsted and Lewis acid/base approaches exemplify the role of hydrolysis and elimination mechanisms on the surface of zinc oxide nanocubes.

  10. Reaction Mechanisms of Metals with Hydrogen Sulfide and Thiols in Model Wine. Part 1: Copper-Catalyzed Oxidation.

    PubMed

    Kreitman, Gal Y; Danilewicz, John C; Jeffery, David W; Elias, Ryan J

    2016-05-25

    Sulfidic off-odors as a result of hydrogen sulfide (H2S) and low-molecular-weight thiols are commonly encountered in wine production. These odors are usually removed by the process of Cu(II) fining, a process that remains poorly understood. The present study aims to elucidate the underlying mechanisms by which Cu(II) interacts with H2S and thiol compounds (RSH) under wine-like conditions. Copper complex formation was monitored along with H2S, thiol, oxygen, and acetaldehyde concentrations after the addition of Cu(II) (50 or 100 μM) to air-saturated model wine solutions containing H2S, cysteine, 6-sulfanylhexan-1-ol, or 3-sulfanylhexan-1-ol (300 μM each). The presence of H2S and thiols in excess to Cu(II) led to the rapid formation of ∼1.4:1 H2S/Cu and ∼2:1 thiol/Cu complexes, resulting in the oxidation of H2S and thiols and reduction of Cu(II) to Cu(I), which reacted with oxygen. H2S was observed to initially oxidize rather than form insoluble copper sulfide. The proposed reaction mechanisms provide insight into the extent to which H2S can be selectively removed in the presence of thiols in wine.

  11. Use of ORP (oxidation-reduction potential) to control oxygen dosing for online sulfide oxidation in anaerobic treatment of high sulfate wastewater.

    PubMed

    Khanal, S K; Shang, C; Huang, J C

    2003-01-01

    In this study, oxidation-reduction potential (ORP) was used as a controlling parameter to regulate oxygen dosing to the recycled biogas for online sulfide oxidation in an upflow anaerobic filter (UAF) system. The UAF was operated with a constant influent COD of 18,000 mg/L, but with different influent sulfates of 1000, 3000 and 6000 mg/L. The reactor was initially operated under a natural ORP of -290 mV (without oxygen injection), and was then followed by oxygenation to raise its ORP by 25 mV above the natural level for each influent sulfate condition. At 6,000 mg/L sulfate without oxygen injection, the dissolved sulfide reached 733.8 mg S/L with a corresponding free sulfide of 250.3 mg S/L, thus showing a considerable inhibition to methanogens. Upon oxygenation to raise its ORP to -265 mV (i.e., a 25 mV increase), the dissolved sulfide was reduced by more than 98.5% with a concomitant 45.9% increase of the methane yield. Under lower influent sulfate levels of 1,000 and 3,000 mg/L, the levels of sulfides produced, even under the natural ORP, did not impose any noticeable toxicity to methanogens. Upon oxygenation to raise the ORP by +25 mV, the corresponding methane yields were actually reduced by 15.5% and 6.2%, respectively. However, such reductions were not due to the adverse impact of the elevated ORP; instead, they were due to a diversion of some organic carbon to support the facultative activities inside the reactor as a result of excessive oxygenation. In other words, to achieve satisfactory sulfide oxidation for the lower influent sulfate conditions, it was not necessary to raise the ORP by as much as +25 mV. The ORP increase actually needed depended on both the influent sulfate and also actual wastewater characteristics. This study had proved that the ORP controlled oxygenation was reliable for achieving consistent online sulfide control.

  12. Acid volatile sulfides oxidation and metals (Mn, Zn) release upon sediment resuspension: laboratory experiment and model development.

    PubMed

    Hong, Yong Seok; Kinney, Kerry A; Reible, Danny D

    2011-03-01

    Sediment from the Anacostia River (Washington, DC, USA) was suspended in aerobic artificial river water for 14 d to investigate the dynamics of dissolved metals release and related parameters including pH, acid volatile sulfides (AVS), and dissolved/solid phase Fe(2+). To better understand and predict the underlying processes, a mathematical model is developed considering oxidation of reduced species, dissolution of minerals, pH changes, and pH-dependent metals' sorption to sediment. Oxidation rate constants of elemental sulfur and zinc sulfide, and a dissolution rate constant of carbonate minerals, were adjusted to fit observations. The proposed model and parameters were then applied, without further calibration, to literature-reported experimental observations of resuspension in an acid sulfate soil collected in a coastal flood plain. The model provided a good description of the dynamics of AVS, Fe(2+), S(0)((s)), pH, dissolved carbonates concentrations, and the release of Ca((aq)), Mg((aq)), and Zn((aq)) in both sediments. Accurate predictions of Mn((aq)) release required adjustment of sorption partitioning coefficient, presumably due to the presence of Mn scavenging by phases not accounted for in the model. The oxidation of AVS (and the resulting release of sulfide-bound metals) was consistent with a two-step process, a relatively rapid AVS oxidation to elemental sulfur (S(0)((s))) and a slow oxidation of S(0)((s)) to SO(4)(2-)((aq)), with an associated decrease in pH from neutral to acidic conditions. This acidification was the dominant factor for the release of metals into the aqueous phase.

  13. Dimethyl Sulfide-Dimethyl Ether and Ethylene Oxide-Ethylene Sulfide Complexes Investigated by Fourier Transform Microwave Spectroscopy and AB Initio Calculation

    NASA Astrophysics Data System (ADS)

    Kawashima, Yoshiyuki; Tatamitani, Yoshio; Mase, Takayuki; Hirota, Eizi

    2015-06-01

    The ground-state rotational spectra of the dimethyl sulfide-dimethyl ether (DMS-DME) and the ethylene oxide and ethylene sulfide (EO-ES) complexes were observed by Fourier transform microwave spectroscopy, and a-type and c-type transitions were assigned for the normal, 34S, and three 13C species of the DMS-DME and a-type and b-type rotational transitions for the normal, 34S, and two 13C species of the EO-ES. The observed transitions were analyzed by using an S-reduced asymmetric-top rotational Hamiltonian. The rotational parameters thus derived for the DMS-DME were found consistent with a structure of Cs symmetry with the DMS bound to the DME by two C-H(DMS)---O and one S---H-C(DME) hydrogen bonds. The barrier height V3 to internal rotation of the "free" methyl group in the DME was determined to be 915.4 (23) wn, which is smaller than that of the DME monomer, 951.72 (70) wn, and larger than that of the DME dimer, 785.4 (52) wn. For the EO-ES complex the observed data were interpreted in the terms of an antiparallel Cs geometry with the EO bound to the ES by two C-H(ES)---O and two S---H-C(EO) hydrogen bonds. We have applied a natural bond orbital (NBO) analysis to the DMS-DME and EO-ES to calculate the stabilization energy CT (= ΔEσσ*), which were closely correlated with the binding energy EB, as found for other related complexes. Y. Niide and M. Hayashi, J. Mol. Spectrosc. 220, 65-79 (2003). Y. Tatamitani, B. Liu, J. Shimada, T. Ogata, P. Ottaviani, A. Maris, W. Caminati, and J. L. Alonso, J. Am. Chem. Soc. 124, 2739-2743 (2002).

  14. Origin and fate of sulfide liquids in hotspot volcanism (La Réunion): Pb isotope constraints from residual Fe-Cu oxides

    NASA Astrophysics Data System (ADS)

    Vlastélic, I.; Gannoun, A.; Di Muro, A.; Gurioli, L.; Bachèlery, P.; Henot, J. M.

    2016-12-01

    Immiscible sulfide liquids in basaltic magmas play an important role in trace metal transport and the sulfur budget of volcanic eruptions. However, sulfides are transient phases, whose origin and fate are poorly constrained. We address these issues by analyzing sulfide destabilization products preserved in lavas from La Réunion Island. Iron oxide globules and coatings, typically 20-80 μm in size, were found to occur in vesicles of differentiated lavas from Piton des Neiges, and recent pumice samples from Piton de la Fournaise. Field and mineralogical evidence indicates that the iron oxides are syn-eruptive phases not resulting from hydrothermal processes. Samples were first studied by Scanning Electron Microscopy. The globules were separated, whereas the smaller spherules and coatings were concentrated by magnetic sorting and acid leaching, and samples were processed through wet chemistry. The Fe oxide phases comprise 49-74 wt.% Fe, 26-40 wt.% O, and up to 6 wt.% Cu, 811 ppm Ni, 140 ppm Bi, and 8.5 ppm Pb. Compared to the host lava, Cu, Ni, and Bi are enriched by a factor of 101-103. Systematic Pb isotope disequilibrium (between 500 ppm and 2.9% for 206Pb/204Pb) exists between Fe oxides and host rocks, with Fe oxides generally displaying less radiogenic ratios. Unradiogenic Pb is a typical signature of sulfide, which tends to concentrate Pb, but not its parent elements U and Th. Thus, both the chemical and isotopic compositions of the vesicle-hosted Fe oxides suggest that they are more or less direct products of the destabilization of immiscible sulfide liquids. Although Pb dominantly partitions into the gas phase during sulfide breakdown, the original Pb isotope signature of sulfide is preserved in the residual oxide. The composition estimated for the parent sulfides (206Pb/204Pb = 18.20-18.77, 207Pb/204Pb = 15.575, and 208Pb/204Pb = 38.2-38.8) precludes a genetic link with the La Réunion plume, and suggests a lithospheric or crustal origin. It is estimated

  15. Hydrogen Sulfide Ameliorates Tobacco Smoke-Induced Oxidative Stress and Emphysema in Mice

    PubMed Central

    Han, Weihong; Dong, Zheng; Dimitropoulou, Christiana

    2011-01-01

    Abstract Aims The mutual interactions between reactive oxygen species, airway inflammation, and alveolar cell death play crucial role in the pathogenesis of chronic obstructive pulmonary disease (COPD). In the present study, we investigated the possibility that hydrogen sulfide (H2S) donor sodium hydrosulfide (NaHS) might be a novel option for intervention in COPD. Results We used a mouse model of tobacco smoke (TS)-induced emphysema. Mice were injected with H2S donor NaHS (50 μmol/kg in 0.25 ml phosphate buffer saline, intraperitoneally) or vehicle daily before exposed to TS for 1 h/day, 5 days/week for 12 and 24 weeks. We found that NaHS ameliorated TS-induced increase in mean linear intercepts, the thickness of bronchial walls, and the numbers of total cell counts as well as neutrophils, monocytes, and tumor necrosis factor α in bronchial alveolar lavage. Moreover, NaHS reduced increases in right ventricular systolic pressure, the thickness of pulmonary vascular walls, and the ratio of RV/LV+S in TS-exposed mice. Further, TS exposure for 12 and 24 weeks reduced the protein contents of cystathionine γ-lyase (CGL), cystathionine β-synthetase (CBS), nuclear erythroid-related factor 2 (Nrf2), Pser473-Akt, as well as glutathione/oxidized glutathione ratio in the lungs. TS-exposed lungs exhibited large amounts of 8-hydroxyguanine-positive and terminal deoxynucleotidyl transferase dUTP nick end labeling-positive cells. Treatment with NaHS increased Pser473-Akt and attenuated TS-induced reduction of CGL, CBS, and Nrf2 as well as glutathione/oxidized glutathione ratio in the lungs. NaHS also reduced amounts of 8-hydroxyguanine-positive, terminal deoxynucleotidyl transferase dUTP nick end labeling-positive cells and active caspase-3 in TS-exposed lungs. Additionally, knocking-down Akt protein abolished the protective effects of NaHS against TS-induced apoptosis and downregulation of Nrf2, CGL, and CBS in pulmonary artery endothelial cells. Conclusion These

  16. Removal of antimony (Sb(V)) from Sb mine drainage: biological sulfate reduction and sulfide oxidation-precipitation.

    PubMed

    Wang, Huawei; Chen, Fulong; Mu, Shuyong; Zhang, Daoyong; Pan, Xiangliang; Lee, Duu-Jong; Chang, Jo-Shu

    2013-10-01

    Antimony (Sb(V)) in Sb mine drainage has adverse effects on the receiving water environments. This study for the first time demonstrated the feasibility of using sulfate-reducing bacteria (SRB) to convert sulfate ions in SMD into sulfides that reduce Sb(V) to Sb(III) and to form complex with Sb(III) as precipitate. The principal compound in the precipitate was stibnite (Sb2S3) at pH 7 and pH 9. The Sb(V) removal mechanism is sulfate-reduction and sulfide oxidization-precipitation, different from the conventional SRB-precipitation processes for heavy metals. The Sb(V)/sulfate ratio is noted an essential parameter affecting the Sb removal efficiency from SMD.

  17. The Diversity of Sulfide Oxidation and Sulfate Reduction Genes Expressed by the Bacterial Communities of the Cariaco Basin, Venezuela

    PubMed Central

    Rodriguez-Mora, Maria J.; Edgcomb, Virginia P.; Taylor, Craig; Scranton, Mary I.; Taylor, Gordon T.; Chistoserdov, Andrei Y.

    2016-01-01

    Qualitative expression of dissimilative sulfite reductase (dsrA), a key gene in sulfate reduction, and sulfide:quinone oxidoreductase (sqr), a key gene in sulfide oxidation was investigated. Neither of the two could be amplified from mRNA retrieved with Niskin bottles but were amplified from mRNA retrieved by the Deep SID. The sqr and sqr-like genes retrieved from the Cariaco Basin were related to the sqr genes from a Bradyrhizobium sp., Methylomicrobium alcaliphilum, Sulfurovum sp. NBC37-1, Sulfurimonas autotrophica, Thiorhodospira sibirica and Chlorobium tepidum. The dsrA gene sequences obtained from the redoxcline of the Cariaco Basin belonged to chemoorganotrophic and chemoautotrophic sulfate and sulfur reducers belonging to the class Deltaproteobacteria (phylum Proteobacteria) and the order Clostridiales (phylum Firmicutes). PMID:27651847

  18. The Diversity of Sulfide Oxidation and Sulfate Reduction Genes Expressed by the Bacterial Communities of the Cariaco Basin, Venezuela.

    PubMed

    Rodriguez-Mora, Maria J; Edgcomb, Virginia P; Taylor, Craig; Scranton, Mary I; Taylor, Gordon T; Chistoserdov, Andrei Y

    2016-01-01

    Qualitative expression of dissimilative sulfite reductase (dsrA), a key gene in sulfate reduction, and sulfide:quinone oxidoreductase (sqr), a key gene in sulfide oxidation was investigated. Neither of the two could be amplified from mRNA retrieved with Niskin bottles but were amplified from mRNA retrieved by the Deep SID. The sqr and sqr-like genes retrieved from the Cariaco Basin were related to the sqr genes from a Bradyrhizobium sp., Methylomicrobium alcaliphilum, Sulfurovum sp. NBC37-1, Sulfurimonas autotrophica, Thiorhodospira sibirica and Chlorobium tepidum. The dsrA gene sequences obtained from the redoxcline of the Cariaco Basin belonged to chemoorganotrophic and chemoautotrophic sulfate and sulfur reducers belonging to the class Deltaproteobacteria (phylum Proteobacteria) and the order Clostridiales (phylum Firmicutes).

  19. Temperature dependence of the heterogeneous reaction of carbonyl sulfide on magnesium oxide.

    PubMed

    Liu, Yongchun; He, Hong; Ma, Qingxin

    2008-04-03

    The experimental determination of rate constants for atmospheric reactions and how these rate constants vary with temperature remain a crucially important part of atmosphere science. In this study, the temperature dependence of the heterogeneous reaction of carbonyl sulfide (COS) on magnesium oxide (MgO) has been investigated using a Knudsen cell reactor and a temperature-programmed reaction apparatus. We found that the adsorption and the heterogeneous reaction are sensitive to temperature. The initial uptake coefficients (gammat(Ini)) of COS on MgO decrease from 1.07 +/- 0.71 x 10-6 to 4.84 +/- 0.60 x 10-7 with the increasing of temperature from 228 to 300 K, and the steady state uptake coefficients (gammat(SS)) increase from 5.31 +/- 0.06 x 10-8 to 1.68 +/- 0.41 x 10-7 with the increasing of temperature from 240 to 300 K. The desorption rate constants (kdes) were also found to increase slightly with the enhancement of temperature. The empirical formula between the uptake coefficients, desorption rate constants and temperature described in the form of Arrhenius expression were obtained. The activation energies for the heterogeneous reaction and desorption of COS on MgO were measured to be 11.02 +/- 0.34 kJ.mol-1 and 6.30 +/- 0.81 kJ.mol-1, respectively. The results demonstrate that the initial uptake of COS on MgO is mainly contributed by an adsorption process and the steady state uptake is due to a catalytic reaction. The environmental implication was also discussed.

  20. Phosphonate–Phosphinate Rearrangement

    PubMed Central

    2014-01-01

    LiTMP metalated dimethyl N-Boc-phosphoramidates derived from 1-phenylethylamine and 1,2,3,4-tetrahydronaphthalen-1-ylamine highly selectively at the CH3O group to generate short-lived oxymethyllithiums. These isomerized to diastereomeric hydroxymethylphosphonamidates (phosphate–phosphonate rearrangement). However, s-BuLi converted the dimethyl N-Boc-phosphoramidate derived from 1-phenylethylamine to the N-Boc α-aminophosphonate preferentially. Only s-BuLi deprotonated dimethyl hydroxymethylphosphonamidates at the benzylic position and dimethyl N-Boc α-aminophosphonates at the CH3O group to induce phosphonate–phosphinate rearrangements. In the former case, the migration of the phosphorus substituent from the nitrogen to the carbon atom followed a retentive course with some racemization because of the involvement of a benzyllithium as an intermediate. PMID:25525945

  1. Effect of hydrogen sulfide on chemical looping of coal-derived synthesis gas over bentonite-supported metal---oxide oxygen carriers

    SciTech Connect

    Tian, H.; Simonyi, T.; Poston, J.; Siriwardane, R.

    2009-01-01

    The effect of hydrogen sulfide (H2S) on the chemical looping combustion of coal-derived synthesis gas with bentonite-supported metal oxidesssuch as iron oxide, nickel oxide, manganese oxide, and copper oxideswas investigated by thermogravimetric analysis, mass spectrometry, and X-ray photoelectron spectroscopy (XPS). During the reaction with synthesis gas containing H2S, metal-oxide oxygen carriers were first reduced by carbon monoxide and hydrogen, and then interacted with H2S to form metal sulfide, which resulted in a weight gain during the reduction/sulfidation step. The reduced/sulfurized compounds could be regenerated to form sulfur dioxide and oxides during the oxidation reaction with air. The reduction/oxidation capacities of iron oxide and nickel oxide were not affected by the presence of H2S, but both manganese oxide and copper oxide showed decreased reduction/oxidation capacities. However, the rates of reduction and oxidation decreased in the presence of H2S for all four metal oxides.

  2. Visible-light-enhanced interactions of hydrogen sulfide with composites of zinc (oxy)hydroxide with graphite oxide and graphene.

    PubMed

    Seredych, Mykola; Mabayoje, Oluwaniyi; Bandosz, Teresa J

    2012-01-17

    Composites of zinc(oxy)hydroxide-graphite oxide and of zinc(oxy)hydroxide-graphene were used as adsorbents of hydrogen sulfide under ambient conditions. The initial and exhausted samples were characterized by XRD, FTIR, potentiometric titration, EDX, thermal analysis, and nitrogen adsorption. An increase in the amount of H(2)S adsorbed/oxidized on their surfaces in comparison with that of pure Zn(OH)(2) is linked to the structure of the composite, the relative number of terminal hydroxyls, and the kind of graphene-based phase used. Although terminal groups are activated by a photochemical process, the graphite oxide component owing to the chemical bonds with the zinc(oxy)hydroxide phase and conductive properties helps in electron transfer, leading to more efficient oxygen activation via the formation of superoxide ions. Elemental sulfur, zinc sulfide, sulfite, and sulfate are formed on the surface. The formation of sulfur compounds on the surface of zinc(oxy)hydroxide during the course of the breakthrough experiments and thus Zn(OH)(2)-ZnS heterojunctions can also contribute to the increased surface activity of our materials. The results show the superiority of graphite oxide in the formation of composites owing to its active surface chemistry and the possibility of interface bond formation, leading to an increase in the number of electron-transfer reactions.

  3. Catalytic performance and deactivation of precipitated iron catalyst for selective oxidation of hydrogen sulfide to elemental sulfur in the waste gas streams from coal gasification

    SciTech Connect

    Mashapa, T.N.; Rademan, J.D.; van Vuuren, M.J.J.

    2007-09-15

    The selective oxidation of hydrogen sulfide to elemental sulfur, using a commercial, precipitated silica promoted ferric oxide based catalyst, was investigated in laboratory and pilot-plant reactors. Low levels of hydrogen sulfide (1-3 vol%) can be readily removed, but a continuous slow decrease in catalyst activity was apparent. X-ray photoelectron spectroscopy showed that the loss of activity was due to the formation of ferrous sulfate, which is known to be less active than the ferric oxide. In addition, studies using a model feed showed that the propene and HCN impurities in the plant feed stocks also act as potent catalyst poisons.

  4. CoQ deficiency causes disruption of mitochondrial sulfide oxidation, a new pathomechanism associated with this syndrome.

    PubMed

    Luna-Sánchez, Marta; Hidalgo-Gutiérrez, Agustín; Hildebrandt, Tatjana M; Chaves-Serrano, Julio; Barriocanal-Casado, Eliana; Santos-Fandila, Ángela; Romero, Miguel; Sayed, Ramy Ka; Duarte, Juan; Prokisch, Holger; Schuelke, Markus; Distelmaier, Felix; Escames, Germaine; Acuña-Castroviejo, Darío; López, Luis C

    2017-01-01

    Coenzyme Q (CoQ) is a key component of the mitochondrial respiratory chain, but it also has several other functions in the cellular metabolism. One of them is to function as an electron carrier in the reaction catalyzed by sulfide:quinone oxidoreductase (SQR), which catalyzes the first reaction in the hydrogen sulfide oxidation pathway. Therefore, SQR may be affected by CoQ deficiency. Using human skin fibroblasts and two mouse models with primary CoQ deficiency, we demonstrate that severe CoQ deficiency causes a reduction in SQR levels and activity, which leads to an alteration of mitochondrial sulfide metabolism. In cerebrum of Coq9(R239X) mice, the deficit in SQR induces an increase in thiosulfate sulfurtransferase and sulfite oxidase, as well as modifications in the levels of thiols. As a result, biosynthetic pathways of glutamate, serotonin, and catecholamines were altered in the cerebrum, and the blood pressure was reduced. Therefore, this study reveals the reduction in SQR activity as one of the pathomechanisms associated with CoQ deficiency syndrome.

  5. Oxidation of chlorinated olefins by Escherichia coli transformed with dimethyl sulfide monooxygenase genes or cumene dioxygenase genes.

    PubMed

    Takami, Wako; Yoshida, Takako; Nojiri, Hideaki; Yamane, Hisakazu; Omori, Toshio

    1999-04-01

    In the present work, it was shown that the dimethyl sulfide (DMS) monooxygenase and the cumene dioxygenase catalyzed oxidation of various chlorinated ethenes, propenes, and butenes. The specific activities of these oxygenases were determined for C(2) to C(4) chlorinated olefins, and the oxidation rates ranged from 0.19 to 4.18 nmol.min(-1).mg(-1) of dry cells by the DMS monooxygenase and from 0.19 to 1.29 nmol.min(-1).mg(-1) of dry cells by the cumene dioxygenase. The oxidation products were identified by gas chromatography-mass spectrometry. Most chlorinated olefins were monooxygenated by the DMS monooxygenase to yield chlorinated epoxides. In the case of the cumene dioxygenase, the substrates lacking any chlorine atom on double-bond carbon atoms were dioxygenated, and those with chlorine atoms attaching to double-bond carbon atoms were monooxygenated to yield allyl alcohols.

  6. Enhanced reactive adsorption of hydrogen sulfide on the composites of graphene/graphite oxide with copper (hydr)oxychlorides.

    PubMed

    Mabayoje, Oluwaniyi; Seredych, Mykola; Bandosz, Teresa J

    2012-06-27

    Composites of copper (hydr)oxychlorides with graphite oxide or graphene were synthesized and used as adsorbents of hydrogen sulfide at dynamic conditions at ambient temperatures. The materials were extensively characterized before and after adsorption in order to link their performance to the surface features. X-ray diffraction, FTIR, thermal analysis, TEM, SEM/EDX, and adsorption of nitrogen were used. It was found that the composite with graphene has the most favorable surface features enhancing reactive adsorption of hydrogen sulfide. The presence of moisture in the H2S stream has a positive effect on the removal process owing to the dissociation process. H2S is retained on the surface via a direct replacement of OH groups and via acid-base reactions with the copper (hydr)oxide. Highly dispersed reduced copper species on the surface of the composite with graphene enhance activation of oxygen and cause formation of sulfites and sulfates. Higher conductivity of the graphene phase than that of graphite oxide helps in electron transfer in redox reactions.

  7. Fourier Transform Microwave Spectra of CO{2}-ETHYLENE Sulfide, CO{2}-ETHYLENE Oxide and CO{2}-PROPYLENE Oxide Complexes

    NASA Astrophysics Data System (ADS)

    Orita, Yukari; Kawashima, Yoshiyuki; Hirota, Eizi

    2010-06-01

    We have previously examined the difference in roles of O and S in structure and dynamics of the CO-ethylene oxide (EO) and CO-ethylene sulfide (ES) complexes. We have extended the investigation to CO{2}-EO and CO{2}-ES for comparison. We have also observed the CO{2}-propylene oxide (PO) complex, which is an important intermediate in the reaction of PO with CO{2} leading to polycarbonate. Both a-type and b-type transitions were observed for the CO{2}-EO and CO{2}-ES, but no c-type transitions were observed at all. We also detected the {34}S and {13}C isotopic species in natural abundance and the species containing {18}OCO and C{18}O% {2}, which were synthesized by burning paper in an {18}O{2} and{% 16}O{2} mixture. By analyzing the observed spectra we concluded the CO{2} moiety of CO{2}-EO and CO{2}-ES located in a plane % prependicular to the three-membered ring and bisecting the COC or CSC angle of EO or ES, respectively, as in the case of CO-EO and CO-ES complexes. An % ab initio MO calculation at the level of MP2/6-311G(d, p) yielded an optimized structure in good agreement with the experimental result. We have derived from the observed spectra the distance, the stretching force constant, and the binding energy of the bonds between the constituents of the CO{2}-EO and CO{2}-ES complexes and have found that the distances of the two complexes were shorter by 0.2Å than those in CO-EO and CO-ES, respectively, and that the intermolecular bonds were two times stronger in the CO{2} complexes than in the corresponding CO complexes. We have concluded from the observed spectra that the CO{2} moiety in CO{2}-PO is located on the PO three-membered ring plane opposite to the methyl group. The constituents in CO{2}-PO were more weakly bound than those in CO{2}-EO and CO{2}-ES. S. Sato, Y. Kawashima, Y. Tatamitani, and E. Hirota, 63rd International Symposium on Molecular Spectroscopy, WF05 (2008).

  8. Dimethyl Sulfide-Dimethyl Ether and Ethylene Oxide-Ethylene Sulfide Complexes Investigated by Fourier Transform Microwave Spectroscopy and Ab Initio Calculation.

    PubMed

    Kawashima, Yoshiyuki; Tatamitani, Yoshio; Mase, Takayuki; Hirota, Eizi

    2015-10-22

    The ground-state rotational spectra of the dimethyl sulfide-dimethyl ether (DMS-DME) and the ethylene oxide-ethylene sulfide (EO-ES) complexes were observed by Fourier transform microwave spectroscopy, and a-type and c-type transitions were assigned for the normal, (34)S, and three (13)C species of the DMS-DME and a-type and b-type transitions for the normal, (34)S, and two (13)C species of the EO-ES complexes. The transition frequencies measured for both the complexes were analyzed by using an S-reduced asymmetric-top rotational Hamiltonian. The rotational parameters thus derived for the DMS-DME were found to be consistent with a structure of Cs symmetry with the DMS bound to the DME by two C-H(DMS)···O and one S···H-C(DME) hydrogen bonds. Some high-Ka lines were found to be split, and we have interpreted these splittings in terms of internal rotations of the two methyl groups of the DMS and of the "free", i.e., outer group, of the DME. Some forbidden transitions were also observed in cases where Ka = 3 levels were involved, for the DMS-DME complex in the internal-rotation E state. The barrier height, V3, to internal rotation of the CH3 in the DME thus derived is smaller than that of the DME monomer, while the V3 of the CH3 groups in the DMS is nearly the same as that of the DMS monomer. For the EO-ES complex, the observed data were interpreted in terms of an antiparallel structure of Cs symmetry with the EO bound to the ES by two C-H(ES)···O and two S···H-C(EO) hydrogen bonds. An attempt was also made to observe a-type transitions of the DMS dimer without success. We have applied a natural bond orbital analysis to the DMS-DME and EO-ES to calculate the stabilization energy CT (= ΔEσσ*), which was correlated closely with the binding energy as found for other related complexes.

  9. Sodium-ion storage properties of nickel sulfide hollow nanospheres/reduced graphene oxide composite powders prepared by a spray drying process and the nanoscale Kirkendall effect

    NASA Astrophysics Data System (ADS)

    Park, G. D.; Cho, J. S.; Kang, Y. C.

    2015-10-01

    Spray-drying and the nanoscale Kirkendall diffusion process are used to prepare nickel sulfide hollow nanospheres/reduced graphene oxide (rGO) composite powders with excellent Na-ion storage properties. Metallic Ni nanopowder-decorated rGO powders, formed as intermediate products, are transformed into composite powders of nickel sulfide hollow nanospheres/rGO with mixed crystal structures of Ni3S2 and Ni9S8 phases by the sulfidation process under H2S gas. Nickel sulfide/rGO composite powders with the main crystal structure of Ni3S2 are also prepared as comparison samples by the direct sulfidation of nickel acetate-graphene oxide (GO) composite powders obtained by spray-drying. In electrochemical properties, the discharge capacities at the 150th cycle of the nickel sulfide/rGO composite powders prepared by sulfidation of the Ni/rGO composite and nickel acetate/GO composite powders at a current density of 0.3 A g-1 are 449 and 363 mA h g-1, respectively; their capacity retentions, calculated from the tenth cycle, are 100 and 87%. The nickel sulfide hollow nanospheres/rGO composite powders possess structural stability over repeated Na-ion insertion and extraction processes, and also show excellent rate performance for Na-ion storage.Spray-drying and the nanoscale Kirkendall diffusion process are used to prepare nickel sulfide hollow nanospheres/reduced graphene oxide (rGO) composite powders with excellent Na-ion storage properties. Metallic Ni nanopowder-decorated rGO powders, formed as intermediate products, are transformed into composite powders of nickel sulfide hollow nanospheres/rGO with mixed crystal structures of Ni3S2 and Ni9S8 phases by the sulfidation process under H2S gas. Nickel sulfide/rGO composite powders with the main crystal structure of Ni3S2 are also prepared as comparison samples by the direct sulfidation of nickel acetate-graphene oxide (GO) composite powders obtained by spray-drying. In electrochemical properties, the discharge capacities at the

  10. Synthesis and structure of tridentate bis(phosphinic amide)-phosphine oxide complexes of yttrium nitrate. Applications of 31P,89Y NMR methods in structural elucidation in solution.

    PubMed

    Popovici, Cristinel; Fernández, Ignacio; Oña-Burgos, Pascual; Roces, Laura; García-Granda, Santiago; Ortiz, Fernando López

    2011-07-07

    The synthesis and characterisation of a tridentate ligand containing two diphenylphosphinic amide side-arms connected through the ortho position to a phenylphosphine oxide moiety and the 1:1 and 2:1 complexes formed with yttrium nitrate are reported for the first time. The free ligand (R(P1)*,S(P3)*)-11 is obtained diastereoselectively by reaction of ortho-lithiated N,N-diisopropyl-P,P-diphenylphosphinic amide with phenylphosphonic dichloride. Complexes [Y((R(P1)*,S(P3)*)-11)(NO(3))(3)] and [Y((R(P1)*,S(P3)*)-11)(2)(NO(3))](NO(3))(2) were isolated by mixing ligand 11 with Y(NO(3))(3)·6H(2)O in acetonitrile at room temperature in a ligand to metal molar ratio of 1:1 and 2:1, respectively. The 1:1 derivative is the product of thermodynamic control when a molar ratio of ligand to yttrium salt of 1:1 is used. The new compounds have been characterised both as the solid (X-ray diffraction) and in solution (multinuclear magnetic resonance). In both yttrium complexes the ligand acts as a tridentate chelate. The arrangement of the two ligands in the 2:1 complex affords a pseudo-meso structure. Tridentate chelation of yttrium(III) in both complexes is retained in solution as evidenced by (89)Y NMR data obtained via(31)P,(89)Y-HMQC, and (89)Y,(31)P-DEPT experiments. The investigation of the solution behaviour of the Y(III) complexes through PGSE NMR diffusion measurements showed that average structures in agreement with the 1:1 and 1:2 stoichiometries are retained in acetonitrile.

  11. Adhesion of Poly(phenylene sulfide) Resin with Polymeric Film of Triazine Thiol on Aluminum Surface Modified by Anodic Oxidation.

    PubMed

    Chung, Eun Hyuk; Jang, Eun Kyung; Hong, Tae Eun; Kim, Jong Pil; Kim, Hyun Gyu; Jin, Jong Sung; Hyun, Myung Ho; Shin, Dong Su; Bae, Jong-Seong; Jeong, Euh Duck

    2015-01-01

    Various surface modifications have been applied to improve the adhesion properties of aluminum for the cap plate and sealing quality of electrolyte on Li ion batteries. In this study, we have tried to find the effective condition for the polymerization of triazine thiols (TT) on modified aluminum surfaces by anodic aluminum oxide. Characterization of polymerized films on aluminum was explored by scanning electron microscopy, X-ray photoelectron spectroscopy, and secondary ion mass spectroscopy analysis. Scanning electron microscopy results reveal that meaningful roughness was formed on aluminum surfaces by anodic oxidation. Secondary ion mass spectroscopy analysis results represent that the peel strength was found to depend on film thickness and the composition of the adhesion layer. As a result, Al/PPS (polyphenylene sulfide) resin assemblies developed in this study have superior adhesive property. Therefore, these assemblies might be a viable candidate for a sealing technique for Li ion batteries.

  12. Controlled oxidation of organic sulfides to sulfoxides under ambient conditions by a series of titanium isopropoxide complexes using environmentally benign H2O2 as an oxidant.

    PubMed

    Panda, Manas K; Shaikh, Mobin M; Ghosh, Prasenjit

    2010-03-07

    Controlled oxidation of organic sulfides to sulfoxides under ambient conditions has been achieved by a series of titanium isopropoxide complexes that use environmentally benign H(2)O(2) as a primary oxidant. Specifically, the [N,N'-bis(2-oxo-3-R(1)-5-R(2)-phenylmethyl)-N,N'-bis(methylene-R(3))-ethylenediamine]Ti(O(i)Pr)(2) [R(1) = t-Bu, R(2) = Me, R(3) = C(7)H(5)O(2) (1b); R(1) = R(2) = t-Bu, R(3) = C(7)H(5)O(2) (2b); R(1) = R(2) = Cl, R(3) = C(7)H(5)O(2) (3b) and R(1) = R(2) = Cl, R(3) = C(6)H(5) (4b)] complexes efficiently catalyzed the sulfoxidation reactions of organic sulfides to sulfoxides at room temperature within 30 min of the reaction time using aqueous H(2)O(2) as an oxidant. A mechanistic pathway, modeled using density functional theory for a representative thioanisole substrate catalyzed by 4b, suggested that the reaction proceeds via a titanium peroxo intermediate 4c', which displays an activation barrier of 22.5 kcal mol(-1) (DeltaG(++)) for the overall catalytic cycle in undergoing an attack by the S atom of the thioanisole substrate at its sigma*-orbital of the peroxo moiety. The formation of the titanium peroxo intermediate was experimentally corroborated by a mild ionization atmospheric pressure chemical ionization (APCI) mass spectrometric technique.

  13. Diallyl Trisulfide Suppresses Oxidative Stress-Induced Activation of Hepatic Stellate Cells through Production of Hydrogen Sulfide.

    PubMed

    Zhang, Feng; Jin, Huanhuan; Wu, Li; Shao, Jiangjuan; Zhu, Xiaojing; Chen, Anping; Zheng, Shizhong

    2017-01-01

    Accumulating data reveal that garlic has beneficial effects against chronic liver disease. We previously reported that diallyl trisulfide (DATS), the primary organosulfur compound in garlic, reduced fibrosis and attenuated oxidative stress in rat fibrotic liver. The present study was aimed at elucidating the underlying mechanisms. The primary rat hepatic stellate cells (HSCs) were cultured and stimulated with hydrogen peroxide (H2O2) for inducing HSC activation under oxidative stress. We examined the effects of DATS on the profibrogenic properties and oxidative stress in H2O2-treated HSCs. The results showed that DATS suppressed and reduced fibrotic marker expression in HSCs. DATS arrested cell cycle at G2/M checkpoint associated with downregulating cyclin B1 and cyclin-dependent kinase 1, induced caspase-dependent apoptosis, and reduced migration in HSCs. Moreover, intracellular levels of reactive oxygen species and lipid peroxide were decreased by DATS, but intracellular levels of glutathione were increased in HSCs. Furthermore, DATS significantly elevated hydrogen sulfide (H2S) levels within HSCs, but iodoacetamide (IAM) reduced H2S levels and significantly abrogated DATS production of H2S within HSCs. IAM also abolished all the inhibitory effects of DATS on the profibrogenic properties and oxidative stress in HSCs. Altogether, we demonstrated an H2S-associated mechanism underlying DATS inhibition of profibrogenic properties and alleviation of oxidative stress in HSCs. Modulation of H2S production may represent a therapeutic remedy for liver fibrosis.

  14. Diallyl Trisulfide Suppresses Oxidative Stress-Induced Activation of Hepatic Stellate Cells through Production of Hydrogen Sulfide

    PubMed Central

    Zhang, Feng; Jin, Huanhuan; Wu, Li; Shao, Jiangjuan; Zhu, Xiaojing; Chen, Anping

    2017-01-01

    Accumulating data reveal that garlic has beneficial effects against chronic liver disease. We previously reported that diallyl trisulfide (DATS), the primary organosulfur compound in garlic, reduced fibrosis and attenuated oxidative stress in rat fibrotic liver. The present study was aimed at elucidating the underlying mechanisms. The primary rat hepatic stellate cells (HSCs) were cultured and stimulated with hydrogen peroxide (H2O2) for inducing HSC activation under oxidative stress. We examined the effects of DATS on the profibrogenic properties and oxidative stress in H2O2-treated HSCs. The results showed that DATS suppressed and reduced fibrotic marker expression in HSCs. DATS arrested cell cycle at G2/M checkpoint associated with downregulating cyclin B1 and cyclin-dependent kinase 1, induced caspase-dependent apoptosis, and reduced migration in HSCs. Moreover, intracellular levels of reactive oxygen species and lipid peroxide were decreased by DATS, but intracellular levels of glutathione were increased in HSCs. Furthermore, DATS significantly elevated hydrogen sulfide (H2S) levels within HSCs, but iodoacetamide (IAM) reduced H2S levels and significantly abrogated DATS production of H2S within HSCs. IAM also abolished all the inhibitory effects of DATS on the profibrogenic properties and oxidative stress in HSCs. Altogether, we demonstrated an H2S-associated mechanism underlying DATS inhibition of profibrogenic properties and alleviation of oxidative stress in HSCs. Modulation of H2S production may represent a therapeutic remedy for liver fibrosis. PMID:28303169

  15. Chiral phosphines in nucleophilic organocatalysis

    PubMed Central

    Xiao, Yumei; Sun, Zhanhu

    2014-01-01

    Summary This review discusses the tertiary phosphines possessing various chiral skeletons that have been used in asymmetric nucleophilic organocatalytic reactions, including annulations of allenes, alkynes, and Morita–Baylis–Hillman (MBH) acetates, carbonates, and ketenes with activated alkenes and imines, allylic substitutions of MBH acetates and carbonates, Michael additions, γ-umpolung additions, and acylations of alcohols. PMID:25246969

  16. Sulfur-oxidizing bacteria in Soap Lake (Washington State), a meromictic, haloalkaline lake with an unprecedented high sulfide content.

