WorldWideScience

Sample records for sulfide oxidizers sulfate

  1. Disguised as a Sulfate Reducer: Growth of the Deltaproteobacterium Desulfurivibrio alkaliphilus by Sulfide Oxidation with Nitrate.

    Science.gov (United States)

    Thorup, Casper; Schramm, Andreas; Findlay, Alyssa J; Finster, Kai W; Schreiber, Lars

    2017-07-18

    This study demonstrates that the deltaproteobacterium Desulfurivibrio alkaliphilus can grow chemolithotrophically by coupling sulfide oxidation to the dissimilatory reduction of nitrate and nitrite to ammonium. Key genes of known sulfide oxidation pathways are absent from the genome of D. alkaliphilus Instead, the genome contains all of the genes necessary for sulfate reduction, including a gene for a reductive-type dissimilatory bisulfite reductase (DSR). Despite this, growth by sulfate reduction was not observed. Transcriptomic analysis revealed a very high expression level of sulfate-reduction genes during growth by sulfide oxidation, while inhibition experiments with molybdate pointed to elemental sulfur/polysulfides as intermediates. Consequently, we propose that D. alkaliphilus initially oxidizes sulfide to elemental sulfur, which is then either disproportionated, or oxidized by a reversal of the sulfate reduction pathway. This is the first study providing evidence that a reductive-type DSR is involved in a sulfide oxidation pathway. Transcriptome sequencing further suggests that nitrate reduction to ammonium is performed by a novel type of periplasmic nitrate reductase and an unusual membrane-anchored nitrite reductase. IMPORTANCE Sulfide oxidation and sulfate reduction, the two major branches of the sulfur cycle, are usually ascribed to distinct sets of microbes with distinct diagnostic genes. Here we show a more complex picture, as D. alkaliphilus , with the genomic setup of a sulfate reducer, grows by sulfide oxidation. The high expression of genes typically involved in the sulfate reduction pathway suggests that these genes, including the reductive-type dissimilatory bisulfite reductases, are also involved in as-yet-unresolved sulfide oxidation pathways. Finally, D. alkaliphilus is closely related to cable bacteria, which grow by electrogenic sulfide oxidation. Since there are no pure cultures of cable bacteria, D. alkaliphilus may represent an

  2. Disguised as a Sulfate Reducer: Growth of the Deltaproteobacterium Desulfurivibrio alkaliphilus by Sulfide Oxidation with Nitrate

    Directory of Open Access Journals (Sweden)

    Casper Thorup

    2017-07-01

    Full Text Available This study demonstrates that the deltaproteobacterium Desulfurivibrio alkaliphilus can grow chemolithotrophically by coupling sulfide oxidation to the dissimilatory reduction of nitrate and nitrite to ammonium. Key genes of known sulfide oxidation pathways are absent from the genome of D. alkaliphilus. Instead, the genome contains all of the genes necessary for sulfate reduction, including a gene for a reductive-type dissimilatory bisulfite reductase (DSR. Despite this, growth by sulfate reduction was not observed. Transcriptomic analysis revealed a very high expression level of sulfate-reduction genes during growth by sulfide oxidation, while inhibition experiments with molybdate pointed to elemental sulfur/polysulfides as intermediates. Consequently, we propose that D. alkaliphilus initially oxidizes sulfide to elemental sulfur, which is then either disproportionated, or oxidized by a reversal of the sulfate reduction pathway. This is the first study providing evidence that a reductive-type DSR is involved in a sulfide oxidation pathway. Transcriptome sequencing further suggests that nitrate reduction to ammonium is performed by a novel type of periplasmic nitrate reductase and an unusual membrane-anchored nitrite reductase.

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

    International Nuclear Information System (INIS)

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

    1983-01-01

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

  4. Disguised as a sulfate reducer: Growth of the Deltaproteobacterium Desulfurivibrio alkaliphilus by Sulfide Oxidation with Nitrate

    DEFF Research Database (Denmark)

    Thorup, Casper; Schramm, Andreas; Findlay, Alyssa Jean Lehsau

    2017-01-01

    This study demonstrates that the deltaproteobacterium Desulfurivibrio alkaliphilus can grow chemolithotrophically by coupling sulfide oxidation to the dissimilatory reduction of nitrate and nitrite to ammonium. Key genes of known sulfide oxidation pathways are absent from the genome of D...... of the sulfate reduction pathway. This is the first study providing evidence that a reductive-type DSR is involved in a sulfide oxidation pathway. Transcriptome sequencing further suggests that nitrate reduction to ammonium is performed by a novel type of periplasmic nitrate reductase and an unusual membrane......-anchored nitrite reductase....

  5. Regeneration of sulfated metal oxides and carbonates

    Science.gov (United States)

    Hubble, Bill R.; Siegel, Stanley; Cunningham, Paul T.

    1978-03-28

    Alkali metal or alkaline earth metal carbonates such as calcium carbonate and magnesium carbonate found in dolomite or limestone are employed for removal of sulfur dioxide from combustion exhaust gases. The sulfated carbonates are regenerated to oxides through use of a solid-solid reaction, particularly calcium sulfide with calcium sulfate to form calcium oxide and sulfur dioxide gas. The regeneration is performed by contacting the sulfated material with a reductant gas such as hydrogen within an inert diluent to produce calcium sulfide in mixture with the sulfate under process conditions selected to permit the sulfide-sulfate, solid-state reaction to occur.

  6. Biotechnological aspects of anaerobic oxidation of methane coupled to sulfate reduction

    NARCIS (Netherlands)

    Meulepas, R.J.W.

    2009-01-01

    Sulfate reduction (SR) can be used for the removal and recovery of metals and oxidized sulfur compounds from waste streams. Sulfate-reducing bacteria reduce oxidized sulfur compounds to sulfide. Subsequently, sulfide can precipitate dissolved metals or can be oxidized to elemental sulfur. Both metal

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

    Science.gov (United States)

    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

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

    Directory of Open Access Journals (Sweden)

    Desirée Villahermosa

    Full Text Available 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

  9. Sulfide Oxidation in the Anoxic Black-Sea Chemocline

    DEFF Research Database (Denmark)

    JØRGENSEN, BB; FOSSING, H.; WIRSEN, CO

    1991-01-01

    per day, occurred in anoxic water at the top of the sulfide zone concurrent with the highest rates of dark CO2 assimilation. The main soluble oxidized products of sulfide were thiosulfate (68-82%) and sulfate. Indirect evidence was presented for the formation of elemental sulfur which accumulated...... that the measured H2S oxidation rates were 4-fold higher than could be explained by the downward flux of organic carbon and too high to balance the availability of electron acceptors such as oxidized iron or manganese. A nitrate maximum at the lower boundary of the O2 zone did not extend down to the sulfide zone....

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

    Energy Technology Data Exchange (ETDEWEB)

    Bekmezci, Ozan K.; Ucar, Deniz [Harran University, Environmental Engineering Department, Osmanbey Campus, 63000 Sanliurfa (Turkey); Kaksonen, Anna H. [CSIRO Land and Water, Underwood Avenue, Floreat, WA 6014 (Australia); Sahinkaya, Erkan, E-mail: erkansahinkaya@yahoo.com [Harran University, Environmental Engineering Department, Osmanbey Campus, 63000 Sanliurfa (Turkey)

    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{sup -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 {sup o}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{sup -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.

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

    Science.gov (United States)

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

    2015-11-01

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

  12. Characterization of 16S rRNA genes from oil field microbial communities indicates the presence of a variety of sulfate-reducing, fermentative, and sulfide-oxidizing bacteria.

    Science.gov (United States)

    Voordouw, G; Armstrong, S M; Reimer, M F; Fouts, B; Telang, A J; Shen, Y; Gevertz, D

    1996-05-01

    Oil field bacteria were characterized by cloning and sequencing of PCR-amplified 16S rRNA genes. A variety of gram-negative, sulfate-reducing bacteria was detected (16 members of the family Desulfovibrionaceae and 8 members of the family Desulfobacteriaceae). In contrast, a much more limited number of anaerobic, fermentative, or acetogenic bacteria was found (one Clostridium sp., one Eubacterium sp., and one Synergistes sp.). Potential sulfide oxidizers and/or microaerophiles (Thiomicrospira, Arcobacter, Campylobacter, and Oceanospirillum spp.) were also detected. The first two were prominently amplified from uncultured production water DNA and represented 28 and 47% of all clones, respectively. Growth on media containing sulfide as the electron donor and nitrate as the electron acceptor and designed for the isolation of Thiomicrospira spp. gave only significant enrichment of the Campylobacter sp., which was shown to be present in different western Canadian oil fields. This newly discovered sulfide oxidizer may provide a vital link in the oil field sulfur cycle by reoxidizing sulfide formed by microbial sulfate or sulfur reduction.

  13. Evaluation of feed COD/sulfate ratio as a control criterion for the biological hydrogen sulfide production and lead precipitation

    International Nuclear Information System (INIS)

    Velasco, Antonio; Ramirez, Martha; Volke-Sepulveda, Tania; Gonzalez-Sanchez, Armando; Revah, Sergio

    2008-01-01

    The ability of sulfate-reducing bacteria to produce hydrogen sulfide and the high affinity of sulfide to react with divalent metallic cations represent an excellent option to remove heavy metals from wastewater. Different parameters have been proposed to control the hydrogen sulfide production by anaerobic bacteria, such as the organic and sulfate loading rates and the feed COD/SO 4 2- ratio. This work relates the feed COD/SO 4 2- ratio with the hydrogen sulfide production and dissolved lead precipitation, using ethanol as carbon and energy source in an up-flow anaerobic sludge blanket reactor. A maximum dissolved sulfide concentration of 470 ± 7 mg S/L was obtained at a feed COD/SO 4 2- ratio of 2.5, with sulfate and ethanol conversions of approximately 94 and 87%, respectively. The lowest dissolved sulfide concentration (145 ± 10 mg S/L) was observed with a feed COD/SO 4 2- ratio of 0.67. Substantial amounts of acetate (510-1730 mg/L) were produced and accumulated in the bioreactor from ethanol oxidation. Although only incomplete oxidation of ethanol to acetate was observed, the consortium was able to remove 99% of the dissolved lead (200 mg/L) with a feed COD/SO 4 2- ratio of 1.5. It was found that the feed COD/SO 4 2- ratio could be an adequate parameter to control the hydrogen sulfide production and the consequent precipitation of dissolved lead

  14. Assessing the Role of Iron Sulfides in the Long Term Sequestration of Uranium by Sulfate-Reducing Bacteria

    Energy Technology Data Exchange (ETDEWEB)

    Hayes, Kim F. [Univ. of Michigan, Ann Arbor, MI (United States); Bi, Yuqiang [Univ. of Michigan, Ann Arbor, MI (United States); Carpenter, Julian [Univ. of Michigan, Ann Arbor, MI (United States); Hyng, Sung Pil [Univ. of Michigan, Ann Arbor, MI (United States); Rittmann, Bruce E. [Arizona State Univ., Tempe, AZ (United States); Zhou, Chen [Arizona State Univ., Tempe, AZ (United States); Vannela, Raveender [Arizona State Univ., Tempe, AZ (United States); Davis, James A. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

    2013-12-31

    This overarching aim of this project was to identify the role of biogenic and synthetic iron-sulfide minerals in the long-term sequestration of reduced U(IV) formed under sulfate-reducing conditions when subjected to re-oxidizing conditions. The work reported herein was achieved through the collaborative research effort conducted at Arizona State University (ASU) and the University of Michigan (UM). Research at ASU, focused on the biogenesis aspects, examined the biogeochemical bases for iron-sulfide production by Desulfovibrio vulgaris, a Gram-negative bacterium that is one of the most-studied strains of sulfate-reducing bacteria. A series of experimental studies were performed to investigate comprehensively important metabolic and environmental factors that affect the rates of sulfate reduction and iron-sulfide precipitation, the mineralogical characteristics of the iron sulfides, and how uranium is reduced or co-reduced by D. vulagaris. FeS production studies revealed that controlling the pH affected the growth of D. vulgaris and strongly influenced the formation and growth of FeS solids. In particular, lower pH produced larger-sized mackinawite (Fe1+xS). Greater accumulation of free sulfide, from more sulfate reduction by D. vulgaris, also led to larger-sized mackinawite and stimulated mackinawite transformation to greigite (Fe3S4) when the free sulfide concentration was 29.3 mM. On the other hand, using solid Fe(III) (hydr)oxides as the iron source led to less productivity of FeS due to their slow and incomplete dissolution and scavenging of sulfide. Furthermore, sufficient free Fe2+, particularly during Fe(III) (hydr)oxide reductions, led to the additional formation of vivianite [Fe3(PO4)2•8(H2O)]. The U(VI) reduction studies revealed that D. vulgaris reduced U(VI) fastest when accumulating sulfide from concomitant sulfate reduction, since direct enzymatic and sulfide