    PubMed

    Sorokin, Dimitry Y; Foti, Mirjam; Pinkart, Holly C; Muyzer, Gerard

    2007-01-01

    Culture-dependent and -independent techniques were used to study the diversity of chemolithoautotrophic sulfur-oxidizing bacteria in Soap Lake (Washington State), a meromictic, haloalkaline lake containing an unprecedentedly high sulfide concentration in the anoxic monimolimnion. Both approaches revealed the dominance of bacteria belonging to the genus Thioalkalimicrobium, which are common inhabitants of soda lakes. A dense population of Thioalkalimicrobium (up to 10(7) cells/ml) was found at the chemocline, which is characterized by a steep oxygen-sulfide gradient. Twelve Thioalkalimicrobium strains exhibiting three different phenotypes were isolated in pure culture from various locations in Soap Lake. The isolates fell into two groups according to 16S rRNA gene sequence analysis. One of the groups was closely related to T. cyclicum, which was isolated from Mono Lake (California), a transiently meromictic, haloalkaline lake. The second group, consisting of four isolates, was phylogenetically and phenotypically distinct from known Thioalkalimicrobium species and unique to Soap Lake. It represented a new species, for which we suggest the name Thioalkalimicrobium microaerophilum sp. nov.

  17. Mineral systems and the thermodynamics of selenites and selenates in the oxidation zone of sulfide ores - a review

    NASA Astrophysics Data System (ADS)

    Charykova, Marina V.; Krivovichev, Vladimir G.

    2016-08-01

    Contemporary mineralogy and geochemistry are concerned with understanding and deciphering processes that occur near the surface of the Earth. These processes are especially important for resolving ecological challenges and developing principles of good environmental management. Selenium oxysalts, selenites and selenates, are relatively rare as minerals; there are presently only 34 known mineral species. Thirty-one "pure" selenites, which contain only selenite anionic groups, are known to occur naturally. The other three minerals each contain two anionic groups: selenate and selenite (schmiederite), selenate and sulphate (olsacherite), and selenate and iodate (carlosruizite). This work is intended to provide a classification of natural selenium oxysalts based on their chemical composition. Selenites belong to a particular mineral system, whose components are chemical elements required to construct the crystal structure of a mineral (species-defining constituents). The number of components represents the minimum number of independent elements necessary to define the composition of the system. All selenites and selenates are divided into two groups: anhydrous selenites (I) and hydrous selenites and selenates (II). The paper also presents systematized data published on the thermodynamics of selenites, which are formed in the weathering zone of sulfide and selenide ores, and determines approaches to the quantitative physicochemical modeling of formation conditions. The Eh-pH diagrams of the Me-Se-H2O systems (Me = Cu, Co, Ni, Fe, Zn, Ca, Al) were calculated and plotted for the average contents of these elements in aqueous weathering solutions in sulfide deposit oxidation zones.

  18. Nickel oxide thin film from electrodeposited nickel sulfide thin film: peroxide sensing and photo-decomposition of phenol.

    PubMed

    Jana, Sumanta; Samai, Subhasis; Mitra, Bibhas C; Bera, Pulakesh; Mondal, Anup

    2014-09-14

    A novel non-enzymatic peroxide sensor has been constructed by using nickel oxide (NiO) thin films as sensing material, which were prepared by a two-step process: (i) electrodeposition of nickel sulfide (NiS) and (ii) thermal air oxidation of as-deposited NiS to NiO. The resultant material is highly porous and comprises interconnected nanofibers. UV-Vis spectroscopy, FTIR spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and field-emission scanning electron microscopy (FESEM) were used for a complete characterization of nanostructured NiO thin films. Cyclic voltammetry study shows that NiO/ITO electrode facilitates the oxidation of hydrogen peroxide and exhibits excellent catalytic activity towards its sensing. The amperometric study of NiO/ITO was carried out to determine the sensitivity, linear range, detection limit of the proposed sensor. The sensor exhibits prominent electrocatalytic activity toward the oxidation of H2O2 with a wide linear range and a low detection limit. The possible use of the synthesized NiO thin films as an effective photocatalyst for the decomposition of phenol is also discussed.

  19. Vibrational study of new Pt(II) and Pd(II) complexes with functionalized nitrogen-containing tertiary phosphine oxides. Ab initio study of ortho-, meta- and para-dimethylphosphinylmethyleneoxyaniline.

    PubMed

    Trendafilova, N; Bauer, G; Georgieva, I; Tosheva, T; Varbanov, S

    2003-01-01

    Vibrational study of new Pt(II) and Pd(II) complexes of functionalized nitrogen-containing tertiary phosphine oxides, namely ortho-, meta- and para-dimethylphosphinylmethyleneoxyaniline (o-, m- and p-dpmoa), (CH3)2P(O)CH2OC6H4NH2, have been presented. Geometry optimization of the ligands was performed at HF/6-31G* and B3LYP/6-31G* levels of the theory. Harmonic frequencies were calculated at HF/6-31G* optimized geometries. Relative gas-phase and solution-phase (H2O and CH3CN) basicities of o-, m- and p-dpmoa ligands have been determined by ab initio calculations at STO-3G level with the Onsager reaction field model. On the basis of the vibrational study, physical and analytical data it was suggested that the ligands in the complexes studied coordinate through the amino group and form square-planar platinum and palladium complexes of the general formula ML2Cl2 (M = Pt, Pd, L = o-, m- and p-dpmoa).

  20. Vibrational study of new Pt(II) and Pd(II) complexes with functionalized nitrogen-containing tertiary phosphine oxides. Ab initio study of ortho-, meta- and para-dimethylphosphinylmethyleneoxyaniline

    NASA Astrophysics Data System (ADS)

    Trendafilova, N.; Bauer, G.; Georgieva, I.; Tosheva, T.; Varbanov, S.

    2003-01-01

    Vibrational study of new Pt(II) and Pd(II) complexes of functionalized nitrogen-containing tertiary phosphine oxides, namely ortho-, meta- and para-dimethylphosphinylmethyleneoxyaniline ( o-, m- and p-dpmoa), (CH 3) 2P(O)CH 2OC 6H 4NH 2, have been presented. Geometry optimization of the ligands was performed at HF/6-31G* and B3LYP/6-31G* levels of the theory. Harmonic frequencies were calculated at HF/6-31G* optimized geometries. Relative gas-phase and solution-phase (H 2O and CH 3CN) basicities of o-, m- and p-dpmoa ligands have been determined by ab initio calculations at STO-3G level with the Onsager reaction field model. On the basis of the vibrational study, physical and analytical data it was suggested that the ligands in the complexes studied coordinate through the amino group and form square-planar platinum and palladium complexes of the general formula ML 2Cl 2 (M=Pt, Pd, L= o-, m- and p-dpmoa).

  1. Geochemical investigation of the galvanic effects during oxidation of pyrite and base-metals sulfides.

    PubMed

    Chopard, Aurélie; Plante, Benoît; Benzaazoua, Mostafa; Bouzahzah, Hassan; Marion, Philippe

    2017-01-01

    Predicting the water quality at mine sites is of significant importance for developing mines with respect for the environment. Acid mine drainage (AMD) occurs when sulfides are in contact with oxygen and water, and several parameters and mechanisms influence final drainage quality. Galvanic interactions influence the reactivity of sulfide minerals, which act as semi-conductors. These galvanic interactions have been insufficiently studied in the context of AMD generation. In this study, the influence of pyrite on the reactivity of sphalerite and chalcopyrite was investigated. Five blends, comprised of free grains of quartz/pyrite, quartz/chalcopyrite, quartz/sphalerite, quartz/pyrite/chalcopyrite, and quartz/pyrite/sphalerite, were subjected to geochemical testing. Five weathering cells were monitored over a 200-day period during which they were leached twice weekly. Leachates were analyzed for pH, Eh, electrical conductivity, and sulfate and metal concentrations. The results of these analyses showed that galvanic interactions occurred between free sulfide grains. Pyrite was galvanically protected over the full testing period in the quartz/pyrite/chalcopyrite blend, and partially protected in the quartz/pyrite/sphalerite blend. Moreover, the release of Cu from chalcopyrite and Zn, Mn, and Cd from sphalerite was accelerated in the presence of pyrite. This work provides a better understanding of the influence of pyrite on chalcopyrite and sphalerite reactivity by highlighting the galvanic effects. In the future, to improve the reliability of AMD prediction tests, galvanic interactions should be considered in both the prediction of the acid generation potential and the estimation of metal and metalloid release rates.

  2. Harnessing Evolutionary Toxins for Signaling: Reactive Oxygen Species, Nitric Oxide and Hydrogen Sulfide in Plant Cell Regulation

    PubMed Central

    Hancock, John T.

    2017-01-01

    During the early periods of evolution, as well as in niche environments today, organisms have had to learn to tolerate the presence of many reactive compounds, such as reactive oxygen species, nitric oxide, and hydrogen sulfide. It is now known that such compounds are instrumental in the signaling processes in plant cells. There are enzymes which can make them, while downstream of their signaling pathways are coming to light. These include the production of cGMP, the activation of MAP kinases and transcription factors, and the modification of thiol groups on many proteins. However, organisms have also had to tolerate other reactive compounds such as ammonia, methane, and hydrogen gas, and these too are being found to have profound effects on signaling in cells. Before a holistic view of how such signaling works, the full effects and interactions of all such reactive compounds needs to be embraced. A full understanding will be beneficial to both agriculture and future therapeutic strategies. PMID:28239389

  3. Phosphine Catalysis of Allenes with Electrophiles

    PubMed Central

    Wang, Zhiming; Xu, Xingzhu; Kwon, Ohyun

    2014-01-01

    Nucleophilic phosphine catalysis of allenes with electrophiles is one of the most powerful and straightforward synthetic strategies for the generation of highly functionalized carbocycle or heterocycle structural motifs, which are present in a wide range of bioactive natural products and medicinally important substances. The reaction topologies can be controlled through judicious choice of the phosphine catalyst and the structural variations of starting materials. This Tutorial Review presents selected examples of nucleophilic phosphine catalysis using allenes and electrophiles. PMID:24663290

  4. Increased photocatalytic activity of Zn(II)/Cu(II) oxides and sulfides by coupling and supporting them onto clinoptilolite nanoparticles in the degradation of benzophenone aqueous solution.

    PubMed

    Esmaili-Hafshejani, Javad; Nezamzadeh-Ejhieh, Alireza

    2016-10-05

    Photocatalytic activity of the coupled ZnO-CuO and ZnS-CuS semiconductors supported onto clinoptilolite nanoparticles (CNP) and micronized one (CMP) was studied in photodegradation of benzophenone (BP) aqueous solution. The ZnO-CuO/CNP (or MCP) and ZnS-CuS/CNP (or MCP) catalysts were prepared via calcination and sulfiding of their Zn(II)-Cu(II) ion-exchanged samples, respectively. XRD patterns confirmed loading of the mentioned semiconductors onto the zeolite, and nano dimension of the catalysts was confirmed by XRD and TEM results. Typical Tauc plots obtained from UV-vis DRS spectra showed red shifts for the band gap energies of the supported coupled semiconductors with respect to the supported monocomponent ones especially for ZnO/NCP and ZnS/NCP catalysts. Also, in both indirect and direct transitions, these red shifts were more considerable in the oxidic systems with respect to the sulfidic systems. Accordingly, the supported oxidic systems showed better photocatalytic activity than the sulfidic one. In the oxidic systems changing the dose of CuO played important role while in the sulfidic systems ZnS played considerable role in the degradation of BP. In the used systems, CuO and ZnS played the main e/h generators in the oxidic and sulfidic systems, respectively, while ZnO and CuS played the preventer e/h recombination. Based on the results, production of e/h is the rate limiting step in the used systems. The maximum degradation activity of the catalysts was obtained at: 0.12gL(-1) of ZnO0.80-CuO3.18/NCP and 0.10gL(-1) of ZnS1.39-CuS2.88/NCP catalysts, initial BP concentration of 30mgL(-1) at pH 7.5.

  5. Reaction Mechanisms of Metals with Hydrogen Sulfide and Thiols in Model Wine. Part 2: Iron- and Copper-Catalyzed Oxidation.

    PubMed

    Kreitman, Gal Y; Danilewicz, John C; Jeffery, David W; Elias, Ryan J

    2016-05-25

    Sulfidic off-odors arising during wine production are frequently removed by Cu(II) fining. In part 1 of this study ( 10.1021/acs.jafc.6b00641 ), the reaction of H2S and thiols with Cu(II) was examined; however, the interaction of iron and copper is also known to play an important synergistic role in mediating non-enzymatic wine oxidation. The interaction of these two metals in the oxidation of H2S and thiols (cysteine, 3-sulfanylhexan-1-ol, and 6-sulfanylhexan-1-ol) was therefore examined under wine-like conditions. H2S and thiols (300 μM) were reacted with Fe(III) (100 or 200 μM) alone and in combination with Cu(II) (25 or 50 μM), and concentrations of H2S and thiols, oxygen, and acetaldehyde were monitored over time. H2S and thiols were shown to be slowly oxidized in the presence of Fe(III) alone and were not bound to Fe(III) under model wine conditions. However, Cu(II) added to model wine containing Fe(III) was quickly reduced by H2S and thiols to form Cu(I) complexes, which then rapidly reduced Fe(III) to Fe(II). Oxidation of Fe(II) in the presence of oxygen regenerated Fe(III) and completed the iron redox cycle. In addition, sulfur-derived oxidation products were observed, and the formation of organic polysulfanes was demonstrated.

  6. In-Situ Generation of Oxide Nanowire Arrays from AgCuZn Alloy Sulfide with Enhanced Electrochemical Oxygen-Evolving Performance.

    PubMed

    Xie, Minghao; Ai, Shiqi; Yang, Jian; Yang, Yudi; Chen, Yihan; Jin, Yong

    2015-08-12

    In this study, AgCuZn sulfide is fabricated on the surface of AgCuZn alloys by hydrothermal sulfuration. This ternary metal sulfide is equipped with enhanced activity toward oxygen evolution reaction (OER) in an alkaline electrolyte. Through comparison of the alloys with diverse compositions, we find out the best electrochemical property of a particular alloy sulfide forming on a AgCuZn substrate (Ag:Cu:Zn=43:49:8). The alloy sulfide exhibits an onset overpotential (η) of 0.27 V with a Tafel slope of 95±2 mV dec(-1) and a current density of 130 mA cm(-2) at η of 0.57 V. Moreover, the obtained AgCuZn sulfide displays excellent stability, where the current density can increase to 130% of the initial value after a water electrolysis test for 100,000 s (27.7 h). Through investigating the electrode before and after the electrocatalysis, we find a remarkable activated process during which self-supported copper-silver oxide nanowire (CuO-Ag2O NW) arrays in situ form on the surface of the electrode. This work provides a feasible strategy for synthesis of high performance nonprecious metal electrocatalysts for water splitting.

  7. Iron sulfide attenuates the methanogenic toxicity of elemental copper and zinc oxide nanoparticles and their soluble metal ion analogs.

    PubMed

    Gonzalez-Estrella, Jorge; Gallagher, Sara; Sierra-Alvarez, Reyes; Field, Jim A

    2016-04-01

    Elemental copper (Cu(0)) and zinc oxide (ZnO) nanoparticle (NP) toxicity to methanogens has been attributed to the release of soluble metal ions. Iron sulfide (FeS) partially controls the soluble concentration of heavy metals and their toxicity in aquatic environments. Heavy metals displace the Fe from FeS forming poorly soluble metal sulfides in the FeS matrix. Therefore, FeS may be expected to attenuate the NP toxicity. This work assessed FeS as an attenuator of the methanogenic toxicity of Cu(0) and ZnO NPs and their soluble salt analogs. The toxicity attenuation capacity of fine (25-75μm) and coarse (500 to 1200μm) preparations of FeS (FeS-f and FeS-c respectively) was tested in the presence of highly inhibitory concentrations of CuCl2, ZnCl2 Cu(0) and ZnO NPs. FeS-f attenuated methanogenic toxicity better than FeS-c. The results revealed that 2.5× less FeS-f than FeS-c was required to recover the methanogenic activity to 50% (activity normalized to uninhibited controls). The results also indicated that a molar FeS-f/Cu(0) NP, FeS-f/ZnO NP, FeS-f/ZnCl2, and FeS-f/CuCl2 ratio of 2.14, 2.14, 4.28, and 8.56 respectively, was necessary to recover the methanogenic activity to >75%. Displacement experiments demonstrated that CuCl2 and ZnCl2 partially displaced Fe from FeS. As a whole, the results indicate that not all the sulfide in FeS was readily available to react with the soluble Cu and Zn ions which may explain the need for a large stoichiometric excess of FeS to highly attenuate Cu and Zn toxicity. Overall, this study provides evidence that FeS attenuates the toxicity caused by Cu(0) and ZnO NPs and their soluble ion analogs to methanogens.

  8. Iron Sulfide Attenuates the Methanogenic Toxicity of Elemental Copper and Zinc Oxide Nanoparticles and their Soluble Metal Ion Analogs

    PubMed Central

    Gonzalez-Estrella, Jorge; Gallagher, Sara; Sierra-Alvarez, Reyes; Field, Jim A.

    2016-01-01

    Elemental copper (Cu0) and zinc oxide (ZnO) nanoparticle (NP) toxicity to methanogens has been attributed to the release of soluble metal ions. Iron sulfide (FeS) partially controls the soluble concentration of heavy metals and their toxicity in aquatic environments. Heavy metals displace the Fe from FeS forming poorly soluble metal sulfides in the FeS matrix. Therefore, FeS may be expected to attenuate the NP toxicity. This work assessed FeS as an attenuator of the methanogenic toxicity of Cu0 and ZnO NPs and their soluble salt analogs. The toxicity attenuation capacity of fine (25–75 µm) and coarse (500 to 1200 µm) preparations of FeS (FeS-f and FeS-c respectively) was tested in the presence of highly inhibitory concentrations of CuCl2, ZnCl2 Cu0 and ZnO NPs. FeS-f attenuated methanogenic toxicity better than FeS-c. The results revealed that 2.5× less FeS-f than FeS-c was required to recover the methanogenic activity to 50% (activity normalized to uninhibited controls). The results also indicated that a molar FeS-f/Cu0 NP, FeS-f/ZnO NP, FeS-f/ZnCl2, and FeS-f/CuCl2 ratio of 2.14, 2.14, 4.28, and 8.56 respectively, was necessary to recover the methanogenic activity to >75%. Displacement experiments demonstrated that CuCl2 and ZnCl2 partially displaced Fe from FeS. As a whole, the results indicate that not all the sulfide in FeS was readily available to react with the soluble Cu and Zn ions which may explain the need for a large stoichiometric excesses of FeS to highly attenuate Cu and Zn toxicity. Overall, this study provides evidence that FeS attenuates the toxicity caused by Cu0 and ZnO NPs and their soluble ion analogs to methanogens. PMID:26803736

  9. Selenium Sulfide

    MedlinePlus

    Selenium sulfide, an anti-infective agent, relieves itching and flaking of the scalp and removes the dry, ... Selenium sulfide comes in a lotion and is usually applied as a shampoo. As a shampoo, selenium ...

  10. Hydrogen Sulfide Inhibits High-Salt Diet-Induced Myocardial Oxidative Stress and Myocardial Hypertrophy in Dahl Rats

    PubMed Central

    Huang, Pan; Shen, Zhizhou; Yu, Wen; Huang, Yaqian; Tang, Chaoshu; Du, Junbao; Jin, Hongfang

    2017-01-01

    The study aimed to examine the protective effect of hydrogen sulfide (H2S) on high-salt-induced oxidative stress and myocardial hypertrophy in salt-sensitive (Dahl) rats. Thirty male Dahl rats and 40 SD rats were included in the study. They were randomly divided into Dahl control (Dahl + NS), Dahl high salt (Dahl + HS), Dahl + HS + NaHS, SD + NS, SD + HS, SD + HS + NaHS, and SD + HS + hydroxylamine (HA). Rats in Dahl + NS and SD + NS groups were given chow with 0.5% NaCl and 0.9% normal saline intraperitoneally daily. Myocardial structure, α-myosin heavy chain (α-MHC) and β-myosin heavy chain (β-MHC) expressions were determined. Endogenous myocardial H2S pathway and oxidative stress in myocardial tissues were tested. Myocardial H2S pathway was downregulated with myocardial hypertrophy featured by increased heart weight/body weight and cardiomyocytes cross-sectional area, decreased α-MHC and increased β-MHC expressions in Dahl rats with high-salt diet (all P < 0.01), and oxidative stress in myocardial tissues was significantly activated, demonstrated by the increased contents of hydroxyl radical, malondialdehyde and oxidized glutathione and decreased total antioxidant capacity, carbon monoxide, catalase, glutathione, glutathione peroxidase, superoxide dismutase (SOD) activities and decreased SOD1 and SOD2 protein expressions (P < 0.05, P < 0.01). However, H2S reduced myocardial hypertrophy with decreased heart weight/body weight and cardiomyocytes cross-sectional area, increased α-MHC, decreased β-MHC expressions and inhibited oxidative stress in myocardial tissues of Dahl rats with high-salt diet. However, no significant difference was found in H2S pathway, myocardial structure, α-MHC and β-MHC protein and oxidative status in myocardial tissues among SD + NS, SD + HS, and SD + HS + NaHS groups. HA, an inhibitor of cystathionine β-synthase, inhibited myocardial H2S pathway (P < 0.01), and stimulated myocardial hypertrophy and oxidative stress in SD rats

  11. Hydrogen Sulfide Inhibits High-Salt Diet-Induced Myocardial Oxidative Stress and Myocardial Hypertrophy in Dahl Rats.

    PubMed

    Huang, Pan; Shen, Zhizhou; Yu, Wen; Huang, Yaqian; Tang, Chaoshu; Du, Junbao; Jin, Hongfang

    2017-01-01

    The study aimed to examine the protective effect of hydrogen sulfide (H2S) on high-salt-induced oxidative stress and myocardial hypertrophy in salt-sensitive (Dahl) rats. Thirty male Dahl rats and 40 SD rats were included in the study. They were randomly divided into Dahl control (Dahl + NS), Dahl high salt (Dahl + HS), Dahl + HS + NaHS, SD + NS, SD + HS, SD + HS + NaHS, and SD + HS + hydroxylamine (HA). Rats in Dahl + NS and SD + NS groups were given chow with 0.5% NaCl and 0.9% normal saline intraperitoneally daily. Myocardial structure, α-myosin heavy chain (α-MHC) and β-myosin heavy chain (β-MHC) expressions were determined. Endogenous myocardial H2S pathway and oxidative stress in myocardial tissues were tested. Myocardial H2S pathway was downregulated with myocardial hypertrophy featured by increased heart weight/body weight and cardiomyocytes cross-sectional area, decreased α-MHC and increased β-MHC expressions in Dahl rats with high-salt diet (all P < 0.01), and oxidative stress in myocardial tissues was significantly activated, demonstrated by the increased contents of hydroxyl radical, malondialdehyde and oxidized glutathione and decreased total antioxidant capacity, carbon monoxide, catalase, glutathione, glutathione peroxidase, superoxide dismutase (SOD) activities and decreased SOD1 and SOD2 protein expressions (P < 0.05, P < 0.01). However, H2S reduced myocardial hypertrophy with decreased heart weight/body weight and cardiomyocytes cross-sectional area, increased α-MHC, decreased β-MHC expressions and inhibited oxidative stress in myocardial tissues of Dahl rats with high-salt diet. However, no significant difference was found in H2S pathway, myocardial structure, α-MHC and β-MHC protein and oxidative status in myocardial tissues among SD + NS, SD + HS, and SD + HS + NaHS groups. HA, an inhibitor of cystathionine β-synthase, inhibited myocardial H2S pathway (P < 0.01), and stimulated myocardial hypertrophy and oxidative stress in SD rats

  12. Hydrogen sulfide improves survival after cardiac arrest and cardiopulmonary resuscitation via a nitric oxide synthase 3 dependent mechanism in mice

    PubMed Central

    Minamishima, Shizuka; Bougaki, Masahiko; Sips, Patrick Y.; De Yu, Jia; Minamishima, Yoji Andrew; Elrod, John W.; Lefer, David J.; Bloch, Kenneth D.; Ichinose, Fumito

    2009-01-01

    Background Sudden cardiac arrest (CA) is one of the leading causes of death worldwide. We sought to evaluate the impact of hydrogen sulfide (H2S) on the outcome after CA and cardiopulmonary resuscitation (CPR) in mouse. Methods and Results Mice were subjected to 8 min of normothermic CA and resuscitated with chest compression and mechanical ventilation. Seven minutes after the onset of CA, mice received sodium sulfide (Na2S, 0.55 mg/kg i.v.) or vehicle 1 min before CPR. There was no difference in the rate of return of spontaneous circulation (ROSC), CPR time to ROSC, and left ventricular (LV) function at ROSC between groups. Administration of Na2S 1 min before CPR markedly improved survival rate at 24h after CPR (15/15) compared to vehicle (10/26, P=0.0001 vs Na2S). Administration of Na2S prevented CA/CPR-induced oxidative stress and ameliorated LV and neurological dysfunction 24h after CPR. Delayed administration of Na2S at 10 min after CPR did not improve outcomes after CA/CPR. Cardioprotective effects of Na2S were confirmed in isolated-perfused mouse hearts subjected to global ischemia and reperfusion. Cardiomyocyte-specific overexpression of cystathionine γ-lyase (CGL, an enzyme that produces H2S) markedly improved outcomes of CA/CPR. Na2S increased phosphorylation of NOS3 in LV and brain cortex, increased serum nitrite/nitrate levels, and attenuated CA-induced mitochondrial injury and cell death. NOS3 deficiency abrogated the protective effects of Na2S on the outcome of CA/CPR. Conclusions These results suggest that administration of Na2S at the time of CPR improves outcome after cardiac arrest possibly via an NOS3-dependent signaling pathway. PMID:19704099

  13. Pyritic event beds and sulfidized Fe (oxyhydr)oxide aggregates in metalliferous black mudstones of the Paleoproterozoic Talvivaara formation, Finland

    NASA Astrophysics Data System (ADS)

    Virtasalo, Joonas J.; Laitala, Jaakko J.; Lahtinen, Raimo; Whitehouse, Martin J.

    2015-12-01

    The Paleoproterozoic, 2.0-1.9 Ga Talvivaara formation of Finland was deposited during the Shunga Event, a worldwide episode of enhanced accumulation of organic-rich sediments in the aftermath of the Lomagundi-Jatuli carbon isotope excursion. Sulfidic carbonaceous mudstones in the Talvivaara formation contain one of the largest known shale-hosted nickel deposits. In order to gain new insight into this Shungian sedimentary environment, sedimentological, petrographical and in situ S and Fe isotopic microanalyses were carried out on samples representing depositional and early-diagenetic conditions. The event-bedded lithology with tidal signatures in the organic-rich mudstones strongly indicates deposition from predominantly river-delivered mud on a highly-productive coastal area, below storm-wave base. The riverine supply of phosphorus, sulfate and iron supported high primary productivity and resulted in strong lateral and vertical chemical gradients in the nearshore waters with a shallow oxic surface layer underlain by euxinic water. The stratigraphic upper part of the Talvivaara formation contains banded intervals of thin alternating pyrite beds and carbonaceous mudstone beds. The pyrite beds were deposited by seaward excursions of the concentrated, acidic Fe-rich river plume subsequent to droughts or dry seasons, which led to intense pyrite precipitation upon mixing with euxinic waters. δ34S and δ56Fe values of the bedded pyrite (median δ34S = - 10.3 ‰ and δ56Fe = - 0.79 ‰) are consistent with the reaction of dissolved Fe(II) with H2S from bacterial sulfate reduction. Organic-rich clayey Fe-monosulfide-bearing granules were transported from the muddy estuary, and enclosed in Fe (oxyhydr)oxide aggregates that were forming by wave and current reworking in nearshore accumulations of river-delivered iron. The isotopic composition of these presently pyrrhotitic inclusions (median δ34S = - 3.3 ‰ and δ56Fe = - 1.6 ‰) indicates microbial iron reduction. The Fe

  14. Protective effects of hydrogen sulfide inhalation on oxidative stress in rats with cotton smoke inhalation-induced lung injury

    PubMed Central

    HAN, ZHI-HAI; JIANG, YI; DUAN, YUN-YOU; WANG, XIAO-YANG; HUANG, YAN; FANG, TING-ZHENG

    2015-01-01

    The aim of the present study was to investigate the mechanism by which hydrogen sulfide (H2S) inhalation protects against oxidative stress in rats with cotton smoke inhalation-induced lung injury. A total of 24 male Sprague-Dawley rats were separated randomly into four groups, which included the control, H2S, smoke and smoke + H2S groups. A rat model of cotton smoke inhalation-induced lung injury was established following inhalation of 30% oxygen for 6 h. In addition, H2S (80 ppm) was inhaled by the rats in the H2S and smoke + H2S groups for 6 h following smoke or sham-smoke inhalation. Enzyme-linked immunosorbent assays were performed to measure various indices in the rat lung homogenate, while the levels of nuclear factor (NF)-κBp65 in the lung tissue of the rats were determined and semiquantitatively analyzed using immunohistochemistry. In addition, quantitative fluorescence polymerase chain reaction was employed to detect the mRNA expression of inducible nitric oxide synthase (iNOS) in the rat lung tissue. The concentrations of malondialdehyde (MDA), nitric oxide (NO), inducible iNOS and NF-κBp65, as well as the sum-integrated optical density of NF-κBp65 and the relative mRNA expression of iNOS, in the rat lung tissue from the smoke + H2S group were significantly lower when compared with the smoke group. The concentrations of MDA, NO, iNOS and NF-κBp65 in the H2S group were comparable to that of the control group. Therefore, inhalation of 80 ppm H2S may reduce iNOS mRNA transcription and the production of iNOS and NO in rats by inhibiting NF-κBp65 activation, subsequently decreasing oxidative stress and cotton smoke inhalation-induced lung injury. PMID:26170929

  15. Mineralogical and chemical assessment of concrete damaged by the oxidation of sulfide-bearing aggregates: Importance of thaumasite formation on reaction mechanisms

    SciTech Connect

    Rodrigues, A.; Duchesne, J.; Fournier, B.; Durand, B.; Rivard, P.; Shehata, M.

    2012-10-15

    Damages in concrete containing sulfide-bearing aggregates were recently observed in the Trois-Rivieres area (Quebec, Canada), characterized by rapid deterioration within 3 to 5 years after construction. A petrographic examination of concrete core samples was carried out using a combination of tools including: stereomicroscopic evaluation, polarized light microscopy, scanning electron microscopy, X-ray diffraction and electron microprobe analysis. The aggregate used to produce concrete was an intrusive igneous rock with different metamorphism degrees and various proportions of sulfide minerals. In the rock, sulfide minerals were often surrounded by a thin layer of carbonate minerals (siderite). Secondary reaction products observed in the damaged concrete include 'rust' mineral forms (e.g. ferric oxyhydroxides such as goethite, limonite (FeO (OH) nH{sub 2}O) and ferrihydrite), gypsum, ettringite and thaumasite. In the presence of water and oxygen, pyrrhotite oxidizes to form iron oxyhydroxides and sulphuric acid. The acid then reacts with the phases of the cement paste/aggregate and provokes the formation of sulfate minerals. Understanding both mechanisms, oxidation and internal sulfate attack, is important to be able to duplicate the damaging reaction in laboratory conditions, thus allowing the development of a performance test for evaluating the potential for deleterious expansion in concrete associated with sulfide-bearing aggregates.

  16. Facile covalent immobilization of cadmium sulfide quantum dots on graphene oxide nanosheets: preparation, characterization, and optical properties

    NASA Astrophysics Data System (ADS)

    Pham, Tuan Anh; Choi, Byung Choon; Jeong, Yeon Tae

    2010-11-01

    A facile approach for the preparation of a novel hybrid material containing graphene and an inorganic semiconducting material, cadmium sulfide quantum dots (CdS QDs), is demonstrated for the first time. First, amino-functionalized CdS QDs were prepared by modifications of the kinetic trapping method. Then, pristine graphite was oxidized and exfoliated to obtain graphene oxide nanosheets (GONS), which were then acylated with thionyl chloride to introduce acyl chloride groups on their surface. Subsequently, immobilization of the CdS QDs on the GONS surface was achieved through an amidation reaction between the amino groups located on the CdS QDs surface and the acyl chloride groups bound to the GONS surface. Fourier transform infrared spectroscopy (FT-IR), 1H nuclear magnetic resonance (1H-NMR), x-ray diffraction (XRD), x-ray photoelectron spectroscopy (XPS), and energy dispersive x-ray (EDX) spectroscopy were employed to investigate the changes in the surface functionalities, while high resolution transmission electron microscopy (HR-TEM) and field emission scanning electronic microscopy (FE-SEM) were used to study the morphologies and distribution of the CdS QDs on the GONS surface. Thermogravimetric analysis (TGA) was employed to characterize the weight loss of the samples on heating. Photoluminescence (PL) measurements were used to study the optical properties of the prepared CdS QDs and the CdS-graphene hybrid material.

  17. Facile covalent immobilization of cadmium sulfide quantum dots on graphene oxide nanosheets: preparation, characterization, and optical properties.

    PubMed

    Pham, Tuan Anh; Choi, Byung Choon; Jeong, Yeon Tae

    2010-11-19

    A facile approach for the preparation of a novel hybrid material containing graphene and an inorganic semiconducting material, cadmium sulfide quantum dots (CdS QDs), is demonstrated for the first time. First, amino-functionalized CdS QDs were prepared by modifications of the kinetic trapping method. Then, pristine graphite was oxidized and exfoliated to obtain graphene oxide nanosheets (GONS), which were then acylated with thionyl chloride to introduce acyl chloride groups on their surface. Subsequently, immobilization of the CdS QDs on the GONS surface was achieved through an amidation reaction between the amino groups located on the CdS QDs surface and the acyl chloride groups bound to the GONS surface. Fourier transform infrared spectroscopy (FT-IR), (1)H nuclear magnetic resonance ((1)H-NMR), x-ray diffraction (XRD), x-ray photoelectron spectroscopy (XPS), and energy dispersive x-ray (EDX) spectroscopy were employed to investigate the changes in the surface functionalities, while high resolution transmission electron microscopy (HR-TEM) and field emission scanning electronic microscopy (FE-SEM) were used to study the morphologies and distribution of the CdS QDs on the GONS surface. Thermogravimetric analysis (TGA) was employed to characterize the weight loss of the samples on heating. Photoluminescence (PL) measurements were used to study the optical properties of the prepared CdS QDs and the CdS-graphene hybrid material.

  18. Hydrogen polysulfide (H2S n ) signaling along with hydrogen sulfide (H2S) and nitric oxide (NO).

    PubMed

    Kimura, Hideo

    2016-11-01

    Hydrogen sulfide (H2S) is a physiological mediator with various roles, including neuro-modulation, vascular tone regulation, and cytoprotection against ischemia-reperfusion injury, angiogenesis, and oxygen sensing. Hydrogen polysulfide (H2S n ), which possesses a higher number of sulfur atoms than H2S, recently emerged as a potential signaling molecule that regulates the activity of ion channels, a tumor suppressor, transcription factors, and protein kinases. Some of the previously reported effects of H2S are now attributed to the more potent H2S n . H2S n is produced by 3-mercaptopyruvate sulfurtransferase (3MST) from 3-mercaptopyruvate (3MP) and is generated by the chemical interaction of H2S with nitric oxide (NO). H2S n sulfhydrates (sulfurates) cysteine residues of target proteins and modifies their activity, whereas H2S sulfurates oxidized cysteine residues as well as reduces cysteine disulfide bonds. This review focuses on the recent progress made in studies concerning the production and physiological roles of H2S n and H2S.

  19. Phosphine-catalyzed reductions of alkyl silyl peroxides by titanium hydride reducing agents: development of the method and mechanistic investigations.

    PubMed

    Harris, Jason R; Haynes, M Taylor; Thomas, Andrew M; Woerpel, K A

    2010-08-06

    A method that allows for the reduction of protected hydroperoxides by employing catalytic amounts of phosphine is presented. The combination of a titanium(IV) alkoxide and a siloxane allowed for the chemoselective reduction of phosphine oxides in the presence of alkyl silyl peroxides. Subsequent reduction of the peroxide moiety by phosphine provided the corresponding silylated alcohols in useful yields. Mechanistic experiments, including crossover experiments, support a mechanism in which the peroxide group was reduced and the silyl group was transferred in a concerted step. Labeling studies with (17)O-labeled peroxides demonstrate that the oxygen atom adjacent to the silicon atom is removed from the silyl peroxide.

  20. Toward the formation of alkylphosphonic acids in phosphine ices

    NASA Astrophysics Data System (ADS)

    Turner, Andrew; Kaiser, Ralf-Ingo

    2016-10-01

    Phosphorus is one of the elemental building blocks of life on Earth and is important for information storage (RNA/DNA), energy transfer (ATP), cell membranes (phospholipids), and structure (bones & teeth). Due to the poor bioavailability of highly oxidized phosphorus (P(V)) found in ubiquitous phosphate (PO43-) minerals, reduced oxidation state (P(III)) compounds have been proposed as a phosphorus source for early life on Earth. Among these, the alkylphosphonic acids, which are the only phosphorus-containing organic compounds discovered in the Murchison meteorite, are a suggested exogenous source of prebiotic phosphorus. Phosphine (PH3) is a known component of the atmospheres of Jupiter and Saturn, and the confirmation of circumstellar phosphine in the carbon-rich envelop of IRC +10216 along with the recent detection of phosphorus in the comet 67P/Churyumov-Gerasimenko provide an additional foundation for studying extraterrestrial phosphorus chemistry and the origins of the alkylphosphonic acids. In the present study, reactions of phosphine ices with water (H2O), carbon dioxide (CO2), and methane (CH4) were investigated using Fourier transform infrared spectroscopy (FTIR), quadrupole mass spectrometry (QMS), and most notably, reflectron time-of-flight mass spectrometry using tunable photoionization (PI-ReTOF-MS). Experiments were conducted at ultra-high vacuum pressures and cryogenic temperatures to better understand reaction pathways and products of phosphorus-containing compounds under icy conditions found in comets or the interstellar medium. The results of this study can provide support to the hypothesis that the alkylphosphonic acids were formed from interstellar phosphine and incorporated into meteorites such as Murchison.

  1. FUNDAMENTAL STUDIES IN ELECTROCHEMISTRY.

    DTIC Science & Technology

    ORGANIC PHOSPHORUS COMPOUNDS), (*ELECTROCHEMISTRY, OXIDATION, REDUCTION, SULFIDES, PHOSPHINE OXIDES, CATALYSTS , FLUORINE COMPOUNDS, BENZENE, POLAROGRAPHIC ANALYSIS, ADSORPTION, ELECTROLYSIS, ELECTRODES.

  2. Hydrogen sulfide modulates the release of nitric oxide and VEGF in human keratinocytes.

    PubMed

    Merighi, Stefania; Gessi, Stefania; Varani, Katia; Fazzi, Debora; Borea, Pier Andrea

    2012-11-01

    Hydrogen sulfide (H(2)S) is a novel signaling molecule with both pro- or anti-inflammatory effect. The present study aimed to: (i) characterize the in vitro effects of H(2)S on human keratinocyte's proliferation and death; (ii) investigate the ability of H(2)S to modulate VEGF and NO production; (iii) examine the intracellular signaling pathways involved in VEGF and NO modulatory effect. We found that exogenous application of H(2)S (NaHS and GYY4137 as H(2)S donors) significantly enhances NO through increase of iNOS, in a manner Akt-dependent. The increment in NO down-regulates ERK1/2 activation thereby resulting in the decrease of VEGF release. We suggest that H(2)S-releasing agents may be promising therapeutics for chronic inflammatory disorders of the skin, i.e. psoriasis, in which NO increases as well as anti-VEGF treatments have been suggested to be novel effective approaches.

  3. Early diagenetic partial oxidation of organic matter and sulfides in the Middle Pennsylvanian (Desmoinesian) Excello Shale Member of the Fort Scott Limestone and equivalents, northern Midcontinent region, USA

    USGS Publications Warehouse

    Hatch, J.R.; Leventhal, M.S.

    1997-01-01

    A process of early diagenetic partial oxidation of organic matter and sulfides has altered the chemical composition of the Middle Pennsylvanian Excello Shale Member of the Fort Scott Limestone and equivalents in the northern Midcontinent region. This process was identified by comparison of organic carbon contents, Rock-Eval hydrogen indices, organic carbon ??13C and element compositions of core and surface mine samples of the Excello Shale Member with analyses of three other underlying and overlying organic-matter-rich marine shales (offshore shale lithofacies) from southern Iowa, northern Missouri, eastern Kansas and northeastern Oklahoma. The end product of the partial oxidation process is shale with relatively low contents of hydrogen-poor, C13-enriched organic matter, lower contents of sulfur and sulfide-forming elements, and relatively unchanged contents of phosphorus and many trace elements (e.g. Cr, Ni, and V). However, because of lower organic carbon contents, element/organic carbon ratios are greatly increased. The partial oxidation process apparently took place during subaerial exposure of the overlying marine carbonate member (Blackjack Creek Member of the Fort Scott Limestone) following a marine regression when meteoric waters percolated down to the level of the Excello muds allowing oxidation of organic matter and sulfides. This hypothesis is supported by earlier workers, who have identified meteoric carbonate cements within, and soil horizons at the top of the Blackjack Creek Member. The period of oxidation is constrained in that organic matter and sulfides in the Little Osage Shale Member of the Fort Scott Limestone and equivalents (immediately overlying the Blackjack Creek Member) appear unaltered. Similar alteration of other shales in the Middle and Upper Pennsylvanian sections may be local to regional in extent and would depend on the extent and duration of the marine regression and be influenced by local variations in permeability and topography

  4. Electrosprayed Metal Oxide Semiconductor Films for Sensitive and Selective Detection of Hydrogen Sulfide

    PubMed Central

    Ghimbeu, Camelia Matei; Lumbreras, Martine; Schoonman, Joop; Siadat, Maryam

    2009-01-01

    Semiconductor metal oxide films of copper-doped tin oxide (Cu-SnO2), tungsten oxide (WO3) and indium oxide (In2O3) were deposited on a platinum coated alumina substrate employing the electrostatic spray deposition technique (ESD). The morphology studied with scanning electron microscopy (SEM) and atomic force microscopy (AFM) shows porous homogeneous films comprising uniformly distributed aggregates of nano particles. The X-ray diffraction technique (XRD) proves the formation of crystalline phases with no impurities. Besides, the Raman cartographies provided information about the structural homogeneity. Some of the films are highly sensitive to low concentrations of H2S (10 ppm) at low operating temperatures (100 and 200 °C) and the best response in terms of Rair/Rgas is given by Cu-SnO2 films (2500) followed by WO3 (1200) and In2O3 (75). Moreover, all the films exhibit no cross-sensitivity to other reducing (SO2) or oxidizing (NO2) gases. PMID:22291557

  5. Electrosprayed metal oxide semiconductor films for sensitive and selective detection of hydrogen sulfide.

    PubMed

    Ghimbeu, Camelia Matei; Lumbreras, Martine; Schoonman, Joop; Siadat, Maryam

    2009-01-01

    Semiconductor metal oxide films of copper-doped tin oxide (Cu-SnO(2)), tungsten oxide (WO(3)) and indium oxide (In(2)O(3)) were deposited on a platinum coated alumina substrate employing the electrostatic spray deposition technique (ESD). The morphology studied with scanning electron microscopy (SEM) and atomic force microscopy (AFM) shows porous homogeneous films comprising uniformly distributed aggregates of nano particles. The X-ray diffraction technique (XRD) proves the formation of crystalline phases with no impurities. Besides, the Raman cartographies provided information about the structural homogeneity. Some of the films are highly sensitive to low concentrations of H(2)S (10 ppm) at low operating temperatures (100 and 200 °C) and the best response in terms of R(air)/R(gas) is given by Cu-SnO(2) films (2500) followed by WO(3) (1200) and In(2)O(3) (75). Moreover, all the films exhibit no cross-sensitivity to other reducing (SO(2)) or oxidizing (NO(2)) gases.

  6. A mathematical model for the bacterial oxidation of a sulfide ore concentrate.

    PubMed

    Nagpal, S; Dahlstrom, D; Oolman, T

    1994-03-05

    The effect of dilution rate and feed solids concentration on the bacterial leaching of a pyrite/arsenopyrite ore concentrate was studied. A mathematical model was developed for the process based on the steady-state data collected over the range of dilution rates (20 to 110 h) and feed solids concentrations (6 to 18% w/v) studied. A modified Monod model with inhibition by arsenic was used to model bacterial ferrous ion oxidation rates. The model assumes that (i) pyrite and arsenopyrite leaching occurs solely by the action of ferric iron produced from the bacterial oxidation of ferrous iron and (ii) bacterial growth rates are proportional to ferrous ion oxidation rate. The equilibrium among the various ionic species present in the leach solution that are likely to have a significant effect on the bioleach process were included in the model. (c) 1994 John Wiley & Sons, Inc.

  7. Simple synthesis of cobalt sulfide nanorods for efficient electrocatalytic oxidation of vanillin in food samples.

    PubMed

    Sivakumar, Mani; Sakthivel, Mani; Chen, Shen-Ming

    2017-03-15

    Well-defined CoS nanorods (NR) were synthesized using a simple hydrothermal method, and were tested as an electrode material for electro-oxidation of vanillin. The NR material was characterized with regard to morphology, crystallinity, and electro-activity by use of appropriate analytical techniques. The resulting CoS NR@Nafion modified glassy carbon electrode (GCE) exhibited efficient electro-oxidation of vanillin with a considerable linear range of current-vs-concentration (0.5-56μM vanillin) and a detection limit of 0.07μM. Also, food samples containing vanillin were studied to test suitability for commercial applications.

  8. Biomolecule conjugation strategy using novel water-soluble phosphine-based chelating agents

    DOEpatents

    Katti, Kattesh V.; Gali, Hariprasad; Volkert, Wynn A.

    2004-08-24

    This invention describes a novel strategy to produce phosphine-functionalized biomolecules (e.g. peptides or proteins) for potential use in the design and development of site-specific radiopharmaceuticals for diagnosis or therapy of specific cancers. Hydrophilic alkyl phosphines, in general, tend to be oxidatively unstable. Therefore, incorporation of such phosphine functionalities on peptide (and other biomolecule) backbones, without oxidizing the P.sup.III centers, is difficult. In this context this discovery reports on a new technology by which phosphines, in the form of bifunctional chelating agents, can be directly incorporated on biomolecular backbones using manual synthetic or solid phase peptide synthesis methodologies. The superior ligating abilities of phosphine ligands, with various diagnostically (e.g. TC-99m) or therapeutically (e.g. Re186/188, Rh-105, Au-199) useful radiometals, coupled with the findings that the resulting complexes demonstrate high in vivo stability makes this approach useful in the development of radiolabeled biomolecules for applications in the design of tumor-specific radiopharmaceuticals.

  9. Hydrogen sulfide oxidation in novel Horizontal-Flow Biofilm Reactors dominated by an Acidithiobacillus and a Thiobacillus species.

    PubMed

    Gerrity, S; Kennelly, C; Clifford, E; Collins, G

    2016-09-01

    Hydrogen Sulfide (H2S) is an odourous, highly toxic gas commonly encountered in various commercial and municipal sectors. Three novel, laboratory-scale, Horizontal-Flow Biofilm Reactors (HFBRs) were tested for the removal of H2S gas from air streams over a 178-day trial at 10°C. Removal rates of up to 15.1 g [H2S] m(-3) h(-1) were achieved, demonstrating the HFBRs as a feasible technology for the treatment of H2S-contaminated airstreams at low temperatures. Bio-oxidation of H2S in the reactors led to the production of H(+) and sulfate (SO(2-)4) ions, resulting in the acidification of the liquid phase. Reduced removal efficiency was observed at loading rates of 15.1 g [H2S] m(-3) h(-1). NaHCO3 addition to the liquid nutrient feed (synthetic wastewater (SWW)) resulted in improved H2S removal. Bacterial diversity, which was investigated by sequencing and fingerprinting 16S rRNA genes, was low, likely due to the harsh conditions prevailing in the systems. The HFBRs were dominated by two species from the genus Acidithiobacillus and Thiobacillus. Nonetheless, there were significant differences in microbial community structure between distinct HFBR zones due to the influence of alkalinity, pH and SO4 concentrations. Despite the low temperature, this study indicates HFBRs have an excellent potential to biologically treat H2S-contaminated airstreams.

  10. Hard X-ray photoelectron and X-ray absorption spectroscopy characterization of oxidized surfaces of iron sulfides

    NASA Astrophysics Data System (ADS)

    Mikhlin, Yuri; Tomashevich, Yevgeny; Vorobyev, Sergey; Saikova, Svetlana; Romanchenko, Alexander; Félix, Roberto

    2016-11-01

    Hard X-ray photoelectron spectroscopy (HAXPES) using an excitation energy range of 2 keV to 6 keV in combination with Fe K- and S K-edge XANES, measured simultaneously in total electron (TEY) and partial fluorescence yield (PFY) modes, have been applied to study near-surface regions of natural polycrystalline pyrite FeS2 and pyrrhotite Fe1-xS before and after etching treatments in an acidic ferric chloride solution. It was found that the following near-surface regions are formed owing to the preferential release of iron from oxidized metal sulfide lattices: (i) a thin, no more than 1-4 nm in depth, outer layer containing polysulfide species, (ii) a layer exhibiting less pronounced stoichiometry deviations and low, if any, concentrations of polysulfide, the composition and dimensions of which vary for pyrite and pyrrhotite and depend on the chemical treatment, and (iii) an extended almost stoichiometric underlayer yielding modified TEY XANES spectra, probably, due to a higher content of defects. We suggest that the extended layered structure should heavily affect the near-surface electronic properties, and processes involving the surface and interfacial charge transfer.

  11. Biological consilience of hydrogen sulfide and nitric oxide in plants: Gases of primordial earth linking plant, microbial and animal physiologies.

    PubMed

    Yamasaki, Hideo; Cohen, Michael F

    2016-05-01

    Hydrogen sulfide (H2S) is produced in the mammalian body through the enzymatic activities of cystathionine β-synthase (CBS), cystathionine γ-lyase (CSE) and 3-mercaptopyruvate sulfurtransferase (3MST). A growing number of studies have revealed that biogenic H2S produced in tissues is involved in a variety of physiological responses in mammals including vasorelaxation and neurotransmission. It is now evident that mammals utilize H2S to regulate multiple signaling systems, echoing the research history of the gaseous signaling molecules nitric oxide (NO) and carbon monoxide (CO) that had previously only been recognized for their cytotoxicity. In the human diet, meats (mammals, birds and fishes) and vegetables (plants) containing cysteine and other sulfur compounds are the major dietary sources for endogenous production of H2S. Plants are primary producers in ecosystems on the earth and they synthesize organic sulfur compounds through the activity of sulfur assimilation. Although plant H2S-producing activities have been known for a long time, our knowledge of H2S biology in plant systems has not been updated to the extent of mammalian studies. Here we review recent progress on H2S studies, highlighting plants and bacteria. Scoping the future integration of H2S, NO and O2 biology, we discuss a possible linkage between physiology, ecology and evolutional biology of gas metabolisms that may reflect the historical changes of the Earth's atmospheric composition.

  12. In site bioimaging of hydrogen sulfide uncovers its pivotal role in regulating nitric oxide-induced lateral root formation.

    PubMed

    Li, Yan-Jun; Chen, Jian; Xian, Ming; Zhou, Li-Gang; Han, Fengxiang X; Gan, Li-Jun; Shi, Zhi-Qi

    2014-01-01

    Hydrogen sulfide (H2S) is an important gasotransmitter in mammals. Despite physiological changes induced by exogenous H2S donor NaHS to plants, whether and how H2S works as a true cellular signal in plants need to be examined. A self-developed specific fluorescent probe (WSP-1) was applied to track endogenous H2S in tomato (Solanum lycopersicum) roots in site. Bioimaging combined with pharmacological and biochemical approaches were used to investigate the cross-talk among H2S, nitric oxide (NO), and Ca(2+) in regulating lateral root formation. Endogenous H2S accumulation was clearly associated with primordium initiation and lateral root emergence. NO donor SNP stimulated the generation of endogenous H2S and the expression of the gene coding for the enzyme responsible for endogenous H2S synthesis. Scavenging H2S or inhibiting H2S synthesis partially blocked SNP-induced lateral root formation and the expression of lateral root-related genes. The stimulatory effect of SNP on Ca(2+) accumulation and CaM1 (calmodulin 1) expression could be abolished by inhibiting H2S synthesis. Ca(2+) chelator or Ca(2+) channel blocker attenuated NaHS-induced lateral root formation. Our study confirmed the role of H2S as a cellular signal in plants being a mediator between NO and Ca(2+) in regulating lateral root formation.

  13. Developing sulfide-oxidizing biofilm on H2S-exhausted carbon for sustainable bio-regeneration and biofiltration.

    PubMed

    Jiang, Xia; Yan, Rong; Tay, Joo Hwa

    2009-05-30

    The feasibility of developing biofilm on exhausted carbon using pre-deposited sulfur compounds as the sole energy source was studied, aiming to re-use them in odor biofiltration. The exhausted carbon with different properties, including surface pH, sulfur content and porosity, was used. A series of off-line trials were conducted to investigate the release of sulfur compounds from the exhausted carbon and the attachment of sulfide-oxidizing bacteria on the exhausted carbon. Without any pre-treatment, a few bacteria attachment on exhausted carbon was observed by SEM, due to possibly the limitation of reduced sulfur compounds release for bacterial growth. The biofilm development was much improved by adding NaOH solution to partially pre-desorb the deposited sulfur into liquid phase, which provided initial energy for bacterial growth. With the attached bacteria, the further significant release of the deposited sulfur was achieved through an additional driving force: biodegradation. The key issues for developing biofilm on exhausted carbon were concluded, which mainly concerned of desorption of pre-deposited reduced sulfur compounds and porosity of carbon. The sulfur-associated reactions occurring in developing biofilm on exhausted carbon was proposed. Bio-regeneration of exhausted carbon in the course of biofilm development was also preliminarily assessed.

  14. Triggers on sulfide saturation in Fe-Ti oxide-bearing, mafic-ultramafic layered intrusions in the Tarim large igneous province, NW China

    NASA Astrophysics Data System (ADS)

    Cao, Jun; Wang, Christina Yan; Xu, Yi-Gang; Xing, Chang-Ming; Ren, Ming-Hao

    2016-08-01

    Three Fe-Ti oxide-bearing layered intrusions (Mazaertag, Wajilitag, and Piqiang) in the Tarim large igneous province (NW China) have been investigated for understanding the relationship of sulfide saturation, Platinum-group element (PGE) enrichment, and Fe-Ti oxide accumulation in layered intrusions. These mafic-ultramafic layered intrusions have low PGE concentrations (<0.4 ppb Os, <0.7 ppb Ir, <1 ppb Ru, <0.2 ppb Rh, <5 ppb Pt, and <8 ppb Pd) and elevated Cu/Pd (2.2 × 104 to 3.3 × 106). The low PGE concentrations of the rocks are mainly attributed to PGE-depleted, parental magma that was produced by low degrees of partial melting of the mantle. The least contaminated rocks of the Mazaertag and Wajilitag intrusions have slightly enriched Os isotopic compositions with γOs(t = 280 Ma) values ranging from +13 to +23, indicating that the primitive magma may have been generated from a convecting mantle, without appreciable input of lithospheric mantle. The Mazaertag and Wajilitag intrusions have near-chondritic γOs(t) values (+13 to +60) against restricted ɛ Nd(t) values (-0.4 to +2.8), indicating insignificant crustal contamination. Rocks of the Piqiang intrusion have relatively low ɛ Nd(t) values of -3.1 to +1.0, consistent with ˜15 to 25 % assimilation of the upper crust. The rocks of the Mazaertag and Wajilitag intrusions have positive correlation of PGE and S, pointing to the control of PGE by sulfide. Poor correlation of PGE and S for the Piqiang intrusion is attributed to the involvement of multiple sulfide-stage liquids with different PGE compositions or sulfide-oxide reequilibration on cooling. These three layered intrusions have little potential of reef-type PGE mineralization. Four criteria are summarized in this study to help discriminate between PGE-mineralized and PGE-unmineralized mafic-ultramafic intrusions.

  15. Oxidation of acid-volatile sulfide in surface sediments increases the release and toxicity of copper to the benthic amphipod Melita plumulosa.

    PubMed

    Simpson, Stuart L; Ward, Daniel; Strom, David; Jolley, Dianne F

    2012-08-01

    Acid-volatile sulfides (AVS) are an important metal-binding phase in sediments. For sediments that contain an excess of AVS over simultaneously extracted metal (SEM) concentrations, acute or chronic effects should not result from the metals Cd, Cu, Ni, Pb and Zn. While AVS phases may exist in surface sediments, the exposure to dissolved oxygen may oxidize the AVS and release metals to more bioavailable forms. We investigated the role of oxidation of AVS, and specifically copper sulfide phases, in surface sediments, in the toxicity to juveniles of the epibenthic amphipod, Melita plumulosa. Sediments containing known amounts of copper sulfide were prepared either in situ by reacting dissolved copper with AVS that had formed in field sediments or created in sediments within the laboratory, or by addition of synthesised CuS to sediments. Regardless of the form of the copper sulfide, considerable oxidation of AVS occurred during the 10-d tests. Sediments that had a molar excess of AVS compared to SEM at the start of the tests, did not always have an excess at the end of the tests. Consistent with the AVS-SEM model, no toxicity was observed for sediments with an excess of AVS throughout the tests. However, the study highlights the need to carefully consider the changes in AVS concentrations during tests, and that measurements of AVS and SEM concentrations should carefully target the materials to which the organisms are being exposed throughout tests, which in the case of juvenile M. plumulosa is the top few mm of the sediments.

  16. Kinetics of reduction of sulfur dioxide by hydrogen sulfide in the presence of sulfoxides, pyridine N-oxide, trioctylphosphine oxide and tributyl phosphate

    SciTech Connect

    Bikbaeva, G.G.; Baranovskaya, E.M.; Nikitin, Yu.E.

    1989-01-01

    The kinetic regularities were studied of the reduction of SO/sub 2/ by hydrogen sulfide in m-xylene containing 0.025 M of aliphatic sulfoxides, (C/sub 1/-C/sub 8/alkyl), diphenyl-, dibenzyl sulfoxides, tributyl phosphate (TBP), trioctylphosphine oxide (TOPO) at 25/degree/C, and 0.001-0.003 M pyridine N-oxide (PyO) at 21-60/degree/C. It was shown that the reaction proceeds with the participation of an SO/sub 2/ complex having the composition of R/sub n/XO...SO/sub 2/ (where X = S, P, N). The kinetic regularities for the reaction taking place in the presence of aromatic sulfoxides are explainable by the contribution to the reaction of intermediate SO/sub 2/ complexes. The equilibrium constants of the complexation of SO/sub 2/ with aliphatic sulfoxides, PyO, TOPO, and TBP and the rate constant of the limiting stage of the reaction were calculated.

  17. Matrix-bound phosphine in Antarctic biosphere.

    PubMed

    Zhu, Renbin; Sun, Liguang; Kong, Deming; Geng, Jinju; Wang, Ning; Wang, Qiang; Wang, Xiaorong

    2006-08-01

    Phosphine (PH(3)) is a natural gaseous carrier of phosphorus in its geochemical cycles, and it might be of importance to the phosphorus balance of natural ecosystem. For the first time phosphine levels were investigated in the Earth's coldest, driest, and most southerly Antarctic biosphere. Matrix-bound phosphine (MBP) was found in sea animal guanos, ornithogenic sediments and soils. Phosphine concentrations varied with different sea animal guanos. Average phosphine concentrations in empire penguin, gentoo penguin, sea lion, skua and gull guanos were 2.54+/-1.28 ng kg(-1), 6.21+/-2.15 ng kg(-1), 9.12+/-4.66 ng kg(-1), 11.90+/-1.29 ng kg(-1) and 14.55+/-6.74 ng kg(-1), respectively. The contents of phosphorus in these various matrixes have an important effect on MBP concentrations. The levels of phosphine appeared an increasing tendency with the content of TP, IP and OP in sea animal guanos, ornithogenic sediments or soils. The correlation between PH(3) and Fe, Mn, Al in these matrixes was also analyzed and discussed. Phosphine showed an obviously positive correlation with Fe in sea animal guanos. However, excessively high Fe, Al and Mn may inhibit the formation of PH(3) in the ornithogenic soils or sediments in the Antarctic biosphere.

  18. Microsensor Measurements of Sulfate Reduction and Sulfide Oxidation in Compact Microbial Communities of Aerobic Biofilms

    PubMed Central

    Kühl, Michael; Jørgensen, Bo Barker

    1992-01-01

    The microzonation of O2 respiration, H2S oxidation, and SO42- reduction in aerobic trickling-filter biofilms was studied by measuring concentration profiles at high spatial resolution (25 to 100 μm) with microsensors for O2, S2-, and pH. Specific reaction rates were calculated from measured concentration profiles by using a simple one-dimensional diffusion reaction model. The importance of electron acceptor and electron donor availability for the microzonation of respiratory processes and their reaction rates was investigated. Oxygen respiration was found in the upper 0.2 to 0.4 mm of the biofilm, whereas sulfate reduction occurred in deeper, anoxic parts of the biofilm. Sulfate reduction accounted for up to 50% of the total mineralization of organic carbon in the biofilms. All H2S produced from sulfate reduction was reoxidized by O2 in a narrow reaction zone, and no H2S escaped to the overlying water. Turnover times of H2S and O2 in the reaction zone were only a few seconds owing to rapid bacterial H2S oxidation. Anaerobic H2S oxidation with NO3- could be induced by addition of nitrate to the medium. Total sulfate reduction rates increased when the availability of SO42- or organic substrate increased as a result of deepening of the sulfate reduction zone or an increase in the sulfate reduction intensity, respectively. PMID:16348687

  19. Molecular and biochemical evidence on the protection of cardiomyocytes from phosphine-induced oxidative stress, mitochondrial dysfunction and apoptosis by acetyl-L-carnitine.

    PubMed

    Baghaei, Amir; Solgi, Reza; Jafari, Abbas; Abdolghaffari, Amir Hossein; Golaghaei, Alireza; Asghari, Mohammad Hossein; Baeeri, Maryam; Ostad, Seyed Nasser; Sharifzadeh, Mohammad; Abdollahi, Mohammad

    2016-03-01

    The aim of the present study was to investigate the efficacy of acetyl-L-carnitine (ALCAR) on pathologic changes of mitochondrial respiratory chain activity, ATP production, oxidative stress, and cellular apoptosis/necrosis induced by aluminum phosphide (AlP) poisoning. The study groups included: the Sham that received almond oil only; the AlP that received oral LD50 dose of aluminum; the AC-100, AC-200, and AC-300 which received concurrent oral LD50 dose of AlP and single 100, 200, and 300 mg/kg of ALCAR by intraperitoneal injection. After 24 h, the rats were sacrificed; the heart and blood sample were taken for measurement of biochemical and mitochondrial factors. The results specified that ALCAR significantly attenuated the oxidative stress (elevated ROS and plasma iron levels) caused by AlP poisoning. ALCAR also increased the activity of cytochrome oxidase, which in turn amplified ATP production. Furthermore, flow cytometric assays and caspase activity indicated that ALCAR prohibited AlP-induced apoptosis in cardiomyocytes.

  20. Anode materials for hydrogen sulfide containing feeds in a solid oxide fuel cell

    NASA Astrophysics Data System (ADS)

    Roushanafshar, Milad

    SOFCs which can directly operate under high concentration of H2S would be economically beneficial as this reduces the cost of gas purification. H2S is highly reactive gas specie which can poison most of the conventional catalysts. As a result, developing anode materials which can tolerate high concentrations of H2S and also display high activity toward electrochemical oxidation of feed is crucial and challenging for this application. The performance of La0.4Sr0.6TiO3+/-delta -Y0.2Ce0.8O2-delta (LST-YDC) composite anodes in solid oxide fuel cells significantly improved when 0.5% H2 S was present in syngas (40% H2, 60% CO) or hydrogen. Gas chromatography and mass spectrometry analyses revealed that the rate of electrochemical oxidation of all fuel components improved when H2S containing syngas was present in the fuel. Electrochemical stability tests performed under potentiostatic condition showed that there was no power degradation for different feeds, and that there was power enhancement when 0.5% H2S was present in various feeds. The mechanism of performance improvement by H2S was discussed. Active anodes were synthesized via wet chemical impregnation of different amounts of La0.4Ce0.6O1.8 (LDC) and La 0.4Sr0.6TiO3 (L4ST) into porous yttria-stabilized zirconia (YSZ). Co-impregnation of LDC with LS4T significantly improved the performance of the cell from 48 mW.cm-2 (L4ST) to 161 mW.cm -2 (LDC-L4ST) using hydrogen as fuel at 900 °C. The contribution of LDC to this improvement was investigated using electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM) as well as transmission electron microscopy (TEM). EIS measurements using symmetrical cells showed that the polarization resistance decreased from 3.1¦O.cm 2 to 0.5 O.cm2 when LDC was co-impregnated with LST, characterized in humidified H2 (3% H2O) at 900 °C. In addition, the microstructure of the cell was modified when LDC was impregnated prior to L4ST into the porous YSZ. TEM and SEM

  1. Low temperature catalytic oxidation of hydrogen sulfide and methanethiol using wood and coal fly ash.

    PubMed

    Kastner, James R; Das, K C; Buquoi, Quentin; Melear, Nathan D

    2003-06-01

    The feasibility of reusing waste material as an inexpensive catalyst to remove sulfur compounds from gaseous waste streams has been demonstrated. Wood and coal fly ash were demonstrated to catalytically oxidize H2S and methanethiol (CH3SH) at low temperatures (23-25 degrees C). Wood ash had a significantly higher surface area compared to coal ash (44.9 vs 7.7 m2/g), resulting in a higher initial H2S removal rate (0.16 vs 0.018 mg/g/min) under similar conditions. Elemental sulfur was determined to be the end product of H2S oxidation, since X-ray diffraction analysis indicated the presence of crystalline sulfur. Catalytic decay occurred apparently due to surface deposition of sulfur and a subsequent decline in surface area (44.9-1.4 m2/g) during the reaction of H2S with the ash. Methanethiol was stoichiometrically converted to dimethyl disulfide ((CH3)2S2) without significant catalytic decay. Catalytic decay was reduced and H2S conversion increased (10% at 1.8 days vs 94% at 4.2 days) when H2S loading was decreased to levels typical of many environmental applications (500 ppmv inlet and 1.43 mg/min vs 60 ppmv, 0.09 mg/ min). Catalyst regeneration using hot water (85 degrees C) washing was possible, but only increased fractional conversion from 0.2 to 0.6 and the initial reaction rate to 50% of the original H2S oxidation activity.

  2. Hydrogen sulfide and nitric oxide metabolites in the blood of free-ranging brown bears and their potential roles in hibernation.

    PubMed

    Revsbech, Inge G; Shen, Xinggui; Chakravarti, Ritu; Jensen, Frank B; Thiel, Bonnie; Evans, Alina L; Kindberg, Jonas; Fröbert, Ole; Stuehr, Dennis J; Kevil, Christopher G; Fago, Angela

    2014-08-01

    During winter hibernation, brown bears (Ursus arctos) lie in dens for half a year without eating while their basal metabolism is largely suppressed. To understand the underlying mechanisms of metabolic depression in hibernation, we measured type and content of blood metabolites of two ubiquitous inhibitors of mitochondrial respiration, hydrogen sulfide (H2S) and nitric oxide (NO), in winter-hibernating and summer-active free-ranging Scandinavian brown bears. We found that levels of sulfide metabolites were overall similar in summer-active and hibernating bears but their composition in the plasma differed significantly, with a decrease in bound sulfane sulfur in hibernation. High levels of unbound free sulfide correlated with high levels of cysteine (Cys) and with low levels of bound sulfane sulfur, indicating that during hibernation H2S, in addition to being formed enzymatically from the substrate Cys, may also be regenerated from its oxidation products, including thiosulfate and polysulfides. In the absence of any dietary intake, this shift in the mode of H2S synthesis would help preserve free Cys for synthesis of glutathione (GSH), a major antioxidant found at high levels in the red blood cells of hibernating bears. In contrast, circulating nitrite and erythrocytic S-nitrosation of glyceraldehyde-3-phosphate dehydrogenase, taken as markers of NO metabolism, did not change appreciably. Our findings reveal that remodeling of H2S metabolism and enhanced intracellular GSH levels are hallmarks of the aerobic metabolic suppression of hibernating bears.

  3. Dibenzothiophene Sulfone-Based Phosphine Oxide Electron Transporters with Unique Asymmetry for High-Efficiency Blue Thermally Activated Delayed Fluorescence Diodes.

    PubMed

    Fan, Chaochao; Duan, Chunbo; Han, Chunmiao; Han, Bin; Xu, Hui

    2016-10-12

    Three asymmetrical electron transporters as dibenzothiophene sulfone (DBSO)-diphenylphosphine oxide (DPPO) hybrids, collectively named mnDBSODPO, were designed and prepared. All of these materials achieve the high triplet energy of ∼3.0 eV to restrain the exciton linkage from emissive layers. The dependence of inductive and steric effects for DPPO groups on the substitution position, the intermolecular interaction suppression, the encapsulations of high-polar DBSO cores, and the favorable electrical performance are successfully integrated on 36DBSODPO, which can simultaneously suppress the exciton quenching by formation of an interfacial dipole and enhancing the charge flux balance. As a result, 36DBSODPO endowed its tetralayer blue thermally activated delayed fluorescence (TADF) devices with impressive performance, including the maximum external quantum efficiency around 19%, and reduced efficiency roll-offs, which verifies the great potential of asymmetrical electron transporting materials for highly efficient TADF devices.

  4. Effects of hydrogen sulfide on hemodynamics, inflammatory response and oxidative stress during resuscitated hemorrhagic shock in rats

    PubMed Central

    2010-01-01

    Introduction Hydrogen sulfide (H2S) has been shown to improve survival in rodent models of lethal hemorrhage. Conversely, other authors have reported that inhibition of endogenous H2S production improves hemodynamics and reduces organ injury after hemorrhagic shock. Since all of these data originate from unresuscitated models and/or the use of a pre-treatment design, we therefore tested the hypothesis that the H2S donor, sodium hydrosulfide (NaHS), may improve hemodynamics in resuscitated hemorrhagic shock and attenuate oxidative and nitrosative stresses. Methods Thirty-two rats were mechanically ventilated and instrumented to measure mean arterial pressure (MAP) and carotid blood flow (CBF). Animals were bled during 60 minutes in order to maintain MAP at 40 ± 2 mm Hg. Ten minutes prior to retransfusion of shed blood, rats randomly received either an intravenous bolus of NaHS (0.2 mg/kg) or vehicle (0.9% NaCl). At the end of the experiment (T = 300 minutes), blood, aorta and heart were harvested for Western blot (inductible Nitric Oxyde Synthase (iNOS), Nuclear factor-κB (NF-κB), phosphorylated Inhibitor κB (P-IκB), Inter-Cellular Adhesion Molecule (I-CAM), Heme oxygenase 1(HO-1), Heme oxygenase 2(HO-2), as well as nuclear respiratory factor 2 (Nrf2)). Nitric oxide (NO) and superoxide anion (O2-) were also measured by electron paramagnetic resonance. Results At the end of the experiment, control rats exhibited a decrease in MAP which was attenuated by NaHS (65 ± 32 versus 101 ± 17 mmHg, P < 0.05). CBF was better maintained in NaHS-treated rats (1.9 ± 1.6 versus 4.4 ± 1.9 ml/minute P < 0.05). NaHS significantly limited shock-induced metabolic acidosis. NaHS also prevented iNOS expression and NO production in the heart and aorta while significantly reducing NF-kB, P-IκB and I-CAM in the aorta. Compared to the control group, NaHS significantly increased Nrf2, HO-1 and HO-2 and limited O2- release in both aorta and heart (P < 0.05). Conclusions NaHS is

  5. Synthesis and characterization of new ternary transition metal sulfide anodes for H 2S-powered solid oxide fuel cell

    NASA Astrophysics Data System (ADS)

    Vorontsov, V.; Luo, J. L.; Sanger, A. R.; Chuang, K. T.

    A number of ternary transition metal sulfides with general composition AB 2S 4 (where A and B are different transition metal atoms) have been prepared and investigated as potential anode catalysts for use in H 2S-powered solid oxide fuel cells (SOFCs). For the initial screening, polarization resistance of the materials was measured in a two electrode symmetrical cell at 700-850 °C. Vanadium-based materials showed the lowest polarization resistance, and so were chosen for subsequent full cell tests using the configuration [H 2S, AV 2S 4/YSZ/Pt, air] (where A = Ni, Cr, Mo). MoV 2S 4 anode had superior activity and performance in the full cell setup, consistent with results from symmetrical cell tests. Polarization curves showed MoV 2S 4 had the lowest potential drop, with up to a 200 mA cm -2 current density at 800 °C. The highest power density of ca. 275 mW cm -2 at 800 °C was obtained with a pure H 2S stream. Polarization resistance of materials was a strong function of current density, and showed a sharp change of slope attributable to a change in the rate-limiting step of the anode reaction mechanism. MoV 2S 4 was chemically stable during prolonged (10 days) exposure to H 2S at 850 °C, and fuel cell performance was stable during continuous 3-day operation at 370 mA cm -2 current density.

  6. Hydrogen sulfide enhances salt tolerance through nitric oxide-mediated maintenance of ion homeostasis in barley seedling roots

    PubMed Central

    Chen, Juan; Wang, Wen-Hua; Wu, Fei-Hua; He, En-Ming; Liu, Xiang; Shangguan, Zhou-Ping; Zheng, Hai-Lei

    2015-01-01

    Hydrogen sulfide (H2S) and nitric oxide (NO) are emerging as messenger molecules involved in the modulation of plant physiological processes. Here, we investigated a signalling network involving H2S and NO in salt tolerance pathway of barley. NaHS, a donor of H2S, at a low concentration of either 50 or 100 μM, had significant rescue effects on the 150 mM NaCl-induced inhibition of plant growth and modulated the K+/Na+ balance by decreasing the net K+ efflux and increasing the gene expression of an inward-rectifying potassium channel (HvAKT1) and a high-affinity K+ uptake system (HvHAK4). H2S and NO maintained the lower Na+ content in the cytoplast by increasing the amount of PM H+-ATPase, the transcriptional levels of PM H+-ATPase (HvHA1) and Na+/H+ antiporter (HvSOS1). H2S and NO modulated Na+ compartmentation into the vacuoles with up-regulation of the transcriptional levels of vacuolar Na+/H+ antiporter (HvVNHX2) and H+-ATPase subunit β (HvVHA-β) and increased in the protein expression of vacuolar Na+/H+ antiporter (NHE1). H2S mimicked the effect of sodium nitroprusside (SNP) by increasing NO production, whereas the function was quenched with the addition of NO scavenger. These results indicated that H2S increased salt tolerance by maintaining ion homeostasis, which were mediated by the NO signal. PMID:26213372

  7. Graphene oxide-facilitated reduction of nitrobenzene in sulfide-containing aqueous solutions.

    PubMed

    Fu, Heyun; Zhu, Dongqiang

    2013-05-07

    The main objective of this study was to test the possibility that graphene-based nanomaterials can mediate environmentally relevant abiotic redox reactions of organic contaminants. We investigated the effect of graphene oxide (GO) on the reduction of nitrobenzene by Na2S in aqueous solutions. With the presence of GO (typically 5 mg/L), the observed pseudofirst-order rate constant (kobs) for the reduction of nitrobenzene was raised by nearly 2 orders of magnitude (from 7.83 × 10(-5) h(-1) to 7.77 × 10(-3) h(-1)), strongly suggesting reaction mediation by GO. As reflected by the combined spectroscopic analyses, GO was reduced in the beginning of the reaction, and hence the reduced GO (RGO) mediated the reduction of nitrobenzene. It was proposed that the zigzag edges of RGO acted as the catalytic active sites, while the basal plane of RGO served as the conductor for the electron transfer during the catalytic process. Furthermore, changing the pH (5.9-9.1) and the presence of dissolved humic acid (10 mg TOC/L) were found to greatly influence the catalytic activity of RGO. The results imply that graphene-based nanomaterials may effectively mediate the reductive transformation of nitroaromatic compounds and can contribute to the natural attenuation and remediation of these chemicals.

  8. Experimental and theoretical study of hydrogen thiocarbonate for heterogeneous reaction of carbonyl sulfide on magnesium oxide.

    PubMed

    Liu, Yongchun; He, Hong

    2009-04-09

    In situ diffuse reflectance infrared Fourier transform spectroscopy combined with derivative spectroscopy analysis, two-dimensional correlation spectroscopy analysis, and quantum chemical calculations were used to investigate the infrared absorbance assignment and the molecular structure of hydrogen thiocarbonate on magnesium oxide. The bands at 1283 and 1257 cm(-1), which had the typical characteristic of intermediate, were observed in experiments for the heterogeneous reaction of COS on MgO. On the basis of two-dimensional correlation spectroscopy analysis and quantum chemical calculations, the band at 1283 cm(-1) was assigned to the v(s) band of bridged thiocarbonate which formed on the two neighboring Mg atoms in the (100) face of MgO crystal, and the band at 1257 cm(-1) was the v(s) band of monodentate thiocarbonate on MgO. The v(as)(OCO) band of thiocarbonates was invisible in the experiment due to their weak absorbance and the interruption of surface carbonate. The formation mechanism of thiocarbonates is proposed, which occurred through a nucleophilic attack of preadsorbed COS by surface -OH groups followed by hydrogen atom transfer from the -OH group to the sulfur atom of preadsorbed COS. The activation energy for the intramolecular proton-transfer reaction of bridged thiocarbonate was calculated to be 18.52 kcal x mol(-1) at the B3LYP/6-31+G(d,p) level of theory.

  9. Phosphine photochemistry in Saturn's atmosphere

    NASA Technical Reports Server (NTRS)

    Kaye, J. A.; Strobel, D. F.

    1983-01-01

    The phosphine photochemistry on Saturn is studied with a 1D photochemical model. The PH3 concentration is rapidly depleted with height (scale height 3.5 km) in the upper troposphere. Formation of P, a probable precursor of P4, (a potential red chromophore in the atmosphere), is highly improbable unless the rate constant for the recombination reaction PH + H2 + M yields PH3 + M is less than 10 to the -41st cm exp 6/molecule-squared sec. Coupling of PH3 and hydrocarbon photochemistry, specifically the C2H2 catalyzed photodissociation of CH, is important. Column production rates of the organophosphorus compounds CH3PH2 and HCP of 3 x 10 to the 8th/sq cm sec are predicted, with potentially observable column densities of greater than 1 x 10 to the 17th/sq cm.

  10. Phosphine photochemistry in Saturn's atmosphere

    NASA Astrophysics Data System (ADS)

    Kaye, J. A.; Strobel, D. F.

    1983-10-01

    The phosphine photochemistry on Saturn is studied with a 1D photochemical model. The PH3 concentration is rapidly depleted with height (scale height 3.5 km) in the upper troposphere. Formation of P, a probable precursor of P4, (a potential red chromophore in the atmosphere), is highly improbable unless the rate constant for the recombination reaction PH + H2 + M yields PH3 + M is less than 10 to the -41st cm exp 6/molecule-squared sec. Coupling of PH3 and hydrocarbon photochemistry, specifically the C2H2 catalyzed photodissociation of CH, is important. Column production rates of the organophosphorus compounds CH3PH2 and HCP of 3 x 10 to the 8th/sq cm sec are predicted, with potentially observable column densities of greater than 1 x 10 to the 17th/sq cm.