  15. Evaluation of feed COD/sulfate ratio as a control criterion for the biological hydrogen sulfide production and lead precipitation

    Energy Technology Data Exchange (ETDEWEB)

    Velasco, Antonio [Direccion General del Centro Nacional de Investigacion y Capacitacion Ambiental-Instituto Nacional de Ecologia, Av. San Rafael Atlixco 186, Col. Vicentina. Iztapalapa, Mexico 09340, D.F. (Mexico)], E-mail: jvelasco@ine.gob.mx; Ramirez, Martha [Direccion General del Centro Nacional de Investigacion y Capacitacion Ambiental-Instituto Nacional de Ecologia, Av. San Rafael Atlixco 186, Col. Vicentina. Iztapalapa, Mexico 09340, D.F. (Mexico); Volke-Sepulveda, Tania [Departamento de Biotecnologia, UAM-Cuajimalpa, San Rafael Atlixco 186, Col. Vicentina. Iztapalapa, Mexico 09340, D.F. (Mexico); Gonzalez-Sanchez, Armando [Departamento de Ingenieria de Procesos, Universidad Autonoma Metropolitana-Iztapalapa, UAM-Cuajimalpa, San Rafael Atlixco 186, Col. Vicentina. Iztapalapa, Mexico 09340, D.F. (Mexico); Revah, Sergio [Departamento de Procesos y Tecnologia, UAM-Cuajimalpa, San Rafael Atlixco 186, Col. Vicentina. Iztapalapa, Mexico 09340, D.F. (Mexico)

    2008-03-01

    The ability of sulfate-reducing bacteria to produce hydrogen sulfide and the high affinity of sulfide to react with divalent metallic cations represent an excellent option to remove heavy metals from wastewater. Different parameters have been proposed to control the hydrogen sulfide production by anaerobic bacteria, such as the organic and sulfate loading rates and the feed COD/SO{sub 4}{sup 2-} ratio. This work relates the feed COD/SO{sub 4}{sup 2-} ratio with the hydrogen sulfide production and dissolved lead precipitation, using ethanol as carbon and energy source in an up-flow anaerobic sludge blanket reactor. A maximum dissolved sulfide concentration of 470 {+-} 7 mg S/L was obtained at a feed COD/SO{sub 4}{sup 2-} ratio of 2.5, with sulfate and ethanol conversions of approximately 94 and 87%, respectively. The lowest dissolved sulfide concentration (145 {+-} 10 mg S/L) was observed with a feed COD/SO{sub 4}{sup 2-} ratio of 0.67. Substantial amounts of acetate (510-1730 mg/L) were produced and accumulated in the bioreactor from ethanol oxidation. Although only incomplete oxidation of ethanol to acetate was observed, the consortium was able to remove 99% of the dissolved lead (200 mg/L) with a feed COD/SO{sub 4}{sup 2-} ratio of 1.5. It was found that the feed COD/SO{sub 4}{sup 2-} ratio could be an adequate parameter to control the hydrogen sulfide production and the consequent precipitation of dissolved lead.

  16. Treatment and electricity harvesting from sulfate/sulfide-containing wastewaters using microbial fuel cell with enriched sulfate-reducing mixed culture

    International Nuclear Information System (INIS)

    Lee, Duu-Jong; Lee, Chin-Yu; Chang, Jo-Shu

    2012-01-01

    Highlights: ► We started up microbial fuel cell (MFC) using enriched sulfate-reducing mixed culture. ► Sulfate-reducing bacteria and anode-respiring bacteria were enriched in anodic biofilms. ► The MFC effectively remove sulfate to elementary sulfur in the presence of lactate. ► The present device can treat sulfate laden wastewaters with electricity harvesting. - Abstract: Anaerobic treatment of sulfate-laden wastewaters can produce excess sulfide, which is corrosive to pipelines and is toxic to incorporated microorganisms. This work started up microbial fuel cell (MFC) using enriched sulfate-reducing mixed culture as anodic biofilms and applied the so yielded MFC for treating sulfate or sulfide-laden wastewaters. The sulfate-reducing bacteria in anodic biofilm effectively reduced sulfate to sulfide, which was then used by neighboring anode respiring bacteria (ARB) as electron donor for electricity production. The presence of organic carbons enhanced MFC performance since the biofilm ARB were mixotrophs that need organic carbon to grow. The present device introduces a route for treating sulfate laden wastewaters with electricity harvesting.

  17. Treatment and electricity harvesting from sulfate/sulfide-containing wastewaters using microbial fuel cell with enriched sulfate-reducing mixed culture

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Duu-Jong, E-mail: cedean@mail.ntust.edu.tw [Department of Chemical Engineering, National Taiwan University, Taipei, Taiwan (China); Department of Chemical Engineering, National Taiwan University of Science and Technology, Taipei, Taiwan (China); Lee, Chin-Yu [Department of Chemical Engineering, National Taiwan University, Taipei, Taiwan (China); Chang, Jo-Shu [Department of Chemical Engineering, National Cheng Kung University, Tainan, Taiwan (China); Center for Bioscience and Biotechnology, National Cheng Kung University, Tainan, Taiwan (China); Research Center for Energy Technology and Strategy, National Cheng Kung University, Tainan, Taiwan (China)

    2012-12-15

    Highlights: Black-Right-Pointing-Pointer We started up microbial fuel cell (MFC) using enriched sulfate-reducing mixed culture. Black-Right-Pointing-Pointer Sulfate-reducing bacteria and anode-respiring bacteria were enriched in anodic biofilms. Black-Right-Pointing-Pointer The MFC effectively remove sulfate to elementary sulfur in the presence of lactate. Black-Right-Pointing-Pointer The present device can treat sulfate laden wastewaters with electricity harvesting. - Abstract: Anaerobic treatment of sulfate-laden wastewaters can produce excess sulfide, which is corrosive to pipelines and is toxic to incorporated microorganisms. This work started up microbial fuel cell (MFC) using enriched sulfate-reducing mixed culture as anodic biofilms and applied the so yielded MFC for treating sulfate or sulfide-laden wastewaters. The sulfate-reducing bacteria in anodic biofilm effectively reduced sulfate to sulfide, which was then used by neighboring anode respiring bacteria (ARB) as electron donor for electricity production. The presence of organic carbons enhanced MFC performance since the biofilm ARB were mixotrophs that need organic carbon to grow. The present device introduces a route for treating sulfate laden wastewaters with electricity harvesting.

  18. Pathways of sulfate and hydrogen sulfide transformations in a BTEX- contaminated groundwater system

    DEFF Research Database (Denmark)

    Einsiedl, Florian; Anneser, B.; Griebler, C.

    2010-01-01

    in complex environmental systems. As a result, compound specific stable isotope signatures in various sulfur species were determined in a tar-oil contaminated site and were linked to the microbial community distribution in the aquifer. The goal of the study was to reach an integrated understanding of sulfur...... intermediate during abiotic oxidation of hydrogen sulphide, with the latter formed during bacterial sulfate reduction. The formed elemental sulfur may be used by the specific microbial community found in this aquifer for the oxidation of organic contaminants such as toluene. In contrast, reoxidation...... of hydrogen sulfide to sulfate by molecular oxygen may affect sulfur cycling within the transition between the unsaturated and the saturated zones and therefore attenuate concentrations of contaminants in groundwater as well....

  19. Sulfide response analysis for sulfide control using a pS electrode in sulfate reducing bioreactors

    NARCIS (Netherlands)

    Villa Gomez, D.K.; Cassidy, J.; Keesman, K.J.; Sampaio, R.M.; Lens, P.N.L.

    2014-01-01

    Step changes in the organic loading rate (OLR) through variations in the influent chemical oxygen demand (CODin) concentration or in the hydraulic retention time (HRT) at constant COD/SO4 2- ratio (0.67) were applied to create sulfide responses for the design of a sulfide control in sulfate reducing

  20. Sulfate and dissolved sulfide variation under low COD/Sulfate ratio in Up-flow Anaerobic Sludge Blanket (UASB treating domestic wastewater

    Directory of Open Access Journals (Sweden)

    Sérvio Túlio Alves Cassini

    2012-04-01

    Full Text Available In this study, the dynamics of sulfate reduction and dissolved sulfide generation (S2-, HS-, H2Saq in liquid phase was evaluated in an UASB reactor treating domestic wastewater with low COD/Sulfate content. The evaluation in the UASB reactor was performed at three sludge heights (0.25, 1.25, 2.25 taps and effluent of the reactor. Sulfate reduction was verified in the reactor, with an average reduction of 24 % throughout the experiment period. However, the dissolved sulfide concentration in the reactor was not higher than 5.0 mg Sdiss/L. The kinetic model of first order showed good fit to describe the sulfate reduction under different COD/sulfate ratio, with K1app between 2.94x10-5 s-1 and 1.17x10-5 s-1 with correlation coefficients for data over 91%. The maximum rate to sulfate reduction was 18.0 mg SO42-/L.h-1 and small variation in COD/sulfate ratio promotes a significant change both in sulfate and sulfide concentrations.

  1. STUDY OF HYDROGEN SULFIDE REMOVAL FROM GROUNDWATER

    Directory of Open Access Journals (Sweden)

    T. Lupascu

    2013-06-01

    Full Text Available The process of the hydrogen sulfide removal from the underground water of the Hancesti town has been investigated. By oxygen bubbling through the water containing hydrogen sulfide, from the Hancesti well tube, sulfur is deposited in the porous structure of studied catalysts, which decreases their catalytic activity. Concomitantly, the process of adsorption / oxidation of hydrogen sulfide to sulfate take place. The kinetic research of the hydrogen sulfide removal from the Hancesti underground water, after its treatment by hydrogen peroxide, proves greater efficiency than in the case of modified carbonic adsorbents. As a result of used treatment, hydrogen sulfide is completely oxidized to sulfates

  2. Removal of hydrogen sulfide as ammonium sulfate from hydropyrolysis product vapors

    Energy Technology Data Exchange (ETDEWEB)

    Marker, Terry L.; Felix, Larry G.; Linck, Martin B.; Roberts, Michael J.

    2017-03-14

    A system and method for processing biomass into hydrocarbon fuels that includes processing a biomass in a hydropyrolysis reactor resulting in hydrocarbon fuels and a process vapor stream and cooling the process vapor stream to a condensation temperature resulting in an aqueous stream. The aqueous stream is sent to a catalytic reactor where it is oxidized to obtain a product stream containing ammonia and ammonium sulfate. A resulting cooled product vapor stream includes non-condensable process vapors comprising H.sub.2, CH.sub.4, CO, CO.sub.2, ammonia and hydrogen sulfide.

  3. Removal of hydrogen sulfide as ammonium sulfate from hydropyrolysis product vapors

    Science.gov (United States)

    Marker, Terry L; Felix, Larry G; Linck, Martin B; Roberts, Michael J

    2014-10-14

    A system and method for processing biomass into hydrocarbon fuels that includes processing a biomass in a hydropyrolysis reactor resulting in hydrocarbon fuels and a process vapor stream and cooling the process vapor stream to a condensation temperature resulting in an aqueous stream. The aqueous stream is sent to a catalytic reactor where it is oxidized to obtain a product stream containing ammonia and ammonium sulfate. A resulting cooled product vapor stream includes non-condensable process vapors comprising H.sub.2, CH.sub.4, CO, CO.sub.2, ammonia and hydrogen sulfide.

  4. Phosphorus mobilization by sulfide oxidation in carbonate sediments from seagrass and unvegetated sites in the US Virgin Islands

    DEFF Research Database (Denmark)

    Jensen, Henning; Pedersen, Ole; Koch, M. R.

    PHOSPHORUS MOBILIZATION BY SULFIDE OXIDATION IN CARBONATE SEDIMENTS FROM SEAGRASS AND UNVEGETATED SITES IN THE US VIRGIN ISLANDS Sulfide produced by sulfate reduction (SR) can be oxidized by seagrass root O2 flux in shallow carbonate sediments low in Fe. The sulfuric acid produced from sulfide...... oxidation, as well as metabolic acids from aerobic respiration, has the potential to mobilize solid phase phosphorus (P) pools in support of seagrass nutrition. Fresh sediments from four US Virgin Islands sites were modestly acidified to near-neutral pH in slurries. Following sulfuric acid amendments...