  11. Removal of methanethiol, dimethyl sulfide, dimethyl disulfide, and hydrogen sulfide from contaminated air by Thiobacillus thioparus TK-m

    SciTech Connect

    Kanagawa, T.; Mikami, E.

    1989-03-01

    Methanethiol, dimethyl sulfide, dimethyl disulfide, and hydrogen sulfide were efficiently removed from contaminated air by Thiobacillus thioparus TK-m and oxidized to sulfate stoichiometrically. More than 99.99% of dimethyl sulfide was removed when the load was less than 4.0 g of dimethyl sulfide per g (dry cell weight) per day.

  12. Molybdenum oxides versus molybdenum sulfides: geometric and electronic structures of Mo₃X(y)⁻ (X = O, S and y = 6, 9) clusters.

    PubMed

    Mayhall, Nicholas J; Becher, Edwin L; Chowdhury, Arefin; Raghavachari, Krishnan

    2011-03-24

    We have conducted a comparative computational investigation of the molecular structure and water adsorption properties of molybdenum oxide and sulfide clusters using density functional theory methods. We have found that while Mo₃O₆⁻ and Mo₃S₆⁻ assume very similar ring-type isomers, Mo₃O₉⁻ and Mo₃S₉⁻ clusters are very different with Mo₃O₉⁻ having a ring-type structure and Mo₃S₉⁻ having a more open, linear-type geometry. The more rigid ∠(Mo-S-Mo) bond angle is the primary geometric property responsible for producing such different lowest energy isomers. By computing molecular complexation energies, it is observed that water is found to adsorb more strongly to Mo₃O₆⁻ than to Mo₃S₆⁻, due to a stronger oxide-water hydrogen bond, although dispersion effects reduce this difference when molybdenum centers contribute to the binding. Investigating the energetics of dissociative water addition to Mo₃X₆⁻ clusters, we find that, while the oxide cluster shows kinetic site-selectivity (bridging position vs terminal position), the sulfide cluster exhibits thermodynamic site-selectivity.

  13. Isolation and Characterization of Strains CVO and FWKO B, Two Novel Nitrate-Reducing, Sulfide-Oxidizing Bacteria Isolated from Oil Field Brine

    PubMed Central

    Gevertz, Diane; Telang, Anita J.; Voordouw, Gerrit; Jenneman, Gary E.

    2000-01-01

    Bacterial strains CVO and FWKO B were isolated from produced brine at the Coleville oil field in Saskatchewan, Canada. Both strains are obligate chemolithotrophs, with hydrogen, formate, and sulfide serving as the only known energy sources for FWKO B, whereas sulfide and elemental sulfur are the only known electron donors for CVO. Neither strain uses thiosulfate as an energy source. Both strains are microaerophiles (1% O2). In addition, CVO grows by denitrification of nitrate or nitrite whereas FWKO B reduces nitrate only to nitrite. Elemental sulfur is the sole product of sulfide oxidation by FWKO B, while CVO produces either elemental sulfur or sulfate, depending on the initial concentration of sulfide. Both strains are capable of growth under strictly autotrophic conditions, but CVO uses acetate as well as CO2 as its sole carbon source. Neither strain reduces sulfate; however, FWKO B reduces sulfur and displays chemolithoautotrophic growth in the presence of elemental sulfur, hydrogen, and CO2. Both strains grow at temperatures between 5 and 40°C. CVO is capable of growth at NaCl concentrations as high as 7%. The present 16s rRNA analysis suggests that both strains are members of the epsilon subdivision of the division Proteobacteria, with CVO most closely related to Thiomicrospira denitrifcans and FWKO B most closely related to members of the genus Arcobacter. The isolation of these two novel chemolithotrophic sulfur bacteria from oil field brine suggests the presence of a subterranean sulfur cycle driven entirely by hydrogen, carbon dioxide, and nitrate. PMID:10831429

  14. Hydrogen sulfide releasing aspirin, ACS14, attenuates high glucose-induced increased methylglyoxal and oxidative stress in cultured vascular smooth muscle cells.

    PubMed

    Huang, Qian; Sparatore, Anna; Del Soldato, Piero; Wu, Lingyun; Desai, Kaushik

    2014-01-01

    Hydrogen sulfide is a gasotransmitter with vasodilatory and anti-inflammatory properties. Aspirin is an irreversible cyclooxygenase inhibitor anti-inflammatory drug. ACS14 is a novel synthetic hydrogen sulfide releasing aspirin which inhibits cyclooxygenase and has antioxidant effects. Methylglyoxal is a chemically active metabolite of glucose and fructose, and a major precursor of advanced glycation end products formation. Methylglyoxal is harmful when produced in excess. Plasma methylglyoxal levels are significantly elevated in diabetic patients. Our aim was to investigate the effects of ACS14 on methylglyoxal levels in cultured rat aortic vascular smooth muscle cells. We used cultured rat aortic vascular smooth muscle cells for the study. Methylglyoxal was measured by HPLC after derivatization, and nitrite+nitrate with an assay kit. Western blotting was used to determine NADPH oxidase 4 (NOX4) and inducible nitric oxide synthase (iNOS) protein expression. Dicholorofluorescein assay was used to measure oxidative stress. ACS14 significantly attenuated elevation of intracellular methylglyoxal levels caused by incubating cultured vascular smooth muscle cells with methylglyoxal (30 µM) and high glucose (25 mM). ACS14, but not aspirin, caused a significant attenuation of increase in nitrite+nitrate levels caused by methylglyoxal or high glucose. ACS14, aspirin, and sodium hydrogen sulfide (NaHS, a hydrogen sulfide donor), all attenuated the increase in oxidative stress caused by methylglyoxal and high glucose in cultured cells. ACS14 prevented the increase in NOX4 expression caused by incubating the cultured VSMCs with MG (30 µM). ACS14, aspirin and NaHS attenuated the increase in iNOS expression caused by high glucose (25 mM). In conclusion, ACS14 has the novel ability to attenuate an increase in methylglyoxal levels which in turn can reduce oxidative stress, decrease the formation of advanced glycation end products and prevent many of the known deleterious effects

  15. Increased oxidative stress and cytotoxicity by hydrogen sulfide in HepG2 cells overexpressing cytochrome P450 2E1.

    PubMed

    Caro, Andres A; Thompson, Sarah; Tackett, Jonathan

    2011-12-01

    The main objectives of this work were to evaluate the effects of hydrogen sulfide on oxidative stress and cytotoxicity parameters in HepG2 cells and to assess the extent to which cytochrome P450 2E1 (CYP2E1) activity modulates the effects of hydrogen sulfide on oxidative stress and cytotoxicity. Sodium hydrosulfide (NaHS) caused time- and concentration-dependent cytotoxicity in both non-P450-expressing HepG2 cells (C34 cells) and CYP2E1-overexpressing HepG2 cells (E47 cells); however, NaHS-dependent cytotoxicity was higher in E47 than C34 cells. Cytotoxicity by NaHS in C34 and E47 cells was mainly necrotic in nature and associated with an early decrease in mitochondrial membrane potential. NaHS caused increased oxidation of lipophilic (C11-BODIPY(581/591)) and hydrophilic (DCFH-DA) probes only in E47 cells, at a time point prior to overt cytotoxicity. Trolox, an amphipathic antioxidant, partially inhibited both the cytotoxicity and the increased oxidative stress detected in E47 cells exposed to NaHS. Cell-permeable iron chelators and CYP2E1 inhibitors significantly inhibited the oxidation of C11-BODIPY(581/591) in E47 cells in the presence of NaHS. NaHS produced lipid peroxidation and cytotoxicity in E47 cells supplemented with a representative polyunsaturated fatty acid (docosahexaenoic acid) but not in C34 cells; these effects were inhibited by α-tocopherol, a lipophilic antioxidant. These data suggest that CYP2E1 enhances H(2)S-dependent cytotoxicity in HepG2 cells through the generation of iron-dependent oxidative stress and lipid peroxidation.

  16. Increased oxidative stress and cytotoxicity by hydrogen sulfide in HepG2 cells overexpressing cytochrome P450 2E1

    PubMed Central

    Caro, Andres A.; Thompson, Sarah; Tackett, Jonathan

    2013-01-01

    The main objectives of this work were to evaluate the effects of hydrogen sulfide on oxidative stress and cytotoxicity parameters in HepG2 cells and to assess the extent to which cytochrome P450 2E1 (CYP2E1) activity modulates the effects of hydrogen sulfide on oxidative stress and cytotoxicity. Sodium hydrosulfide (NaHS) caused time- and concentration-dependent cytotoxicity in both non-P450-expressing HepG2 cells (C34 cells) and CYP2E1-overexpressing HepG2 cells (E47 cells); however, NaHS-dependent cytotoxicity was higher in E47 than C34 cells. Cytotoxicity by NaHS in C34 and E47 cells was mainly necrotic in nature and associated with an early decrease in mitochondrial membrane potential. NaHS caused increased oxidation of lipophilic (C11-BODIPY581/591) and hydrophilic (DCFH-DA) probes only in E47 cells, at a time point prior to overt cytotoxicity. Trolox, an amphipathic antioxidant, partially inhibited both the cytotoxicity and the increased oxidative stress detected in E47 cells exposed to NaHS. Cell-permeable iron chelators and CYP2E1 inhibitors significantly inhibited the oxidation of C11-BODIPY581/591 in E47 cells in the presence of NaHS. NaHS produced lipid peroxidation and cytotoxicity in E47 cells supplemented with a representative polyunsaturated fatty acid (docosahexaenoic acid) but not in C34 cells; these effects were inhibited by α-tocopherol, a lipophilic antioxidant. These data suggest that CYP2E1 enhances H2S-dependent cytotoxicity in HepG2 cells through the generation of iron-dependent oxidative stress and lipid peroxidation. PMID:21850523

  17. Biogeochemistry of dissolved hydrogen sulfide species and carbonyl sulfide in the western North Atlantic Ocean

    NASA Astrophysics Data System (ADS)

    Radford-Knȩry, Joël; Cutter, Gregory A.

    1994-12-01

    The biogeochemistry of total sulfide dissolved in the open ocean is a poorly understood component of the global sulfur cycle. Here, the cycling of total sulfide was examined in the western North Atlantic Ocean using specially developed sampling and analytical methods. Total sulfide (particulate + dissolved sulfide) concentrations ranged from <2-550 pmol/L; concentrations were highest in the mixed layer and decreased with depth. Significant levels (up to 19 pmol/L) of free sulfide (uncomplexed sulfide) were determined in the top 50 m of the water column. Sources of total sulfide were examined. In particular, the rate of carbonyl sulfide (OCS) hydrolysis was redetermined under oceanographic conditions, and the depth distribution of OCS was examined. The patterns of near-surface enrichment (up to 150 pmol/L) and depletion at depth observed in OCS depth profiles suggest in situ production of OCS. To quantify the sources and sinks of total sulfide in the mixed layer of the Sargasso Sea, a budget was constructed. The rate of total sulfide production was 5.5 pmol L-1 h-1 (OCS hydrolysis + atmospheric input), and total sulfide removal rate was 115 pmol L -1 h-1 (oxidation + particulate sinking). The significant difference between the known sources and sinks indicates that other processes are important for the cycling of sulfide. Similarities in the depth distribution of total sulfide and chlorophyll a, and results from recent laboratory experiments argue strongly in favor of biological involvement in the production of total sulfide in the open ocean.

  18. Metabolism in the Uncultivated Giant Sulfide-Oxidizing Bacterium Thiomargarita Namibiensis Assayed Using a Redox-Sensitive Dye

    NASA Astrophysics Data System (ADS)

    Bailey, J.; Flood, B.; Ricci, E.

    2014-12-01

    The colorless sulfur bacteria are non-photosynthetic chemolithotrophs that live at interfaces between nitrate, or oxygen, and hydrogen sulfide. In sulfidic settings such as cold seeps and oxygen minimum zones, these bacteria are thought to constitute a critical node in the geochemical cycling of carbon, sulfur, nitrogen, and phosphorous. Many of these bacteria remain uncultivated and their metabolisms and physiologies are incompletely understood. Thiomargarita namibiensis is the largest of these sulfur bacteria, with individual cells reaching millimetric diameters. Despite the current inability to maintain a Thiomargarita culture in the lab, their large size allows for individual cells to be followed in time course experiments. Here we report on the novel use of a tetrazolium-based dye that measures the flux of NADH production from catabolic pathways via a colorimetric response. Staining with this dye allows for metabolism to be detected, even in the absence of observable cell division. When coupled to microscopy, this approach also allows for metabolism in Thiomargaritato be differentiated from that of epibionts or contaminants in xenic samples. The results of our tetrazolium dye-based assay suggests that Thiomargarita is the most metabolically versatile under anoxic conditions where it appears capable of using acetate, succinate, formate, thiosulfate, citrate, thiotaurine, hydrogen sulfide, and perhaps hydrogen as electron donors. Under hypoxic conditions, staining results suggest the utilization of acetate, citrate, and hydrogen sulfide. Cells incubated under oxic conditions showed the weakest tetrazolium staining response, and then only to hydrogen sulfide and questionably succinate. These initial results using a redox sensitive dye suggest that Thiomargarita is most metabolically versatile under anaerobic and hypoxic conditions. The results of this assay can be further evaluated using molecular approaches such as transcriptomics, as well as provide cultivation

  19. Synthesis, Characterization, and Catalytic Activity of Sulfided Silico-Alumino-Titanate (Si-Al-Ti) Mixed Oxides Xerogels Supported Ni-Mo Catalyst

    SciTech Connect

    Al-Adwani, H.A.; Anthony, R.G.; Gardner, T.J.; Thammachote, N.

    1999-02-24

    Layered semicrystalline silico-alumino-titanate (Si-Al-Ti) mixed oxides were synthesized by a modified sol-gel method with hydrothermal synthesis temperatures less than 200 C and autogenic pressure. The solid products are semicrystalline materials with a surface area of 136-367 m{sup 2}/g and a monomodal pore size distribution with an average pore diameter of 3.6-4.7 nrn. The catalytic activity for pyrene hydrogenation in a batch reactor at 300 C and 500 psig was determined for sulfided Ni-Mo supported on the Si-Al-Ti mixed oxide. The activity was a function of the support composition the heat treatment before and after loading the active metals, the addition of organic templates, and different methods of metal loading. The most active sulfided Ni-Mo/Si-Al-Ti catalyst has an activity in the same range as the commercial catalyst, Shell 324, but the metal loading is 37% less than the commercial catalyst.

  20. Synthesis, characterization, and catalytic activity of sulfided silico-alumino-titanate (Si-Al-Ti) mixed oxides xerogels supported Ni-Mo catalyst

    SciTech Connect

    Al-Adwani, H.A.; Thammachote, N.; Anthony, R.G.; Gardner, T.J.

    1998-07-25

    Layered semicrystalline silico-alumino-titanate (Si-Al-Ti) mixed oxides were synthesized by a modified sol-gel method with hydrothermal synthesis temperatures less than 200 C and autogenic pressure. The solid products are semicrystalline materials with a surface area of 136--367 m{sup 2}/g and a monomodal pore size distribution with an average pore diameter of 36--47 {angstrom}. The catalytic activity for pyrene hydrogenation in a batch reactor at 300 C and 500 psig was determined for sulfided Ni-Mo supported on the Si-Al-Ti mixed oxide. The activity was a function of the support composition, the heat treatment before and after loading the active metals, the addition of organic templates, and different methods of metal loading. The most active sulfided Ni-Mo/Si-Al-Ri catalyst has an activity in the same range as the commercial catalyst, Shell 324, but the metal loading is 37% less than the commercial catalyst.

  1. Hydrogen sulfide in signaling pathways.

    PubMed

    Olas, Beata

    2015-01-15

    For a long time hydrogen sulfide (H₂S) was considered a toxic compound, but recently H₂S (at low concentrations) has been found to play an important function in physiological processes. Hydrogen sulfide, like other well-known compounds - nitric oxide (NO) and carbon monoxide (CO) is a gaseous intracellular signal transducer. It regulates the cell cycle, apoptosis and the oxidative stress. Moreover, its functions include neuromodulation, regulation of cardiovascular system and inflammation. In this review, I focus on the metabolism of hydrogen sulfide (including enzymatic pathways of H₂S synthesis from l- and d-cysteine) and its signaling pathways in the cardiovascular system and the nervous system. I also describe how hydrogen sulfide may be used as therapeutic agent, i.e. in the cardiovascular diseases.

  2. Selective Irreversible Inhibition of Neuronal and Inducible Nitric-oxide Synthase in the Combined Presence of Hydrogen Sulfide and Nitric Oxide*

    PubMed Central

    Heine, Christian L.; Schmidt, Renate; Geckl, Kerstin; Schrammel, Astrid; Gesslbauer, Bernd; Schmidt, Kurt; Mayer, Bernd; Gorren, Antonius C. F.

    2015-01-01

    Citrulline formation by both human neuronal nitric-oxide synthase (nNOS) and mouse macrophage inducible NOS was inhibited by the hydrogen sulfide (H2S) donor Na2S with IC50 values of ∼2.4·10−5 and ∼7.9·10−5 m, respectively, whereas human endothelial NOS was hardly affected at all. Inhibition of nNOS was not affected by the concentrations of l-arginine (Arg), NADPH, FAD, FMN, tetrahydrobiopterin (BH4), and calmodulin, indicating that H2S does not interfere with substrate or cofactor binding. The IC50 decreased to ∼1.5·10−5 m at pH 6.0 and increased to ∼8.3·10−5 m at pH 8.0. Preincubation of concentrated nNOS with H2S under turnover conditions decreased activity after dilution by ∼70%, suggesting irreversible inhibition. However, when calmodulin was omitted during preincubation, activity was not affected, suggesting that irreversible inhibition requires both H2S and NO. Likewise, NADPH oxidation was inhibited with an IC50 of ∼1.9·10−5 m in the presence of Arg and BH4 but exhibited much higher IC50 values (∼1.0–6.1·10−4 m) when Arg and/or BH4 was omitted. Moreover, the relatively weak inhibition of nNOS by Na2S in the absence of Arg and/or BH4 was markedly potentiated by the NO donor 1-(hydroxy-NNO-azoxy)-l-proline, disodium salt (IC50 ∼ 1.3–2.0·10−5 m). These results suggest that nNOS and inducible NOS but not endothelial NOS are irreversibly inhibited by H2S/NO at modest concentrations of H2S in a reaction that may allow feedback inhibition of NO production under conditions of excessive NO/H2S formation. PMID:26296888

  3. Leaching of zinc sulfide by Thiobacillus ferrooxidans: Bacterial oxidation of the sulfur product layer increases the rate of zinc sulfide dissolution at high concentrations of ferrous ions

    SciTech Connect

    Fowler, T.A.; Crundwell, F.K.

    1999-12-01

    This paper reports the results of leaching experiments conducted with and without Thiobacillus ferroxidans at the same conditions in solution. The extent of leaching of ZnS with Bacteria is significantly higher than that without bacteria at high concentrations of ferrous ions. A porous layer of elemental sulfur is present on the surfaces of the chemically leached particles, which no sulfur is present on the surfaces of the bacterially leached particles. The analysis of the data using the shrinking-core model shows that the chemical leaching of ZnS is limited by the diffusion of ferrous ions through the sulfur product layer at high concentrations of ferrous ions. The analysis of the data shows that diffusion through the product layer does not limit the rate of dissolution when bacteria are present. This suggests that the action of T.ferroxidans in oxidizing the sulfur formed on the particle surface is to remove the barrier to diffusion by ferrous ions.

  4. Leaching of Zinc Sulfide by Thiobacillus ferrooxidans: Bacterial Oxidation of the Sulfur Product Layer Increases the Rate of Zinc Sulfide Dissolution at High Concentrations of Ferrous Ions

    PubMed Central

    Fowler, T. A.; Crundwell, F. K.

    1999-01-01

    This paper reports the results of leaching experiments conducted with and without Thiobacillus ferrooxidans at the same conditions in solution. The extent of leaching of ZnS with bacteria is significantly higher than that without bacteria at high concentrations of ferrous ions. A porous layer of elemental sulfur is present on the surfaces of the chemically leached particles, while no sulfur is present on the surfaces of the bacterially leached particles. The analysis of the data using the shrinking-core model shows that the chemical leaching of ZnS is limited by the diffusion of ferrous ions through the sulfur product layer at high concentrations of ferrous ions. The analysis of the data shows that diffusion through the product layer does not limit the rate of dissolution when bacteria are present. This suggests that the action of T. ferrooxidans in oxidizing the sulfur formed on the particle surface is to remove the barrier to diffusion by ferrous ions. PMID:10583978

  5. Synthesis, physicochemical analysis of two new hemilabile ether-phosphine ligands and their first stable bis-ether-phosphine/cobalt(II) tetrahedral complexes

    NASA Astrophysics Data System (ADS)

    Warad, Ismail; Barakat, Assem

    2017-04-01

    New tridentate ether-phosphine {P, 2O} and ether-phosphine oxide {OP, 2O} ligands with P and O donor-atoms have been synthesized starting from ClCH2CH(OCH3)2. The oxidation process of Ph2PCH2CH(OCH3)2 to its oxide derivative Ph2P(dbnd O)CH2CH(OCH3)2 was monitored by 31P NMR for the first time. The desired ligands and their Co(II) complexes structures were deduced from IR, EA, MS, NMR, UV-Vis., TG/DTG and XRD physical measurements. The tridentate chelating coordination behavior of the ether-phosphine wasn't detected leading only to the mono-dentate coordination mode through the phosphorous atoms to set up a X2Co[η1-Ph2PCH2CH(OCH3)2]2 as final isomer formula (X = Cl or Br). The Cl2Co[η1-Ph2PCH2CH(OCH3)2]2 isomer belongs to complex 1 was supported by single crystal measurement. Polar/non-polar intermolecular short contacts were detected by XRD and Hirshfeld surface theoretical analysis.

  6. Thiazoyl phosphines. Design, reactivity, and complexation.

    PubMed

    Zablocka, Maria; Oshovsky, Gennady; Duhayon, Carine; Ladeira, Sonia; Caminade, Anne-Marie; Mignani, Serge; Majoral, Jean-Pierre

    2016-06-21

    In spite of the numerous possible applications of thiazoles as ligands for catalysis and as active molecules in medicinal chemistry, only a few studies have dealt with their versatile chemistry. Several selective modifications of the structure of these derivatives and mainly of thiazoyl phosphines are detailed, thus illustrating the great possibilities to tailor at will their structures and therefore their properties. The formation of Ru and Au complexes is reported. Six of these new thiazoyl phosphines were characterized by X-ray crystallography as well as two of their gold complexes.

  7. Nonaqueous System of Iron-Based Ionic Liquid and DMF for the Oxidation of Hydrogen Sulfide and Regeneration by Electrolysis.

    PubMed

    Guo, Zhihui; Zhang, Tingting; Liu, Tiantian; Du, Jun; Jia, Bing; Gao, Shujing; Yu, Jiang

    2015-05-05

    To improve the hydrogen sulfide removal efficiency with the application of an iron-based imidazolium chloride ionic liquid (Fe(III)-IL) as desulfurizer, Fe(II) and N,N-dimethylformamide (DMF) are introduced to Fe(III)-IL to construct a new nonaqueous desulfurization system (Fe(III/II)-IL/DMF). Following desulfurization, the system can be regenerated using the controlled-potential electrolysis method. The addition of Fe(II) in Fe(III)-IL is beneficial for the hydrogen sulfide removal and the electrochemical regeneration of the desulfurizer. The addition of DMF in Fe(III/II)-IL does not change the structure of Fe(III/II)-IL but clearly decreases the acidity, increases the electrolytic current, and decreases the stability of the Fe-Cl bond in Fe(III/II)-IL. Fe(III/II)-IL/DMF can remove hydrogen sulfide and can be regenerated through an electrochemical method more efficiently than can Fe(III/II)-IL. After six cycles, the desulfurization efficiency remains higher than 98%, and the average conversion rate of Fe(II) is essentially unchanged. No sulfur peroxidation occurs, and the system remains stable. Therefore, this new nonaqueous system has considerable potential for removing H2S in pollution control applications.

  8. Carbonyl sulfide

    Integrated Risk Information System (IRIS)

    Carbonyl sulfide ; CASRN 463 - 58 - 1 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic

  9. Selenium sulfide

    Integrated Risk Information System (IRIS)

    Selenium sulfide ; CASRN 7446 - 34 - 6 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic

  10. Hydrogen sulfide

    Integrated Risk Information System (IRIS)

    EPA / 635 / R - 03 / 005 www.epa.gov / iris TOXICOLOGICAL REVIEW OF HYDROGEN SULFIDE ( CAS No . 7783 - 06 - 4 ) In Support of Summary Information on the Integrated Risk Information System ( IRIS ) June 2003 U.S . Environmental Protection Agency Washington , DC DISCLAIMER This document has been revie

  11. Exploring the main function of reduced graphene oxide nano-flakes in a nickel cobalt sulfide counter electrode for dye-sensitized solar cell

    NASA Astrophysics Data System (ADS)

    Lu, Man-Ning; Lin, Jeng-Yu; Wei, Tzu-Chien

    2016-11-01

    Addition of carbonaceous materials into transition metal sulfide counter electrode (CE) of a dye-sensitized solar cell (DSSC) is a common method to improve the performance of the CE and consequent photovoltaic performance. This improvement is almost without exception attributed to the improvement of overall conductivity after the carbonaceous material addition; however, the root function of these carbonaceous materials in promoting the solar cell efficiency is seldom discussed. In this study, highly crystallized nickel cobalt sulfide (NCS) micro-particles were mixed with a small portion of home-made reduced graphene oxide (rGO) nano-flakes. This NCS/rGO hybrid is subjected to extensive characterizations including X-ray diffraction, Raman spectroscopy, field emission scanning microscopy and electrochemical impedance spectroscopy. It is found that the rGO acts bi-functionally including a co-catalyst in accelerating the tri-iodide reduction for the main NCS catalysts, conductivity promotor to decrease the series resistance of the CE. Proved by electrochemical impedance spectroscopy, it is confirmed that the decrease in series resistance is less insignificant than that in charge transfer resistance, indicating rGO functions more profoundly as a co-catalyst than as a conductivity promotor. Moreover, an argument to highlight the requirement of a CE in a dim-light optimized DSSC is also proposed.

  12. Hydrophosphorylation of alkynes with phosphinous acids

    SciTech Connect

    Nifant'ev, E.E.; Solovetskaya, L.A.; Magdeeva, R.K.

    1986-03-20

    A feature of the homolytic hydrophosphorylation of alkynes, as compared with alkenes, is more ready addition of phosphinous acids in presence of benzoyl peroxides. A difference was found in the hydrophosphorylation of acetylenes with dibutylphosphinous acid and with diarylphosphinous acids: the latter tend to form diaddition products.

  13. Elevated Inducible Nitric Oxide Levels and Decreased Hydrogen Sulfide Levels Can Predict the Risk of Coronary Artery Ectasia in Kawasaki Disease.

    PubMed

    Song, Ruixia; Liu, Guiying; Li, Xiaohui; Xu, Wenya; Liu, Jia; Jin, Hongfang

    2016-02-01

    Kawasaki disease (KD) is a vasculitis disease in children that is associated with coronary artery ectasia (CAE). We investigated whether inducible nitric oxide synthase (i-NOS) and hydrogen sulfide (H2S) could be used to predict CAE secondary to KD. We enrolled 65 children with KD (35 cases with CAE and 30 cases without CAE), 33 healthy children, and 32 children with fever but without vasculitis disease (febrile group). We measured plasma nitric oxide (NO), total nitric oxide synthase (Total-NOS), i-NOS, constructive nitric oxide synthase (c-NOS) levels, and H2S content in all patients. Plasma NO, Total-NOS, i-NOS, and H2S were higher in KD children than in healthy and febrile children (P < 0.05). The i-NOS level was higher in KD children with CAE compared to those without CAE, while the H2S was lower (both P < 0.05). Using a combination of i-NOS (higher than 10 U/mL) and H2S (lower than 3.31 μmol/L) to predict CAE had 80 % sensitivity and 81 % specificity (P < 0.05). Elevated plasma i-NOS and decreased plasma H2S levels in the acute phase of KD have good predictive value for CAE and may be used to guide appropriate clinical treatment and prevent future cardiovascular complications.

  14. Multicomponent reactions of phosphines, diynedioates, and aryl aldehydes generated furans appending reactive phosphorus ylides through cumulated trienoates as key intermediates: a phosphine α-addition-δ-evolvement of an anion pathway.

    PubMed

    Deng, Jie-Cheng; Chuang, Shih-Ching

    2014-11-07

    Multicomponent reactions of phosphines, diynedioates, and aryl aldehydes have been demonstrated, providing trisubstituted furans appending reactive phosphorus ylides, through cumulated trienoates as key intermediates. The proposed trienoate intermediates, 1,5-dipolar species formed via nucleophilic α-attack of phosphines toward diynedioates (α-addition-δ-evolvement of an anion, abbreviated αAδE), undergo addition to aryl aldehydes followed by 5-endo-dig cyclization, proton transfer, and resonance to give trisubstituted furans. Furthermore, the phosphorus ylides are oxidized to α-keto ester furans and utilized as Wittig reagents.

  15. Synthesis and anti-cancer potential of the positional isomers of NOSH-aspirin (NBS-1120) a dual nitric oxide and hydrogen sulfide releasing hybrid.

    PubMed

    Vannini, Federica; MacKessack-Leitch, Andrew C; Eschbach, Erin K; Chattopadhyay, Mitali; Kodela, Ravinder; Kashfi, Khosrow

    2015-10-15

    We recently reported the synthesis of NOSH-aspirin, a novel hybrid compound capable of releasing both nitric oxide (NO) and hydrogen sulfide (H2S). In NOSH-aspirin, the two moieties that release NO and H2S are covalently linked at the 1, 2 positions of acetyl salicylic acid, i.e., ortho-NOSH-aspirin. Here we report on the synthesis of meta- and para-NOSH-aspirins. We also made a head-to-head evaluation of the effects of these three positional isomers of NOSH-aspirin on colon cancer cell kinetics and induction of reactive oxygen species, which in recent years has emerged as a key event in causing cancer cell regression. Electron donating/withdrawing groups incorporated about the benzoate moiety significantly affected the potency of these compounds with respect to colon cancer cell growth inhibition.

  16. Polysulfides (H2Sn) produced from the interaction of hydrogen sulfide (H2S) and nitric oxide (NO) activate TRPA1 channels

    PubMed Central

    Miyamoto, Ryo; Koike, Shin; Takano, Yoko; Shibuya, Norihiro; Kimura, Yuka; Hanaoka, Kenjiro; Urano, Yasuteru; Ogasawara, Yuki; Kimura, Hideo

    2017-01-01

    Hydrogen sulfide (H2S) exerts synergistic effects with another gaseous signaling molecule nitric oxide (NO) on ion channels and vasculature. However, the mechanism of the synergy is not well understood. Here, we show that the interaction between H2S and NO generates polysulfides (H2Sn), which activate transient receptor potential ankyrin 1 (TRPA1) channels. High performance liquid chromatography with tandem mass spectrometry analysis, along with the imaging of intracellular Ca2+ and H2Sn, showed that H2Sn and their effects were abolished by cyanolysis and by reducing substances such as dithiothreitol (DTT), cysteine, and glutathione (GSH). However, the effects of nitroxyl or nitrosopersulfide, other potential products of H2S and NO interaction, are not affected by cyanolysis or reducing substances. This study demonstrates that H2Sn are products of synergy between H2S and NO and provides a new insight into the signaling mechanisms. PMID:28378773

  17. Geothermal hydrogen sulfide removal

    SciTech Connect

    Urban, P.

    1981-04-01

    UOP Sulfox technology successfully removed 500 ppM hydrogen sulfide from simulated mixed phase geothermal waters. The Sulfox process involves air oxidation of hydrogen sulfide using a fixed catalyst bed. The catalyst activity remained stable throughout the life of the program. The product stream composition was selected by controlling pH; low pH favored elemental sulfur, while high pH favored water soluble sulfate and thiosulfate. Operation with liquid water present assured full catalytic activity. Dissolved salts reduced catalyst activity somewhat. Application of Sulfox technology to geothermal waters resulted in a straightforward process. There were no requirements for auxiliary processes such as a chemical plant. Application of the process to various types of geothermal waters is discussed and plans for a field test pilot plant and a schedule for commercialization are outlined.

  18. Sulfur Dioxide Enhances Endogenous Hydrogen Sulfide Accumulation and Alleviates Oxidative Stress Induced by Aluminum Stress in Germinating Wheat Seeds

    PubMed Central

    Zhu, Dong-Bo; Hu, Kang-Di; Guo, Xi-Kai; Liu, Yong; Hu, Lan-Ying; Li, Yan-Hong; Wang, Song-Hua; Zhang, Hua

    2015-01-01

    Aluminum ions are especially toxic to plants in acidic soils. Here we present evidences that SO2 protects germinating wheat grains against aluminum stress. SO2 donor (NaHSO3/Na2SO3) pretreatment at 1.2 mM reduced the accumulation of superoxide anion, hydrogen peroxide, and malondialdehyde, enhanced the activities of guaiacol peroxidase, catalase, and ascorbate peroxidase, and decreased the activity of lipoxygenase in germinating wheat grains exposed to Al stress. We also observed higher accumulation of hydrogen sulfide (H2S) in SO2-pretreated grain, suggesting the tight relation between sulfite and sulfide. Wheat grains geminated in water for 36 h were pretreated with or without 1 mM SO2 donor for 12 h prior to exposure to Al stress for 48 h and the ameliorating effects of SO2 on wheat radicles were studied. SO2 donor pretreatment reduced the content of reactive oxygen species, protected membrane integrity, and reduced Al accumulation in wheat radicles. Gene expression analysis showed that SO2 donor pretreatment decreased the expression of Al-responsive genes TaWali1, TaWali2, TaWali3, TaWali5, TaWali6, and TaALMT1 in radicles exposed to Al stress. These results suggested that SO2 could increase endogenous H2S accumulation and the antioxidant capability and decrease endogenous Al content in wheat grains to alleviate Al stress. PMID:26078810

  19. Oxygen atom transfer reactions from dioxygen to phosphines via a bridging sulfur dioxide in a trinuclear cluster complex of rhenium, [(Ph(3)P)(2)N][Re(3)(mu(3)-S)(mu-S)(2)(mu-SO(2))Cl(6)(PMe(2)Ph)(3)].

    PubMed

    Saito, Taro; Sunaga, Tomoaki; Sakai, Nobuaki; Nakamura, Yoichi; Yamamoto, Saori; Iriuchijima, Daisuke; Yoza, Kenji

    2005-06-13

    A trinuclear rhenium sulfide cluster complex, [(Ph(3)P)(2)N][Re(3)(mu(3)-S)(mu-S)(3)Cl(6)(PMe(2)Ph)(3)], synthesized from Re(3)S(7)Cl(7), dimethylphenylphosphine, and [(Ph(3)P)(2)N]Cl is readily converted to a bridging SO(2) complex, [(Ph(3)P)(2)N][Re(3)(mu(3)-S)(mu-S)(2)(mu-SO(2))Cl(6)(PMe(2)Ph)(3)], by reaction with O(2). The oxygen atoms on the SO(2) ligand react with phosphines or phosphites to form phosphine oxides or phosphates, and the original cluster complex is recovered. The reaction course has been monitored by (31)P NMR as well as by UV-vis spectroscopy. The catalytic oxygenation of PMePh(2) in the presence of the SO(2) complex shows that turnovers are 8 per hour at 23 degrees C in CDCl(3). The X-ray structures of the cluster complexes are described.

  20. The inhibition of mitochondrial cytochrome oxidase by the gases carbon monoxide, nitric oxide, hydrogen cyanide and hydrogen sulfide: chemical mechanism and physiological significance.

    PubMed

    Cooper, Chris E; Brown, Guy C

    2008-10-01

    The four gases, nitric oxide (NO), carbon monoxide (CO), hydrogen sulfide (H(2)S) and hydrogen cyanide (HCN) all readily inhibit oxygen consumption by mitochondrial cytochrome oxidase. This inhibition is responsible for much of their toxicity when they are applied externally to the body. However, recently these gases have all been implicated, to greater or lesser extents, in normal cellular signalling events. In this review we analyse the chemistry of this inhibition, comparing and contrasting mechanism and discussing physiological consequences. The inhibition by NO and CO is dependent on oxygen concentration, but that of HCN and H(2)S is not. NO and H(2)S are readily metabolised by oxidative processes within cytochrome oxidase. In these cases the enzyme may act as a physiological detoxifier of these gases. CO oxidation is much slower and unlikely to be as physiologically important. The evidence for normal physiological levels of these gases interacting with cytochrome oxidase is equivocal, in part because there is little robust data about their steady state concentrations. A reasonable case can be made for NO, and perhaps CO and H(2)S, inhibiting cytochrome oxidase in vivo, but endogenous levels of HCN seem unlikely to be high enough.

  1. Effect of Nitrate on Biogenic Sulfide Production

    PubMed Central

    Jenneman, Gary E.; McInerney, M. J.; Knapp, Roy M.

    1986-01-01

    The addition of 59 mM nitrate inhibited biogenic sulfide production in dilute sewage sludge (10% [vol/vol]) amended with 20 mM sulfate and either acetate, glucose, or hydrogen as electron donors. Similar results were found when pond sediment or oil field brines served as the inoculum. Sulfide production was inhibited for periods of at least 6 months and was accompanied by the oxidation of resazurin from its colorless reduced state to its pink oxidized state. Lower amounts of nitrate (6 or 20 mM) and increased amounts of sewage sludge resulted in only transient inhibition of sulfide production. The addition of 156 mM sulfate to bottles with 59 mM nitrate and 10% (vol/vol) sewage sludge or pond sediment resulted in sulfide production. Nitrate, nitrite, and nitrous oxide were detected during periods where sulfide production was inhibited, whereas nitrate, nitrite, and nitrous oxide were below detectable levels at the time sulfide production began. The oxidation of resazurin was attributed to an increase in nitrous oxide which persisted in concentration of about 1.0 mM for up to 5 months. The numbers of sulfate-reducing organisms decreased from 106 CFU ml−1 sludge to less than detectable levels after prolonged incubation of oxidized bottles. The addition of 10 mM glucose to oxidized bottles after 14.5 weeks of incubation resulted in rereduction of the resazurin and subsequent sulfide production. The prolonged inhibition of sulfide production was attributed to an increase in oxidation-reduction potential due to biogenic production of nitrous oxide, which appeared to have a cytotoxic effect on sulfate-reducing populations. PMID:16347078

  2. Disruption of iron homeostasis increases phosphine toxicity in Caenorhabditis elegans.

    PubMed

    Cha'on, Ubon; Valmas, Nicholas; Collins, Patrick J; Reilly, Paul E B; Hammock, Bruce D; Ebert, Paul R

    2007-03-01

    The aim of this study is to identify the biochemical mechanism of phosphine toxicity and resistance, using Caenorhabditis elegans as a model organism. To date, the precise mode of phosphine action is unclear. In this report, we demonstrate the following dose-dependent actions of phosphine, in vitro: (1) reduction of ferric iron (Fe3+) to ferrous iron (Fe2+), (2) release of iron from horse ferritin, (3) and the peroxidation of lipid as a result of iron release from ferritin. Using in situ hybridization, we show that the ferritin genes of C. elegans, both ferritin-1 and ferritin-2, are expressed along the digestive tract with greatest expression at the proximal and distal ends. Basal expression of the ferritin-2 gene, as determined by quantitative PCR, is approximately 80 times that of ferritin-1. However, transcript levels of ferritin-1 are induced at least 20-fold in response to phosphine, whereas there is no change in the level of ferritin-2. This resembles the reported pattern of ferritin gene regulation by iron, suggesting that phosphine toxicity may be related to an increase in the level of free iron. Indeed, iron overload increases phosphine toxicity in C. elegans at least threefold. Moreover, we demonstrate that suppression of ferritin-2 gene expression by RNAi, significantly increases sensitivity to phosphine. This study identifies similarities between phosphine toxicity and iron overload and demonstrates that phosphine can trigger iron release from storage proteins, increasing lipid peroxidation, leading to cell injury and/or cell death.