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

    Energy Technology Data Exchange (ETDEWEB)

    Gevertz, D.; Zimmerman, S. [Agouron Institute, La Jolla, CA (United States); Jenneman, G.E. [Phillips Petroleum Company, Bartlesville, OK (United States)] [and others

    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.

  6. Microbial Oxidation of Iron Sulfides in Anaerobic Environments

    DEFF Research Database (Denmark)

    Vaclavkova, Sarka

    Abstract (shortened): Iron sulfides (FeSx), representing 0.04-10 % of Danish dry soil weight, oxidize in a presence of oxygen, releasing sulfuric acid and free iron. Environmental impact of FeSx oxidation is commonly seen on agricultural sites cultivated by drainage as acid sulfate soil formation....... MISON was found to count for about 1/3 of the net NO3- reduction in MISON active environments, despite the presence of alternative electron donor, organic carbon. The rate of MISON was found to be dependent on the available reactive surface area of FeSx and on the microorganism involved. The findings...

  7. An XPS [x-ray photoelectron spectroscopy] study of the sulfidation-regeneration cycle of a hydroprocessing catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Shang, D.Y.; Adnot, A.; Kaliaguine, S. (Laval Univ., Ste-Foy, PQ (Canada)); Chmielowiec, J. (Petro Canada Products Co., Mississauga, ON (Canada))

    1993-10-01

    The formation of sulfates in an industrial Ni-W hydroprocessing (HP) catalyst was investigated by x-ray photoelectron spectroscopy (XPS). A small fluidized bed test unit with on-line sampling device was constructed to simulate industrial sulfidation and oxyregeneration processes of HP catalysts. The results obtained show that the sulfates observed on the surface of sulfided catalysts are not formed during the sulfidation process. Two oxidation processes seem to be responsible for the formation of sulfates: one happens when the catalyst is exposed to air before it is properly cooled and the other is a slow conversion at ambient temperature. The two different processes might be associated to different sulfidic species formed during the sulfidation processes, with the sulfides in the bulk of catalyst particles being more easily oxidized than the ones on the external surface of the catalyst particles. The sulfate formed during the air oxidation of sulfided catalysts, as well as that after oxyregeneration, is not aluminum sulfate but nickel sulfate in both cases. XPS results also indicate that oxygenates in the feedstock are not directly involved in the sulfate formation. 18 refs., 9 figs., 6 tabs.

  8. Characterization of 16S rRNA genes from oil field microbial communities indicates the presence of a variety of sulfate-reducing, fermentative, and sulfide-oxidizing bacteria.

    OpenAIRE

    Voordouw, G; Armstrong, S M; Reimer, M F; Fouts, B; Telang, A J; Shen, Y; Gevertz, D

    1996-01-01

    Oil field bacteria were characterized by cloning and sequencing of PCR-amplified 16S rRNA genes. A variety of gram-negative, sulfate-reducing bacteria was detected (16 members of the family Desulfovibrionaceae and 8 members of the family Desulfobacteriaceae). In contrast, a much more limited number of anaerobic, fermentative, or acetogenic bacteria was found (one Clostridium sp., one Eubacterium sp., and one Synergistes sp.). Potential sulfide oxidizers and/or microaerophiles (Thiomicrospira,...

  9. A recovery installation for sodium sulfates, thiosulfates and sulfides from waste water resulting from hydrogen sulfide fabrication

    International Nuclear Information System (INIS)

    Mazilu, Mihai; Costescu, Sanda

    2002-01-01

    An installation for recovery of sodium sulfate and sulfur suspensions from waste water was conceived. It consists from a preheater, vacuum evaporator and a refrigerating system with drum and scraper. This equipment concentration the solution by eliminating in the first stage the water in the vacuum evaporator. The water resulting at this stage is chemically pure and can be discharged in the sewage sludge system. The concentrated solution is then directed to the refrigerating system with drum and scrapper. Here the sodium sulfates, thiosulfates and sulfides get crystallized onto the drum surface. The resulting aqueous solution to be discharged in the sewage sludge system is previously analyzed as in case of the absent of the recovery installation, but the amount of pollutants will be much lower because sulfates, thiosulfates and sulfides were already recovered as scales from the drum. These solid scales can be used in detergent industry

  10. Monitoring sulfide and sulfate-reducing bacteria

    Energy Technology Data Exchange (ETDEWEB)

    Tanner, R.S.

    1995-12-31

    Simple yet precise and accurate methods for monitoring sulfate-reducing bacteria (SRB) and sulfide remain useful for the study of bacterial souring and corrosion. Test kits are available to measure sulfide in field samples. A more precise methylene blue sulfide assay for both field and laboratory studies is described here. Improved media, compared to that in API RP-38, for enumeration of SRB have been formulated. One of these, API-RST, contained cysteine (1.1 mM) as a reducing agent, which may be a confounding source of sulfide. While cysteine was required for rapid enumeration of SRB from environmental samples, the concentration of cysteine in medium could be reduced to 0.4 mM. It was also determined that elevated levels of yeast extract (>1 g/liter) could interfere with enumeration of SRB from environmental samples. The API-RST medium was modified to a RST-11 medium. Other changes in medium composition, in addition to reduction of cysteine, included reduction of the concentration of phosphate from 3.4 mM to 2.2 mM, reduction of the concentration of ferrous iron from 0.8 mM to 0.5 mM and preparation of a stock mineral solution to ease medium preparation. SRB from environmental samples could be enumerated in a week in this medium.

  11. Growth and chemosensory behavior of sulfate-reducing bacteria in oxygen-sulfide gradients

    DEFF Research Database (Denmark)

    Sass, Andrea M.; Wieland, Andrea Eschemann; Kühl, Michael

    2002-01-01

    Growth and chemotactic behavior in oxic–anoxic gradients were studied with two freshwater and four marine strains of sulfate-reducing bacteria related to the genera Desulfovibrio, Desulfomicrobium or Desulfobulbus. Cells were grown in oxygen–sulfide counter-gradients within tubes filled with agar...... chemotactically to lactate, nitrate, sulfate and thiosulfate, and even sulfide functioned as an attractant. In oxic–anoxic gradients the bacteria moved away from high oxygen concentrations and formed bands at the outer edge of the oxic zone at low oxygen concentration (... to actively change the extension and slope of the gradients by oxygen reduction with lactate or even sulfide as electron donor. Generally, the chemotactic behavior was in agreement with a defense strategy that re-establishes anoxic conditions, thus promoting anaerobic growth and, in a natural community...

  12. Hydrogen sulfide oxidation without oxygen - oxidation products and pathways

    International Nuclear Information System (INIS)

    Fossing, H.

    1992-01-01

    Hydrogen sulfide oxidation was studied in anoxic marine sediments-both in undisturbed sediment cores and in sediment slurries. The turn over of hydrogen sulfide was followed using 35 S-radiolabeled hydrogen sulfide which was injected into the sediment. However, isotope exchange reactions between the reduced sulfur compounds, in particular between elemental sulfur and hydrogen sulfide, influenced on the specific radioactivity of these pools. It was, therefore, not possible to measure the turn over rates of the reduced sulfur pools by the radiotracer technique but merely to use the radioisotope to demonstrate some of the oxidation products. Thiosulfate was one important intermediate in the anoxic oxidation of hydrogen sulfide and was continuously turned over by reduction, oxidation and disproportionation. The author discusses the importance of isotope exchange and also presents the results from experiments in which both 35 S-radiolabeled elemental sulfur, radiolabeled hydrogen sulfide and radiolabeled thiosulfate were used to study the intermediates in the oxidative pathways of the sulfur cycle

  13. Assessing the Role of Iron Sulfides in the Long Term Sequestration of U by Sulfate Reducing Bacteria

    Energy Technology Data Exchange (ETDEWEB)

    Rittman, Bruce; Zhou, Chen; Vannela, Raveender

    2013-12-31

    This four-year project’s overarching aim was to identify the role of biogenic and synthetic iron-sulfide minerals in the long-term sequestration of reduced U(IV) formed under sulfate-reducing conditions when subjected to re-oxidizing conditions. As stated in this final report, significant progress was achieved through the collaborative research effort conducted at Arizona State University (ASU) and the University of Michigan (UM).

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

    Directory of Open Access Journals (Sweden)

    Shiue-Lin eLi

    2015-02-01

    Full Text Available 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 + 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 0 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.

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

    Science.gov (United States)

    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 FeS 2 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. Copyright © 2017 Elsevier Ltd. All rights reserved.

  16. Inhibition of sulfate reduction by iron, cadmium and sulfide in granular sludge

    International Nuclear Information System (INIS)

    Gonzalez-Silva, Blanca M.; Briones-Gallardo, Roberto; Razo-Flores, Elias; Celis, Lourdes B.

    2009-01-01

    This study investigated the inhibition effect of iron, cadmium and sulfide on the substrate utilization rate of sulfate reducing granular sludge. A series of batch experiments in a UASB reactor were conducted with different concentrations of iron (Fe 2+ , 4.0-8.5 mM), cadmium (Cd 2+ , 0.53-3.0 mM) and sulfide (4.2-10.6 mM), the reactor was fed with ethanol at 1 g chemical oxygen demand (COD)/L and sulfate to yield a COD/SO 4 2- (g/g) ratio of 0.5. The addition of iron, up to a concentration of 8.1 mM, had a positive effect on the substrate utilization rate which increased 40% compared to the rate obtained without metal addition (0.25 g COD/g VSS-d). Nonetheless, iron concentration of 8.5 mM inhibited the specific substrate utilization rate by 57% compared to the substrate utilization rate obtained in the batch amended with 4.0 mM Fe 2+ (0.44 g COD/g VSS-d). Cadmium had a negative effect on the specific substrate utilization rate at the concentrations tested; at 3.0 mM Cd 2+ the substrate utilization rate was inhibited by 44% compared with the substrate utilization rate without metal addition. Cadmium precipitation with sulfide did not decrease the inhibition of cadmium on sulfate reduction. These results could have important practical implications mainly when considering the application of the sulfate reducing process to treat effluents with high concentrations of sulfate and dissolved metals such as iron and cadmium.

  17. The removal of hydrogen sulfide from gas streams using an aqueous metal sulfate absorbent : Part II. the regeneration of copper sulfide to copper oxide - An experimental study

    NARCIS (Netherlands)

    Ter Maat, H.; Hogendoorn, J. A.; Versteeg, G. F.

    2005-01-01

    Aim of this study was to investigate the possibilities for a selective and efficient method to convert copper(II) sulfide (CuS) into copper(II) oxide (CuO). The oxidation of copper sulfide has been studied experimentally using a thermogravimetric analyzer (TGA) at temperatures ranging from 450 to

  18. Novel processes for anaerobic sulfate production from elemental sulfur by sulfate-reducing bacteria

    Science.gov (United States)

    Lovley, D.R.; Phillips, E.J.P.

    1994-01-01

    Sulfate reducers and related organisms which had previously been found to reduce Fe(III) with H2 or organic electron donors oxidized S0 to sulfate when Mn(IV) was provided as an electron acceptor. Organisms catalyzing this reaction in washed cell suspensions included Desulfovibrio desulfuricans, Desulfomicrobium baculatum. Desulfobacterium autotrophicum, Desulfuromonas acetoxidans, and Geobacter metallireducens. These organisms produced little or no sulfate from S0 with Fe(III) as a potential electron acceptor or in the absence of an electron acceptor. In detailed studies with Desulfovibrio desulfuricans, the stoichiometry of sulfate and Mn(II) production was consistent with the reaction S0 + 3 MnO2 + 4H+ ???SO42- + 3Mn(II) + 2H2O. None of the organisms evaluated could be grown with S0 as the sole electron donor and Mn(IV) as the electron acceptor. In contrast to the other sulfate reducers evaluated, Desulfobulbus propionicus produced sulfate from S0 in the absence of an electron acceptor and Fe(III) oxide stimulated sulfate production. Sulfide also accumulated in the absence of Mn(IV) or Fe(III). The stoichiometry of sulfate and sulfide production indicated that Desulfobulbus propionicus disproportionates S0 as follows: 4S0 + 4H2O???SO42- + 3HS- + 5 H+. Growth of Desulfobulbus propionicus with S0 as the electron donor and Fe(III) as a sulfide sink and/or electron acceptor was very slow. The S0 oxidation coupled to Mn(IV) reduction described here provides a potential explanation for the Mn(IV)-dependent sulfate production that previous studies have observed in anoxic marine sediments. Desulfobulbus propionicus is the first example of a pure culture known to disproportionate S0.