  3. Cationic ruthenium alkylidene catalysts bearing phosphine ligands.

    PubMed

    Endo, Koji; Grubbs, Robert H

    2016-02-28

    The discovery of highly active catalysts and the success of ionic liquid immobilized systems have accelerated attention to a new class of cationic metathesis catalysts. We herein report the facile syntheses of cationic ruthenium catalysts bearing bulky phosphine ligands. Simple ligand exchange using silver(i) salts of non-coordinating or weakly coordinating anions provided either PPh3 or chelating Ph2P(CH2)nPPh2 (n = 2 or 3) ligated cationic catalysts. The structures of these newly reported catalysts feature unique geometries caused by ligation of the bulky phosphine ligands. Their activities and selectivities in standard metathesis reactions were also investigated. These cationic ruthenium alkylidene catalysts reported here showed moderate activity and very similar stereoselectivity when compared to the second generation ruthenium dichloride catalyst in ring-closing metathesis, cross metathesis, and ring-opening metathesis polymerization assays.

  4. Transition metal sulfide loaded catalyst

    DOEpatents

    Maroni, V.A.; Iton, L.E.; Pasterczyk, J.W.; Winterer, M.; Krause, T.R.

    1994-04-26

    A zeolite-based catalyst is described for activation and conversion of methane. A zeolite support includes a transition metal (Mo, Cr or W) sulfide disposed within the micropores of the zeolite. The catalyst allows activation and conversion of methane to C[sub 2]+ hydrocarbons in a reducing atmosphere, thereby avoiding formation of oxides of carbon.

  5. Transition metal sulfide loaded catalyst

    DOEpatents

    Maroni, Victor A.; Iton, Lennox E.; Pasterczyk, James W.; Winterer, Markus; Krause, Theodore R.

    1994-01-01

    A zeolite based catalyst for activation and conversion of methane. A zeolite support includes a transition metal (Mo, Cr or W) sulfide disposed within the micropores of the zeolite. The catalyst allows activation and conversion of methane to C.sub.2 + hydrocarbons in a reducing atmosphere, thereby avoiding formation of oxides of carbon.

  6. The hydrogen sulfide releasing compounds ATB-346 and diallyl trisulfide attenuate streptozotocin-induced cognitive impairment, neuroinflammation, and oxidative stress in rats: involvement of asymmetric dimethylarginine.

    PubMed

    Mostafa, Dalia K; El Azhary, Nesrine M; Nasra, Rasha A

    2016-07-01

    Hydrogen sulfide (H2S) has attracted interest as a gaseous mediator involved in diverse processes in the nervous system, particularly with respect to learning and memory. However, its therapeutic potential in Alzheimer disease (AD) is not fully explored. Therefore, the effects of H2S-releasing compounds against AD-like behavioural and biochemical abnormalities were investigated. Memory deficit was induced by intracerberoventicular injection of streptozotocin (STZ, 3 mg·kg(-1)). Animals were randomly assigned into 5 groups (12 rats each): normal control, STZ treated, and 3 drug-treated groups receiving naproxen, H2S-releasing naproxen (ATB-346), and diallyl trisulfide in 20, 32, 40 mg·kg(-1)·day(-1), respectively. Memory function was assessed by passive avoidance and T-maze tasks. After 21 days, hippocampal IL-6, malondialdehyde, reduced glutathione (GSH), asymmetric dimethylarginine (ADMA), and acetylcholinestrase activity were determined. ATB-346 and diallyl trisulfide ameliorated behavioural performance and reduced malondialdehyde, ADMA, and acetylcholinestrase activity while increasing GSH. This study demonstrates the beneficial effects of H2S release in STZ-induced memory impairment by modulation of neuroinflammation, oxidative stress, and cholinergic function. It also delineates the implication of ADMA to the cognitive impairment induced by STZ. These findings draw the attention to H2S-releasing compounds as new candidates for treating neurodegenerative disorders that have prominent oxidative and inflammatory components such as AD.

  7. Facile room-temperature synthesis of carboxylated graphene oxide-copper sulfide nanocomposite with high photodegradation and disinfection activities under solar light irradiation

    NASA Astrophysics Data System (ADS)

    Yu, Shuyan; Liu, Jincheng; Zhu, Wenyu; Hu, Zhong-Ting; Lim, Teik-Thye; Yan, Xiaoli

    2015-11-01

    Carboxylic acid functionalized graphene oxide-copper (II) sulfide nanoparticle composite (GO-COOH-CuS) was prepared from carboxylated graphene oxide and copper precursor in dimethyl sulfoxide (DMSO) by a facile synthesis process at room temperature. The high-effective combination, the interaction between GO-COOH sheets and CuS nanoparticles, and the enhanced visible light absorption were confirmed by transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM), X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), thermo gravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflectance spectra (DRS) and Photoluminescence (PL) spectra. The as-synthesized GO-COOH-CuS nanocomposite exhibited excellent photocatalytic degradation performance of phenol and rhodamine B, high antibacterial activity toward E. coli and B. subtilis, and good recovery and reusability. The influence of CuS content, the synergistic reaction between CuS and GO-COOH, and the charge-transfer mechanism were systematically investigated. The facile and low-energy synthesis process combined with the excellent degradation and antibacterial performance signify that the GO-COOH-CuS has a great potential for water treatment application.

  8. Facile room-temperature synthesis of carboxylated graphene oxide-copper sulfide nanocomposite with high photodegradation and disinfection activities under solar light irradiation

    PubMed Central

    Yu, Shuyan; Liu, Jincheng; Zhu, Wenyu; Hu, Zhong-Ting; Lim, Teik-Thye; Yan, Xiaoli

    2015-01-01

    Carboxylic acid functionalized graphene oxide-copper (II) sulfide nanoparticle composite (GO-COOH-CuS) was prepared from carboxylated graphene oxide and copper precursor in dimethyl sulfoxide (DMSO) by a facile synthesis process at room temperature. The high-effective combination, the interaction between GO-COOH sheets and CuS nanoparticles, and the enhanced visible light absorption were confirmed by transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM), X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), thermo gravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflectance spectra (DRS) and Photoluminescence (PL) spectra. The as-synthesized GO-COOH-CuS nanocomposite exhibited excellent photocatalytic degradation performance of phenol and rhodamine B, high antibacterial activity toward E. coli and B. subtilis, and good recovery and reusability. The influence of CuS content, the synergistic reaction between CuS and GO-COOH, and the charge-transfer mechanism were systematically investigated. The facile and low-energy synthesis process combined with the excellent degradation and antibacterial performance signify that the GO-COOH-CuS has a great potential for water treatment application. PMID:26553709

  9. Horizon-specific oxidation of acid volatile sulfide (AVS) in relation to the toxicity of cadmium spiked into a freshwater sediment

    SciTech Connect

    Leonard, E.N.; Mattson, V.R.; Ankley, G.T.

    1994-12-31

    To evaluate the effects of oxidative processes on acid volatile sulfide concentrations in various horizons of whole sediment cores, in relation to the toxicity of a metal (cadmium), the authors used an artificial system to ``age`` Cd-spiked sediment samples under a constant flow of fresh Lake Superior water. Sediments from Pequaywan Lake, MN (ca. 12 umol AVS/g) were spiked so as to achieve (nominal) cadmium: AVS molar ratios of 0.02 (control), 0.2, 0.8, 1.2 and 3.0. At 0, 24 and 48 days post-spiking, sediment cores were removed from the aging system and tested for toxicity to the amphipod Hyalella azteca. At the same time, horizons from replicate sediment cores were prepared for analysis by freezing, and then cutting them into 10--20 mm increments. The sediment horizons were analyzed for AVS and simultaneously extracted cadmium concentrations, and pore water concentrations of cadmium. Relatively little oxidation of surficial AVS concentrations was observed, even at aging times up to 48 d. By 48 d, pore water concentrations of cadmium were slightly elevated at all spiking concentrations, but were increased greatly at cadmium:AVS ratios greater than one. Hyalella azteca mortality was generally predictable based on surficial cadmium:AVS ratios or pore water cadmium concentrations.

  10. Triphenyl Phosphine-Functionalized Chitosan Nanoparticles Enhanced Antitumor Efficiency Through Targeted Delivery of Doxorubicin to Mitochondria

    NASA Astrophysics Data System (ADS)

    Hou, Jiahui; Yu, Xiwei; Shen, Yaping; Shi, Yijie; Su, Chang; Zhao, Liang

    2017-02-01

    Mitochondria as an important organ in eukaryotic cells produced energy through oxidative phosphorylation and also played an important role in regulating the apoptotic signal transduction process. Importantly, mitochondria like nuclei also contained the functional DNA and were very sensitive to anticancer drugs which could effectively inhibit the synthesis of nucleic acid, especially the production of DNA. In this work, we designed novel triphenyl phosphine (TPP)-conjugated chitosan (CS) nanoparticles (NPs) for efficient drug delivery to cell mitochondria. The results showed that compared with free doxorubicin (Dox), Dox-loaded TPP-NPs were specifically distributed in mitochondria of tumor cells and interfered with the function of mitochondria, thus resulted in the higher cytotoxicity and induced the significant cell apoptosis effect. Taken together, triphenyl phosphine-conjugated chitosan nanoparticles may become a promising mitochondria-targeting nanocarrier candidate for enhancing antitumor effects.

  11. Triphenyl Phosphine-Functionalized Chitosan Nanoparticles Enhanced Antitumor Efficiency Through Targeted Delivery of Doxorubicin to Mitochondria.

    PubMed

    Hou, Jiahui; Yu, Xiwei; Shen, Yaping; Shi, Yijie; Su, Chang; Zhao, Liang

    2017-12-01

    Mitochondria as an important organ in eukaryotic cells produced energy through oxidative phosphorylation and also played an important role in regulating the apoptotic signal transduction process. Importantly, mitochondria like nuclei also contained the functional DNA and were very sensitive to anticancer drugs which could effectively inhibit the synthesis of nucleic acid, especially the production of DNA. In this work, we designed novel triphenyl phosphine (TPP)-conjugated chitosan (CS) nanoparticles (NPs) for efficient drug delivery to cell mitochondria. The results showed that compared with free doxorubicin (Dox), Dox-loaded TPP-NPs were specifically distributed in mitochondria of tumor cells and interfered with the function of mitochondria, thus resulted in the higher cytotoxicity and induced the significant cell apoptosis effect. Taken together, triphenyl phosphine-conjugated chitosan nanoparticles may become a promising mitochondria-targeting nanocarrier candidate for enhancing antitumor effects.

  12. Preparation of phosphines through C–P bond formation

    PubMed Central

    Wauters, Iris; Debrouwer, Wouter

    2014-01-01

    Summary Phosphines are an important class of ligands in the field of metal-catalysis. This has spurred the development of new routes toward functionalized phosphines. Some of the most important C–P bond formation strategies were reviewed and organized according to the hybridization of carbon in the newly formed C–P bond. PMID:24991257

  13. Searching for Practically Useful P-Chirogenic Phosphine Ligands.

    PubMed

    Imamoto, Tsuneo

    2016-12-01

    In this account, the design, synthesis, and application of P-chirogenic phosphine ligands that have been mainly carried out in our laboratory over the last three decades are described. Various enantiopure P-chirogenic phosphine ligands have been efficiently prepared by using phosphine boranes as intermediates. Conformationally rigid and electron-rich P-chirogenic phosphine ligands possessing C2 symmetry as well as a bulky alkyl group and a small group at the phosphorus atoms exhibit excellent enantioselectivities and catalytic efficiency in a variety of transition-metal-catalyzed asymmetric reactions. Enantiopure 2,3-bis(tert-butylmethylphosphino)quinoxaline (QuinoxP*) is an air-stable crystalline solid that shows superior enantioinduction ability in catalytic asymmetric syntheses. Mechanistic studies of Rh-catalyzed asymmetric hydrogenation using structurally simple P-chirogenic phosphine ligands, such as tBu-BisP*, are briefly described.

  14. Recent findings on sinks for sulfide in gravity sewer networks.

    PubMed

    Nielsen, A H; Hvitved-Jacobsen, T; Vollertsen, J

    2006-01-01

    Sulfide buildup in sewer networks is associated with several problems, including health impacts, corrosion of sewer structures and odor nuisance. In recent years, significant advances in the knowledge of the major processes governing sulfide buildup in sewer networks have been made. This paper summarizes this newly obtained knowledge and emphasizes important implications of the findings. Model simulations of the in-sewer processes important for the sulfur cycle showed that sulfide oxidation in the wetted biofilm is typically the most important sink for dissolved sulfide in gravity sewers. However, sulfide emission and thereby potential hydrogen sulfide buildup in the sewer atmosphere is of particular importance in sewers constructed with large diameter pipes, in sewers constructed with steep slopes and in sewers conveying low pH wastewater. Precipitation of metal sulfides is only important when the sulfide concentration in the wastewater is low; i.e. less than 1 g Sm(-3).

  15. Crystal and Magnetic Structures of the Oxide Sulfides CaCoSO and BaCoSO.

    PubMed

    Salter, Edward J T; Blandy, Jack N; Clarke, Simon J

    2016-02-15

    CaCoSO, synthesized from CaO, Co, and S at 900 °C, is isostructural with CaZnSO and CaFeSO. The structure is non-centrosymmetric by virtue of the arrangement of the vertex-sharing CoS3O tetrahedra which are linked by their sulfide vertices to form layers. The crystal structure adopts space group P63mc (No. 186), and the lattice parameters are a = 3.7524(9) Å and c = 11.138(3) Å at room temperature with two formula units in the unit cell. The compound is highly insulating, and powder neutron diffraction measurements reveal long-range antiferromagnetic order with a propagation vector k = (1/3, 1/3, 1/2). The magnetic scattering from a powder sample can be modeled starting from a 120° arrangement of Co(2+) spin vectors in the triangular planes and then applying a canting out of the planes which can be modeled in the magnetic space group C(c)c (space group 9.40 in the Belov, Neronova, and Smirnova (BNS) scheme) with Co(2+) moments of 2.72(5) μ(B). The antiferromagnetic structure of the recently reported compound BaCoSO, which has a very different crystal structure from CaCoSO, is also described, and this magnetic structure and the magnitude of the ordered moment (2.75(2) μ(B)) are found by experiment to be similar to those predicted computationally.

  16. Diallyl trisulfide protects against ethanol-induced oxidative stress and apoptosis via a hydrogen sulfide-mediated mechanism.

    PubMed

    Chen, Lian-Yun; Chen, Qin; Zhu, Xiao-Jing; Kong, De-Song; Wu, Li; Shao, Jiang-Juan; Zheng, Shi-Zhong

    2016-07-01

    Garlic is one natural source of organic sulfur containing compounds and has shown promise in the treatment of chronic liver disease. Dietary garlic consumption is inversely correlated with the progression of alcoholic fatty liver (AFL), although the exact underlying mechanisms are not clear. Our previous studies also have shown that diallyl trisulfide (DATS), the primary organosulfur compound from Allium sativum L, displayed anti-lipid deposition and antioxidant properties in AFL. The aim of the present study was to clarify the underlying mechanisms. In the present study, we used the intragastric infusion model of alcohol administration and human normal liver cell line LO2 cultured with suitable ethanol to mimic the pathological condition of AFL. We showed that accumulation of intracellular reactive oxygen species (ROS) was lowered significantly by the administration of DATS, but antioxidant capacity was increased by DATS. Additionally, DATS inhibited hepatocyte apoptosis via down-regulating Bax expression and up-regulating Bcl-2 expression, and attenuated alcohol-induced caspase-dependent apoptosis. More importantly, using iodoacetamide (IAM) to block hydrogen sulfide (H2S) production from DATS, we noted that IAM abolished all the above effects of DATS in ethanol-treated LO2 cells. Lastly, we found DATS could increase the expressions of cystathionine gamma-lyase (CSE) and cystathionine beta-synthase (CBS), the major H2S-producing enzymes. These results demonstrate that DATS protect against alcohol-induced fatty liver via a H2S-mediated mechanism. Therefore, targeting H2S may play a therapeutic role for AFL.

  17. Oxidation of hydrogen sulfide and methanethiol to thiosulfate by rat tissues: a specialized function of the colonic mucosa.

    PubMed

    Furne, J; Springfield, J; Koenig, T; DeMaster, E; Levitt, M D

    2001-07-15

    Colonic bacteria release large quantities of the highly toxic thiols hydrogen sulfide (H(2)S) and methanethiol (CH(3)SH). These gases rapidly permeate the colonic mucosa, and tissue damage would be expected if the mucosa could not detoxify these compounds rapidly. We previously showed that rat cecal mucosa metabolizes these thiols via conversion to thiosulfate. The purpose of the present study in rats was to determine if this conversion of thiols to thiosulfate is (a) a generalized function of many tissues, or (b) a specialized function of the colonic mucosa. The tissues studied were mucosa from the cecum, right colon, mid-colon, ileum, and stomach; liver; muscle; erythrocytes; and plasma. The metabolic rate was determined by incubating homogenates of the various tissues with H(2)(35)S and CH(3)(35)SH and measuring the rate of incorporation of (35)S into thiosulfate and sulfate. The detoxification activity of H(2)S (expressed as nmol/mg per min) that resulted in thiosulfate production was at least eight times greater for cecal and right colonic mucosa than for the non-colonic tissues. Thiosulfate production from CH(3)SH was at least five times more rapid for cecal and right colonic mucosa than for the non-colonic tissues. We conclude that colonic mucosa possesses a specialized detoxification system that allows this tissue to rapidly metabolize H(2)S and CH(3)SH to thiosulfate. Presumably, this highly developed system protects the colon from what otherwise might be injurious concentrations of H(2)S and CH(3)SH. Defects in this detoxification pathway possibly could play a role in the pathogenesis of various forms of colitis.

  18. Sulfide chemiluminescence detection

    DOEpatents

    Spurlin, S.R.; Yeung, E.S.

    1985-11-26

    A method is described for chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction and a specifically designed chemiluminescence detection cell for the reaction. 4 figs.

  19. Sulfide chemiluminescence detection

    DOEpatents

    Spurlin, Stanford R.; Yeung, Edward S.

    1985-01-01

    A method of chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction and a specifically designed chemiluminescence detection cell for the reaction.

  20. Applications of bacterial cellulose as precursor of carbon and composites with metal oxide, metal sulfide and metal nanoparticles: A review of recent advances.

    PubMed

    Foresti, M L; Vázquez, A; Boury, B

    2017-02-10

    This mini review is limited to very recent studies (last 5-10 years) on two major issues, concerning: the production and physical/chemical modification of bacterial cellulose (BC), and its transformation into carbon and integrated synthesis of metal oxides (TiO2, ZnO, Fe3O4, etc.), metal sulfide (ZnS, CdS, etc.) and metal nanoparticles (Au, Ag, Pt, Pd, etc.) within bacterial cellulose nanoribbons network. We believe that the crossover of these two domains could be of considerable interest in the view of improving the performance of materials prepared with bacterial cellulose. The diversity of these nanomaterials allows targeting of many very different properties/applications: electrochemical devices, catalysis and photocatalysis, sensors, etc. After an introduction to the most important chemical and physical characteristics of BC, production parameters, and its physical and chemical modifications, we review the use of BC as a precursor of inorganic materials like carbon and composites with metal or inorganic nanoparticles.

  1. The thermodynamics of arsenates, selenites, and sulfates in the oxidation zone of sulfide ores. XI. Solubility of synthetic chalcomenite analog and zinc selenite at 25°C

    NASA Astrophysics Data System (ADS)

    Charykova, M. V.; Krivovichev, V. G.; Ivanova, N. M.; Semenova, V. V.

    2015-12-01

    The aim of this study is the synthesis of CuSeO3·2H2O (chalcomenite analog), ZnSeO3·2H2O, and ZnSeO3·H2O and the investigation of their solubility in water. CuSeO3·2H2O has been synthesized from solutions of Cu nitrate and Na selenite, while Zn selenites were synthesized from solutions of Zn nitrate and Na selenite. The samples obtained have been examined with X-ray diffraction and infrared and Raman spectroscopy. The solubility has been determined using the isothermal saturation method in ampoules at 25°C. The solubility has been calculated using the Geochemist's Workbench (GMB 9.0) software package. Solubility products have been calculated for CuSeO3·2H2O (10-10.63), ZnSeO3·2H2O (10-8.35), and ZnSeO3·H2O (10-7.96). The database used comprises thermodynamic characteristics of 46 elements, 47 base particles, 48 redox pairs, 551 particles in solution, and 624 solid phases. The Eh-pH diagrams of the Zn-Se-H2O and Cu-Se-H2O systems were plotted for the average contents of these elements in underground water in oxidation zones of sulfide deposits.

  2. An ultrasensitive electrochemiluminescence sensor based on reduced graphene oxide-copper sulfide composite coupled with capillary electrophoresis for determination of amlodipine besylate in mice plasma.

    PubMed

    Wei, Yanfen; Wang, Hao; Sun, Shuangjiao; Tang, Lifu; Cao, Yupin; Deng, Biyang

    2016-12-15

    A new electrochemiluminescence (ECL) sensor based on reduced graphene oxide-copper sulfide (rGO-CuS) composite coupled with capillary electrophoresis (CE) was constructed for the ultrasensitive detection of amlodipine besylate (AML) for the first time. In this work, rGO-CuS composite was synthesized by one-pot hydrothermal method and used for electrode modification. The electrochemical and ECL behaviors of the sensor were investigated. More than 5-fold enhance in ECL intensity was observed after modified with rGO-CuS composite. The results can be ascribed to the presence of rGO-CuS composite on the electrode surface that facilitates the electron transfer rate between the electroactive center of Ru(bpy)3(2+) and the electrode. The ECL sensor was coupled with CE to improve the selectivity and the CE-ECL parameters that affect separation and detection were optimized. Under the optimum conditions, the linear ranges for AML was 0.008-5.0μg/mL with a detection limit of 2.8ng/mL (S/N=3). The method displayed the advantages of high sensitivity, good selectivity, wide linear range, low detection limit and fine reproducibility, and was used to analyze AML in mice plasma with a satisfactory result, which holds a great potential in the field of pharmaceutical analysis.

  3. Oxidative Cleavage of C=S and P=S Bonds at an Al(I) Center: Preparation of Terminally Bound Aluminum Sulfides.

    PubMed

    Chu, Terry; Vyboishchikov, Sergei F; Gabidullin, Bulat; Nikonov, Georgii I

    2016-10-10

    The treatment of cyclic thioureas with the aluminum(I) compound NacNacAl (1; NacNac=[ArNC(Me)CHC(Me)NAr](-) , Ar=2,6-Pr(i)2 C6 H3 ) resulted in oxidative cleavage of the C=S bond and the formation of 3 and 5, the first monomeric aluminum complexes with an Al=S double bond stabilized by N-heterocyclic carbenes. Compound 1 also reacted with triphenylphosphine sulfide in a similar manner, which resulted in cleavage of the P=S bond and production of the adduct [NacNacAl=S(S=PPh3 )] (8). The Al=S double bond in 3 can react with phenyl isothiocyanate to furnish the cycloaddition product 9 and zwitterion 10 as a result of coupling between the liberated carbene and PhN=C=S. All novel complexes were characterized by multinuclear NMR spectroscopy, and the structures of 5, 9, and 10 were confirmed by X-ray diffraction analysis. The nature of the Al=S bond in 5 was also probed by DFT calculations.

  4. Hydrogen sulfide potentiates interleukin-1{beta}-induced nitric oxide production via enhancement of extracellular signal-regulated kinase activation in rat vascular smooth muscle cells

    SciTech Connect

    Jeong, Sun-Oh; Pae, Hyun-Ock; Oh, Gi-Su; Jeong, Gil-Saeng; Lee, Bok-Soo; Lee, Seoul; Kim, Du Yong; Rhew, Hyun Yul; Lee, Kang-Min; Chung, Hun-Taeg . E-mail: htchung@wonkwang.ac.kr

    2006-07-07

    Hydrogen sulfide (H{sub 2}S) and nitric oxide (NO) are endogenously synthesized from L-cysteine and L-arginine, respectively. They might constitute a cooperative network to regulate their effects. In this study, we investigated whether H{sub 2}S could affect NO production in rat vascular smooth muscle cells (VSMCs) stimulated with interleukin-1{beta} (IL-1{beta}). Although H{sub 2}S by itself showed no effect on NO production, it augmented IL-{beta}-induced NO production and this effect was associated with increased expression of inducible NO synthase (iNOS) and activation of nuclear factor (NF)-{kappa}B. IL-1{beta} activated the extracellular signal-regulated kinase 1/2 (ERK1/2), and this activation was also enhanced by H{sub 2}S. Inhibition of ERK1/2 activation by the selective inhibitor U0126 inhibited IL-1{beta}-induced NF-{kappa}B activation, iNOS expression, and NO production either in the absence or presence of H{sub 2}S. Our findings suggest that H{sub 2}S enhances NO production and iNOS expression by potentiating IL-1{beta}-induced NF-{kappa}B activation through a mechanism involving ERK1/2 signaling cascade in rat VSMCs.

  5. Improved sodium-storage performance of stannous sulfide@reduced graphene oxide composite as high capacity anodes for sodium-ion batteries

    NASA Astrophysics Data System (ADS)

    Wu, Lin; Lu, Haiyan; Xiao, Lifen; Ai, Xinping; Yang, Hanxi; Cao, Yuliang

    2015-10-01

    Stannous sulfide@reduced graphene oxide (SnS@RGO) composite is successfully synthesized via a facile precipitation route. The structural and morphological characterizations reveal SnS@RGO composites are composed of SnS nanoparticles of the size 5-10 nm, which are uniformly anchored on the surface of RGO. The electrochemical measurements demonstrate the reversible capacity of the SnS@RGO composite - that includes contributions from the conversion reaction of SnS to Sn and NaxS and the alloying reaction of Sn to NaxSn. The SnS@RGO electrode exhibits a reversible capacity of 457 mAh g-1 at 20 mA g-1, superior cycling stability (94% capacity retention over 100 cycles at 100 mA g-1) and adequate rate performance. Compared to the neat SnS nanoparticles, the enhanced electrochemical performance of the SnS@RGO composite is primarily due to the incorporation of RGO as a highly conductive, flexible component as well as possessing a large available surface area, which provides desirable properties such as improved electronic contact between active materials, aggregation suppression of intermediate products, and alleviation of the volume change during sodiation and desodiation. Encouraging experimental results suggest that the SnS@RGO composite is a promising material to achieve a high-capacity and stable anode for NIBs.

  6. Process and apparatus for generating elemental sulfur and re-usable metal oxide from spent metal sulfide sorbents

    DOEpatents

    Ayala, Raul E.; Gal, Eli

    1995-01-01

    A process and apparatus for generating elemental sulfur and re-usable metal oxide from spent metal-sulfur compound. Spent metal-sulfur compound is regenerated to re-usable metal oxide by moving a bed of spent metal-sulfur compound progressively through a single regeneration vessel having a first and second regeneration stage and a third cooling and purging stage. The regeneration is carried out and elemental sulfur is generated in the first stage by introducing a first gas of sulfur dioxide which contains oxygen at a concentration less than the stoichiometric amount required for complete oxidation of the spent metal-sulfur compound. A second gas containing sulfur dioxide and excess oxygen at a concentration sufficient for complete oxidation of the partially spent metal-sulfur compound, is introduced into the second regeneration stage. Gaseous sulfur formed in the first regeneration stage is removed prior to introducing the second gas into the second regeneration stage. An oxygen-containing gas is introduced into the third cooling and purging stage. Except for the gaseous sulfur removed from the first stage, the combined gases derived from the regeneration stages which are generally rich in sulfur dioxide and lean in oxygen, are removed from the regenerator as an off-gas and recycled as the first and second gas into the regenerator. Oxygen concentration is controlled by adding air, oxygen-enriched air or pure oxygen to the recycled off-gas.

  7. Hydrogen Sulfide Regulates Salt Tolerance in Rice by Maintaining Na+/K+ Balance, Mineral Homeostasis and Oxidative Metabolism Under Excessive Salt Stress

    PubMed Central

    Mostofa, Mohammad G.; Saegusa, Daisuke; Fujita, Masayuki; Tran, Lam-Son Phan

    2015-01-01

    Being a salt sensitive crop, rice growth and development are frequently affected by soil salinity. Hydrogen sulfide (H2S) has been recently explored as an important priming agent regulating diverse physiological processes of plant growth and development. Despite its enormous prospects in plant systems, the role of H2S in plant stress tolerance is still elusive. Here, a combined pharmacological, physiological and biochemical approach was executed aiming to examine the possible mechanism of H2S in enhancement of rice salt stress tolerance. We showed that pretreating rice plants with H2S donor sodium bisulfide (NaHS) clearly improved, but application of H2S scavenger hypotaurine with NaHS decreased growth and biomass-related parameters under salt stress. NaHS-pretreated salt-stressed plants exhibited increased chlorophyll, carotenoid and soluble protein contents, as well as suppressed accumulation of reactive oxygen species (ROS), contributing to oxidative damage protection. The protective mechanism of H2S against oxidative stress was correlated with the elevated levels of ascorbic acid, glutathione, redox states, and the enhanced activities of ROS- and methylglyoxal-detoxifying enzymes. Notably, the ability to decrease the uptake of Na+ and the Na+/K+ ratio, as well as to balance mineral contents indicated a role of H2S in ion homeostasis under salt stress. Altogether, our results highlight that modulation of the level of endogenous H2S genetically or exogenously could be employed to attain better growth and development of rice, and perhaps other crops, under salt stress. Furthermore, our study reveals the importance of the implication of gasotransmitters like H2S for the management of salt stress, thus assisting rice plants to adapt to adverse environmental changes. PMID:26734015

  8. Compositions, ages, and diagenetic histories of the carbonate, sulfide, oxide, and phosphatic concretions at Gay Head, Massachusetts

    USGS Publications Warehouse

    Poppe, L.J.; Commeau, R.F.; O'Leary, D. W.

    1988-01-01

    The calcite/ankerite concretions were formed in a hot, seasonally arid, caliche-prone environment of early Raritan age; the pyrite, marcasite, and siderite concretions precipitated in sediments deposited in low-energy, marshy, estuarine environments of late Raritan age. The phosphate concretions formed in a middle to inner shelf environment. The goethite and lepidocrocite concretions are secondary oxidation or alteration products of the prexistent Cretaceous concretions that were excavated during the Pleistocene and incorporated into the glacial drift. -from Authors

  9. Gas cleaning and hydrogen sulfide removal for COREX coal gas by sorption enhanced catalytic oxidation over recyclable activated carbon desulfurizer.

    PubMed

    Sun, Tonghua; Shen, Yafei; Jia, Jinping

    2014-02-18

    This paper proposes a novel self-developed JTS-01 desulfurizer and JZC-80 alkaline adsorbent for H2S removal and gas cleaning of the COREX coal gas in small-scale and commercial desulfurizing devices. JTS-01 desulfurizer was loaded with metal oxide (i.e., ferric oxides) catalysts on the surface of activated carbons (AC), and the catalyst capacity was improved dramatically by means of ultrasonically assisted impregnation. Consequently, the sulfur saturation capacity and sulfur capacity breakthrough increased by 30.3% and 27.9%, respectively. The whole desulfurizing process combined selective adsorption with catalytic oxidation. Moreover, JZC-80 adsorbent can effectively remove impurities such as HCl, HF, HCN, and ash in the COREX coal gas, stabilizing the system pressure drop. The JTS-01 desulfurizer and JZC-80 adsorbent have been successfully applied for the COREX coal gas cleaning in the commercial plant at Baosteel, Shanghai. The sulfur capacity of JTS-01 desulfurizer can reach more than 50% in industrial applications. Compared with the conventional dry desulfurization process, the modified AC desulfurizers have more merit, especially in terms of the JTS-01 desulfurizer with higher sulfur capacity and low pressure drop. Thus, this sorption enhanced catalytic desulfurization has promising prospects for H2S removal and other gas cleaning.

  10. The Hydrolysis of Carbonyl Sulfide at Low Temperature: A Review

    PubMed Central

    Zhao, Shunzheng; Yi, Honghong; Tang, Xiaolong; Jiang, Shanxue; Gao, Fengyu; Zhang, Bowen; Zuo, Yanran; Wang, Zhixiang

    2013-01-01

    Catalytic hydrolysis technology of carbonyl sulfide (COS) at low temperature was reviewed, including the development of catalysts, reaction kinetics, and reaction mechanism of COS hydrolysis. It was indicated that the catalysts are mainly involved metal oxide and activated carbon. The active ingredients which can load on COS hydrolysis catalyst include alkali metal, alkaline earth metal, transition metal oxides, rare earth metal oxides, mixed metal oxides, and nanometal oxides. The catalytic hydrolysis of COS is a first-order reaction with respect to carbonyl sulfide, while the reaction order of water changes as the reaction conditions change. The controlling steps are also different because the reaction conditions such as concentration of carbonyl sulfide, reaction temperature, water-air ratio, and reaction atmosphere are different. The hydrolysis of carbonyl sulfide is base-catalyzed reaction, and the force of the base site has an important effect on the hydrolysis of carbonyl sulfide. PMID:23956697

  11. Marine diagenesis of hydrothermal sulfide

    SciTech Connect

    Moammar, M.O.

    1985-01-01

    An attempt is made to discuss the artificial and natural oxidation and hydrolysis of hydrothermal sulfide upon interaction with normal seawater. Synthetic and natural ferrosphalerite particles used in kinetic oxidation and hydrolysis studies in seawater develop dense, crystalline coatings consisting of ordered and ferrimagnetic delta-(Fe, Zn)OOH. Due to the formation of this reactive diffusion barrier, the release of Zn into solution decreases rapidly, and sulfide oxidation is reduced to a low rate determined by the diffusion of oxygen through the oxyhydroxide film. This also acts as an efficient solvent for ions such as Zn/sup 2 +/, Ca/sup 2 +/, and possibly Cd/sup 2 +/, which contribute to the stabilization of the delta-FeOOH structure. The oxidation of sulfide occurs in many seafloor spreading areas, such as 21/sup 0/N on the East Pacific Ridge. In these areas the old surface of the sulfide chimneys are found to be covered by an orange stain, and sediment near the base of nonactive vents is also found to consist of what has been referred to as amorphous iron oxide and hydroxide. This thesis also discusses the exceedingly low solubility of zinc in seawater, from delta-(Fe, Zn)OOH and the analogous phase (zinc-ferrihydroxide) and the zinc exchange minerals, 10-A manganate and montmorillonite. The concentrations of all four are of the same magnitude (16, 36.4, and 12 nM, respectively) as the zinc concentration in deep ocean water (approx. 10 nM), which suggests that manganates and montmorillonite with iron oxyhydroxides control zinc concentration in the deep ocean.

  12. Complete genome sequence of the moderately thermophilic mineral-sulfide-oxidizing firmicute Sulfobacillus acidophilus type strain (NALT)

    SciTech Connect

    Anderson, Iain; Chertkov, Olga; Chen, Amy; Saunders, Elizabeth H; Lapidus, Alla L.; Nolan, Matt; Lucas, Susan; Hammon, Nancy; Deshpande, Shweta; Cheng, Jan-Fang; Han, Cliff; Tapia, Roxanne; Goodwin, Lynne A.; Pitluck, Sam; Liolios, Konstantinos; Pagani, Ioanna; Ivanova, N; Mikhailova, Natalia; Pati, Amrita; Palaniappan, Krishna; Land, Miriam L; Pan, Chongle; Rohde, Manfred; Pukall, Rudiger; Goker, Markus; Detter, J. Chris; Woyke, Tanja; Bristow, James; Eisen, Jonathan; Markowitz, Victor; Hugenholtz, Philip; Kyrpides, Nikos C; Klenk, Hans-Peter; Mavromatis, K

    2012-01-01

    Sulfobacillus acidophilus Norris et al. 1996 is a member of the genus Sulfobacillus which comprises five species of the order Clostridiales. Sulfobacillus species are of interest for comparison to other sulfur and iron oxidizers and also have biomining applications. This is the first completed genome sequence of a type strain of the genus Sulfobacillus, and the second published genome of a member of the species S. acidophilus. The genome, which consists of one chromosome and one plasmid with a total size of 3,557,831 bp, harbors 3,626 protein-coding and 69 RNA genes, and is a part of the Genomic Encyclopedia of Bacteria and Archaea project.

  13. Monitoring sulfide-oxidizing biofilm activity on cement surfaces using non-invasive self-referencing microsensors.

    PubMed

    Cheng, Liqiu; House, Mitch W; Weiss, W Jason; Banks, M Katherine

    2016-02-01

    Microbially influenced corrosion (MIC) in concrete results in significant cost for infrastructure maintenance. Prior studies have employed molecular techniques to identify microbial community species in corroded concrete, but failed to explore bacterial activity and functionality during deterioration. In this study, biofilms of different sulfur-oxidizing bacteria compositions were developed on the surface of cement paste samples to simulate the natural ecological succession of microbial communities during MIC processes. Noninvasive, self-referencing (SR) microsensors were used to quantify real time changes of oxygen, hydrogen ion and calcium ion flux for the biofilm to provide more information about bacterial behavior during deterioration. Results showed higher transport rates in oxygen consumption, and hydrogen ion at 4 weeks than 2 weeks, indicating increased bacterial activity over time. Samples with five species biofilm had the highest hydrogen ion and calcium ion transport rates, confirming attribution of acidophilic sulfur-oxidizing microorganisms (ASOM). Differences in transport rates between three species samples and two species samples confirmed the diversity between Thiomonas intermedia and Starkeya novella. The limitations of SR sensors in corrosion application could be improved in future studies when combined with molecular techniques to identify the roles of major bacterial species in the deterioration process.

  14. Sulfide, the first inorganic substrate for human cells.

    PubMed

    Goubern, Marc; Andriamihaja, Mireille; Nübel, Tobias; Blachier, François; Bouillaud, Frédéric

    2007-06-01

    Hydrogen sulfide (H2S) is produced inside the intestine and is known as a poison that inhibits cellular respiration at the level of cytochrome oxidase. However, sulfide is used as an energetic substrate by many photo- and chemoautotrophic bacteria and by animals such as the lugworm Arenicola marina. The concentrations of sulfide present in their habitats are comparable with those present in the human colon. Using permeabilized colonic cells to which sulfide was added by an infusion pump we show that the maximal respiratory rate of colonocyte mitochondria in presence of sulfide compares with that obtained with succinate or L-alpha-glycerophosphate. This oxidation is accompanied by mitochondrial energization. In contrast, other cell types not naturally exposed to high concentration of sulfide showed much lower oxidation rates. Mitochondria showed a very high affinity for sulfide that permits its use as an energetic substrate at low micromolar concentrations, hence, below the toxic level. However, if the supply of sulfide exceeds the oxidation rate, poisoning renders mitochondria inefficient and our data suggest that an anaerobic mechanism involving partial reversion of Krebs cycle already known in invertebrates takes place. In conclusion, this work provides additional and compelling evidence that sulfide is not only a toxic compound. According to our study, sulfide appears to be the first inorganic substrate for mammalian cells characterized thus far.

  15. Thermodynamics of Complex Sulfide Inclusion Formation in Ca-Treated Al-Killed Structural Steel

    NASA Astrophysics Data System (ADS)

    Guo, Yin-tao; He, Sheng-ping; Chen, Gu-jun; Wang, Qian

    2016-08-01

    Controlling the morphology of the sulfide inclusion is of vital importance in enhancing the properties of structural steel. Long strip-shaped sulfides in hot-rolled steel can spherize when, instead of the inclusion of pure single-phase MnS, the guest is a complex sulfide, such as an oxide-sulfide duplex and a solid-solution sulfide particle. In this study, the inclusions in a commercial rolled structural steel were investigated. Spherical and elongated oxide-sulfide duplex as well as single-phase (Mn,Ca)S solid solution inclusions were observed in the steel. A thermodynamic equilibrium between the oxide and sulfide inclusions was proposed to understand the oxide-sulfide duplex inclusion formation. Based on the equilibrium solidification principle, thermodynamic discussions on inclusion precipitation during the solidification process were performed for both general and resulfurized structural steel. The predicted results of the present study agreed well with the experimental ones.