  19. Structurally bound sulfide and sulfate in apatite from the Philips Mine iron oxide - apatite deposit, New York, USA: A tracer of redox changes

    Science.gov (United States)

    Sadove, G.; Konecke, B.; Fiege, A.; Simon, A. C.

    2017-12-01

    Multiple competing hypotheses attempt to explain the genesis of iron oxide-apatite (IOA) ore deposits. Many studies have investigated the chemistry of apatite because the abundances of F and Cl can distinguish magmatic vs. hydrothermal processes. Recent experiments demonstrate that apatite incorporates S6+, S4+, and S2-, and that total sulfur (∑S) as well as the S6+/∑S ratio in apatite vary systematically as a function of oxygen fugacity [1], providing information about sulfur budget and redox. Here, we present results from X-ray absorption near-edge structure (XANES) spectroscopy at the S K-edge, electron microprobe analyses, cathodoluminescence (CL) imaging, and element mapping of apatite from the Philip's Mine IOA deposit, southern Adirondack Mountains, USA. The Philip's Mine apatite contains inclusions of pyrite and pyrrhotite, where the latter includes iron oxide and Ni-rich domains. The apatite also contains inclusions of monazite, and exhibits complex CL zonation coincident with variations in the abundances of REE and S. The presence of monazite fingerprints fluid-mediated dissolution-reprecipitation of originally REE-enriched apatite [2]. The S XANES spectra reveal varying proportions of structurally bound S6+ and S2-, as the S6+/∑S ratio ranges from sulfide-only to sulfate-only. Notably, sulfide-dominated domains contain higher S contents than sulfate-dominated regions. These observations are consistent with co-crystallization of apatite and monosulfide solid solution (MSS) at reducing conditions, followed by decomposition of MSS to pyrrhotite, pyrite and intermediate solid solution (ISS, which is not preserved; [3]). Metasomatism of that assemblage by an oxidized fluid resulted in formation of monazite in apatite and iron oxide domains in pyrrhotite. We conclude that the deposit formed by a H2S-Fe-rich volatile phase, possibly evolved from a rather primitive magmatic source, which is consistent with the low Ti content of magnetite. The deposit was

  20. The effect of sulfate concentration on (sub)millimeter-scale sulfide δ 34S in hypersaline cyanobacterial mats over the diurnal cycle

    Science.gov (United States)

    Fike, David A.; Finke, Niko; Zha, Jessica; Blake, Garrett; Hoehler, Tori M.; Orphan, Victoria J.

    2009-10-01

    sulfur (elevated sulfate reduction rates and extensive sulfide oxidation) at and above the chemocline. This isotopic gradient is observed in both day and night enrichments and suggests that, despite the close physical association between cyanobacteria and select sulfate-reducing bacteria, photosynthetic forcing has no substantive impact on δ 34S in these cyanobacterial mats. Perhaps equally surprising, large, spatially-coherent δ 34S oscillations (˜20-30‰ over 1 mm) occurred at depths up to ˜1.5 cm below the mat surface. These gradients must arise in situ from differential microbial metabolic activity and fractionation during sulfide production at depth. Sulfate concentrations were the dominant control on the spatial variability of sulfide δ 34S. Decreased sulfate concentrations diminished both vertical and lateral δ 34S variability, suggesting that small-scale variations of δ 34S can be diagnostic for reconstructing past sulfate concentrations, even when original sulfate δ 34S is unknown.

  1. Inhibition of sulfate reduction by iron, cadmium and sulfide in granular sludge

    Energy Technology Data Exchange (ETDEWEB)

    Gonzalez-Silva, Blanca M. [Division de Ciencias Ambientales, Instituto Potosino de Investigacion Cientifica y Tecnologica, Camino a la Presa San Jose 2055, Lomas 4a. Seccion, 78216, San Luis Potosi, S.L.P. (Mexico); Briones-Gallardo, Roberto [Facultad de Ingenieria-Instituto de Metalurgia, Universidad Autonoma de San Luis Potosi, Sierra Leona 550, Lomas 2a. Seccion, 78210, San Luis Potosi, S.L.P. (Mexico); Razo-Flores, Elias [Division de Ciencias Ambientales, Instituto Potosino de Investigacion Cientifica y Tecnologica, Camino a la Presa San Jose 2055, Lomas 4a. Seccion, 78216, San Luis Potosi, S.L.P. (Mexico); Celis, Lourdes B., E-mail: celis@ipicyt.edu.mx [Division de Ciencias Ambientales, Instituto Potosino de Investigacion Cientifica y Tecnologica, Camino a la Presa San Jose 2055, Lomas 4a. Seccion, 78216, San Luis Potosi, S.L.P. (Mexico)

    2009-12-15

    This study investigated the inhibition effect of iron, cadmium and sulfide on the substrate utilization rate of sulfate reducing granular sludge. A series of batch experiments in a UASB reactor were conducted with different concentrations of iron (Fe{sup 2+}, 4.0-8.5 mM), cadmium (Cd{sup 2+}, 0.53-3.0 mM) and sulfide (4.2-10.6 mM), the reactor was fed with ethanol at 1 g chemical oxygen demand (COD)/L and sulfate to yield a COD/SO{sub 4}{sup 2-} (g/g) ratio of 0.5. The addition of iron, up to a concentration of 8.1 mM, had a positive effect on the substrate utilization rate which increased 40% compared to the rate obtained without metal addition (0.25 g COD/g VSS-d). Nonetheless, iron concentration of 8.5 mM inhibited the specific substrate utilization rate by 57% compared to the substrate utilization rate obtained in the batch amended with 4.0 mM Fe{sup 2+} (0.44 g COD/g VSS-d). Cadmium had a negative effect on the specific substrate utilization rate at the concentrations tested; at 3.0 mM Cd{sup 2+} the substrate utilization rate was inhibited by 44% compared with the substrate utilization rate without metal addition. Cadmium precipitation with sulfide did not decrease the inhibition of cadmium on sulfate reduction. These results could have important practical implications mainly when considering the application of the sulfate reducing process to treat effluents with high concentrations of sulfate and dissolved metals such as iron and cadmium.

  2. Sources and Contributions of Oxygen During Microbial Pyrite Oxidation: the Triple Oxygen Isotopes of Sulfate

    Science.gov (United States)

    Ziegler, K.; Coleman, M. L.; Mielke, R. E.; Young, E. D.

    2008-12-01

    The triple isotopes of oxygen (Δ17O' = δ17O'-0.528 × δ18O' using logarithmic deltas) can trace the oxygen sources of sulfate produced during sulfide oxidation, an important biogeochemical process on Earth's surface and possibly also on Mars [1]. δ18OSO4 compositions are determined by the isotopic selectivity of the mechanism(s) responsible for their changes, and the δ18O value of the reactants (O2 vs. H2O). The relative proportional importance and contribution of each of those sources and mechanisms, as well as their associated isotopic fractionations, are not well understood. We are investigating the use of Δ 17O as a quantitative and qualitative tracer for the different processes and oxygen sources involved in sulfate production. Δ17O signatures are distinct fingerprints of these reservoirs, independent of fractionation factors that can be ambiguous. We conducted controlled abiotic and biotic (Acidithiobacillus ferrooxidans, A.f.) laboratory experiments in which water was spiked with 18O, allowing us to quantify the sources of sulfate oxygen and therefore the processes attending sulfate formation. Results of this Δ17O tracer study show that A.f. microbes initiate pyrite S-oxidation within hours of exposure, and that sulfate is produced from ~90% atmospheric oxygen. This initial lag-phase (behavior in the initial lag-phase will aid in the understanding of the ecological conditions required for microbial populations to establish and survive. An exponential phase of growth, facilitated by microbial Fe2+-oxidation, follows. The source of sulfate rapidly switches to abiotic sulfide oxidation during exponential growth and the source of oxygen switches from atmospheric O2 to nearly ~100% water. Pending acquisition of complimentary chemistry data (in progress), we interpret our isotope data to indicate that the biotic fractionation factor ɛ18OSO4-O2 of at least ~ -25 to - 35‰ is augmented by microbially induced kinetic fractionation; it is larger than

  3. Isolation of Ochrobactrum sp.QZ2 from sulfide and nitrite treatment system

    International Nuclear Information System (INIS)

    Mahmood, Qaisar; Hu Baolan; Cai Jing; Zheng Ping; Azim, Muhammad Rashid; Jilani, Ghulam; Islam, Ejazul

    2009-01-01

    A bacterial strain QZ2 was isolated from sludge of anoxic sulfide-oxidizing (ASO) reactor. Based on 16S rDNA sequence analysis and morphology, the isolate was identified as Ochrobactrum sp. QZ2. The strain was facultative chemolithotroph, able of using sulfide to reduce nitrite anaerobically. It produced either elemental sulfur or sulfate as the product of sulfide oxidation, depending on the initial sulfide and nitrite concentrations. The optimum growth pH and temperature for Ochrobactrum sp. QZ2 were found as 6.5-7.0 and 30 deg. C, respectively. The specific growth rate (μ) was found as 0.06 h -1 with a doubling time of 19.75 h; the growth seemed more sensitive to highly alkaline pH. Ochrobactrum sp. QZ2 catalyzed sulfide oxidation to sulfate was more sensitive to sulfide compared with nitrite as indicated by IC 50 values for sulfide and nitrite utilization implying that isolate was relatively more tolerant to nitrite. The comparison of physiology of Ochrobactrum sp. QZ2 with those of other known sulfide-oxidizing bacteria suggested that the present isolate resembled to Ochrobactrum anthropi in its denitrification ability.

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

    Science.gov (United States)

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

    2012-01-01

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

  5. THE IMPACT OF BIOSTIMULATION ON THE FATE OF SULFATE AND ASSOCIATED SULFUR DYNAMICS IN GROUNDWATER

    Science.gov (United States)

    Miao, Ziheng; Carreón-Diazconti, Concepcion; Carroll, Kenneth C.; Brusseau, Mark L.

    2014-01-01

    The impact of electron-donor addition on sulfur dynamics for a groundwater system with low levels of metal contaminants was evaluated with a pilot-scale biostimulation test conducted at a former uranium mining site. Geochemical and stable-isotope data collected before, during, and after the test were analyzed to evaluate the sustainability of sulfate reducing conditions induced by the test, the fate of hydrogen sulfide, and the impact on aqueous geochemical conditions. The results of site characterization activities conducted prior to the test indicated the absence of measurable bacterial sulfate reduction. The injection of an electron donor (ethanol) induced bacterial sulfate reduction, as confirmed by an exponential decrease of sulfate concentration in concert with changes in oxidation-reduction potential, redox species, alkalinity, production of hydrogen sulfide, and fractionation of δ34S-sulfate. High, stoichiometrically-equivalent hydrogen sulfide concentrations were not observed until several months after the start of the test. It is hypothesized that hydrogen sulfide produced from sulfate reduction was initially sequestered in the form of iron sulfides until the exhaustion of readily reducible iron oxides associated with the sediment. The fractionation of δ34S for sulfate was atypical, wherein the enrichment declined in the latter half of the experiment. It was conjectured that mixing effects associated with the release of sulfate from sulfate minerals associated with the sediments, along with possible sulfide re-oxidation contributed to this behavior. The results of this study illustrate the biogeochemical complexity that is associated with in-situ biostimulation processes involving bacterial sulfate reduction. PMID:25016586

  6. The impact of biostimulation on the fate of sulfate and associated sulfur dynamics in groundwater

    Science.gov (United States)

    Miao, Ziheng; Carreón-Diazconti, Concepcion; Carroll, Kenneth C.; Brusseau, Mark L.

    2014-08-01

    The impact of electron-donor addition on sulfur dynamics for a groundwater system with low levels of metal contaminants was evaluated with a pilot-scale biostimulation test conducted at a former uranium mining site. Geochemical and stable-isotope data collected before, during, and after the test were analyzed to evaluate the sustainability of sulfate reducing conditions induced by the test, the fate of hydrogen sulfide, and the impact on aqueous geochemical conditions. The results of site characterization activities conducted prior to the test indicated the absence of measurable bacterial sulfate reduction. The injection of an electron donor (ethanol) induced bacterial sulfate reduction, as confirmed by an exponential decrease of sulfate concentration in concert with changes in oxidation-reduction potential, redox species, alkalinity, production of hydrogen sulfide, and fractionation of δ34S-sulfate. High, stoichiometrically-equivalent hydrogen sulfide concentrations were not observed until several months after the start of the test. It is hypothesized that hydrogen sulfide produced from sulfate reduction was initially sequestered in the form of iron sulfides until the exhaustion of readily reducible iron oxides within the sediment. The fractionation of δ34S for sulfate was atypical, wherein the enrichment declined in the latter half of the experiment. It was conjectured that mixing effects associated with the release of sulfate from sulfate minerals associated with the sediments, along with possible sulfide re-oxidation contributed to this behavior. The results of this study illustrate the biogeochemical complexity that is associated with in-situ biostimulation processes involving bacterial sulfate reduction.