  16. Cadmium sulfide quantum dots supported on gallium and indium oxide for visible-light-driven hydrogen evolution from water.

    PubMed

    Pan, Yun-xiang; Zhuang, Huaqiang; Hong, Jindui; Fang, Zheng; Liu, Hai; Liu, Bin; Huang, Yizhong; Xu, Rong

    2014-09-01

    In this work, CdS quantum dots (QDs) supported on Ga2O3 and In2O3 are applied for visible-light-driven H2 evolution from aqueous solutions that contain lactic acid. With Pt as the cocatalyst, the H2 evolution rates on CdS/Pt/Ga2O3 and CdS/Pt/In2O3 are as high as 995.8 and 1032.2 μmol h(-1), respectively, under visible light (λ>420 nm) with apparent quantum efficiencies of 43.6 and 45.3% obtained at 460 nm, respectively. These are much higher than those on Pt/CdS (108.09 μmol h(-1)), Pt/Ga2O3 (0.12 μmol h(-1)), and Pt/In2O3 (0.05 μmol h(-1)). The photocatalysts have been characterized thoroughly and their band structures and photocurrent responses have been measured. The band alignment between the CdS QDs and In2O3 can lead to interfacial charge separation, which cannot occur between the CdS QDs and Ga2O3. Among the various possible factors that contribute to the high H2 evolution rates on CdS/Pt/oxide, the surface properties of the metal oxides play important roles, which include (i) the anchoring of CdS QDs and Pt nanoparticles for favorable interactions and (ii) the efficient trapping of photogenerated electrons from the CdS QDs because of surface defects (such as oxygen defects) based on photoluminescence and photocurrent studies.

  17. Stimulation of gaseous phosphine production from Antarctic seabird guanos and ornithogenic soils.

    PubMed

    Zhu, Renbin; Liu, Yashu; Sun, Jianjun; Sun, Liguang; Geng, Jinju

    2009-01-01

    Matrix-bound phosphine (MBP) is a general term used to indicate non-gaseous reduced phosphorus compounds that are transformed into phosphine gas upon reaction with bases or acids. Antarctic seabird guanos and ornithogenic soils were used as materials to compare the different digestion methods for transforming matrix-bound phosphine into phosphine gas. The results demonstrated that more phosphine gas in most of Antarctic environmental materials was formed of matrix-bound phosphine by caustic digestion than by acidic digestion. The comparative study on different digestion methods also revealed that the fraction of MBP converted to gaseous phosphine during the digestion depended on the temperature. The optimal digestion temperature was close to 70 degrees C and the optimal digestion time was about 20 min. Acidic conditions were more favorable for the release of matrix-bound phosphine compared to the neutral conditions. A proper water dilution can increase the production and emission of phosphine from the Antarctic penguin guanos.

  18. Production of glycolic acid by chemolithotrophic iron- and sulfur-oxidizing bacteria and its role in delineating and sustaining acidophilic sulfide mineral-oxidizing consortia.

    PubMed

    Nancucheo, Ivan; Johnson, D Barrie

    2010-01-01

    Glycolic acid was detected as an exudate in actively growing cultures of three chemolithotrophic acidophiles that are important in biomining operations, Leptospirillum ferriphilum, Acidithiobacillus (At.) ferrooxidans, and At. caldus. Although similar concentrations of glycolic acid were found in all cases, the concentrations corresponded to ca. 24% of the total dissolved organic carbon (DOC) in cultures of L. ferriphilum but only ca. 5% of the total DOC in cultures of the two Acidithiobacillus spp. Rapid acidification (to pH 1.0) of the culture medium of At. caldus resulted in a large increase in the level of DOC, although the concentration of glycolic acid did not change in proportion. The archaeon Ferroplasma acidiphilum grew in the cell-free spent medium of At. caldus; glycolic acid was not metabolized, although other unidentified compounds in the DOC pool were metabolized. Glycolic acid exhibited levels of toxicity with 21 strains of acidophiles screened similar to those of acetic acid. The most sensitive species were chemolithotrophs (L. ferriphilum and At. ferrivorans), while the most tolerant species were chemoorganotrophs (Acidocella, Acidobacterium, and Ferroplasma species), and the ability to metabolize glycolic acid appeared to be restricted (among acidophiles) to Firmicutes (chiefly Sulfobacillus spp.). Results of this study help explain why Sulfobacillus spp. rather than other acidophiles are the main organic carbon-degrading bacteria in continuously fed stirred tanks used to bioprocess sulfide mineral concentrates and also why temporary cessation of pH control in these systems, resulting in rapid acidification, often results in a plume of the archaeon Ferroplasma.

  19. Additive cardioprotection by pharmacological postconditioning with hydrogen sulfide and nitric oxide donors in mouse heart: S-sulfhydration vs. S-nitrosylation.

    PubMed

    Sun, Junhui; Aponte, Angel M; Menazza, Sara; Gucek, Marjan; Steenbergen, Charles; Murphy, Elizabeth

    2016-05-01

    Hydrogen sulfide (H2S), as a gaseous signalling molecule, has been found to play important roles in postconditioning (PostC)-induced cardioprotection. Similar to nitric oxide (NO)-mediated protein S-nitrosylation (SNO), recent studies suggest that H2S could regulate protein function through another redox-based post-translational modification on protein cysteine residue(s), i.e. S-sulfhydration (SSH). In this study, we examined whether there are changes in protein SSH associated with cardioprotection induced by treatment with H2S on reperfusion. In addition, we also examined whether there is cross talk between H2S and NO. Compared with control, treatment on reperfusion with NaHS (H2S donor, 100 µmol/L) significantly reduced post-ischaemic contractile dysfunction and infarct size. A comparable cardioprotective effect could be also achieved by reperfusion treatment with SNAP (NO donor, 10 µmol/L). Interestingly, simultaneous reperfusion with both donors had an additive protective effect. In addition, C-PTIO (NO scavenger, 20 µmol/L) eliminated the protection induced by NaHS and also the additive protection by SNAP + NaHS together. Using a modified biotin switch method, we observed a small increase in SSH following NaHS treatment on reperfusion. We also found that NaHS treatment on reperfusion increases SNO to a level comparable to that with SNAP treatment. In addition, there was an additive increase in SNO but not SSH when SNAP and NaHS were added together at reperfusion. Thus, part of the benefit of NaHS is an increase in SNO, and the magnitude of the protective effect is related to the magnitude of the increase in SNO.

  20. Effects of Tai Chi exercise on blood pressure and plasma levels of nitric oxide, carbon monoxide and hydrogen sulfide in real-world patients with essential hypertension.

    PubMed

    Pan, Xiaogui; Zhang, Yi; Tao, Sai

    2015-01-01

    Objective was to investigate the effects of Tai Chi exercise on nitric oxide (NO), carbon monoxide (CO) and hydrogen sulfide (H2S) levels, and blood pressure (BP) in patients with essential hypertension (EH). EH patients were assigned to the Tai Chi exercise group (HTC, n = 24), and hypertension group (HP, n = 16) by patients' willingness. Healthy volunteers matched for age and gender were recruited as control (NP, n = 16). HTC group performed Tai Chi (60 min/d, 6 d/week) for 12 weeks. Measurements (blood glucose, cholesterol, NO, CO, H2S and BP) were obtained at week 0, 6, and 12. SBP, MAP, and low-density lipoprotein cholesterol levels decreased, and high-density lipoprotein cholesterol levels increased by week 12 in the HTC group (all p < 0.05 versus baseline). Plasma NO, CO, and H2S levels in the HTC group were increased after 12 weeks (all p < 0.05 versus baseline). SBP, DBP and MAP levels were significantly lower in the HTC than in the HP group (all p < 0.05). However, no changes were observed in the HP and NP groups. Correlations were observed between changes in SBP and changes in NO, CO and H2S (r = -0.45, -0.51 and -0.46, respectively, all p < 0.05), and between changes in MAP and changes in NO, CO and H2S (r = -0.36, -0.45 and -0.42, respectively, all p < 0.05). In conclusion, Tai Chi exercise seems to have beneficial effects on BP and gaseous signaling molecules in EH patients. However, further investigation is required to understand the exact mechanisms underlying these observations, and to confirm these results in a larger cohort.

  1. Hydrogen sulfide generated by L-cysteine desulfhydrase acts upstream of nitric oxide to modulate abscisic acid-dependent stomatal closure.

    PubMed

    Scuffi, Denise; Álvarez, Consolación; Laspina, Natalia; Gotor, Cecilia; Lamattina, Lorenzo; García-Mata, Carlos

    2014-12-01

    Abscisic acid (ABA) is a well-studied regulator of stomatal movement. Hydrogen sulfide (H2S), a small signaling gas molecule involved in key physiological processes in mammals, has been recently reported as a new component of the ABA signaling network in stomatal guard cells. In Arabidopsis (Arabidopsis thaliana), H2S is enzymatically produced in the cytosol through the activity of l-cysteine desulfhydrase (DES1). In this work, we used DES1 knockout Arabidopsis mutant plants (des1) to study the participation of DES1 in the cross talk between H2S and nitric oxide (NO) in the ABA-dependent signaling network in guard cells. The results show that ABA did not close the stomata in isolated epidermal strips of des1 mutants, an effect that was restored by the application of exogenous H2S. Quantitative reverse transcription polymerase chain reaction analysis demonstrated that ABA induces DES1 expression in guard cell-enriched RNA extracts from wild-type Arabidopsis plants. Furthermore, stomata from isolated epidermal strips of Arabidopsis ABA receptor mutant pyrabactin-resistant1 (pyr1)/pyrabactin-like1 (pyl1)/pyl2/pyl4 close in response to exogenous H2S, suggesting that this gasotransmitter is acting downstream, although acting independently of the ABA receptor cannot be ruled out with this data. However, the Arabidopsis clade-A PROTEIN PHOSPHATASE2C mutant abscisic acid-insensitive1 (abi1-1) does not close the stomata when epidermal strips were treated with H2S, suggesting that H2S required a functional ABI1. Further studies to unravel the cross talk between H2S and NO indicate that (1) H2S promotes NO production, (2) DES1 is required for ABA-dependent NO production, and (3) NO is downstream of H2S in ABA-induced stomatal closure. Altogether, data indicate that DES1 is a unique component of ABA signaling in guard cells.

  2. Leptin-Induced Endothelium-Dependent Vasorelaxation of Peripheral Arteries in Lean and Obese Rats: Role of Nitric Oxide and Hydrogen Sulfide

    PubMed Central

    Jamroz-Wiśniewska, Anna; Gertler, Arieh; Solomon, Gili; Wood, Mark E.; Whiteman, Matthew; Bełtowski, Jerzy

    2014-01-01

    Adipose tissue hormone leptin induces endothelium-dependent vasorelaxation mediated by nitric oxide (NO) and endothelium-derived hyperpolarizing factors (EDHF). Previously it has been demonstrated that in short-term obesity the NO-dependent and the EDHF-dependent components of vascular effect of leptin are impaired and up-regulated, respectively. Herein we examined the mechanism of the EDHF-dependent vasodilatory effect of leptin and tested the hypothesis that alterations of acute vascular effects of leptin in obesity are accounted for by chronic hyperleptinemia. The study was performed in 5 groups of rats: (1) control, (2) treated with exogenous leptin for 1 week to induce hyperleptinemia, (3) obese, fed highly-palatable diet for 4 weeks, (4) obese treated with pegylated superactive rat leptin receptor antagonist (PEG-SRLA) for 1 week, (5) fed standard chow and treated with PEG-SRLA. Acute effect of leptin on isometric tension of mesenteric artery segments was measured ex vivo. Leptin relaxed phenylephrine-preconstricted vascular segments in NO- and EDHF-dependent manner. The NO-dependent component was impaired and the EDHF-dependent component was increased in the leptin-treated and obese groups and in the latter group both these effects were abolished by PEG-SRLA. The EDHF-dependent vasodilatory effect of leptin was blocked by either the inhibitor of cystathionine γ-lyase, propargylglycine, or a hydrogen sulfide (H2S) scavenger, bismuth (III) subsalicylate. The results indicate that NO deficiency is compensated by the up-regulation of EDHF in obese rats and both effects are accounted for by chronic hyperleptinemia. The EDHF-dependent component of leptin-induced vasorelaxation is mediated, at least partially, by H2S. PMID:24475175

  3. Phosphorus-containing polymers from THPS. IV: Synthesis and properties of phosphorus-containing polybenzoxazines as a green route for recycling toxic phosphine (PH3) tail gas.

    PubMed

    Tan, Zhi-Wei; Sun, Jian; Wu, Cheng-Yan; Qiu, Jin-Jun; Liu, Cheng-Mei

    2017-01-15

    A convenient route to convert the highly toxic phosphine (PH3) tail gas into high-performance polybenzoxazines was first described in this paper. Two aliphatic polyamines, namely tris(aminomethyl)phosphine oxide and bis(aminomethyl)phenylphosphine oxide, were synthesized from tetrakis(hydroxymethyl)phosphonium sulfate (THPS), a green derivative of PH3 tail gas. And then two novel phosphorus-containing benzoxazine monomers, tris(3,4-dihydro-2H-1,3-benzoxazin-3-yl-methyl)phosphine oxide (TBOz) and benzylbis(3,4-dihydro-2H-1,3-benzoxazin-3-yl-methyl) phosphine oxide (BBOz) were prepared by three-steps procedure. FT-IR and DSC technologies were adopted to study the thermal-initiated polymerization behaviors of two benzoxazine monomers. Thermal properties of these crosslinked polymers were studied by TGA and DMA. The results display that the polybenzoxazines (PTBOz and PBBOz) exhibite good thermal stabilities and high glass transition temperatures. The char yield of polybanzoxazine is high as 47% and indiactes that phosphorus-containing polybenzoxazines show high fire-retardancy. The surface free energies of the PTBOz and PBBOz are 37.1 and 40.4mJm(-2) by Owens two-liquid method. The dielectric properties of the PTBOz and PBBOz remaine near constant in the experimental frequency range.

  4. Sulfide in surface waters of the western Atlantic Ocean

    NASA Astrophysics Data System (ADS)

    Cutter, Gregory A.; Krahforst, Christian F.

    1988-11-01

    Using newly developed techniques, some preliminary data on hydrogen sulfide in surface waters of the western Atlantic have been obtained. Concentrations of total sulfide range from <0.1 to 1.1 nmol/L, and vary on a diel basis. At these concentrations, sulfide may affect the cycling of several trace metals via the formation of stable complexes. Production of sulfide in oxygenated seawater may occur through the hydrolysis of carbonyl sulfide or by sulfate reduction within macroscopic particles in the water column. Removal mechanisms can include oxidation, complexation with particulate trace metals, and metal sulfide precipitation. However, the temporal and spatial distributions suggest a complex set of processes governing the behavior of sulfide in the surface ocean.

  5. Sulfide elimination by intermittent nitrate dosing in sewer sediments.

    PubMed

    Liu, Yanchen; Wu, Chen; Zhou, Xiaohong; Zhu, David Z; Shi, Hanchang

    2015-01-01

    The formation of hydrogen sulfide in biofilms and sediments in sewer systems can cause severe pipe corrosions and health hazards, and requires expensive programs for its prevention. The aim of this study is to propose a new control strategy and the optimal condition for sulfide elimination by intermittent nitrate dosing in sewer sediments. The study was carried out based on lab-scale experiments and batch tests using real sewer sediments. The intermittent nitrate dosing mode and the optimal control condition were investigated. The results indicated that the sulfide-intermittent-elimination strategy by nitrate dosing is advantageous for controlling sulfide accumulation in sewer sediment. The oxidation-reduction potential is a sensitive indicator parameter that can reflect the control effect and the minimum N/S (nitrate/sulfide) ratio with slight excess nitrate is necessary for optimal conditions of efficient sulfide control with lower carbon source loss. The optimal control condition is feasible for the sulfide elimination in sewer systems.

  6. Microstructure degradation of YSZ in Ni/YSZ anodes of SOFC operated in phosphine-containing fuels

    SciTech Connect

    Chen, Yun; Chen, Song; Hackett, Gregory; Finklea, Harry; Zondlod, John; Celik, Ismail; Song, Xueyan; Gerdes, Kirk

    2013-03-07

    The interaction of trace (ppm) phosphine with the nickel/yttria stabilized zirconia (YSZ) anode of commercial solid oxide fuel cells has been investigated and evaluated for both synthesis gas and hydrogen fuels in an effort to examine P–Y reactions. The Ni poisoning effects reported in literature were confirmed and degradation was examined by electrochemical methods and post-test microstructural and chemical analyses. The results indicate that P-induced degradation rates and mechanisms are fuel dependent and that degradation of cells operated in synthesis gas (syngas) with phosphine is more severe than that of cells operated in hydrogen with phosphine. As reported in published literature, a cell operated in syngas containing 10 ppm phosphine demonstrated significant microstructural degradation within the Ni phase, including formation of Ni–P phases concentrated on the outer layer of the anode and significant pitting corrosion in the Ni grains. In this research, a previously undetected YPO{sub 4} phase is observed at the YSZ/YSZ/Ni triple grain junctions located at the interface with the YSZ electrolyte. Tetragonal YSZ (t-YSZ) and cubic-YSZ (c-YSZ) domains with sizes of several tens of nanometers are also newly observed along the Ni/YSZ interface. These observations contrast with data obtained for a cell operated in dry hydrogen with phosphine, where no YPO{sub 4} phase is observed and the alternating t-YSZ and c-YSZ domains at the Ni/YSZ interface are smaller with typical sizes of 5–10 nm. The data imply that electrolyte attack by P is a potentially debilitating mode of degradation in SOFC anodes, and that the associated reaction mechanisms and rates are worthy of further examination.

  7. Hydroxyalkyl phosphine compounds for use as diagnostic and therapeutic pharmaceuticals

    DOEpatents

    Katti, K.V.; Singh, P.R.; Reddy, V.S.; Katti, K.K.; Volkert, W.A.; Ketring, A.R.

    1999-03-02

    This research discloses a compound and method of making a compound for use as a diagnostic or therapeutic pharmaceutical comprises a functionalized hydroxyalkyl phosphine ligand and a metal combined with the ligand. 16 figs.

  8. Nucleophilic Chiral Phosphines: Powerful and Versatile Catalysts for Asymmetric Annulations

    PubMed Central

    Xiao, Yumei; Guo, Hongchao; Kwon, Ohyun

    2016-01-01

    Recent advances in chiral-phosphine-catalyzed asymmetric annulation reactions; including annulations of allenes, alkynes, Morita–Baylis–Hillman (MBH) carbonates, and ketenes; and their applications in the synthesis of bioactive molecules and natural products are reviewed. PMID:28077882

  9. Asymmetric Synthesis of Chiral Atropisomeric Bis-Aryl Organophosphorus from Menthyl H-Phosphinate.

    PubMed

    Ma, Yan-Na; Yang, Shang-Dong

    2016-04-01

    This review describes new methods for the synthesis of chiral monophosphine ligands with menthyl phenylphosphinate as a chiral auxiliary through asymmetric Suzuki-Miyaura cross-coupling reactions and asymmetric C-H functionalization. The chiral menthyl phenylphosphinate as a chiral auxiliary is easy to prepare and the menthyl group can easily be transformed into other functional groups, with the chiral center synchronously remaining. These methodologies provide highly efficient and practical strategies for the synthesis of novel axially chiral biaryl monophosphine oxides and their corresponding phosphines. Meanwhile, these reactions are easy to handle and exhibit wide scope for substrates with excellent diastereomeric ratios.

  10. SULFIDE MINERALS IN SEDIMENTS

    EPA Science Inventory

    The formation processes of metal sulfides in sediments, especially iron sulfides, have been the subjects of intense scientific research because of linkages to the global biogeochemical cycles of iron, sulfur, carbon, and oxygen. Transition metal sulfides (e.g., NiS, CuS, ZnS, Cd...

  11. Cadmium sulfide membranes

    DOEpatents

    Spanhel, Lubomir; Anderson, Marc A.

    1991-10-22

    A method is described for the creation of novel q-effect cadmium sulfide membranes. The membranes are made by first creating a dilute cadmium sulfide colloid in aqueous suspension and then removing the water and excess salts therefrom. The cadmium sulfide membrane thus produced is luminescent at room temperature and may have application in laser fabrication.

  12. Cadmium sulfide membranes

    DOEpatents

    Spanhel, Lubomir; Anderson, Marc A.

    1992-07-07

    A method is described for the creation of novel q-effect cadmium sulfide membranes. The membranes are made by first creating a dilute cadmium sulfide colloid in aqueous suspension and then removing the water and excess salts therefrom. The cadmium sulfide membrane thus produced is luminescent at room temperature and may have application in laser fabrication.

  13. Phosphine derivatives of sparfloxacin - Synthesis, structures and in vitro activity

    NASA Astrophysics Data System (ADS)

    Komarnicka, Urszula K.; Starosta, Radosław; Guz-Regner, Katarzyna; Bugla-Płoskońska, Gabriela; Kyzioł, Agnieszka; Jeżowska-Bojczuk, Małgorzata

    2015-09-01

    We synthesized two derivatives of sparfloxacin (HSf): aminomethyl(diphenyl)phosphine (PSf) and its oxide (OPSf). The compounds were characterized by NMR spectroscopy, MS and elemental analysis. In addition, the molecular structures of the compounds were determined using DFT and X-ray (OPSf) analysis. The antibacterial activity of HSf and both derivatives was tested against four reference and fifteen clinical Gram-positive and Gram-negative strains of bacteria (sensitive or resistant to fluoroquinolones). The results showed that the activity of PSf was similar to or higher than the activity of HSf, while OPSf was found significantly less active. The compounds were also tested in vitro toward the following cancer cell lines: mouse colon carcinoma (CT26) and human lung adenocarcinoma (A549). Regardless of the cancer cell line, derivatization of HSf resulted in the gradual increase of cytotoxicity. OPSf exhibited the highest one (4 h - incubation time: IC50(CT26) = 51.0 ± 1.2; IC50(A549) = 74.9 ± 1.4 and 24 h: IC50(CT26) = 109.2 ± 8.8; IC50(A549) = 52.7 ± 9.2).

  14. Hydrogen sulfide alleviates toxic effects of arsenate in pea seedlings through up-regulation of the ascorbate-glutathione cycle: Possible involvement of nitric oxide.

    PubMed

    Singh, Vijay Pratap; Singh, Samiksha; Kumar, Jitendra; Prasad, Sheo Mohan

    2015-06-01

    In plants, hydrogen sulfide (H2S) is an emerging novel signaling molecule that is involved in growth regulation and abiotic stress responses. However, little is known about its role in the regulation of arsenate (As(V)) toxicity. Therefore, hydroponic experiments were conducted to investigate whether sodium hydrosulfide (NaHS; a source of H2S) is involved in the regulation of As(V) toxicity in pea seedlings. Results showed that As(V) caused decreases in growth, photosynthesis (measured as chlorophyll fluorescence) and nitrogen content, which was accompanied by the accumulation of As. As(V) treatment also reduced the activities of cysteine desulfhydrase and nitrate reductase, and contents of H2S and nitric oxide (NO). However, addition of NaHS ameliorated As(V) toxicity in pea seedlings, which coincided with the increased contents of H2S and NO. The cysteine level was higher under As(V) treatment in comparison to all other treatments (As-free; NaHS; As(V)+NaHS). The content of reactive oxygen species (ROS) and damage to lipids, proteins and membranes increased by As(V) while NaHS alleviated these effects. Enzymes of the ascorbate-glutathione cycle (AsA-GSH cycle) showed inhibition of their activities following As(V) treatment while their activities were increased by application of NaHS. The redox status of ascorbate and glutathione was disturbed by As(V) as indicated by a steep decline in their reduced/oxidized ratios. However, simultaneous NaHS application restored the redox status of the ascorbate and glutathione pools. The results of this study demonstrated that H2S and NO might both be involved in reducing the accumulation of As and triggering up-regulation of the AsA-GSH cycle to counterbalance ROS-mediated damage to macromolecules. Furthermore, the results suggest a crucial role of H2S in plant priming, and in particular for pea seedlings in mitigating As(V) stress.

  15. Mitochondria and sulfide: a very old story of poisoning, feeding, and signaling?

    PubMed

    Bouillaud, Frédéric; Blachier, François

    2011-07-15

    Sulfide is a molecule with toxicity comparable to that of cyanide. It inhibits mitochondrial cytochrome oxidase at submicromolar concentrations. However, at even lower concentrations, sulfide is a substrate for the mitochondrial electron transport chain in mammals, and is comparable to succinate. This oxidation involves a sulfide quinone reductase. Sulfide is thus oxidized before reaching a toxic concentration, which explains why free sulfide concentrations are very low in mammals, even though sulfide is constantly released as a result of cellular metabolism. It has been suggested that sulfide has signaling properties in mammals like two other gases, NO and CO, which are also cytochrome oxidase inhibitors. The oxidation of sulfide by mitochondria creates further complexity in the description/use of sulfide signaling in mammals. In fact, in the many studies reported in the literature, the sulfide concentrations that have been used were well within the range that affects mitochondrial activity. This review focuses on the relevance of sulfide bioenergetics to sulfide biology and discusses the case of colonocytes, which are routinely exposed to higher sulfide concentrations. Finally, we offer perspectives for future studies on the relationship between the two opposing aspects of this Janus-type molecule, sulfide.

  16. Hydrogen sulfide in hemostasis: friend or foe?

    PubMed

    Olas, Beata

    2014-06-25

    Hydrogen sulfide (H2S) is a well known toxic gas that is synthesized from the amino acids: cysteine (Cys) and homocysteine (Hcy) by three enzymes: cystathionine-β-synthase (CBS), cystathionine-γ-lyase (CSE) and mercaptopyruvate sulfurtransferase (3-MST). Hydrogen sulfide, like carbon monoxide (CO) or nitric oxide (NO) is a signaling molecule in different biological systems, including the cardiovascular system. Moreover, hydrogen sulfide plays a role in the pathogenesis of various cardiovascular diseases. It modulates different elements of hemostasis (activation of blood platelet, and coagulation process) as well as proliferation and apoptosis of vascular smooth muscle cells. However, the biological role and the therapeutic potential of H2S is not clear. This review summarizes the different functions of hydrogen sulfide in hemostasis.

  17. Hydrogen Sulfide Generated by l-Cysteine Desulfhydrase Acts Upstream of Nitric Oxide to Modulate Abscisic Acid-Dependent Stomatal Closure1[C][W

    PubMed Central

    Scuffi, Denise; Álvarez, Consolación; Laspina, Natalia; Gotor, Cecilia; Lamattina, Lorenzo; García-Mata, Carlos

    2014-01-01

    Abscisic acid (ABA) is a well-studied regulator of stomatal movement. Hydrogen sulfide (H2S), a small signaling gas molecule involved in key physiological processes in mammals, has been recently reported as a new component of the ABA signaling network in stomatal guard cells. In Arabidopsis (Arabidopsis thaliana), H2S is enzymatically produced in the cytosol through the activity of l-cysteine desulfhydrase (DES1). In this work, we used DES1 knockout Arabidopsis mutant plants (des1) to study the participation of DES1 in the cross talk between H2S and nitric oxide (NO) in the ABA-dependent signaling network in guard cells. The results show that ABA did not close the stomata in isolated epidermal strips of des1 mutants, an effect that was restored by the application of exogenous H2S. Quantitative reverse transcription polymerase chain reaction analysis demonstrated that ABA induces DES1 expression in guard cell-enriched RNA extracts from wild-type Arabidopsis plants. Furthermore, stomata from isolated epidermal strips of Arabidopsis ABA receptor mutant pyrabactin-resistant1 (pyr1)/pyrabactin-like1 (pyl1)/pyl2/pyl4 close in response to exogenous H2S, suggesting that this gasotransmitter is acting downstream, although acting independently of the ABA receptor cannot be ruled out with this data. However, the Arabidopsis clade-A PROTEIN PHOSPHATASE2C mutant abscisic acid-insensitive1 (abi1-1) does not close the stomata when epidermal strips were treated with H2S, suggesting that H2S required a functional ABI1. Further studies to unravel the cross talk between H2S and NO indicate that (1) H2S promotes NO production, (2) DES1 is required for ABA-dependent NO production, and (3) NO is downstream of H2S in ABA-induced stomatal closure. Altogether, data indicate that DES1 is a unique component of ABA signaling in guard cells. PMID:25266633

  18. Hydrogen sulfide inhibits nitric oxide production and nuclear factor-kappaB via heme oxygenase-1 expression in RAW264.7 macrophages stimulated with lipopolysaccharide.

    PubMed

    Oh, Gi-Su; Pae, Hyun-Ock; Lee, Bok-Soo; Kim, Byeong-Nam; Kim, Jong-Moon; Kim, Hyung-Ryong; Jeon, Seon Bok; Jeon, Woo Kyu; Chae, Han-Jung; Chung, Hun-Taeg

    2006-07-01

    Hydrogen sulfide (H(2)S), a regulatory gaseous molecule that is endogenously synthesized by cystathionine gamma-lyase (CSE) and/or cystathionine beta-synthase (CBS) from L-cysteine (L-Cys) metabolism, is a putative vasodilator, and its role in nitric oxide (NO) production is unexplored. Here, we show that at noncytotoxic concentrations, H(2)S was able to inhibit NO production and inducible NO synthase (iNOS) expression via heme oxygenase (HO-1) expression in RAW264.7 macrophages stimulated with lipopolysaccharide (LPS). Both H(2)S solution prepared by bubbling pure H(2)S gas and NaSH, a H(2)S donor, dose dependently induced HO-1 expression through the activation of the extracellular signal-regulated kinase (ERK). Pretreatment with H(2)S or NaHS significantly inhibited LPS-induced iNOS expression and NO production. Moreover, NO production in LPS-stimulated macrophages that are expressing CSE mRNA was significantly reduced by the addition of L-Cys, a substrate for H(2)S, but enhanced by the selective CSE inhibitor beta-cyano-L-alanine but not by the CBS inhibitor aminooxyacetic acid. While either blockage of HO activity by the HO inhibitor, tin protoporphyrin IX, or down-regulation of HO-1 expression by HO-1 small interfering RNA (siRNA) reversed the inhibitory effects of H(2)S on iNOS expression and NO production, HO-1 overexpression produced the same inhibitory effects of H(2)S. In addition, LPS-induced nuclear factor (NF)-kappaB activation was diminished in RAW264.7 macrophages preincubated with H(2)S. Interestingly, the inhibitory effect of H(2)S on NF-kappaB activation was reversed by the transient transfection with HO-1 siRNA, but was mimicked by either HO-1 gene transfection or treatment with carbon monoxide (CO), an end product of HO-1. CO treatment also inhibited LPS-induced NO production and iNOS expression via its inactivation of NF-kappaB. Collectively, our results suggest that H(2)S can inhibit NO production and NF-kappaB activation in LPS

  19. A new process for removing hydrogen sulfide from gas

    SciTech Connect

    Bhatia, K.; Allford, K.T.

    1986-01-01

    A novel, patented sour gas sweetening process was introduced to the gas processing industry in September, 1984. This new process is referred to as the one-step process in this paper. The one-step process selectively removes hydrogen sulfide from sour gases and converts dissolved hydrogen sulfide directly to sulfur in a bubble tower filled with the sweetener solution. The sweetener, a proprietary formulation, is an alkaline solution of oxidizing and buffering agents. Oxidation of hydrogen sulfide to sulfur is achieved by a liquid phase oxidation technique.

  20. Phosphine and methylphosphine production by simulated lightning—a study for the volatile phosphorus cycle and cloud formation in the earth atmosphere

    NASA Astrophysics Data System (ADS)

    Glindemann, Dietmar; Edwards, Marc; Schrems, Otto

    Phosphine (PH 3), was recently found worldwide even in the remote atmosphere (Naturwissenschaften83(1996a)131; Atmos. Environ. 37(2003)24 29). It is of interest to find natural mechanisms which could produce phosphine gas and drive a volatile link of the atmospheric phosphorus cycle and the formation of phosphoric acid as possible condensation nuclei for clouds. Here, we report on simulated lightning exposing sodium phosphate in a reducing medium (methane model atmosphere or organic matter) for 5 s to a spark induced by microwave. The gas product analyzed by gas chromatography contained phosphine (yield up to 0.6 g kg -1 phosphate P) and methylphosphine (CH 3)PH 2 (yield up to 0.02 g kg -1 phosphate P). We suggest a plasma-chemical formation mechanism where organic compounds or methane or secondary hydrogen thereof reduce phosphate to phosphine of which a small fraction can subsequently react with methyl radicals to form methylphosphine. A small yield of 6 mg phosphine per kg phosphate P was even obtained in methane free medium, by simple plasmatic recombination of inorganic phosphorus. We believe that methane and hydrogen are useful model substances of pyrolytic gases with high reducing power which may form if lightning strikes biomass, soil and aerosol. These results suggest evidence that phosphine and methylphosphine (detectable in the field by intense garlic odor) are produced when atmospheric lightning strikes the ground or aerosol which is containing oxidized forms of phosphorus and chemical reductants. Additional reviewed data show that laboratory lightning was able to reduce a much more significant portion of phosphate to phosphite (up to 25% yield), methylphosphonic acid (up to 8.5% yield) and traces of hypophosphite in a matter of seconds.

  1. Genes related to mitochondrial functions are differentially expressed in phosphine-resistant and -susceptible Tribolium castaneum

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Phosphine is a valuable fumigant to control pest populations in stored grains and grain products. However, recent studies indicate a substantial increase in phosphine resistance in major stored-cereal pests worldwide. To understand the molecular bases of phosphine resistance in insects, we used RNA-...

  2. Microbial control of hydrogen sulfide production

    SciTech Connect

    Montgomery, A.D.; Bhupathiraju, V.K.; Wofford, N.; McInerney, M.J.

    1995-12-31

    A sulfide-resistant strain of Thiobacillus denitrificans, strain F, prevented the accumulation of sulfide by Desulfovibrio desulfuricans when both organisms were grown in liquid medium. The wild-type strain of T. denitrificans did not prevent the accumulation of sulfide produced by D. desulfuricans. Strain F also prevented the accumulation of sulfide by a mixed population of sulfate-reducing bacteria enriched from an oil field brine. Fermentation balances showed that strain F stoichiometrically oxidized the sulfide produced by D. desulfuricans and the oil field brine enrichment to sulfate. The ability of a strain F to control sulfide production in an experimental system of cores and formation water from the Redfield, Iowa, natural gas storage facility was also investigated. A stable, sulfide-producing biofilm was established in two separate core systems, one of which was inoculated with strain F while the other core system (control) was treated in an identical manner, but was not inoculated with strain F. When formation water with 10 mM acetate and 5 mM nitrate was injected into both core systems, the effluent sulfide concentrations in the control core system ranged from 200 to 460 {mu}M. In the test core system inoculated with strain F, the effluent sulfide concentrations were lower, ranging from 70 to 110 {mu}M. In order to determine whether strain F could control sulfide production under optimal conditions for sulfate-reducing bacteria, the electron donor was changed to lactate and inorganic nutrients (nitrogen and phosphate sources) were added to the formation water. When nutrient-supplemented formation water with 3.1 mM lactate and 10 mM nitrate was used, the effluent sulfide concentrations of the control core system initially increased to about 3,800 {mu}M, and then decreased to about 1,100 {mu}M after 5 weeks. However, in the test core system inoculated with strain F, the effluent sulfide concentrations were much lower, 160 to 330 {mu}M.

  3. Hydrogen Sulfide--Mechanisms of Toxicity and Development of an Antidote.

    PubMed

    Jiang, Jingjing; Chan, Adriano; Ali, Sameh; Saha, Arindam; Haushalter, Kristofer J; Lam, Wai-Ling Macrina; Glasheen, Megan; Parker, James; Brenner, Matthew; Mahon, Sari B; Patel, Hemal H; Ambasudhan, Rajesh; Lipton, Stuart A; Pilz, Renate B; Boss, Gerry R

    2016-02-15

    Hydrogen sulfide is a highly toxic gas-second only to carbon monoxide as a cause of inhalational deaths. Its mechanism of toxicity is only partially known, and no specific therapy exists for sulfide poisoning. We show in several cell types, including human inducible pluripotent stem cell (hiPSC)-derived neurons, that sulfide inhibited complex IV of the mitochondrial respiratory chain and induced apoptosis. Sulfide increased hydroxyl radical production in isolated mouse heart mitochondria and F2-isoprostanes in brains and hearts of mice. The vitamin B12 analog cobinamide reversed the cellular toxicity of sulfide, and rescued Drosophila melanogaster and mice from lethal exposures of hydrogen sulfide gas. Cobinamide worked through two distinct mechanisms: direct reversal of complex IV inhibition and neutralization of sulfide-generated reactive oxygen species. We conclude that sulfide produces a high degree of oxidative stress in cells and tissues, and that cobinamide has promise as a first specific treatment for sulfide poisoning.

  4. Influence of pipe material and surfaces on sulfide related odor and corrosion in sewers.

    PubMed

    Nielsen, Asbjørn Haaning; Vollertsen, Jes; Jensen, Henriette Stokbro; Wium-Andersen, Tove; Hvitved-Jacobsen, Thorkild

    2008-09-01

    Hydrogen sulfide oxidation on sewer pipe surfaces was investigated in a pilot scale experimental setup. The experiments were aimed at replicating conditions in a gravity sewer located immediately downstream of a force main where sulfide related concrete corrosion and odor is often observed. During the experiments, hydrogen sulfide gas was injected intermittently into the headspace of partially filled concrete and plastic (PVC and HDPE) sewer pipes in concentrations of approximately 1,000 ppm(v). Between each injection, the hydrogen sulfide concentration was monitored while it decreased because of adsorption and subsequent oxidation on the pipe surfaces. The experiments showed that the rate of hydrogen sulfide oxidation was approximately two orders of magnitude faster on the concrete pipe surfaces than on the plastic pipe surfaces. Removal of the layer of reaction (corrosion) products from the concrete pipes was found to reduce the rate of hydrogen sulfide oxidation significantly. However, the rate of sulfide oxidation was restored to its background level within 10-20 days. A similar treatment had no observable effect on hydrogen sulfide removal in the plastic pipe reactors. The experimental results were used to model hydrogen sulfide oxidation under field conditions. This showed that the gas-phase hydrogen sulfide concentration in concrete sewers would typically amount to a few percent of the equilibrium concentration calculated from Henry's law. In the plastic pipe sewers, significantly higher concentrations were predicted because of the slower adsorption and oxidation kinetics on such surfaces.

  5. Unintentional poisoning by phosphine released from aluminum phosphide.

    PubMed

    Shadnia, S; Mehrpour, O; Abdollahi, M

    2008-01-01

    Aluminum phosphide as a releaser of phosphine gas is used as a grain preservative. In this case report, we describe an accidental severe poisoning in a 35-year-old woman, her 18-year-old daughter, and 6-year-old son caused by inhalation of phosphine gas released from 20 tablets of aluminum phosphide stored in 15 rice bags. The boy died 2 days after exposure before admission to hospital and any special treatment, but the others were admitted 48 h after exposure. They had signs and symptoms of severe toxicity, and their clinical course included metabolic acidosis, electrocardiographic changes, and hypotension. They were treated by intravenous administration of sodium bicarbonate, magnesium sulfate, and calcium gluconate. The patients were discharged after 3 days and followed up for 1 week after discharge. Rapid absorption of phosphine by inhalation, induction of hyperglycemia, and surviving of patients are interesting issues of this case report.

  6. Development of an extractive spectrophotometric method for estimation of uranium in ore leach solutions using 2-ethylhexyl phosphonic acid-mono-2-ethylhexyl ester (PC88A) and tri-n-octyl phosphine oxide (TOPO) mixture as extractant and 2-(5-bromo-2-pyridylozo)-5-diethyl aminophenol (Br-PADAP) as chromophore.