  7. Sulfide oxidation in a biofilter

    DEFF Research Database (Denmark)

    Pedersen, Claus Lunde; Dezhao, Liu; Hansen, Michael Jørgen

    Observed hydrogen sulfide uptake rates in a biofilter treating waste air from a pig farm were too high to be explained within conventional limits of sulfide solubility, diffusion in a biofilm and bacterial metabolism. Clone libraries of 16S and 18S rRNA genes from the biofilter found no sulfide...... higher hydrogen sulfide uptake followed by oxidation catalyzed by iron-containing enzymes such as cytochrome c oxidase in a process uncoupled from energy conservation....

  8. Sulfide oxidation in a biofilter

    DEFF Research Database (Denmark)

    Pedersen, Claus Lunde; Liu, Dezhao; Hansen, Michael Jørgen

    2012-01-01

    Observed hydrogen sulfide uptake rates in a biofilter treating waste air from a pig farm were too high to be explained within conventional limits of sulfide solubility, diffusion in a biofilm and bacterial metabolism. Clone libraries of 16S and 18S rRNA genes from the biofilter found no sulfide...... higher hydrogen sulfide uptake followed by oxidation catalyzed by iron-containing enzymes such as cytochrome c oxidase in a process uncoupled from energy conservation....

  9. Application of Biostimulation for Remediation of Sulfate-Contaminated Groundwater at a Mining Site

    Science.gov (United States)

    Miao, Z.; Carroll, K. C.; Carreon, C.; Brusseau, M. L.

    2011-12-01

    There is growing concern regarding sulfate contamination of groundwater. One innovative in-situ remediation option under investigation is biostimulation through addition of electron-donor amendments to enhance sulfate reduction. Two pilot-scale ethanol-injection tests were conducted at a former uranium mining site that is contaminated with sulfate and nitrate (with a lack of heavy metals), and for which there appears to be minimal natural attenuation of sulfate. The first test was a push-pull test that had a limited zone of influence, while the second test was a single-well injection test in which additional downgradient wells were monitored. For both tests, sulfate concentrations began to decline within a few weeks of injection, after nitrate concentrations were significantly reduced. Concomitantly, aqueous concentrations of manganese, iron, and hydrogen sulfide increased from background. Monitoring over many months revealed that the declines in sulfate concentration conformed to exponential decay, with first-order decay rates of approximately 0.01 /d. Analysis of sulfur stable isotope data indicated that the decrease in sulfate concentrations was microbially mediated. The results also indicated that sulfides formed during sulfate reduction may have undergone partial re-oxidation. This study illustrates the feasibility of using ethanol injection for remediation of sulfate-contaminated groundwater. However, re-oxidation of sulfides (both metal sulfide precipitates and hydrogen sulfide gas) is a potential issue of significance that would need to be addressed.

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

    Science.gov (United States)

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

    2004-02-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Rodrigues, A. [Centre de Recherche sur les Infrastructures en Beton (CRIB), Universite Laval, 1065 ave de la Medecine, Quebec, QC, Canada G1V 0A6 (Canada); Duchesne, J., E-mail: josee.duchesne@ggl.ulaval.ca [Centre de Recherche sur les Infrastructures en Beton (CRIB), Universite Laval, 1065 ave de la Medecine, Quebec, QC, Canada G1V 0A6 (Canada); Fournier, B. [Centre de Recherche sur les Infrastructures en Beton (CRIB), Universite Laval, 1065 ave de la Medecine, Quebec, QC, Canada G1V 0A6 (Canada); Durand, B. [Institut de recherche d' Hydro-Quebec (IREQ), 1740 boul. Lionel-Boulet, Varennes, QC, Canada J3X 1S1 (Canada); Rivard, P. [Universite de Sherbrooke, Sherbrooke, QC, Canada J1K 2R1 (Canada); Shehata, M. [Ryerson University, 350 Victoria Street, Toronto, ON, Canada M5B 2K3 (Canada)

    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.

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

    International Nuclear Information System (INIS)

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

    2012-01-01

    Damages in concrete containing sulfide-bearing aggregates were recently observed in the Trois-Rivières 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 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.

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

    Science.gov (United States)

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

    2015-01-01

    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. PMID:26318450

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

    Science.gov (United States)

    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. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

  15. Increase in Nutrients, Mercury, and Methylmercury as a Consequence of Elevated Sulfate Reduction to Sulfide in Experimental Wetland Mesocosms

    Science.gov (United States)

    Myrbo, A.; Swain, E. B.; Johnson, N. W.; Engstrom, D. R.; Pastor, J.; Dewey, B.; Monson, P.; Brenner, J.; Dykhuizen Shore, M.; Peters, E. B.

    2017-11-01

    Microbial sulfate reduction (MSR) in both freshwater and marine ecosystems is a pathway for the decomposition of sedimentary organic matter (OM) after oxygen has been consumed. In experimental freshwater wetland mesocosms, sulfate additions allowed MSR to mineralize OM that would not otherwise have been decomposed. The mineralization of OM by MSR increased surface water concentrations of ecologically important constituents of OM: dissolved inorganic carbon, dissolved organic carbon, phosphorus, nitrogen, total mercury, and methylmercury. Increases in surface water concentrations, except for methylmercury, were in proportion to cumulative sulfate reduction, which was estimated by sulfate loss from the surface water into the sediments. Stoichiometric analysis shows that the increases were less than would be predicted from ratios with carbon in sediment, indicating that there are processes that limit P, N, and Hg mobilization to, or retention in, surface water. The highest sulfate treatment produced high levels of sulfide that retarded the methylation of mercury but simultaneously mobilized sedimentary inorganic mercury into surface water. As a result, the proportion of mercury in the surface water as methylmercury peaked at intermediate pore water sulfide concentrations. The mesocosms have a relatively high ratio of wall and sediment surfaces to the volume of overlying water, perhaps enhancing the removal of nutrients and mercury to periphyton. The presence of wild rice decreased sediment sulfide concentrations by 30%, which was most likely a result of oxygen release from the wild rice roots. An additional consequence of the enhanced MSR was that sulfate additions produced phytotoxic levels of sulfide in sediment pore water.

  16. Realizing high-rate sulfur reduction under sulfate-rich conditions in a biological sulfide production system to treat metal-laden wastewater deficient in organic matter.

    Science.gov (United States)

    Sun, Rongrong; Zhang, Liang; Zhang, Zefeng; Chen, Guang-Hao; Jiang, Feng

    2017-12-22

    Biological sulfur reduction can theoretically produce sufficient sulfide to effectively remove and recover heavy metals in the treatment of organics-deficient sulfate-rich metal-laden wastewater such as acid mine drainage and metallurgic wastewater, using 75% less organics than biological sulfate reduction. However, it is still unknown whether sulfur reduction can indeed compete with sulfate reduction, particularly under high-strength sulfate conditions. The aim of this study was to investigate the long-term feasibility of biological sulfur reduction under high sulfate conditions in a lab-scale sulfur-reducing biological sulfide production (BSP) system with sublimed sulfur added. In the 169-day trial, an average sulfide production rate (SPR) as high as 47 ± 9 mg S/L-h was achieved in the absence of sulfate, and the average SPR under sulfate-rich conditions was similar (53 ± 10 mg S/L-h) when 1300 mg S/L sulfate were fed with the influent. Interestingly, sulfate was barely reduced even at such a high strength and contributed to only 1.5% of total sulfide production. Desulfomicrobium was identified as the predominant sulfidogenic bacterium in the bioreactor. Batch tests further revealed that this sulfidogenic bacteria used elemental sulfur as the electron acceptor instead of the highly bioavailable sulfate, during which polysulfide acted as an intermediate, leading to an even higher bioavailability of sulfur than sulfate. The pathway of sulfur to sulfide conversion via polysulfide in the presence of both sulfur and sulfate was discussed. Collectively, when conditions favor polysulfide formation, sulfur reduction can be a promising and attractive technology to realize a high-rate and low-cost BSP process for treating sulfate-rich metal-laden wastewater. Copyright © 2017 Elsevier Ltd. All rights reserved.

  17. Desulfotignum phosphitoxidans sp. nov., a new marine sulfate reducer that oxidizes phosphite to phosphate.

    Science.gov (United States)

    Schink, Bernhard; Thiemann, Volker; Laue, Heike; Friedrich, Michael W

    2002-05-01

    A new sulfate-reducing bacterium was isolated from marine sediment with phosphite as sole electron donor and CO(2) as the only carbon source. Strain FiPS-3 grew slowly, with doubling times of 3-4 days, and oxidized phosphite, hydrogen, formate, acetate, fumarate, pyruvate, glycine, glutamate, and other substrates nearly completely, with concomitant reduction of sulfate to sulfide. Acetate was formed as a side product to a small extent. Glucose, arabinose, and proline were partly oxidized and partly fermented to acetate plus propionate. Growth with phosphite, hydrogen, or formate was autotrophic. Also, in the presence of sulfate, CO dehydrogenase was present, and added acetate did not increase growth rates or growth yields. In the absence of sulfate, phosphite oxidation was coupled to homoacetogenic acetate formation, with growth yields similar to those in the presence of sulfate. Cells were small rods, 0.6 - 0.8 x 2-4 microm in size, and gram-negative, with a G+C content of 53.9 mol%. They contained desulforubidin, but no desulfoviridin. Based on sequence analysis of the 16S rRNA gene and the sulfite reductase genes dsrAB, strain FiPS-3 was found to be closely related to Desulfotignum balticum. However, physiological properties differed in many points from those of D. balticum. These findings justify the establishment of a new species, Desulfotignum phosphitoxidans.

  18. Sulfide Generated by Sulfate Reduction is a Primary Controller of the Occurrence of Wild Rice (Zizania palustris) in Shallow Aquatic Ecosystems

    Science.gov (United States)

    Myrbo, A.; Swain, E. B.; Engstrom, D. R.; Coleman Wasik, J.; Brenner, J.; Dykhuizen Shore, M.; Peters, E. B.; Blaha, G.

    2017-11-01

    Field observations suggest that surface water sulfate concentrations control the distribution of wild rice, an aquatic grass (Zizania palustris). However, hydroponic studies show that sulfate is not toxic to wild rice at even unrealistically high concentrations. To determine how sulfate might directly or indirectly affect wild rice, potential wild rice habitat was characterized for 64 chemical and physical variables in over 100 sites spanning a relatively steep climatic and geological gradient in Minnesota. Habitat suitability was assessed by comparing the occurrence of wild rice with the field variables, through binary logistic regression. This analysis demonstrated that sulfide in sediment pore water, generated by the microbial reduction of sulfate that diffuses or advects into the sediment, is the primary control of wild rice occurrence. Water temperature and water transparency independently control the suitability of habitat for wild rice. In addition to generating phytotoxic sulfide, sulfate reduction also supports anaerobic decomposition of organic matter, releasing nutrients that can compound the harm of direct sulfide toxicity. These results are important because they show that increases in sulfate loading to surface water can have multiple negative consequences for ecosystems, even though sulfate itself is relatively benign.

  19. The usage of sulfide and thiosulfate ions by purple non-sulfur bacteria Rhodopseudomonas yavorovii

    Directory of Open Access Journals (Sweden)

    O. V. Tarabas

    2017-07-01

    Full Text Available This article covers the patterns of oxidation of sulfide and thiosulfate ions by bacteria Rhodopseudomonas yavorovii Ya-2016 under different cultivation conditions. In the environments with 1.4–5.6 мМ Na2S2O3, R. yavorovii Ya-2016 bacteria accumulated biomass of 1.4–1.6 g/l, which was higher than biomass (1.2-0.6 g/l accumulated by the bacteria with the same concentrations of Na2S × 9H2O. The efficiency of oxidation of 1.4, 2.8, 5.6 мМ sulfide- and thiosulfate-ions as donors of electrons by the bacteria equaled 97.4, 42.6, 18.7 and 68.8, 28.0, 3.7%, respectively. As a result of bacterial oxidation of 1.4 мМ hydrogen sulfide and sodium thiosulphate in the environment accumulation of 0.13–1.30 мМ sulfate-ions occurs, and the element sulfur becomes an intermediate metabolite in the environment with Na2S×9H2O. R. yavorovii Ya-2016 bacteria are capable of using sulfate-ions as a single source of sulfate at increase in photptrophs. In the environment with 2.5 мМ sulfate-ions concentration the bacteria biomass was 1.4 g/l, the bacteria assimilated 17.7% of sulfates. Because purple non-sulfur bacteria R. yavorovii Ya-2016 are capable of using sulfide-ions as donors of electrons of anoxygenic photosynthesis and using sulfate-ions as a single source of sulfate, they could be successfully used in the technologies of remediating the environment from compounds of sulfur.

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

    Digital Repository Service at National Institute of Oceanography (India)

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

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

  1. Microbial control of hydrogen sulfide production

    Energy Technology Data Exchange (ETDEWEB)

    Montgomery, A.D.; Bhupathiraju, V.K.; Wofford, N.; McInerney, M.J. [Univ. of Oklahoma, Tulsa, OK (United States)] [and others

    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.

  2. Adsorption of water, sulfates and chloride on arsenopyrite surface

    Science.gov (United States)

    Silva, Juliana C. M.; dos Santos, Egon C.; de Oliveira, Aline; Heine, Thomas; De Abreu, Heitor A.; Duarte, Hélio A.

    2018-03-01

    Arsenopyrite is one of the sulfide minerals responsible for acid rock drainage (ARD) and is one of the most hazardous in regions affected by mining activities. This phenomenon involves complex reaction mechanism. Although it is intensely investigated, there is a lack of consensus concerning the reaction mechanisms and more information is still necessary. In this work, the adsorption of water, hydrochloric acid, and sulfuric acid on arsenopyrite (001) surface was investigated by means of Density Functional calculations and the results compared to other sulfides aiming to understand the mineral/water interface. The interaction of the chemical species with the (001) FeAsS surface is the first step to understand the intricate oxidation mechanism of arsenopyrite. Molecular water adsorption on (001) FeAsS is more favored than the adsorption of sulfate favoring the dissolution of sulfates and enhancing its oxidation. The estimated adsorption energies of water, sulfates and chloride on other sulfide minerals are compared with the estimated values for arsenopyrite and the chemical reactivity differences discussed in detail.

  3. Plutonium oxides analysis. Sulfur potentiometric analysis

    International Nuclear Information System (INIS)

    Anon.

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

  4. Methanol as electron donor for thermophilic biological sulfate and sulfite reduction

    NARCIS (Netherlands)

    Weijma, J.

    2000-01-01

    Sulfur oxyanions (e.g. sulfate, sulfite) can be removed from aqueous waste- and process streams by biological reduction with a suitable electron donor to sulfide, followed by partial chemical or biological oxidation of sulfide to elemental sulfur. The aim of the research described in this

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

    International Nuclear Information System (INIS)

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

    2011-01-01

    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.

  6. Assessment of sand quality on concrete performance : examination of acidic and sulfate/sulfide-bearing sands.

    Science.gov (United States)

    2014-12-01

    The purpose of this research is to examine how the presence of sulfide- and sulfate-containing : minerals in acidic aggregates may affect the properties of mortar and concrete. Analyses were : performed to compare two sands from a deposit in the Geor...

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

    Science.gov (United States)

    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. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

    Science.gov (United States)

    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.

  9. Sulfidation of carbon-supported iron oxide catalysts

    NARCIS (Netherlands)

    Ramselaar, W.L.T.M.; Hadders, R.H.; Gerkema, E.; Beer, de V.H.J.; Oers, van E.M.; Kraan, van der A.M.

    1989-01-01

    The sulfidation of carbon-supported iron oxide catalysts was studied by means of in-situ Mössbauer spectroscopy at temperatures down to 4.2 K. The catalysts were dried in two different ways and then sulfided in a flow of 10% H2S in H2 at temperatures between 293 and 773 K. Thiophene

  10. A physiologically based kinetic model for bacterial sulfide oxidation.

    Science.gov (United States)

    Klok, Johannes B M; de Graaff, Marco; van den Bosch, Pim L F; Boelee, Nadine C; Keesman, Karel J; Janssen, Albert J H

    2013-02-01

    In the biotechnological process for hydrogen sulfide removal from gas streams, a variety of oxidation products can be formed. Under natron-alkaline conditions, sulfide is oxidized by haloalkaliphilic sulfide oxidizing bacteria via flavocytochrome c oxidoreductase. From previous studies, it was concluded that the oxidation-reduction state of cytochrome c is a direct measure for the bacterial end-product formation. Given this physiological feature, incorporation of the oxidation state of cytochrome c in a mathematical model for the bacterial oxidation kinetics will yield a physiologically based model structure. This paper presents a physiologically based model, describing the dynamic formation of the various end-products in the biodesulfurization process. It consists of three elements: 1) Michaelis-Menten kinetics combined with 2) a cytochrome c driven mechanism describing 3) the rate determining enzymes of the respiratory system of haloalkaliphilic sulfide oxidizing bacteria. The proposed model is successfully validated against independent data obtained from biological respiration tests and bench scale gas-lift reactor experiments. The results demonstrate that the model is a powerful tool to describe product formation for haloalkaliphilic biomass under dynamic conditions. The model predicts a maximum S⁰ formation of about 98 mol%. A future challenge is the optimization of this bioprocess by improving the dissolved oxygen control strategy and reactor design. Copyright © 2012 Elsevier Ltd. All rights reserved.

  11. Azo dye decolorization assisted by chemical and biogenic sulfide

    Energy Technology Data Exchange (ETDEWEB)

    Prato-Garcia, Dorian [Laboratory for Research on Advanced Processes for Water Treatment, Unidad Académica Juriquilla, Instituto de Ingeniería, Universidad Nacional Autónoma de México, Blvd. Juriquilla 3001, Querétaro 76230 (Mexico); Cervantes, Francisco J. [División de Ciencias Ambientales, Instituto Potosino de Investigación Científica y Tecnológica, Camino a la Presa de San José 2055, San Luis Potosí 78216 (Mexico); Buitrón, Germán, E-mail: gbuitronm@ii.unam.mx [Laboratory for Research on Advanced Processes for Water Treatment, Unidad Académica Juriquilla, Instituto de Ingeniería, Universidad Nacional Autónoma de México, Blvd. Juriquilla 3001, Querétaro 76230 (Mexico)

    2013-04-15

    Highlights: ► Azo dyes were reduced efficiently by chemical and biogenic sulfide. ► Biogenic sulfide was more efficient than chemical sulfide. ► There was no competition between dyes and sulfate for reducing equivalents. ► Aromatic amines barely affected the sulfate-reducing process. -- Abstract: The effectiveness of chemical and biogenic sulfide in decolorizing three sulfonated azo dyes and the robustness of a sulfate-reducing process for simultaneous decolorization and sulfate removal were evaluated. The results demonstrated that decolorization of azo dyes assisted by chemical sulfide and anthraquinone-2,6-disulfonate (AQDS) was effective. In the absence of AQDS, biogenic sulfide was more efficient than chemical sulfide for decolorizing the azo dyes. The performance of sulfate-reducing bacteria in attached-growth sequencing batch reactors suggested the absence of competition between the studied azo dyes and the sulfate-reducing process for the reducing equivalents. Additionally, the presence of chemical reduction by-products had an almost negligible effect on the sulfate removal rate, which was nearly constant (94%) after azo dye injection.

  12. Regional sulfate-hematite-sulfide zoning in the auriferous Mariana anticline, Quadrilátero Ferrífero of Minas Gerais, Brazil

    Science.gov (United States)

    Cabral, Alexandre Raphael; Koglin, Nikola; Strauss, Harald; Brätz, Helene; Kwitko-Ribeiro, Rogerio

    2013-10-01

    The distribution of mineral deposits, characterised as barite deposits, hematite-rich auriferous deposits and auriferous tourmaline-sulfide deposits, displays a regional sulfate-hematite-sulfide zoning along the thrust-delineated limbs of the Mariana anticline, in the south-eastern part of the Quadrilátero Ferrífero of Minas Gerais, Brazil. Cross-cut relationships of barite veins and sulfide lodes indicate that sulfidation occurred in a late-tectonic context, which is here attributed to the collapse of the ˜0.6-Ga Brasiliano thrust front. Reconnaissance S-isotopic data from barite and pyrite (Antônio Pereira barite deposit and its adjacent gold deposit, respectively), and arsenopyrite (Passagem de Mariana gold deposit), suggest a new interpretation for the hydrothermal fluid overprint in the Mariana anticline. The Antônio Pereira barite has Δ33S values that are near zero, constraining the sulfate source to rocks younger than 2.45 Ga. The barite-δ34S values are between +19.6 and +20.8 ‰. The Passagem arsenopyrite and tourmaline have Co/Ni ratios that define a positive linear trend with the Antônio Pereira pyrite. The latter has homogenous δ34S values, between +8.8 and +8.9 ‰, which are compatible with thermochemical reduction of aqueous sulfate with the S-isotopic composition of the Antônio Pereira barite.

  13. The Evolution of Sulfide in Shallow Aquatic Ecosystem Sediments: An Analysis of the Roles of Sulfate, Organic Carbon, and Iron and Feedback Constraints Using Structural Equation Modeling

    Science.gov (United States)

    Pollman, C. D.; Swain, E. B.; Bael, D.; Myrbo, A.; Monson, P.; Shore, M. D.

    2017-11-01

    The generation of elevated concentrations of sulfide in sediment pore waters that are toxic to rooted macrophytes is problematic in both marine and freshwaters. In marine waters, biogeochemical conditions that lead to toxic levels of sulfide generally relate to factors that affect oxygen dynamics or the sediment iron concentration. In freshwaters, increases in surface water sulfate have been implicated in decline of Zizania palustris (wild rice), which is important in wetlands across the Great Lakes region of North America. We developed a structural equation (SE) model to elucidate key variables that govern the evolution of sulfide in pore waters in shallow aquatic habitats that are potentially capable of supporting wild rice. The conceptual basis for the model is the hypothesis that dissimilatory sulfate reduction is limited by the availability of both sulfate and total organic carbon (TOC) in the sediment. The conceptual model also assumes that pore water sulfide concentrations are constrained by the availability of pore water iron and that sediment iron supports the supply of dissolved iron to the pore water. A key result from the SE model is that variations in three external variables (sulfate, sediment TOC, and sediment iron) contribute nearly equally to the observed variations in pore water sulfide. As a result, management efforts to mitigate against the toxic effects of pore water sulfide on macrophytes such as wild rice should approach defining a protective sulfate threshold as an exercise tailored to the geochemistry of each site that quantitatively considers the effects of ambient concentrations of sediment Fe and TOC.

  14. Sulfidation of alumina-supported iron and iron-molybdenum oxide catalysts

    NARCIS (Netherlands)

    Ramselaar, W.L.T.M.; Crajé, M.W.J.; Hadders, R.H.; Gerkema, E.; Beer, de V.H.J.; Kraan, van der A.M.

    1990-01-01

    The transition of alumina-supported iron and iron-molybdenum catalysts from the oxidic precursor to the sulfided catalysts was systematically studied by means of in-situ Mössbauer spectroscopy at room temperature. This enabled the adjudgement of various sulfidic phases in the sulfided catalysts. The

  15. Constraining Δ33S signatures of Archean seawater sulfate with carbonate-associated sulfate

    Science.gov (United States)

    Peng, Y.; Bao, H.; Bekker, A.; Hofmann, A.

    2017-12-01

    Non-mass dependent sulfur isotope deviation of S-bearing phases in Archean sedimentary strata, and expressed as Δ33S, has a consistent pattern, i.e., sulfide (pyrite) predominantly bear positive Δ33S values, while Paleoarchean sulfate (barite) has negative Δ33S values. This pattern was later corroborated by observations of negative Δ33S values in Archean volcanogenic massive sulfide deposits and negative Δ33S values in early diagenetic nodular pyrite with a wide range of δ34S values, which is thought to be due to microbial sulfate reduction. These signatures have provided a set of initial conditions for a mechanistic interpretation at physical chemistry level. Unlike the younger geological times when large bodies of seawater evaporite deposits are common, to expand seawater sulfate records, carbonate-associated sulfate (CAS) was utilized as a proxy for ancient seawater sulfate. CAS extracted from the Archean carbonates carries positive Δ33S values. However, CAS could be derived from pyrite oxidation following exposure to modern oxidizing conditions and/or during laboratory extraction procedures. It is, therefore, important for us understanding context of the overall early earth atmospheric condition to empirically confirm whether Archean seawater sulfate was generally characterized by negative Δ33S signatures. Combined δ18O, Δ17O, δ34S, and Δ33S analyses of sequentially extracted water-leachable sulfate (WLS) and acid-leachable sulfate (ALS = CAS) and δ34S and Δ33S analyses of pyrite can help to identify the source of extracted sulfate. We studied drill-core samples of Archean carbonates from the 2.55 Ga Malmani and Campell Rand supgroups, South Africa. Our preliminary results show that 1) neither WLS nor ALS were extracted from samples with extremely low pyrite contents (less than 0.05 wt.%); 2) extractable WLS and ALS is present in samples with relatively high pyrite contents (more than 1 wt.%), and that δ34S and Δ33S values of WLS, ALS, and

  16. Interaction distances in oxides, sulfides and selenides with face-centered packing

    International Nuclear Information System (INIS)

    Kesler, Ya.A.