    PubMed

    Biswas, Sujoy; Pathak, P N; Roy, S B

    2012-06-01

    An extractive spectrophotometric analytical method has been developed for the determination of uranium in ore leach solution. This technique is based on the selective extraction of uranium from multielement system using a synergistic mixture of 2-ethylhexyl phosphonic acid-mono-2-ethylhexyl ester (PC88A) and tri-n-octyl phosphine oxide (TOPO) in cyclohexane and color development from the organic phase aliquot using 2-(5-Bromo-2-pyridylazo)-5-diethyl aminophenol (Br-PADAP) as chromogenic reagent. The absorption maximum (λ(max)) for UO(2)(2+)-Br-PADAP complex in organic phase samples, in 64% (v/v) ethanol containing buffer solution (pH 7.8) and 1,2-cyclohexylenedinitrilotetraacetic acid (CyDTA) complexing agent, has been found to be at 576 nm (molar extinction coefficient, ɛ: 36,750 ± 240 L mol(-1)cm(-1)). Effects of various parameters like stability of complex, ethanol volume, ore matrix, interfering ions etc. on the determination of uranium have also been evaluated. Absorbance measurements as a function of time showed that colored complex is stable up to > 24h. Presence of increased amount of ethanol in colored solution suppresses the absorption of a standard UO(2)(2+)-Br-PADAP solution. Analyses of synthetic standard as well as ore leach a solution show that for 10 determination relative standard deviation (RSD) is < 2%. The accuracy of the developed method has been checked by determining uranium using standard addition method and was found to be accurate with a 98-105% recovery rate. The developed method has been applied for the analysis of a number of uranium samples generated from uranium ore leach solutions and results were compared with standard methods like inductively coupled plasma emission spectrometry (ICPAES). The determined values of uranium concentrations by these methods are within ± 2%. This method can be used to determine 2.5-250 μg mL(-1) uranium in ore leach solutions with high accuracy and precision.

  7. Simulation of sulfide buildup in wastewater and atmosphere of sewer networks.

    PubMed

    Nielsen, A H; Yongsiri, C; Hvitved-Jacobsen, T; Vollertsen, J

    2005-01-01

    A model concept for prediction of sulfide buildup in sewer networks is presented. The model concept is an extension to--and a further development of--the WATS model (Wastewater Aerobic-anaerobic Transformations in Sewers), which has been developed by Hvitved-Jacobsen and co-workers at Aalborg University. In addition to the sulfur cycle, the WATS model simulates changes in dissolved oxygen and carbon fractions of different biodegradability. The sulfur cycle was introduced via six processes: 1. sulfide production taking place in the biofilm covering the permanently wetted sewer walls; 2. biological sulfide oxidation in the permanently wetted biofilm; 3. chemical and biological sulfide oxidation in the water phase; 4. sulfide precipitation with metals present in the wastewater; 5. emission of hydrogen sulfide to the sewer atmosphere and 6. adsorption and oxidation of hydrogen sulfide on the moist sewer walls where concrete corrosion may take place.

  8. Studies of Polymer-Bound Macrocyclic Polytertiary Phosphines.

    DTIC Science & Technology

    1983-07-31

    Polymer-Bound ?4acrocyclic Polytertiary Fnl c~//q 73, Phosphines 6.PERFORMING o-46. REponR NUMBER 7. AUTI4OR(s) 6. CONTRACT OR GRANT NUMBER(s) tt 2P...Macrocyclic Polytertiary Phosphines 2/1/79 - 7/31/83 P.I., Evan P. Kyba Department of Chemistry University of Texas at Austin Austin, Texas 78712 Approved...transformed into 22 (L = HOMe), which is the operating catalyst in asymmetric hydrogenations of enamides. 1 3 More recently we have described the structure of

  9. Extraction of uranium by macroporous bifunctional phosphinic acid resin

    SciTech Connect

    Sabharwal, K.N.; Rao, P.R.V.; Srinivasan, M.

    1995-05-01

    The extraction of U(VI), Th(IV) and a number of fission products from nitric acid medium by a newly synthesised macroporous bifunctional phosphinic acid resin has been studied. The extraction of uranium from sulphuric acid medium has also been studied. While the gel type phosphinic acid resins seems to pose a number of problems in practical applications, the macroporous type resins are shown to be suitable for a variety of applications where conventional ion exchange resins are of limited use. 12 refs., 5 figs., 3 tabs.

  10. Weathering of sulfides on Mars

    NASA Technical Reports Server (NTRS)

    Burns, Roger G.; Fisher, Duncan S.

    1987-01-01

    Pyrrhotite-pentlandite assemblages in mafic and ultramafic igneous rocks may have contributed significantly to the chemical weathering reactions that produce degradation products in the Martian regolith. By analogy and terrestrial processes, a model is proposed whereby supergene alteration of these primary Fe-Ni sulfides on Mars has generated secondary sulfides (e.g., pyrite) below the water table and produced acidic groundwater containing high concentrations of dissolved Fe, Ni, and sulfate ions. The low pH solutions also initiated weathering reactions of igneous feldspars and ferromagnesian silicates to form clay silicate and ferric oxyhydroxide phases. Near-surface oxidation and hydrolysis of ferric sulfato-and hydroxo-complex ions and sols formed gossan above the water table consisting of poorly crystalline hydrated ferric sulfates (e.g., jarosite), oxides (ferrihydrite, goethite), and silica (opal). Underlying groundwater, now permafrost contains hydroxo sulfato complexes of Fe, Al, Mg, Ni, which may be stabilized in frozen acidic solutions beneath the surface of Mars. Sublimation of permafrost may replenish colloidal ferric oxides, sulfates, and phyllosilicates during dust storms on Mars.

  11. Sulfide Mineralogy and Geochemistry

    NASA Astrophysics Data System (ADS)

    Dilles, John

    2007-02-01

    Reviews in Mineralogy and Geochemistry Series, Volume 61 David J. Vaughan, Editor Geochemical Society and Mineralogical Society of America; ISBN 0-939950-73-1 xiii + 714 pp.; 2006; $40. Sulfide minerals as a class represent important minor rock-forming minerals, but they are generally known as the chief sources of many economic metallic ores. In the past two decades, sulfide research has been extended to include important roles in environmental geology of sulfide weathering and resultant acid mine drainage, as well as in geomicrobiology in which bacteria make use of sulfides for metabolic energy sources. In the latter respect, sulfides played an important role in early evolution of life on Earth and in geochemical cycling of elements in the Earth's crust and hydrosphere.

  12. Bis(allyl)-ruthenium(iv) complexes with phosphinous acid ligands as catalysts for nitrile hydration reactions.

    PubMed

    Tomás-Mendivil, Eder; Francos, Javier; González-Fernández, Rebeca; González-Liste, Pedro J; Borge, Javier; Cadierno, Victorio

    2016-09-14

    Several mononuclear ruthenium(iv) complexes with phosphinous acid ligands [RuCl2(η(3):η(3)-C10H16)(PR2OH)] have been synthesized (78-86% yield) by treatment of the dimeric precursor [{RuCl(μ-Cl)(η(3):η(3)-C10H16)}2] (C10H16 = 2,7-dimethylocta-2,6-diene-1,8-diyl) with 2 equivalents of different aromatic, heteroaromatic and aliphatic secondary phosphine oxides R2P([double bond, length as m-dash]O)H. The compounds [RuCl2(η(3):η(3)-C10H16)(PR2OH)] could also be prepared, in similar yields, by hydrolysis of the P-Cl bond in the corresponding chlorophosphine-Ru(iv) derivatives [RuCl2(η(3):η(3)-C10H16)(PR2Cl)]. In addition to NMR and IR data, the X-ray crystal structures of representative examples are discussed. Moreover, the catalytic behaviour of complexes [RuCl2(η(3):η(3)-C10H16)(PR2OH)] has been investigated for the selective hydration of organonitriles in water. The best results were achieved with the complex [RuCl2(η(3):η(3)-C10H16)(PMe2OH)], which proved to be active under mild conditions (60 °C), with low metal loadings (1 mol%), and showing good functional group tolerance.

  13. Process for scavenging hydrogen sulfide from hydrocarbon gases

    SciTech Connect

    Fox, I.

    1981-01-20

    A process for scavenging hydrogen sulfide from hydrocarbon gases utilizes iron oxide particles of unique chemical and physical properties. These particles have large surface area, and are comprised substantially of amorphous Fe/sub 2/O/sub 3/ containing a crystalline phase of Fe/sub 2/O/sub 3/, Fe/sub 3/O/sub 4/ and combinations thereof. In scavenging hydrogen sulfide, the iron oxide particles are suspended in a liquid which enters into intimate mixing contact with hydrocarbon gases; the hydrogen sulfide is reacted at an exceptional rate and only acid-stable reaction products are formed. Thereafter, the sweetened hydrocarbon gases are collected.

  14. (2-{[2-(diphenyl-phosphino)phen-yl]thio}-phen-yl)diphenyl-phosphine sulfide.

    PubMed

    Alvarez-Larena, Angel; Martinez-Cuevas, Francisco J; Flor, Teresa; Real, Juli

    2012-11-01

    In the title compound, C(36)H(28)P(2)S(2), the dihedral angle between the central benzene rings is 66.95 (13)°. In the crystal, molecules are linked via C(ar)-H⋯π and π-π inter-actions [shortest centroid-centroid distance between benzene rings = 3.897 (2) Å].

  15. Modeling of Sulfide Microenvironments on Mars

    NASA Technical Reports Server (NTRS)

    Schwenzer, S. P.; Bridges, J. C.; McAdam, A.; Steer, E. D.; Conrad, P. G.; Kelley, S. P.; Wiens, R. C.; Mangold, N.; Grotzinger, J.; Eigenbrode, J. L.; Franz, H. B.; Sutter, B.

    2016-01-01

    Yellowknife Bay (YKB; sol 124-198) is the second site that the Mars Science Laboratory Rover Curiosity investigated in detail on its mission in Gale Crater. YKB represents lake bed sediments from an overall neutral pH, low salinity environment, with a mineralogical composition which includes Ca-sulfates, Fe oxide/hydroxides, Fe-sulfides, amorphous material, and trioctahedral phyllosilicates. We investigate whether sulfide alteration could be associated with ancient habitable microenvironments in the Gale mudstones. Some textural evidence for such alteration may be pre-sent in the nodules present in the mudstone.

  16. On the chemical biology of the nitrite/sulfide interaction.

    PubMed

    Cortese-Krott, Miriam M; Fernandez, Bernadette O; Kelm, Malte; Butler, Anthony R; Feelisch, Martin

    2015-04-30

    Sulfide (H2S/HS(-)) has been demonstrated to exert an astounding breadth of biological effects, some of which resemble those of nitric oxide (NO). While the chemistry, biochemistry and potential pathophysiology of the cross-talk between sulfide and NO have received considerable attention lately, a comparable assessment of the potential biological implications of an interaction between nitrite and sulfide is lacking. This is surprising inasmuch as nitrite is not only a known bioactive oxidation product of NO, but also efficiently converted to S-nitrosothiols in vivo; the latter have been shown to rapidly react with sulfide in vitro, leading to formation of S/N-hybrid species including thionitrite (SNO(-)) and nitrosopersulfide (SSNO(-)). Moreover, nitrite is used as a potent remedy against sulfide poisoning in the clinic. The chemistry of interaction between nitrite and sulfide or related bioactive metabolites including polysulfides and elemental sulfur has been extensively studied in the past, yet much of this information appears to have been forgotten. In this review, we focus on the potential chemical biology of the interaction between nitrite and sulfide or sulfane sulfur molecules, calling attention to the fundamental chemical properties and reactivities of either species and discuss their possible contribution to the biology, pharmacology and toxicology of both nitrite and sulfide.

  17. High temperature regenerable hydrogen sulfide removal agents

    DOEpatents

    Copeland, Robert J.

    1993-01-01

    A system for high temperature desulfurization of coal-derived gases using regenerable sorbents. One sorbent is stannic oxide (tin oxide, SnO.sub.2), the other sorbent is a metal oxide or mixed metal oxide such as zinc ferrite (ZnFe.sub.2 O.sub.4). Certain otherwise undesirable by-products, including hydrogen sulfide (H.sub.2 S) and sulfur dioxide (SO.sub.2) are reused by the system, and elemental sulfur is produced in the regeneration reaction. A system for refabricating the sorbent pellets is also described.

  18. Copper(II) mediated hydrogen sulfide and thiol oxidation to disulfides and organic polysulfanes, and their reductive cleavage in wine: Mechanistic elucidation and potential applications.

    PubMed

    Kreitman, Gal Y; Danilewicz, John C; Jeffery, David William; Elias, Ryan J

    2017-03-05

    Fermentation-derived volatile sulfur compounds (VSCs) are undesirable in wine and are often remediated in a process known as copper fining. In the present study, the addition of Cu(II) to model and real wine systems containing hydrogen sulfide (H2S) and thiols provided evidence for the generation of disulfides (disulfanes) and organic polysulfanes. Cu(II) fining of a white wine spiked with glutathione, H2S, and methanethiol (MeSH) resulted in the generation of MeSH-glutathione disulfide and trisulfane. In the present study, the mechanisms underlying the interaction of H2S and thiols with Cu(II) is discussed, and a prospective diagnostic test for releasing volatile sulfur compounds from their non-volatile forms in wine is investigated. This test utilized a combination of reducing agents, metal chelators, and low oxygen conditions to promote the release of H2S and MeSH, at levels above their reported sensory thresholds, from red and white wines that were otherwise free of sulfidic off-odors at the time of addition.

  19. Interstellar hydrogen sulfide.

    NASA Technical Reports Server (NTRS)

    Thaddeus, P.; Kutner, M. L.; Penzias, A. A.; Wilson, R. W.; Jefferts, K. B.

    1972-01-01

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

  20. Phosphine Chemistry on Mo(110) and Oxidized Mo(110)

    DTIC Science & Technology

    1993-01-01

    temperature the O(KLL) peak of MoOx (0(520 eV)/Mo(187 eV) ratioy = shoulder (85 K) developed; it originates from multilayer phys- 0.3). It was found...400 TEMPERATURE (K) MOOx (o/Mo-4.0J Figure 6. Comparison of PH3 TPD spectra from PH3/Mo(I 10) and from PH3/D2/Mo(l 10). so 150 250 350 450 550

  1. Influence of sulfide concentration on the corrosion behavior of titanium in a simulated oral environment.

    PubMed

    Harada, Rino; Takemoto, Shinji; Kinoshita, Hideaki; Yoshinari, Masao; Kawada, Eiji

    2016-05-01

    This study assessed the corrosion behavior of titanium in response to sulfide by determining the effects of sulfide concentration and pH over immersion period. Corrosion was evaluated through changes in color, glossiness, surface characterization, and titanium release. Sulfide solutions were prepared in 3 different concentrations with Na2S, each in pH unadjusted (sulfide-alkaline) and pH adjusted to 7.5 (sulfide-neutral). Titanium discoloration increased and glossiness decreased as sulfide concentration and immersion period increased in sulfide-alkaline solutions. Coral-like complexes were observed on the surface of these specimens, which became more pronounced as concentration increased. Small amounts of titanium release were detected in sulfide-alkaline solutions; however, this was not affected by immersion periods. Corrosion was indicated through considerable surface oxidation suggesting the formation of a thick oxide layer. No significant changes in color and glossiness, or titanium release were indicated for titanium specimens immersed in sulfide-neutral solutions indicating that pH had a significant effect on corrosion. Our findings suggest that a thick oxide layer on the titanium surface was formed in sulfide-alkaline solutions due to excessive oxidation.

  2. Metabolism of S-(2-chloro-1,1,2-trifluoroethyl)-L-cysteine to hydrogen sulfide and the role of hydrogen sulfide in S-(2-chloro-1,1,2-trifluoroethyl)-L-cysteine-induced mitochondrial toxicity.

    PubMed

    Banki, K; Elfarra, A A; Lash, L H; Anders, M W

    1986-07-31

    The nephrotoxic cysteine S-conjugate S-(2-chloro-1,1,2-trifluoroethyl)-L-cysteine (CTFC) is metabolized by kidney homogenates and subcellular fractions to pyruvate and a reactive thiol, which is cytotoxic and partially decomposes to yield hydrogen sulfide and thiosulfate. Although hydrogen sulfide is a potent mitochondrial poison, the mitochondrial toxicity of CTFC is not attributable to hydrogen sulfide formation, as shown by different sites of inhibition of mitochondrial respiration by CTFC and hydrogen sulfide. The efficient mitochondrial oxidation of hydrogen sulfide apparently serves to protect mitochondria against the toxic effects of hydrogen sulfide generated from CTFC.

  3. Diurnal changes in pore water sulfide concentrations in the seagrass Thalassia testudinum beds: the effects of seagrasses on sulfide dynamics.

    PubMed

    Lee; Dunton

    2000-12-20

    The dynamics of the seagrass-sulfide interaction were examined in relation to diel changes in sediment pore water sulfide concentrations in Thalassia testudinum beds and adjacent bare areas in Corpus Christi Bay and lower Laguna Madre, Texas, USA, during July 1996. Pore water sulfide concentrations in seagrass beds were significantly higher than in adjacent bare areas and showed strong diurnal variations; levels significantly decreased during mid-day at shallow sediment depths (0-10 cm) containing high below-ground tissue biomass and surface area. In contrast, diurnal variations in sediment sulfide concentrations were absent in adjacent bare patches, and at deeper (>10 cm) sediment depths characterized by low below-ground plant biomass or when the grasses were experimentally shaded. These observations suggest that the mid-day depressions in sulfide levels are linked to the transport of photosynthetically produced oxygen to seagrass below-ground tissues that fuels sediment sulfide oxidation. Lower sulfide concentrations in bare areas are likely a result of low sulfate reduction rates due to low organic matter available for remineralization. Further, high reoxidation rates due to rapid exchange between anoxic pore water and oxic overlying water are probably stimulated in bare areas by higher current velocity on the sediment surface than in seagrass beds. The dynamics of pore water sulfides in seagrass beds suggest no toxic sulfide intrusion into below-ground tissues during photosynthetic periods and demonstrate that the sediment chemical environment is considerably modified by seagrasses. The reduced sediment sulfide levels in seagrass beds during photosynthetic periods will enhance seagrass production through reduced sulfide toxicity to seagrasses and sediment microorganisms related to the nutrient cycling.

  4. Thioclava pacifica gen. nov., sp. nov., a novel facultatively autotrophic, marine, sulfur-oxidizing bacterium from a near-shore sulfidic hydrothermal area.

    PubMed

    Sorokin, Dimitry Yu; Tourova, Tatjana P; Spiridonova, Elizaveta M; Rainey, Fred A; Muyzer, Gerard

    2005-05-01

    Strain TL 2(T) was isolated on mineral medium with thiosulfate from a near-shore sulfidic hydrothermal area in Matupi Harbour on the island of New Britain, Papua New Guinea. The cells varied from long filaments with swollen ends, often aggregated, to short rods, depending on the growth conditions. The bacterium was obligately aerobic and grew autotrophically with thiosulfate as energy source or heterotrophically with organic acids and sugars. In thiosulfate-limited continuous culture, mu(max) and Y(max) for autotrophic growth were 0.1 h(-1) and 3 g protein mol(-1), respectively. From the various reduced sulfur compounds tested, only thiosulfate and sulfide supported active respiration. Inorganic carbon was assimilated via the Calvin cycle. Presence of the 'green'-type of form I RubisCO gene was detected. Growth was possible from 15 to 47 degrees C with an optimum at 35 degrees C, pH 6.5-8.5 with an optimum at pH 8.0, and between 10 and 90 g NaCl l(-1) with an optimum at 35 g l(-1). Phylogenetic analysis based on 16S rRNA and cbbL gene sequences demonstrated that strain TL 2(T) forms a separate lineage within the alpha-3 subdivision of the Proteobacteria, distantly related to the genera Rhodovulum and Rhodobacter. On the basis of these results, a novel genus and species, Thioclava pacifica gen. nov., sp. nov., is proposed to accommodate strain TL 2(T) (= DSM 10166(T) = UNIQEM 229(T)).

  5. Functional analysis of three sulfide:quinone oxidoreductase homologs in Chlorobaculum tepidum.

    PubMed

    Chan, Leong-Keat; Morgan-Kiss, Rachael M; Hanson, Thomas E

    2009-02-01

    Sulfide:quinone oxidoreductase (SQR) catalyzes sulfide oxidation during sulfide-dependent chemo- and phototrophic growth in bacteria. The green sulfur bacterium Chlorobaculum tepidum (formerly Chlorobium tepidum) can grow on sulfide as the sole electron donor and sulfur source. C. tepidum contains genes encoding three SQR homologs: CT0117, CT0876, and CT1087. This study examined which, if any, of the SQR homologs possess sulfide-dependent ubiquinone reduction activity and are required for growth on sulfide. In contrast to CT0117 and CT0876, transcripts of CT1087 were detected only when cells actively oxidized sulfide. Mutation of CT0117 or CT1087 in C. tepidum decreased SQR activity in membrane fractions, and the CT1087 mutant could not grow with >or=6 mM sulfide. Mutation of both CT0117 and CT1087 in C. tepidum completely abolished SQR activity, and the double mutant failed to grow with >or=4 mM sulfide. A C-terminal His(6)-tagged CT1087 protein was membrane localized, as was SQR activity. Epitope-tagged CT1087 was detected only when sulfide was actively consumed by cells. Recombinantly produced CT1087 and CT0117 proteins had SQR activity, while CT0876 did not. In summary, we conclude that, under the conditions tested, both CT0117 and CT1087 function as SQR proteins in C. tepidum. CT0876 may support the growth of C. tepidum at low sulfide concentrations, but no evidence was found for SQR activity associated with this protein.

  6. Advances in Nucleophilic Phosphine Catalysis of Alkenes, Allenes, Alkynes, and MBHADs

    PubMed Central

    Fan, Yi Chiao

    2014-01-01

    In nucleophilic phosphine catalysis, tertiary phosphines undergo conjugate additions to activated carbon–carbon multiple bonds to form β-phosphonium enolates, β-phosphonium dienolates, β-phosphonium enoates, and vinyl phosphonium ylides as intermediates. When these reactive zwitterionic species react with nucleophiles and electrophiles, they may generate carbo- and heterocycles with multifarious molecular architectures. This Article describes the reactivities of these phosphonium zwitterions, the applications of phosphine catalysis in the syntheses of biologically active compounds and natural products, and recent developments in the enantioselective phosphine catalysis. PMID:24196409

  7. Effects of phosphine on the neural regulation of gas exchange in Periplaneta americana.

    PubMed

    Woodman, James D; Haritos, Victoria S; Cooper, Paul D

    2008-04-01

    Phosphine is used for fumigating stored commodities, however an understanding of the physiological response to phosphine in insects is limited. Here we show how the central pattern generator for ventilation in the central nervous system (CNS) responds to phosphine and influences normal resting gas exchange. Using the American cockroach, Periplaneta americana, that perform discontinuous gas exchange (DGE) at rest, we simultaneously measure ventilatory nervous output from the intact CNS, VCO(2) and water loss from live specimens. Exposure to 800 ppm phosphine at 25 degrees C for 2 h (n=13) during recording did not cause any mortality or obvious sub-lethal effects. Within 60 s of introducing phosphine into the air flow, all animals showed a distinct CNS response accompanied by a burst release of CO(2). The initial ventilatory response to phosphine displaced DGE and was typically followed by low, stable and continuous CO(2) output. CNS output was highest and most orderly under normoxic conditions during DGE. Phosphine caused a series of ventilatory CNS spikes preceding almost complete cessation of CNS output. Minimal CNS output was maintained during the 2 h normoxic recovery period and DGE was not reinstated. VCO(2) was slightly reduced and water loss significantly lower during the recovery period compared with those rates prior to phosphine exposure. A phosphine narcosis effect is rejected based on animals remaining alert at all times during exposure.

  8. Measurement and biological significance of the volatile sulfur compounds hydrogen sulfide, methanethiol and dimethyl sulfide in various biological matrices.

    PubMed

    Tangerman, Albert

    2009-10-15

    This review deals with the measurement of the volatile sulfur compounds hydrogen sulfide, methanethiol and dimethyl sulfide in various biological matrices of rats and humans (blood, serum, tissues, urine, breath, feces and flatus). Hydrogen sulfide and methanethiol both contain the active thiol (-SH) group and appear in the free gaseous form, in the acid-labile form and in the dithiothreitol-labile form. Dimethyl sulfide is a neutral molecule and exists only in the free form. The foul odor of these sulfur volatiles is a striking characteristic and plays a major role in bad breath, feces and flatus. Because sulfur is a biologically active element, the biological significance of the sulfur volatiles are also highlighted. Despite its highly toxic properties, hydrogen sulfide has been lately recommended to become the third gasotransmitter, next to nitric oxide and carbon monoxide, based on high concentration found in healthy tissues, such as blood and brain. However, there is much doubt about the reliability of the assay methods used. Many artifacts in the sulfide assays exist. The methods to detect the various forms of hydrogen sulfide are critically reviewed and compared with findings of our group. Recent findings that free gaseous hydrogen sulfide is absent in whole blood urged the need to revisit its role as a blood-borne signaling molecule.

  9. Retrievals of Jovian Tropospheric Phosphine from Cassini/CIRS

    NASA Technical Reports Server (NTRS)

    Irwin, P. G. J.; Parrish, P.; Fouchet, T.; Calcutt, S. B.; Taylor, F. W.; Simon-Miller, A. A.; Nixon, C. A.

    2004-01-01

    On December 30th 2000, the Cassini-Huygens spacecraft reached the perijove milestone on its continuing journey to the Saturnian system. During an extended six-month encounter, the Composite Infrared Spectrometer (CIRS) returned spectra of the Jovian atmosphere, rings and satellites from 10-1400 cm(exp -1) (1000-7 microns) at a programmable spectral resolution of 0.5 to 15 cm(exp -1). The improved spectral resolution of CIRS over previous IR instrument-missions to Jupiter, the extended spectral range, and higher signal-to-noise performance provide significant advantages over previous data sets. CIRS global observations of the mid-infrared spectrum of Jupiter at medium resolution (2.5 cm(exp -1)) have been analysed both with a radiance differencing scheme and an optimal estimation retrieval model to retrieve the spatial variation of phosphine and ammonia fractional scale height in the troposphere between 60 deg S and 60 deg N at a spatial resolution of 6 deg. The ammonia fractional scale height appears to be high over the Equatorial Zone (EZ) but low over the North Equatorial Belt (NEB) and South Equatorial Belt (SEB) indicating rapid uplift or strong vertical mixing in the EZ. The abundance of phosphine shows a similar strong latitudinal variation which generally matches that of the ammonia fractional scale height. However while the ammonia fractional scale height distribution is to a first order symmetric in latitude, the phosphine distribution shows a North/South asymmetry at mid latitudes with higher amounts detected at 40 deg N than 40 deg S. In addition the data show that while the ammonia fractional scale height at this spatial resolution appears to be low over the Great Red Spot (GRS), indicating reduced vertical mixing above the approx. 500 mb level, the abundance of phosphine at deeper levels may be enhanced at the northern edge of the GRS indicating upwelling.

  10. Phosphine-boronates: efficient bifunctional organocatalysts for Michael addition.

    PubMed

    Baslé, Olivier; Porcel, Susana; Ladeira, Sonia; Bouhadir, Ghenwa; Bourissou, Didier

    2012-05-11

    Phosphine-boronates R(2)P(o-C(6)H(4))B(OR')(2) have been evaluated as bifunctional organocatalysts for the Michael addition of malonate pronucleophiles to methylvinylketone. The presence of the Lewis acidic boron center adjacent to phosphorus significantly improves catalytic performance. Isolation and complete characterization of a key intermediate, namely a β-phosphonium enolate, substantiate the role of the Lewis acidic moiety in the catalytic process.

  11. Biaryl Phosphine Ligands in Palladium-Catalyzed Amination

    PubMed Central

    Surry, David S.

    2012-01-01

    Palladium-catalyzed amination of aryl halides has undergone rapid development in the last 12 years. This has been largely driven by implementation of new classes of ligands. Biaryl phosphines have proven to provide especially active catalysts in this context. This review discusses the applications that these catalysts have found in C-N cross-coupling in heterocycle synthesis, pharmaceuticals, materials science and natural product synthesis. PMID:18663711

  12. Electrochemical Properties of Palladium and Platinum Phosphine Complexes.

    DTIC Science & Technology

    1985-09-30

    19 .3 Molecular orbital Energy Diagram for Square Planar Pd-Phosphine Complexes.......................... 20 4 Cyclic Voltammogram...hydrogen, and therefore cause reaction 6 and 7 to be more difficult than reaction 1. Similar results have been observed with lead, indium, cadmium ... voltammetry : trans-PdIIL 2x2 , where L = PPh 3, PBu 3, PCy3, NHMe 2 (Ph - phenyl, Bu = n-butyl, Cy = cyclohexyl, Me methyl) and X = Cl or I; cis-PdII(LL)X2

  13. Metal Sulfides as Sensing Materials for Chemoresistive Gas Sensors

    PubMed Central

    Gaiardo, Andrea; Fabbri, Barbara; Guidi, Vincenzo; Bellutti, Pierluigi; Giberti, Alessio; Gherardi, Sandro; Vanzetti, Lia; Malagù, Cesare; Zonta, Giulia

    2016-01-01

    This work aims at a broad overview of the results obtained with metal-sulfide materials in the field of chemoresistive gas sensing. Indeed, despite the well-known electrical, optical, structural and morphological features previously described in the literature, metal sulfides present lack of investigation for gas sensing applications, a field in which the metal oxides still maintain a leading role owing to their high sensitivity, low cost, small dimensions and simple integration, in spite of the wide assortment of sensing materials. However, despite their great advantages, metal oxides have shown significant drawbacks, which have led to the search for new materials for gas sensing devices. In this work, Cadmium Sulfide and Tin (IV) Sulfide were investigated as functional materials for thick-film chemoresistive gas-sensors fabrication and they were tested both in thermo- and in photo-activation modes. Furthermore, electrical characterization was carried out in order to verify their gas sensing properties and material stability, by comparing the results obtained with metal sulfides to those obtained by using their metal-oxides counterparts. The results highlighted the possibility to use metal sulfides as a novel class of sensing materials, owing to their selectivity to specific compounds, stability, and the possibility to operate at room temperature. PMID:26927120

  14. Micro-aeration for hydrogen sulfide removal from biogas

    NASA Astrophysics Data System (ADS)

    Duangmanee, Thanapong

    The presence of sulfur compounds (e.g. protein, sulfate, thiosulfate, sulfite, etc.) in the feed stream generates highly corrosive and odorous hydrogen sulfide during anaerobic digestion. The high sulfide level in the biogas stream is not only poisonous to many novel metal catalysts employed in thermo-catalytic processes but also reduces the quality of methane to produce renewable energy. This study used an innovative, low-maintenance, low-cost biological sulfide removal technology to remove sulfides simultaneously from both gas and liquid phase. ORP (Oxidation-Reduction-Potential) was used as the controlling parameter to precisely regulate air injection to the sulfide oxidizing unit (SOU). The microaeration technique provided just enough oxygen to partially oxidize sulfides to elemental sulfur without inhibiting methanogenesis. The SOU was equipped with a diffuser at the bottom for the dispersion of sulfide-laden biogas and injected air throughout the column. The SOU can be operated as a standalone unit or coupled with an anaerobic digester to simultaneously remove sulfide from the biogas and effluent. The integrated system was capable of reducing hydrogen sulfide in biogas from 2,450 to less than 2 ppmV with minimal sulfate production at the highest available sulfide loading rate of 0.24 kg/m3-day. More than 98% of sulfide removed was recovered as elemental sulfur. However, the standalone SOU was able to operate at high hydrogen sulfide loading of 1.46 kg/m 3-day at inlet sulfide concentration of 3000 ppmV and reduce the off-gas hydrogen sulfide concentrations to less than 10 ppmV. The experiment also revealed that the ORP controlled aeration was sensitive enough to prevent oxygen overdosing (dampening effect) during unexpected surges of aeration. Using generalized linear regression, a model predicting output H2S concentration based on input H2S concentrations, SOU medium heights, and biogas flow rates, was derived. With 95% confidence, output H2S concentration

  15. Iron sulfide minerals in Black Sea sediments

    NASA Astrophysics Data System (ADS)

    Franke, C.; Robin, E.; Henkel, S.; Kasten, S.; Bleil, U.

    2009-04-01

    This study presents an integrated geochemical, environmental magnetic, and electron microscopic approach to better understand the physicochemical processes in deep sea sediments from the northwestern Black Sea. The investigated gravity core GC 214 was retrieved in 2007 during RV Meteor cruise M72/1 west of the Crimean Peninsula in a water depth of 1686 mbsf. Geochemical analyses of the pore water and solid phase indicate non-steady state sedimentation. The oxygen-depleted water column conditions, anaerobic oxidation of methane (AOM) and related microbially-driven sulfate reduction favor a highly complex iron sulfide mineral assemblage in the sediment column. The detailed magnetic susceptibility and remanence measurements indicate an irregularly stratified depth profile showing intervals of particularly high values. Further environmental magnetic analyses depict strongly elevated coercivities for those depth horizons, suggesting greigite as one of the main magnetic carrier minerals. Automated chemical classification (ACC), using electron dispersive spectrometer (EDS) attached to a JEOL840 scanning electron microscope (SEM), on dispersed particle samples permitted the identification of greigite (Fe3S4) next to pyrrhotite (Fe7S8), pyrite (FeS2) and monosulfides (FeS), but also allowed for the absolute quantification of the various mineral phases. These analyses were carried out on magnetic extracts and density separates to be able to calculate budgets between the different present iron sulfides. We obtained excellent correlations between the different iron sulfide concentrations and the magnetic signal. Additional analyses on polished sections yield inside into the details of the sulfidization pathways along the depth profile of the sediment sequence and help to develop a more general process model for this particular geochemical (paleo-)environment. Keywords: Black Sea, iron sulfides, environmental magnetism, anaerobic oxidation of methane (AOM), scanning electron

  16. Redox biochemistry of hydrogen sulfide.

    PubMed

    Kabil, Omer; Banerjee, Ruma

    2010-07-16

    H(2)S, the most recently discovered gasotransmitter, might in fact be the evolutionary matriarch of this family, being both ancient and highly reduced. Disruption of gamma-cystathionase in mice leads to cardiovascular dysfunction and marked hypertension, suggesting a key role for this enzyme in H(2)S production in the vasculature. However, patients with inherited deficiency in gamma-cystathionase apparently do not present vascular pathology. A mitochondrial pathway disposes sulfide and couples it to oxidative phosphorylation while also exposing cytochrome c oxidase to this metabolic poison. This report focuses on the biochemistry of H(2)S biogenesis and clearance, on the molecular mechanisms of its action, and on its varied biological effects.

  17. SULFIDE METHOD PLUTONIUM SEPARATION

    DOEpatents

    Duffield, R.B.

    1958-08-12

    A process is described for the recovery of plutonium from neutron irradiated uranium solutions. Such a solution is first treated with a soluble sullide, causing precipitation of the plutoniunn and uraniunn values present, along with those impurities which form insoluble sulfides. The precipitate is then treated with a solution of carbonate ions, which will dissolve the uranium and plutonium present while the fission product sulfides remain unaffected. After separation from the residue, this solution may then be treated by any of the usual methods, such as formation of a lanthanum fluoride precipitate, to effect separation of plutoniunn from uranium.

  18. Hydrogen sulfide - cysteine cycle system enhances cadmium tolerance through alleviating cadmium-induced oxidative stress and ion toxicity in Arabidopsis roots

    PubMed Central

    Jia, Honglei; Wang, Xiaofeng; Dou, Yanhua; Liu, Dan; Si, Wantong; Fang, Hao; Zhao, Chen; Chen, Shaolin; Xi, Jiejun; Li, Jisheng

    2016-01-01

    Cadmium (Cd2+) is a common toxic heavy metal ion. We investigated the roles of hydrogen sulfide (H2S) and cysteine (Cys) in plant responses to Cd2+ stress. The expression of H2S synthetic genes LCD and DES1 were induced by Cd2+ within 3 h, and endogenous H2S was then rapidly released. H2S promoted the expression of Cys synthesis-related genes SAT1 and OASA1, which led to endogenous Cys accumulation. The H2S and Cys cycle system was stimulated by Cd2+ stress, and it maintained high levels in plant cells. H2S inhibited the ROS burst by inducing alternative respiration capacity (AP) and antioxidase activity. H2S weakened Cd2+ toxicity by inducing the metallothionein (MTs) genes expression. Cys promoted GSH accumulation and inhibited the ROS burst, and GSH induced the expression of phytochelatin (PCs) genes, counteracting Cd2+ toxicity. In summary, the H2S and Cys cycle system played a key role in plant responses to Cd2+ stress. The Cd2+ tolerance was weakened when the cycle system was blocked in lcddes1-1 and oasa1 mutants. This paper is the first to describe the role of the H2S and Cys cycle system in Cd2+ stress and to explore the relevant and specificity mechanisms of H2S and Cys in mediating Cd2+ stress. PMID:28004782

  19. One-step solvothermal tailoring the compositions and phases of nickel cobalt sulfides on conducting oxide substrates as counter electrodes for efficient dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Huang, Niu; Li, Guowang; Huang, Hua; Sun, Panpan; Xiong, Tianli; Xia, Zhifen; Zheng, Fang; Xu, Jixing; Sun, Xiaohua

    2016-12-01

    Several nickel cobalt sulfide (Ni-Co-S) counter electrodes (CEs) are prepared, and the Ni-Co-S nanoparticles are in-situ grown on SnO2: F (FTO) transparent conductive glasses via a facile solvothermal process, in which thiourea is used as the sulfurizing reagent. The X-ray diffraction, scanning electron microscopy, and energy dispersive spectrometer are employed to measure the microstructure and composition of the Ni-Co-S CEs. When a proper amount of thiourea is adopted, fine crystalline NiCo2S4 CE is obtained. When the amount of thiourea is small or large, (Ni,Co)4S3 or (Ni,Co)3S4 CE is acquired, respectively. Cyclic voltammetry, electrochemical impedance spectroscopy, Tafel polarization and open-circuit voltage decay (OCVD) measurements all demonstrate that the electrocatalytic activities and electrical conductivities of these Ni-Co-S CEs all approach or exceed those of Pt-pyrolysis CE. Their superior electrochemical performances are further confirmed by fabricating DSSCs with the Ni-Co-S CEs, they display similar or better photo-electric conversion efficiencies to/than the Pt-pyrolysis counterpart.