    1993-01-01

    Concept of characteristic distances (CD) was specified with account of the principle of topologically face-centered anion packing: calculation method was presented and boundary conditions of CD concept applicability were considered. Tables of CD in oxides, sulfides and selenides, obtained in result of self-consistent calculations on the basis of experimental crystallographic data, are presented. Pair correlations between CD in oxides, sulfides and selenides were considered, their relationship with cation electron structure was established. Peculiarities of chemical bond in oxides, sulfides and selenides with face-centered anion packing were discussed

  17. Thioarsenate Formation Coupled with Anaerobic Arsenite Oxidation by a Sulfate-Reducing Bacterium Isolated from a Hot Spring

    Directory of Open Access Journals (Sweden)

    Geng Wu

    2017-07-01

    Full Text Available Thioarsenates are common arsenic species in sulfidic geothermal waters, yet little is known about their biogeochemical traits. In the present study, a novel sulfate-reducing bacterial strain Desulfotomaculum TC-1 was isolated from a sulfidic hot spring in Tengchong geothermal area, Yunnan Province, China. The arxA gene, encoding anaerobic arsenite oxidase, was successfully amplified from the genome of strain TC-1, indicating it has a potential ability to oxidize arsenite under anaerobic condition. In anaerobic arsenite oxidation experiments inoculated with strain TC-1, a small amount of arsenate was detected in the beginning but became undetectable over longer time. Thioarsenates (AsO4-xSx2- with x = 1–4 formed with mono-, di- and tri-thioarsenates being dominant forms. Tetrathioarsenate was only detectable at the end of the experiment. These results suggest that thermophilic microbes might be involved in the formation of thioarsenates and provide a possible explanation for the widespread distribution of thioarsenates in terrestrial geothermal environments.

  18. Thioarsenate Formation Coupled with Anaerobic Arsenite Oxidation by a Sulfate-Reducing Bacterium Isolated from a Hot Spring.

    Science.gov (United States)

    Wu, Geng; Huang, Liuqin; Jiang, Hongchen; Peng, Yue'e; Guo, Wei; Chen, Ziyu; She, Weiyu; Guo, Qinghai; Dong, Hailiang

    2017-01-01

    Thioarsenates are common arsenic species in sulfidic geothermal waters, yet little is known about their biogeochemical traits. In the present study, a novel sulfate-reducing bacterial strain Desulfotomaculum TC-1 was isolated from a sulfidic hot spring in Tengchong geothermal area, Yunnan Province, China. The arxA gene, encoding anaerobic arsenite oxidase, was successfully amplified from the genome of strain TC-1, indicating it has a potential ability to oxidize arsenite under anaerobic condition. In anaerobic arsenite oxidation experiments inoculated with strain TC-1, a small amount of arsenate was detected in the beginning but became undetectable over longer time. Thioarsenates (AsO 4-x S x 2- with x = 1-4) formed with mono-, di- and tri-thioarsenates being dominant forms. Tetrathioarsenate was only detectable at the end of the experiment. These results suggest that thermophilic microbes might be involved in the formation of thioarsenates and provide a possible explanation for the widespread distribution of thioarsenates in terrestrial geothermal environments.

  19. Reaction between vanadium trichloride oxide and hydrogen sulfide

    International Nuclear Information System (INIS)

    Yajima, Akimasa; Matsuzaki, Ryoko; Saeki, Yuzo

    1978-01-01

    The details of the reaction between vanadium trichloride oxide and hydrogen sulfide were examined at 20 and 60 0 C. The main products by the reaction were vanadium dichloride oxide, sulfur, and hydrogen chloride. In addition to these products, small amounts of vanadium trichloride, vanadium tetrachloride, disulfur dichloride, and sulfur dioxide were formed. The formations of the above-mentioned reaction products can be explained as follows: The first stage is the reaction between vanadium trichloride oxide and hydrogen sulfide, 2VOCl 3 (l) + H 2 S(g)→2VOCl 2 (s) + S(s) + 2HCl(g). Then the resulting sulfur reacts with the unreacted vanadium trichloride oxide, 2VOCl 3 (l) + 2S(s)→2VOCl 2 (s) + S 2 Cl 2 (l). The resulting disulfur dichloride subsequently reacts with the unreacted vanadium trichloride oxide, 2VOCl 3 (l) + S 2 Cl 2 (l)→2VCl 4 (l) + S(s) + SO 2 (g). The resulting vanadium tetrachloride reacts with the sulfur formed during the reaction, 2VCl 4 (l) + 2S(s)→2VCl 3 (s) + S 2 Cl 2 (l), and also reacts with hydrogen sulfide, 2VCl 4 (l) + H 2 S(g)→2VCl 3 (s) + S(s) + 2HCl(g). (auth.)

  20. Heavy metal speciation in solid-phase materials from a bacterial sulfate reducing bioreactor using sequential extraction procedure combined with acid volatile sulfide analysis.

    Science.gov (United States)

    Jong, Tony; Parry, David L

    2004-04-01

    Heavy metal mobility, bioavailability and toxicity depends largely on the chemical form of metals and ultimately determines potential for environmental pollution. For this reason, determining the chemical form of heavy metals and metalloids, immobilized in sludges by biological mediated sulfate reduction, is important to evaluate their mobility and bioavailability. A modified Tessier sequential extraction procedure (SEP), complemented with acid volatile sulfide (AVS) and simultaneous extracted metals (SEM) measurements, were applied to determine the partitioning of five heavy metals (defined as Fe, Ni, Zn and Cu, and the metalloid As) in anoxic solid-phase material (ASM) from an anaerobic, sulfate reducing bioreactor into six operationally defined fractions. These fractions were water soluble, exchangeable, bound to carbonates (acid soluble), bound to Fe-Mn oxides (reducible), bound to organic matter and sulfides (oxidizable) and residual. It was found that the distribution of Fe, Ni, Zn, Cu and As in ASM was strongly influenced by its association with the above solid fractions. The fraction corresponding to organic matter and sulfides appeared to be the most important scavenging phases of As, Fe, Ni, Zn and Cu in ASM (59.8-86.7%). This result was supported by AVS and SEM (Sigma Zn, Ni and Cu) measurements, which indicated that the heavy metals existed overwhelmingly as sulfides in the organic matter and sulfide fraction. A substantial amount of Fe and Ni at 16.4 and 20.1%, respectively, were also present in the carbonate fraction, while an appreciable portion of As (18.3%) and Zn (19.4%) was bound to Fe-Mn oxides. A significant amount of heavy metals was also associated with the residual fraction, ranging from 2.1% for Zn to 18.8% for As. Based on the average total extractable heavy metal (TEHM) values, the concentration of heavy metals in the ASM was in the order of Cu > Ni > Zn > Fe > As. If the mobility and bioavailability of heavy metals are assumed to be

  1. Mechanism of Na2SO4 Promoting Nickel Extraction from Sulfide Concentrates by Sulfation Roasting-Water Leaching

    Science.gov (United States)

    Li, Guangshi; Cheng, Hongwei; Chen, Sha; Lu, Xionggang; Xu, Qian; Lu, Changyuan

    2018-06-01

    As a more environmentally friendly and energy-efficient route, the sulfation roasting-water leaching technique has been developed for highly effective extraction of non-ferrous metals from nickel sulfide concentrate in the presence of a Na2SO4 additive. The effects of several important roasting parameters—the roasting temperature, the addition of Na2SO4, the holding time, and the heating rate in particular—have been investigated. The results suggest that about 90 pct Ni, 92 pct Co, 95 pct Cu, and leached from the calcine roasted under the optimum conditions. Furthermore, the behavior and mechanism of the Na2SO4 additive in the roasting process have been well addressed by detailed characterization of the roasted product and leaching residue using quantitative phase analysis (QPA) and energy dispersive spectroscopy (EDS) mapping. The Na2SO4 additive was observed to play a noticeable role in promoting the sulfation degree of valuable metals by forming liquid phases [Na2Me(SO4)2] at the outermost layer, which can create a suitable dynamic environment for sulfation. Thus, addition of Na2SO4 might be conducive to an alternative metallurgical process involving complex sulfide ores.

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

    DEFF Research Database (Denmark)

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

    2011-01-01

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

  3. Removal of dimethyl sulfide by the combination of non-thermal plasma and biological process.

    Science.gov (United States)

    Wei, Z S; Li, H Q; He, J C; Ye, Q H; Huang, Q R; Luo, Y W

    2013-10-01

    A bench scale system integrated with a non-thermal plasma (NTP) and a biotricking filtration (BTF) unit for the treatment of gases containing dimethyl sulfide (DMS) was investigated. DMS removal efficiency in the integrated system was up to 96%. Bacterial communities in the BTF were assessed by PCR-DGGE, which play the dominant role in the biological processes of metabolism, sulfur oxidation, sulfate-reducing and carbon oxidation. The addition of ozone from NTP made microbial community in BTF more complicated and active for DMS removal. The NTP oxidize DMS to simple compounds such as methanol and carbonyl sulfide; the intermediate organic products and DMS are further oxidized to sulfate, carbon dioxide, water vapors by biological degradation. These results show that NTP-BTF is achievable and open new possibilities for applying the integrated with NTP and BTF to odour gas treatment. Copyright © 2013 The Authors. Published by Elsevier Ltd.. All rights reserved.

  4. Catalytic oxidation of sulfide in drinking water treatment: activated carbon as catalyst; Katalytische Oxidation von Sulfid bei der Trinkwasseraufbereitung: Aktivkohle als Katalysator

    Energy Technology Data Exchange (ETDEWEB)

    Hultsch, V; Grischek, T; Wolff, D; Worch, E [Technische Univ. Dresden (Germany). Inst. fuer Wasserchemie; Gun, J [Hebrew Univ. of Jerusalem (Israel). Div. of Environmental Sciences, Fredy and Nadine Herrmann School of Applied Science

    2001-07-01

    In regions with warm climate and limited water resources high sulfide concentrations in groundwater can cause problems during drinking water treatment. Aeration of the raw water is not always sufficient to ensure the hydrogen sulfide concentration below the odour threshold value for hydrogen sulfide. As an alternative, activated carbon can be used as a catalyst for sulfide oxidation of raw water. The use of different types of activated carbon was investigated in kinetic experiments. Both Catalytic Carbon from Calgon Carbon and granulated activated carbon from Norit showed high catalytic activities. The results of the experiments are discussed with regard to the practical use of activated carbon for the elimination of hydrogen sulfide during drinking water treatment. (orig.)

  5. Regulation of bacterial sulfate reduction and hydrogen sulfide fluxes in the central Namibian coastal upwelling zone

    DEFF Research Database (Denmark)

    Bruchert, V.; Jørgensen, BB; Neumann, K.

    2003-01-01

    The coastal upwelling system off central Namibia is one of the most productive regions of the oceans and is characterized by frequently occurring shelf anoxia with severe effects for the benthic life and fisheries. We present data on water column dissolved oxygen, sulfide, nitrate and nitrite, pore......-depleted bottom waters, the oxygen minimum zone on the continental slope, and the lower continental slope below the oxygen minimum zone. High concentrations of dissolved sulfide, up to 22 mM, in the near-surface sediments of the inner shelf result from extremely high rates of bacterial sulfate reduction...

  6. Oxidation and Precipitation of Sulfide in Sewer Networks

    DEFF Research Database (Denmark)

    Nielsen, A. H.

    risks and corrosion of concrete and metals. Most of the problems relate to the buildup of hydrogen sulfide in the atmosphere of sewer networks. In this respect, the processes of the sulfur cycle are of fundamental importance in ultimately determining the extent of such problems. This study focused...... calibrated and validated against field data. In the extension to the WATS model, sulfur transformations were described by six processes: 1. Sulfide production taking place in the biofilm and sediments covering the permanently wetted sewer walls; 2. Biological sulfide oxidation in the permanently wetted...... to the sewer atmosphere, potentially resulting in concrete corrosion. The extended WATS model represents a major improvement over previously developed models for prediction of sulfide buildup in sewer networks. Compared to such models, the major processes governing sulfide buildup in sewer networks...