  20. Hydrogen Sulfide Prolongs Postharvest Storage of Fresh-Cut Pears (Pyrus pyrifolia) by Alleviation of Oxidative Damage and Inhibition of Fungal Growth

    PubMed Central

    Gao, Shuai-Ping; Wu, Jun; Li, Yan-Hong; Zheng, Ji-Lian; Han, Yi; Liu, Yong-Sheng; Zhang, Hua

    2014-01-01

    Hydrogen sulfide (H2S) has proved to be a multifunctional signaling molecule in plants and animals. Here, we investigated the role of H2S in the decay of fresh-cut pears (Pyrus pyrifolia). H2S gas released by sodium hydrosulfide (NaHS) prolonged the shelf life of fresh-cut pear slices in a dose-dependent manner. Moreover, H2S maintained higher levels of reducing sugar and soluble protein in pear slices. H2S significantly reduced the accumulation of hydrogen peroxide (H2O2), superoxide radicals (•O2−) and malondialdehyde (MDA). Further investigation showed that H2S fumigation up-regulated the activities of antioxidant enzymes ascorbate peroxidase (APX), catalase (CAT), and guaiacol peroxidase (POD), while it down-regulated those of lipoxygenase (LOX), phenylalanine ammonia lyase (PAL) and polyphenol oxidase (PPO). Furthermore, H2S fumigation effectively inhibited the growth of two fungal pathogens of pear, Aspergillus niger and Penicillium expansum, suggesting that H2S can be developed as an effective fungicide for postharvest storage. The present study implies that H2S is involved in prolonging postharvest storage of pears by acting as an antioxidant and fungicide. PMID:24454881

  1. Air-stable platinum and palladium complexes featuring bis[2,4-bis(trifluoromethyl)phenyl]phosphinous acid ligands.

    PubMed

    Kurscheid, Boris; Neumann, Beate; Stammler, Hans-Georg; Hoge, Berthold

    2011-12-23

    Secondary phosphane oxides, R(2)P(O)H, are commonly used as preligands for transition-metal complexes of phosphinous acids, R(2)P-OH (R=alkyl, aryl), which are relevant as efficient catalysts in cross-coupling processes. In contrast to previous work by other groups, we are interested in the ligating properties of an electron-deficient phosphinous acid, (R(f))(2)P-OH, bearing the strongly electron-withdrawing and sterically demanding 2,4-bis(trifluoromethyl)phenyl group towards catalysis-relevant metals, such as palladium and platinum. The preligand bis[2,4-bis(trifluoromethyl)phenyl]phosphane oxide, (R(f))(2)P(O)H, reacts smoothly with solid platinum(II) dichloride yielding the trans-configured phosphinous acid platinum complex trans-[PtCl(2)({2,4-(CF(3))(2)C(6)H(3)}(2)POH)(2)]. The deprotonation of one phosphinous acid ligand with an appropriate base leads to the cis-configured monoanion complex cis-[PtCl(2)({2,4-(CF(3))(2)C(6)H(3)}(2)PO)(2)H](-), featuring the quasi-chelating phosphinous acid phosphinito unit, (R(f))(2)P-O-H···O=P(R(f))(2), which exhibits a strong hydrogen bridge substantiated by an O···O distance of 245.1(4) pm. The second deprotonation step is accompanied by a rearrangement to afford the trans-configured dianion trans-[PtCl(2)({2,4-(CF(3))(2)C(6)H(3)}(2)PO)(2)](2-). The reaction of (R(f))(2)P(O)H with solid palladium(II) dichloride initially yields a mononuclear palladium complex [PdCl(2)({2,4-(CF(3))(2)C(6)H(3)}(2)POH)(2)], which condenses under liberation of HCl to the neutral dinuclear palladium complex [Pd(2)(μ-Cl)(2){({2,4-(CF(3))(2)C(6)H(3)}(2)PO)(2)H}(2)]. The equilibrium between the mononuclear [PdCl(2)({2,4-(CF(3))(2)C(6)H(3)}(2)POH)(2)] and dinuclear [Pd(2)(μ-Cl)(2){({2,4-(CF(3))(2)C(6)H(3)}(2)PO)(2)H}(2)] palladium complexes is reversible and can be shifted in each direction by the addition of base or HCl, respectively. Treatment of palladium(II) hexafluoroacetylacetonate, [Pd(F(6)acac)(2)], with a slight excess of (R(f))(2)P

  2. Experiments in Thermodynamics and Kinetics of Phosphine Substitution in (p-Cymene)RuCl[subscript 2](PR[subscript 3])

    ERIC Educational Resources Information Center

    Ozerov, Oleg V.; Fafard, Claudia M.; Hoffman, Norris W.

    2007-01-01

    This manuscript describes a set of three experiments that investigates the thermodynamic and kinetic aspects of phosphine substitution at a Ru center. In the first experiment, the students synthesize a Ru organometallic complex containing a phosphine ligand. In the second, equilibria for phosphine substitution involving several different…

  3. Zinc sulfide liquefaction catalyst

    DOEpatents

    Garg, Diwakar

    1984-01-01

    A process for the liquefaction of carbonaceous material, such as coal, is set forth wherein coal is liquefied in a catalytic solvent refining reaction wherein an activated zinc sulfide catalyst is utilized which is activated by hydrogenation in a coal derived process solvent in the absence of coal.

  4. Sulfidation of a Novel Iron Sorbent Supported on Lignite Chars during Hot Coal Gas Desulfurization

    NASA Astrophysics Data System (ADS)

    Yin, Fengkui; Yu, Jianglong; Gupta, Sushil; Wang, Shaoyan; Wang, Dongmei; Yang, Li; Tahmasebi, Arash

    The sulfidation behavior of novel iron oxide sorbents supported using activated-chars during desulfurization of hot coal gases has been studied. The sulfidation of the char-supported sorbents was investigated using a fixed-bed quartz reactor in the temperature range of 673K to 873K. The product gases were analyzed using a GC equipped with a TCD and a FPD detector. The sorbent samples before and after sulfidation were examined using SEM and XRD.

  5. Utilization of Hyperbaric Oxygen Therapy and Induced Hypothermia After Hydrogen Sulfide Exposure

    PubMed Central

    Asif, Mir J.; Exline, Matthew C.

    2013-01-01

    Hydrogen sulfide is a toxic gas produced as a byproduct of organic waste and many industrial processes. Hydrogen sulfide exposure symptoms may vary from mild (dizziness, headaches, nausea) to severe lactic acidosis via its inhibition of oxidative phosphorylation, leading to cardiac arrhythmias and death. Treatment is generally supportive. We report the case of a patient presenting with cardiac arrest secondary to hydrogen sulfide exposure treated with both hyperbaric oxygen therapy and therapeutic hypothermia with great improvement in neurologic function. PMID:22004989

  6. Dibenzyl Sulfide Metabolism by White Rot Fungi

    PubMed Central

    Van Hamme, Jonathan D.; Wong, Eddie T.; Dettman, Heather; Gray, Murray R.; Pickard, Michael A.

    2003-01-01

    Microbial metabolism of organosulfur compounds is of interest in the petroleum industry for in-field viscosity reduction and desulfurization. Here, dibenzyl sulfide (DBS) metabolism in white rot fungi was studied. Trametes trogii UAMH 8156, Trametes hirsuta UAMH 8165, Phanerochaete chrysosporium ATCC 24725, Trametes versicolor IFO 30340 (formerly Coriolus sp.), and Tyromyces palustris IFO 30339 all oxidized DBS to dibenzyl sulfoxide prior to oxidation to dibenzyl sulfone. The cytochrome P-450 inhibitor 1-aminobenzotriazole eliminated dibenzyl sulfoxide oxidation. Laccase activity (0.15 U/ml) was detected in the Trametes cultures, and concentrated culture supernatant and pure laccase catalyzed DBS oxidation to dibenzyl sulfoxide more efficiently in the presence of 2,2′-azinobis(3-ethylbenzthiazoline-6-sulfonate) (ABTS) than in its absence. These data suggest that the first oxidation step is catalyzed by extracellular enzymes but that subsequent metabolism is cytochrome P-450 mediated. PMID:12571066

  7. Aerobic and anaerobic degradation of a range of alkyl sulfides by a denitrifying marine bacterium

    USGS Publications Warehouse

    Visscher, P.T.; Taylor, B.F.

    1993-01-01

    A pure culture of a bacterium was obtained from a marine microbial mat by using an anoxic medium containing dimethyl sulfide (DMS) and nitrate. The isolate grew aerobically or anaerobically as a denitrifier on alkyl sulfides, including DMS, dimethyl disulfide, diethyl sulfide (DES), ethyl methyl sulfide, dipropyl sulfide, dibutyl sulfide, and dibutyl disulfide. Cells grown on an alkyl sulfide or disulfide also oxidized the corresponding thiols, namely, methanethiol, ethanethiol, propanethiol, or butanethiol. Alkyl sulfides were metabolized by induced or derepressed cells with oxygen, nitrate, or nitrite as electron acceptor. Cells grown on DMS immediately metabolized DMS, but there was a lag before DES was consumed; with DES-grown cells, DES was immediately used but DMS was used only after a lag. Chloramphenicol prevented the eventual use of DES by DMS-grown cells and DMS use by DES-grown cells, respectively, indicating separate enzymes for the metabolism of methyl and ethyl groups. Growth was rapid on formate, acetate, propionate, and butyrate but slow on methanol. The organism also grew chemolithotrophically on thiosulfate with a decrease in pH; growth required carbonate in the medium. Growth on sulfide was also carbonate dependent but slow. The isolate was identified as a Thiobacillus sp. and designated strain ASN-1. It may have utility for removing alkyl sulfides, and also nitrate, nitrite, and sulfide, from wastewaters.

  8. Interaction of thiols with n-type cadmium sulfide and n-type cadmium selenide in aqueous solutions: adsorption of thiolate anion and efficient photoelectrochemical oxidation to disulfides

    SciTech Connect

    Natan, M.J.; Thackeray, J.W.; Wrighton, M.S.

    1986-08-14

    Organic thiols, RSH = cysteamine, 2-mercaptoethanol, penicillamine, or cysteine, effectively suppress photoanodic decomposition of n-CdS and n-CdSe in aqueous solution and undergo efficient controlled potential photoelectrochemical oxidation to the corresponding disulfides, RSSR. Photovoltage greater than 700 mV is observed for certain thiols upon excitation of the semiconductor anode with light of energy greater than the band gap. As electrodes for preparative electrosynthesis, both illuminated n-CdS and n-CdSe offer significant electrical energy savings compared to conventional electrochemical oxidation in the dark at a Pt electrode. The oxidation of RSH to RSSR at n-CdS and n-CdSe has been studied under various conditions.

  9. Nitrite as an antidote for acute hydrogen sulfide intoxication

    SciTech Connect

    Beck, J.F.; Bradbury, C.M.; Connors, A.J.; Donini, J.C.

    1981-11-01

    The detoxification of hydrogen sulfide (H/sub 2/S) by a heme catalyzed oxidation was examined as part of an on-going study of H/sub 2/S toxicity. Interlocking O/sub 2/ absorption and sulfide depletion data indicate that both oxyhemoglobin and methemoglobin are effective catalytic agents. Although the latter is more efficacious, the life time of excess sulfide in the presence of oxygen and either of the above is of the order of minutes. It has also been established that the formation of methemoglobin following nitrite administration occurs preferentially under oxygen poor conditions. Under an atmospheric or oxygen enriched environment, which favors sulfide depletion, the nitrite retards sulfide oxidation. Thus nitrite as an antidote for acute H/sub 2/S intoxication can only be effective within the first few minutes after the exposure, at which time resuscitation and/or ventilation of the victim is likely to produce conditions in which the nitrite actually slows sulfide removal.

  10. Electrochemical sulfide removal and caustic recovery from spent caustic streams.

    PubMed

    Vaiopoulou, Eleni; Provijn, Thomas; Prévoteau, Antonin; Pikaar, Ilje; Rabaey, Korneel

    2016-04-01

    Spent caustic streams (SCS) are produced during alkaline scrubbing of sulfide containing sour gases. Conventional methods mainly involve considerable chemical dosing or energy expenditures entailing high cost but limited benefits. Here we propose an electrochemical treatment approach involving anodic sulfide oxidation preferentially to sulfur coupled to cathodic caustic recovery using a two-compartment electrochemical system. Batch experiments showed sulfide removal efficiencies of 84 ± 4% with concomitant 57 ± 4% efficient caustic production in the catholyte at a final concentration of 6.4 ± 0.1 wt% NaOH (1.6 M) at an applied current density of 100 A m(-2). Subsequent long-term continuous experiments showed that stable cell voltages (i.e. 2.7 ± 0.1 V) as well as constant sulfide removal efficiencies of 67 ± 5% at a loading rate of 47 g(S) L(-1) h(-1) were achieved over a period of 77 days. Caustic was produced at industrially relevant strengths for scrubbing (i.e. 5.1 ± 0.9 wt% NaOH) at current efficiencies of 96 ± 2%. Current density between 0 and 200 A m(-2) and sulfide loading rates of 50-200 g(S) L(-1) d(-1) were tested. The higher the current density the more oxidized the sulfur species produced and the higher the sulfide oxidation. On the contrary, high loading rate resulted in a reduction of sulfide oxidation efficiency. The results obtained in this study together with engineering calculations show that the proposed process could represent a cost-effective approach for sodium and sulfur recovery from SCS.

  11. The hydrogen sulfide metabolite trimethylsulfonium is found in human urine

    PubMed Central

    Lajin, Bassam; Francesconi, Kevin A.

    2016-01-01

    Hydrogen sulfide is the third and most recently discovered gaseous signaling molecule following nitric oxide and carbon monoxide, playing important roles both in normal physiological conditions and disease progression. The trimethylsulfonium ion (TMS) can result from successive methylation reactions of hydrogen sulfide. No report exists so far about the presence or quantities of TMS in human urine. We developed a method for determining TMS in urine using liquid chromatography-electrospray ionization-triple quadrupole mass spectrometry (LC-ESI-QQQ), and applied the method to establish the urinary levels of TMS in a group of human volunteers. The measured urinary levels of TMS were in the nanomolar range, which is commensurate with the steady-state tissue concentrations of hydrogen sulfide previously reported in the literature. The developed method can be used in future studies for the quantification of urinary TMS as a potential biomarker for hydrogen sulfide body pools. PMID:27247020

  12. One-Step In Situ Growth of Iron-Nickel Sulfide Nanosheets on FeNi Alloy Foils: High-Performance and Self-Supported Electrodes for Water Oxidation.

    PubMed

    Yuan, Cheng-Zong; Sun, Zhong-Ti; Jiang, Yi-Fan; Yang, Zheng-Kun; Jiang, Nan; Zhao, Zhi-Wei; Qazi, Umair Yaqub; Zhang, Wen-Hua; Xu, An-Wu

    2017-03-10

    Efficient and durable oxygen evolution reaction (OER) catalysts are highly required for the cost-effective generation of clean energy from water splitting. For the first time, an integrated OER electrode based on one-step direct growth of metallic iron-nickel sulfide nanosheets on FeNi alloy foils (denoted as FeNi3 S2 /FeNi) is reported, and the origin of the enhanced OER activity is uncovered in combination with theoretical and experimental studies. The obtained FeNi3 S2 /FeNi electrode exhibits highly catalytic activity and long-term stability toward OER in strong alkaline solution, with a low overpotential of 282 mV at 10 mA cm(-2) and a small Tafel slope of 54 mV dec(-1) . The excellent activity and satisfactory stability suggest that the as-made electrode provides an attractive alternative to noble metal-based catalysts. Combined with density functional theory calculations, exceptional OER performance of FeNi3 S2 /FeNi results from a combination of efficient electron transfer properties, more active sites, the suitable O2 evolution kinetics and energetics benefited from Fe doping. This work not only simply constructs an excellent electrode for water oxidation, but also provides a deep understanding of the underlying nature of the enhanced OER performance, which may serve as a guide to develop highly effective and integrated OER electrodes for water splitting.

  13. Regeneration of elemental sulfur in a simultaneous sulfide and nitrate removal reactor under different dissolved oxygen conditions.

    PubMed

    Wang, Xiaowei; Zhang, Yu; Zhou, Jiti; Zhang, Tingting; Chen, Mingxiang

    2015-04-01

    A continuous reactor in microaerobic conditions was adopted for sulfide-oxidizing, nitrate-reducing and elemental sulfur (S(0)) regenerating, simultaneously. The results showed that appropriate dissolved oxygen (DO) enhanced S(0) regeneration efficiency, sulfide oxidation efficiency, and nitrate reduction efficiency. When the DO concentration was 0.1-0.3 mg L(-1), the microaerobic bioreactor simultaneously converted 8.16 kg-Sm(-3)d(-1) of sulfide to S(0) and 2.48 kg-Nm(-3)d(-1) of nitrate to nitrogen with the sulfide and nitrate removal efficiency of 100% and 90% respectively. Compared with anaerobic sulfide and nitrate removal process previously reported, the loading sulfide was higher and more S(0) was generated during the operation in microaerobic reactor. Analysis using the 16S rDNA gene clone library revealed that Azoarcus, Thauera, Paracoccus, Sulfurospirillum, Arcobacter and Clostridium were the dominant microorganisms in the sulfide and nitrate removal system.

  14. Diffusible gas transmitter signaling in the copepod crustacean Calanus finmarchicus: identification of the biosynthetic enzymes of nitric oxide (NO), carbon monoxide (CO) and hydrogen sulfide (H2S) using a de novo assembled transcriptome.

    PubMed

    Christie, Andrew E; Fontanilla, Tiana M; Roncalli, Vittoria; Cieslak, Matthew C; Lenz, Petra H

    2014-06-01

    Neurochemical signaling is a major component of physiological/behavioral control throughout the animal kingdom. Gas transmitters are perhaps the most ancient class of molecules used by nervous systems for chemical communication. Three gases are generally recognized as being produced by neurons: nitric oxide (NO), carbon monoxide (CO) and hydrogen sulfide (H2S). As part of an ongoing effort to identify and characterize the neurochemical signaling systems of the copepod Calanus finmarchicus, the biomass dominant zooplankton in much of the North Atlantic Ocean, we have mined a de novo assembled transcriptome for sequences encoding the neuronal biosynthetic enzymes of these gases, i.e. nitric oxide synthase (NOS), heme oxygenase (HO) and cystathionine β-synthase (CBS), respectively. Using Drosophila proteins as queries, two NOS-, one HO-, and one CBS-encoding transcripts were identified. Reverse BLAST and structural analyses of the deduced proteins suggest that each is a true member of its respective enzyme family. RNA-Seq data collected from embryos, early nauplii, late nauplii, early copepodites, late copepodites and adults revealed the expression of each transcript to be stage specific: one NOS restricted primarily to the embryo and the other was absent in the embryo but expressed in all other stages, no CBS expression in the embryo, but present in all other stages, and HO expressed across all developmental stages. Given the importance of gas transmitters in the regulatory control of a number of physiological processes, these data open opportunities for investigating the roles these proteins play under different life-stage and environmental conditions in this ecologically important species.

  15. Acute Oral Toxicity Potential of 4-Nitrophenyl Methkyl Phenyl Phosphinate.

    DTIC Science & Technology

    1982-09-01

    methyl phenyl phosphinate Chemical Abstract Service Registry No.: None Molecular structure: C Ii NO P 13 12 4 .0 0~ NO., CH3 o o...C 56.33 56.17 H 4.36 4.28 N 5.05 5.14 P 11.17 11.25 2. Chemical Name: Polysorbate 80 (Tween 80) Chemical Abstract Service Registry No.: 9005-65-6...administration particularly in chronic toxicity studies in experimental data. 3. Chemical Name: Citric Acid, monohydrate Chemical Abstract Service

  16. Synthesis and evaluation of novel biochar-based and metal oxide-based catalysts for removal of model tar (toluene), ammonia, and hydrogen sulfide from simulated producer gas

    NASA Astrophysics Data System (ADS)

    Bhandari, Pushpak

    Gasification is a thermochemical conversion process in which carbonaceous feedstock is gasified in a controlled atmosphere to generate producer gas. The producer gas is used for production of heat, power, fuels and chemicals. Various contaminants such as tars, NH3, and H2S in producer gas possess many problems due to their corrosive nature and their ability to clog and deactivate catalysts. In this study, several catalysts were synthesized, characterized, and tested for removal of three contaminants (toluene (model tar), NH3, and H2S) from the biomass-generated producer gas. Biochar, a catalyst, was generated from gasification of switchgrass. Activated carbon and acidic surface activated carbon were synthesized using ultrasonication method from biochar. Acidic surface was synthesized by coating activated carbon with dilute acid. Mixed metal oxide catalysts were synthesized from hydrotalcite precursors using novel synthesis technique using microwave and ultrasonication. Surface area of activated carbon (˜900 m2/g) was significantly higher than that of its precursor biochar (˜60 m2/g). Surface area of metal oxide catalyst was approximately 180 m2/g after calcination. Biochar, activated carbon, and acidic surface activated carbon showed toluene removal efficiencies of approximately 78, 88, and 88 %, respectively, when the catalysts were tested individually with toluene in the presence of producer gas at 800 °C. The toluene removal efficiencies increased to 86, 91, and 97 % using biochar, activated carbon and acidic surface activated carbon, respectively in the presence of NH3 and H2S in the producer gas. Increase in toluene removal efficiencies in presence of NH3 and H2S indicates that NH3 and H 2S play a role in toluene reforming reactions during simultaneous removal of contaminants. Toluene removal efficiency for mixed metal oxide was approximately 83%. Ammonia adsorption capacities were 0.008 g NH3/g catalyst for biochar and 0.03g NH3/g catalyst for activated

  17. Arsenic speciation in natural sulfidic geothermal waters

    NASA Astrophysics Data System (ADS)

    Keller, Nicole S.; Stefánsson, Andri; Sigfússon, Bergur

    2014-10-01

    The speciation of arsenic in natural sulfidic geothermal waters was studied using chemical analyses and thermodynamic aqueous speciation calculations. Samples were collected in three geothermal systems in Iceland, having contrasting H2S concentrations in the reservoir (high vs. low). The sampled waters contained 7-116 ppb As and <0.01-77.6 ppm H2S with pH of 8.56-9.60. The analytical setup used for the determination of arsenic species (Ion Chromatography-Hydride Generation Atomic Fluorescence Spectrometry, IC-HG-AFS) was field-deployed and the samples analyzed within ∼5 min of sampling in order to prevent changes upon storage, which were shown to be considerable regardless of the sample storage method used. Nine aqueous arsenic species were detected, among others arsenite (HnAsO3n-3), thioarsenite (HnAsS3n-3), arsenate (HnAsO4n-3), monothioarsenate (HnAsSO3n-3), dithioarsenate (HnAsS2O2n-3), trithioarsenate (HnAsS3O) and tetrathioarsenate (HnAsS4n-3). The results of the measured aqueous arsenic speciation in the natural geothermal waters and comparison with thermodynamic calculations reveal that the predominant factors determining the species distribution are sulfide concentration and pH. In alkaline waters with low sulfide concentrations the predominant species are AsIII oxyanions. This can be seen in samples from a liquid-only well, tapping water that is H2S-poor and free of oxygen. At intermediate sulfide concentration AsIII and AsV thio species become important and predominate at high sulfide concentration, as seen in two-phase well waters, which have high H2S concentrations in the reservoir. Upon oxidation, for instance due to mixing of the reservoir fluid with oxygenated water upon ascent to the surface, AsV oxyanions form, as well as AsV thio complexes if the sulfide concentration is intermediate to high. This oxidation process can be seen in samples from hot springs in the Geysir geothermal area. While the thermodynamic modeling allows for a first

  18. Volcanogenic massive sulfide occurrence model: Chapter C in Mineral deposit models for resource assessment

    USGS Publications Warehouse

    Shanks, W.C. Pat; Koski, Randolph A.; Mosier, Dan L.; Schulz, Klaus J.; Morgan, Lisa A.; Slack, John F.; Ridley, W. Ian; Dusel-Bacon, Cynthia; Seal, Robert R., II; Piatak, Nadine M.; Shanks, W.C. Pat; Thurston, Roland

    2012-01-01

    An unusual feature of VMS deposits is the common association of stratiform "exhalative" deposits precipitated from hydrothermal fluids emanating into bottom waters. These deposits may extend well beyond the margins of massive sulfide and are typically composed of silica, iron, and manganese oxides, carbonates, sulfates, sulfides, and tourmaline.

  19. The Determination of Hydrogen Sulfide in Stack Gases, Iodometric Titration After Sulfite Removal.

    ERIC Educational Resources Information Center

    Robles, E. G.

    The determination of hydrogen sulfide in effluents from coal-fired furnaces and incinerators is complicated by the presence of sulfur oxides (which form acids). Organic compounds also may interfere with or prevent the formation of the cadmium sulfide precipitate or give false positive results because of reaction with iodine. The report presents a…

  20. ELECTROCHEMICAL DETERMINATION OF HYDROGEN SULFIDE AT CARBON NANOTUBE MODIFIED ELECTRODES. (R830900)

    EPA Science Inventory

    Carbon nanotube (CNT) modified glassy carbon electrodes exhibiting a strong and stable electrocatalytic response towards sulfide are described. A substantial (400 mV) decrease in the overvoltage of the sulfide oxidation reaction (compared to ordinary carbon electrodes) is...

  1. Ternary spinel cadmium stannate, cadmium indate, and zinc stannate and binary tin oxide and indium oxide transparent conducting oxides as front contact materials for cadmium sulfide/cadmium tellurium photovoltaic devices

    NASA Astrophysics Data System (ADS)

    Mamazza, Robert, Jr.

    Transparent conducting oxides (TCO's) of Cd2SnO 4 (cadmium stannate), CdIn2O4 (cadmium indate), and Zn2SnO4 (zinc stannate) thin films were investigated from a materials and applications point of view through. All films were deposited by co-sputtering using either binary oxide or metallic (reactive sputtering) targets. The film properties were investigated as a function of film composition and stoichiometry. The effect of process parameters such as deposition temperatures, and post-deposition heat treatments on the structural and electro-optical properties of the films were also investigated extensively. All as-deposited films were found to be amorphous independent of substrate deposition temperature. The electro-optical and crystallographic properties were heavily dependant on the post deposition heat treatments. Cd2SnO4, Zn 2SnO4, and CdIn2O4 all produced highly transparent films with average transmission values (400--900 nm range) of 92%, 93%, and 90%, respectively. Cd2SnO4 and CdIn 2O4 were highly conductive with resistivity values as low as 2.01 x 10-4 O-cm and 2.90 x 10 -4 O-cm, respectively. Conversely, Zn2SnO 4 was not able to produce highly conductive films, with the lowest resistivity being 4.3 x 10-3 O-cm. CdTe solar cells were fabricated using al the above materials as front contacts or as high-ρ layers in bi-layer structures. All cells were of the superstrate configuration: Low-ρ TCO/high-ρ TCO/CdS/CdTe/Back contact. Only the TCO layers were varied; the remainder of the device was held constant. In most cases the inclusion of a high-ρ TCO layer was found to improve solar cell performance, especially in regard to the open circuit voltage. Cd2SnO4 was the exception. The incorporation of Zn2SnO4 as a high-ρ layer enabled a greatest current collection from high energy wavelengths through an apparent thinning effect on the CdS. This increased the overall short circuit current density to values in excess of 24.9 mA/cm2. The standard device consisted of

  2. Do garlic-derived allyl sulfides scavenge peroxyl radicals?

    PubMed

    Amorati, Riccardo; Pedulli, Gian Franco

    2008-03-21

    The chain-breaking antioxidant activities of two garlic-derived allyl sulfides, i.e. diallyl disulfide (1), the main component of steam-distilled garlic oil, and allyl methyl sulfide (3) were evaluated by studying the thermally initiated autoxidation of cumene or styrene in their presence. Although the rate of cumene oxidation was reduced by addition of both 1 and 3, the dependence on the concentration of the two sulfides could not be explained on the basis of the classic antioxidant mechanism as with phenolic antioxidants. The rate of oxidation of styrene, on the other hand, did not show significant changes upon addition of either 1 or 3. This unusual behaviour was explained in terms of the co-oxidant effect, consisting in the decrease of the autoxidation rate of a substrate forming tertiary peroxyl radicals (i.e. cumene) upon addition of little amounts of a second oxidizable substrate giving rise instead to secondary peroxyl radicals. The relevant rate constants for the reaction of ROO(.) with 1 and 3 were measured as 1.6 and 1.0 M(-1) s(-1), respectively, fully consistent with the H-atom abstraction from substituted sulfides. It is therefore concluded that sulfides 1 and 3 do not scavenge peroxyl radicals and therefore cannot be considered chain-breaking antioxidants.

  3. Sulfide-driven arsenic mobilization from arsenopyrite and black shale pyrite

    USGS Publications Warehouse

    Zhu, W.; Young, L.Y.; Yee, N.; Serfes, M.; Rhine, E.D.; Reinfelder, J.R.

    2008-01-01

    We examined the hypothesis that sulfide drives arsenic mobilization from pyritic black shale by a sulfide-arsenide exchange and oxidation reaction in which sulfide replaces arsenic in arsenopyrite forming pyrite, and arsenide (As-1) is concurrently oxidized to soluble arsenite (As+3). This hypothesis was tested in a series of sulfide-arsenide exchange experiments with arsenopyrite (FeAsS), homogenized black shale from the Newark Basin (Lockatong formation), and pyrite isolated from Newark Basin black shale incubated under oxic (21% O2), hypoxic (2% O2, 98% N2), and anoxic (5% H2, 95% N2) conditions. The oxidation state of arsenic in Newark Basin black shale pyrite was determined using X-ray absorption-near edge structure spectroscopy (XANES). Incubation results show that sulfide (1 mM initial concentration) increases arsenic mobilization to the dissolved phase from all three solids under oxic and hypoxic, but not anoxic conditions. Indeed under oxic and hypoxic conditions, the presence of sulfide resulted in the mobilization in 48 h of 13-16 times more arsenic from arsenopyrite and 6-11 times more arsenic from isolated black shale pyrite than in sulfide-free controls. XANES results show that arsenic in Newark Basin black shale pyrite has the same oxidation state as that in FeAsS (-1) and thus extend the sulfide-arsenide exchange mechanism of arsenic mobilization to sedimentary rock, black shale pyrite. Biologically active incubations of whole black shale and its resident microorganisms under sulfate reducing conditions resulted in sevenfold higher mobilization of soluble arsenic than sterile controls. Taken together, our results indicate that sulfide-driven arsenic mobilization would be most important under conditions of redox disequilibrium, such as when sulfate-reducing bacteria release sulfide into oxic groundwater, and that microbial sulfide production is expected to enhance arsenic mobilization in sedimentary rock aquifers with major pyrite-bearing, black

  4. Sulfide-Driven Arsenic Mobilization from Arsenopyrite and Black Shale Pyrite

    SciTech Connect

    Zhu, W.; Young, L; Yee, N; Serfes, M; Rhine, E; Reinfelder, J

    2008-01-01

    We examined the hypothesis that sulfide drives arsenic mobilization from pyritic black shale by a sulfide-arsenide exchange and oxidation reaction in which sulfide replaces arsenic in arsenopyrite forming pyrite, and arsenide (As-1) is concurrently oxidized to soluble arsenite (As+3). This hypothesis was tested in a series of sulfide-arsenide exchange experiments with arsenopyrite (FeAsS), homogenized black shale from the Newark Basin (Lockatong formation), and pyrite isolated from Newark Basin black shale incubated under oxic (21% O2), hypoxic (2% O2, 98% N2), and anoxic (5% H2, 95% N2) conditions. The oxidation state of arsenic in Newark Basin black shale pyrite was determined using X-ray absorption-near edge structure spectroscopy (XANES). Incubation results show that sulfide (1 mM initial concentration) increases arsenic mobilization to the dissolved phase from all three solids under oxic and hypoxic, but not anoxic conditions. Indeed under oxic and hypoxic conditions, the presence of sulfide resulted in the mobilization in 48 h of 13-16 times more arsenic from arsenopyrite and 6-11 times more arsenic from isolated black shale pyrite than in sulfide-free controls. XANES results show that arsenic in Newark Basin black shale pyrite has the same oxidation state as that in FeAsS (-1) and thus extend the sulfide-arsenide exchange mechanism of arsenic mobilization to sedimentary rock, black shale pyrite. Biologically active incubations of whole black shale and its resident microorganisms under sulfate reducing conditions resulted in sevenfold higher mobilization of soluble arsenic than sterile controls. Taken together, our results indicate that sulfide-driven arsenic mobilization would be most important under conditions of redox disequilibrium, such as when sulfate-reducing bacteria release sulfide into oxic groundwater, and that microbial sulfide production is expected to enhance arsenic mobilization in sedimentary rock aquifers with major pyrite-bearing, black

  5. Suicide with hydrogen sulfide.

    PubMed

    Sams, Ralph Newton; Carver, H Wayne; Catanese, Charles; Gilson, Thomas

    2013-06-01

    This presentation will address the recent rise of suicide deaths resulting from the asphyxiation by hydrogen sulfide (H2S) gas.Hydrogen sulfide poisoning has been an infrequently encountered cause of death in medical examiner practice. Most H2S deaths that have been reported occurred in association with industrial exposure.More recently, H2S has been seen in the commission of suicide, particularly in Japan. Scattered reports of this phenomenon have also appeared in the United States.We have recently observed 2 intentional asphyxial deaths in association with H2S. In both cases, the decedents committed suicide in their automobiles. They generated H2S by combining a sulfide-containing tree spray with toilet bowl cleaner (with an active ingredient of hydrogen chloride acid). Both death scenes prompted hazardous materials team responses because of notes attached to the victims' car windows indicating the presence of toxic gas. Autopsy findings included discoloration of lividity and an accentuation of the gray matter of the brain. Toxicology testing confirmed H2S exposure with the demonstration of high levels of thiosulfate in blood.In summary, suicide with H2S appears to be increasing in the United States.

  6. Effect of the phosphine steric and electronic profile on the Rh-promoted dehydrocoupling of phosphine-boranes.

    PubMed

    Hooper, Thomas N; Huertos, Miguel A; Jurca, Titel; Pike, Sebastian D; Weller, Andrew S; Manners, Ian

    2014-04-07

    The electronic and steric effects in the stoichiometric dehydrocoupling of secondary and primary phosphine-boranes H3B·PR2H [R = 3,5-(CF3)2C6H3; p-(CF3)C6H4; p-(OMe)C6H4; adamantyl, Ad] and H3B·PCyH2 to form the metal-bound linear diboraphosphines H3B·PR2BH2·PR2H and H3B·PRHBH2·PRH2, respectively, are reported. Reaction of [Rh(L)(η(6)-FC6H5)][BAr(F)4] [L = Ph2P(CH2)3PPh2, Ar(F) = 3,5-(CF3)2C6H3] with 2 equiv of H3B·PR2H affords [Rh(L)(H)(σ,η-PR2BH3)(η(1)-H3B·PR2H)][BAr(F)4]. These complexes undergo dehydrocoupling to give the diboraphosphine complexes [Rh(L)(H)(σ,η(2)-PR2·BH2PR2·BH3)][BAr(F)4]. With electron-withdrawing groups on the phosphine-borane there is the parallel formation of the products of B-P cleavage, [Rh(L)(PR2H)2][BAr(F)4], while with electron-donating groups no parallel product is formed. For the bulky, electron rich, H3B·P(Ad)2H no dehydrocoupling is observed, but an intermediate Rh(I) σ phosphine-borane complex is formed, [Rh(L){η(2)-H3B·P(Ad)2H}][BAr(F)4], that undergoes B-P bond cleavage to give [Rh(L){η(1)-H3B·P(Ad)2H}{P(Ad)2H}][BAr(F)4]. The relative rates of dehydrocoupling of H3B·PR2H (R = aryl) show that increasingly electron-withdrawing substituents result in faster dehydrocoupling, but also suffer from the formation of the parallel product resulting from P-B bond cleavage. H3B·PCyH2 undergoes a similar dehydrocoupling process, and gives a mixture of stereoisomers of the resulting metal-bound diboraphosphine that arise from activation of the prochiral P-H bonds, with one stereoisomer favored. This diastereomeric mixture may also be biased by use of a chiral phosphine ligand. The selectivity and efficiencies of resulting catalytic dehydrocoupling processes are also briefly discussed.

  7. Unsaturated phosphinic analogues of gamma-aminobutyric acid as GABA(C) receptor antagonists.

    PubMed

    Chebib, M; Vandenberg, R J; Froestl, W; Johnston, G A

    1997-06-25

    The phosphinic and methylphosphinic analogues of gamma-aminobutyric acid (GABA) are potent GABA(C) receptor antagonists but are even more potent as GABA(B) receptor agonists. Conformationally restricted unsaturated phosphinic and methylphosphinic analogues of GABA and some potent GABA(B) receptor phosphonoamino acid antagonists were tested on GABA(C) receptors in Xenopus oocytes expressing human retinal rho1 mRNA. 3-Aminopropyl-n-butyl-phosphinic acid (CGP36742), an orally active GABA(B) receptor antagonist, was found to be a moderately potent GABA(C) receptor antagonist (IC50 = 62 microM). The unsaturated methylphosphinic and phosphinic analogues of GABA were competitive antagonists of the GABA(C) receptors, the order of potency being [(E)-3-aminopropen-1-yl]methylphosphinic acid (CGP44530, IC50 = 5.53 microM) > [(E)-3-aminopropen-1-yl]phosphinic acid (CGP38593, IC50 = 7.68 microM) > [(Z)-3-aminopropen-1-yl]methylphosphinic acid (CGP70523, IC50 = 38.94 microM) > [(Z)-3-aminopropen-1-yl]phosphinic acid (CGP70522, IC50 > 100 microM). This order of potency differs from that reported for these compounds as GABA(B) receptor agonists, where the phosphinic acids are more potent than the corresponding methylphosphinic acids.

  8. Oxygenated phosphine fumigation for control of Epiphyas postvittana (Lepidoptera: Tortricidae) eggs on lettuce.

    PubMed

    Liu, Samuel S; Liu, Yong-Biao; Simmons, Gregory S

    2014-08-01

    Light brown apple moth, Epiphyas postvittana (Walker), is a quarantined pest in most countries. Its establishment in California and potential spread to other parts of the state and beyond make it urgent to develop effective postharvest treatments to control the pest on fresh commodities. Fumigation with cylindered phosphine at low temperature has emerged to be a practical methyl bromide alternative treatment for postharvest pest control on fresh commodities. However, its use to control E. postvittana eggs on sensitive commodities such as lettuce is problematic. E. postvittana eggs are tolerant of phosphine and long phosphine treatment also injures lettuce. In the current study, E. postvittana eggs were subjected to oxygenated phosphine fumigations to develop an effective treatment at a low storage temperature of 2 degrees C. In addition, soda lime as a CO2 absorbent was tested to determine its effects in reducing and preventing injuries to lettuce associated with phosphine fumigations. Three-day fumigation with 1,000 ppm phosphine under 60% O2 achieved 100% mortality of E. postvittana eggs in small-scale laboratory tests. In the presence of the CO2 absorbent, a 3-d large-scale fumigation of lettuce with 1,700 ppm phosphine under 60% O2 resulted in a relative egg mortality of 99.96% without any negative effect on lettuce quality. The 3-d fumigation treatment without the CO2 absorbent, however, resulted in significant injuries to lettuce and consequential quality reductions. The study demonstrated that oxygenated phosphine fumigation has the potential to control E. postvittana eggs and the CO2 absorbent has the potential to prevent injuries and quality reductions of lettuce associated with long-term oxygenated phosphine fumigation.

  9. Aerobic and anaerobic transformations of sulfide in a sewer system--field study and model simulations.

    PubMed

    Nielsen, Asbjørn Haaning; Vollertsen, Jes; Jensen, Henriette Stokbro; Madsen, Heidi Ina; Hvitved-Jacobsen, Thorkild

    2008-01-01

    The formation and fate of sulfide in a force main and a downstream-located gravity sewer were investigated in an extensive field study. Sulfide formation in the force main was significant. However, during 14 minutes of transport in the gravity sewer, the sulfide concentration decreased 30%, on average. An application of a conceptual sewer process model for simulating the formation and fate of sulfide was demonstrated. Overall, the model predicted that approximately 90% of the decrease of the sulfide concentration in the gravity sewer was the result of sulfide oxidation and that only a small fraction entered the sewer atmosphere, causing odor and corrosion. Even so, the model predicted concrete corrosion rates of up to 1.2 mm/y in the gravity sewer section.

  10. Froth flotation of oil-bearing metal sulfide wastes

    SciTech Connect

    Miller, R.L.; Atwood, R.L.; Ye, Yi

    1991-12-01

    An industrial wastewater, including plating wastes, is treated with sodium sulfide and ferrous sulfate to form a sulfide-oxide precipitate containing chromium and other toxic metals. Hydrocarbons, in the water, coat the sulfide-oxide particles, impeding metal recovery. Froth flotation, without reagent addition, was found to recover 93.9% of the solids from the sludge with simultaneous rejection of 89% of the water. Methyl isobutyl carbinol (MIBC) improved recovery and potassium amyl xanthate improved both recovery and grade. The process design has wastewater feed (without MIBC) to the rougher circuit. The rougher concentrate is conditioned with MIBC and fed to a cleaner circuit to achieve a high grade concentrate. About 95% of the water is recirculated to the waste treatment plant. 3 refs., 3 figs., 4 tabs.

  11. Froth flotation of oil-bearing metal sulfide wastes

    SciTech Connect

    Miller, R.L. ); Atwood, R.L.; Ye, Yi )

    1991-01-01

    An industr