  7. An eco-friendly oxidation of sulfide compounds

    Indian Academy of Sciences (India)

    An improved green route has been developed for the oxidation of sulfide compounds. Albendazole is converted to ricobendazole or albendazole sulfone using H₂O₂ as an oxidant and H₂O as the solvent. High yields of the corresponding products were obtained by carrying out the reaction at room temperature.

  8. Hydrogen sulfide production by sulfate-reducing bacteria utilizing additives eluted from plastic resins.

    Science.gov (United States)

    Tsuchida, Daisuke; Kajihara, Yusuke; Shimidzu, Nobuhiro; Hamamura, Kengo; Nagase, Makoto

    2011-06-01

    In the present study it was demonstrated that organic additives eluted from plastic resins could be utilized as substrates by sulfate-reducing bacteria. Two laboratory-scale experiments, a microcosm experiment and a leaching experiment, were conducted using polyvinyl chloride (PVC) as a model plastic resin. In the former experiment, the conversion of sulfate to sulfide was evident in microcosms that received plasticized PVC as the sole carbon source, but not in those that received PVC homopolymer. Additionally, dissolved organic carbon accumulated only in microcosms that received plasticized PVC, indicating that the dissolved organic carbon originated from additives. In the leaching experiment, phenol and bisphenol A were found in the leached solutions. These results suggest that the disposal of waste plastics in inert waste landfills may result in the production of H(2)S.

  9. REACTION PRODUCTS AND CORROSION OF MOLYBDENUM ELECTRODE IN GLASS MELT CONTAINING ANTIMONY OXIDES AND SODIUM SULFATE

    Directory of Open Access Journals (Sweden)

    JIŘÍ MATĚJ

    2012-09-01

    Full Text Available The products on the interface of a molybdenum electrode and glass melt were investigated primarily at 1400°C in three model glass melts without ingredients, with 1 % Sb2O3 and with 1 % Sb2O3 and 0.5 % SO3 (wt. %, both under and without load by alternating current. Corrosion of the molybdenum electrode in glass melt without AC load is higher by one order of magnitude if antimony oxides are present. The corrosion continues to increase if sulfate is present in addition to antimony oxides. Isolated antimony droplets largely occur on the electrode-glass melt interface, and numerous droplets are also dissipated in the surrounding glass if only antimony oxides are present in the glass melt. A comparatively continuous layer of antimony occurs on the interface if SO3 is also present, antimony being always in contact with molybdenum sulfide. Almost no antimony droplets are dissipated in the glass melt. The total amount of precipitated antimony also increases. The presence of sulfide on the interface likely facilitates antimony precipitation. The reaction of molybdenum with antimony oxides is inhibited in sites covered by an antimony layer. The composition of sulfide layers formed at 1400°C approximates that of Mo2S3. At 1100°C, the sulfide composition approximates that of MoS4. Corrosion multiplies in the glass melt without additions through the effect of AC current, most molybdenum being separated in the form of metallic particles. Corrosion also increases in the glass melt containing antimony oxides. This is due to increased corrosion in the neighborhood of the separated antimony droplets. This mechanism also results in the loosening of molybdenum particles. The amount of precipitated antimony also increases through the effect of the AC current. AC exerts no appreciable effect on either corrosion, the character of the electrode-glass interface, or antimony precipitation in the glass melt containing SO3.

  10. Terminal processes in the anaerobic degradation of an algal-bacterial mat in a high-sulfate hot spring

    International Nuclear Information System (INIS)

    Ward, D.M.; Olson, G.J.

    1980-01-01

    The algal-bacterial mat of a high-sulfate hot spring (Bath Lake) provided an environment in which to compare terminal processes involved in anaerobic decomposition. Sulfate reduction was found to dominate methane production, as indicated by comparison of initial electron flow through the two processes, rapid conversion of [2- 14 C]acetate to 14 CO 2 and not to 14 CH 4 , and the lack of rapid reduction of NaH 14 CO 3 to 14 CH 4 . Sulfate reduction was the dominant process at all depth intervals, but a marked decrease of sulfate reduction and sulfate-reducing bacteria was observed with depth. Concurrent methanogenesis was indicated by the presence of viable methanogenic bacteria and very low but detectable rates of methane production. A marked increase in methane production was observed after sulfate depletion despite high concentrations of sulfide (>1.25 mM), indicating that methanogenesis was not inhibited by sulfide in the natural environment. Although a sulfate minimum and sulfide maximum occurred in the region of maximal sulfate reduction, the absence of sulfate depletion in interstitial water suggests that methanogenesis is always severely limited in Bath Lake sediments. Low initial methanogenesis was not due to anaerobic methane oxidation

  11. Sulfate reduction at low pH to remediate acid mine drainage

    International Nuclear Information System (INIS)

    Sánchez-Andrea, Irene; Sanz, Jose Luis; Bijmans, Martijn F.M.; Stams, Alfons J.M.

    2014-01-01

    Highlights: • Acid mine drainage (AMD) is an important environmental concern. • Remediation through biological sulfate reduction and metal recovery can be applied for AMD. • Microbial community composition has a major impact on the performance of bioreactors to treat AMD. • Acidophilic SRB are strongly influenced by proton, sulfide and organic acids concentration. - Abstract: Industrial activities and the natural oxidation of metallic sulfide-ores produce sulfate-rich waters with low pH and high heavy metals content, generally termed acid mine drainage (AMD). This is of great environmental concern as some heavy metals are highly toxic. Within a number of possibilities, biological treatment applying sulfate-reducing bacteria (SRB) is an attractive option to treat AMD and to recover metals. The process produces alkalinity, neutralizing the AMD simultaneously. The sulfide that is produced reacts with the metal in solution and precipitates them as metal sulfides. Here, important factors for biotechnological application of SRB such as the inocula, the pH of the process, the substrates and the reactor design are discussed. Microbial communities of sulfidogenic reactors treating AMD which comprise fermentative-, acetogenic- and SRB as well as methanogenic archaea are reviewed

  12. Sulfate reduction at low pH to remediate acid mine drainage

    Energy Technology Data Exchange (ETDEWEB)

    Sánchez-Andrea, Irene, E-mail: irene.sanchezandrea@wur.nl [Departamento de Biología Molecular, Universidad Autónoma de Madrid, 28049 Madrid (Spain); Laboratory of Microbiology, Wageningen University, Dreijenplein 10, 6703 HB Wageningen (Netherlands); Sanz, Jose Luis [Departamento de Biología Molecular, Universidad Autónoma de Madrid, 28049 Madrid (Spain); Bijmans, Martijn F.M. [Wetsus, Centre of Sustainable Water Technology, P.O. Box 1113, 8900 CC Leeuwarden (Netherlands); Stams, Alfons J.M. [Laboratory of Microbiology, Wageningen University, Dreijenplein 10, 6703 HB Wageningen (Netherlands); IBB – Institute for Biotechnology and Bioengineering, Centre of Biological Engineering, University of Minho, 4710-057 Braga (Portugal)

    2014-03-01

    Highlights: • Acid mine drainage (AMD) is an important environmental concern. • Remediation through biological sulfate reduction and metal recovery can be applied for AMD. • Microbial community composition has a major impact on the performance of bioreactors to treat AMD. • Acidophilic SRB are strongly influenced by proton, sulfide and organic acids concentration. - Abstract: Industrial activities and the natural oxidation of metallic sulfide-ores produce sulfate-rich waters with low pH and high heavy metals content, generally termed acid mine drainage (AMD). This is of great environmental concern as some heavy metals are highly toxic. Within a number of possibilities, biological treatment applying sulfate-reducing bacteria (SRB) is an attractive option to treat AMD and to recover metals. The process produces alkalinity, neutralizing the AMD simultaneously. The sulfide that is produced reacts with the metal in solution and precipitates them as metal sulfides. Here, important factors for biotechnological application of SRB such as the inocula, the pH of the process, the substrates and the reactor design are discussed. Microbial communities of sulfidogenic reactors treating AMD which comprise fermentative-, acetogenic- and SRB as well as methanogenic archaea are reviewed.

  13. Key factors influencing rates of heterotrophic sulfate reduction in active seafloor hydrothermal massive sulfide deposits

    Directory of Open Access Journals (Sweden)

    Kiana Laieikawai Frank

    2015-12-01

    Full Text Available Hydrothermal vents are thermally and geochemically dynamic habitats, and the organisms therein are subject to steep gradients in temperature and chemistry. To date, the influence of these environmental dynamics on microbial sulfate reduction has not been well constrained. Here, via multivariate experiments, we evaluate the effects of key environmental variables (temperature, pH, H2S, SO42-, DOC on sulfate reduction rates and metabolic energy yields in material recovered from a hydrothermal flange from the Grotto edifice in the Main Endeavor Field, Juan de Fuca Ridge. Sulfate reduction was measured in batch reactions across a range of physico-chemical conditions. Temperature and pH were the strongest stimuli, and maximum sulfate reduction rates were observed at 50 °C and pH 6, suggesting that the in situ community of sulfate-reducing organisms in Grotto flanges may be most active in a slightly acidic and moderate thermal/chemical regime. At pH 4, sulfate reduction rates increased with sulfide concentrations most likely due to the mitigation of metal toxicity. While substrate concentrations also influenced sulfate reduction rates, energy-rich conditions muted the effect of metabolic energetics on sulfate reduction rates. We posit that variability in sulfate reduction rates reflect the response of the active microbial consortia to environmental constraints on in situ microbial physiology, toxicity, and the type and extent of energy limitation. These experiments help to constrain models of the spatial contribution of heterotrophic sulfate reduction within the complex gradients inherent to seafloor hydrothermal deposits.

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

    Science.gov (United States)

    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

  15. The lithiation and acyl transfer reactions of phosphine oxides, sulfides and boranes in the synthesis of cyclopropanes

    DEFF Research Database (Denmark)

    Clarke, Celia; Fox, David J; Pedersen, Daniel Sejer

    2009-01-01

    Phosphine oxides are lithiated much faster than phosphine sulfides and phosphine boranes. Phosphine sulfides are in turn lithiated much more readily than phosphine boranes. It was possible to trap a phosphine sulfide THF in one case which upon treatment with t-BuOK gave cyclopropane, showing...... that phosphine sulfides readily undergo both phosphinoyl transfer and cyclopropane ring closure just like their phosphine oxide counterparts. The obtained data show that phosphine oxides are easily lithiated and undergo phosphoryl transfer much more readily and faster than phosphine sulfides and phosphine...... boranes. The observations suggest that it would be possible to perform reactions involving phosphine oxides in the presence of phosphine boranes or phosphine sulfides, potentially allowing regioselective alkylation of phosphine oxides in the presence of phosphine boranes or phosphine sulfides....

  16. [Investigation of stages of chemical leaching and biooxidation during the extraction of gold from sulfide concentrates].

    Science.gov (United States)

    Murav'ev, M I; Fomchenko, N V; Kondrat'eva, T V

    2015-01-01

    We examined the chemical leaching and biooxidation stages in a two-stage biooxidation process of an auriferous sulfide concentrate containing pyrrhotite, arsenopyrite and pyrite. Chemical leaching of the concentrate (slurry density at 200 g/L) by ferric sulfate biosolvent (initial concentration at 35.6 g/L), which was obtained by microbial oxidation of ferrous sulfate for 2 hours at 70°C at pH 1.4, was allowed to oxidize 20.4% ofarsenopyrite and 52.1% of sulfur. The most effective biooxidation of chemically leached concentrate was observed at 45°C in the presence of yeast extract. Oxidation of the sulfide concentrate in a two-step process proceeded more efficiently than in one-step. In a two-step mode, gold extraction from the precipitate was 10% higher and the content of elemental sulfur was two times lower than in a one-step process.

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

    NARCIS (Netherlands)

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

    1976-01-01

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

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

    Science.gov (United States)

    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. © 2011 American Chemical Society

  19. Enrichment and immobilization of sulfide removal microbiota applied for environmental biological remediation of aquaculture area

    International Nuclear Information System (INIS)

    Zhao, Yang-Guo; Zheng, Yu; Tian, Weijun; Bai, Jie; Feng, Gong; Guo, Liang; Gao, Mengchun

    2016-01-01

    To remove sulfide in the deteriorating aquaculture sediment and water, sulfide-oxidizing microbiota was enriched from Jiaozhou Bay, China, by using sulfide-rich medium. Composition and structure of microbial communities in the enrichments were investigated by 16S rDNA molecular biotechniques. Results showed that microbial community structure continuously shifted and the abundance of sulfate reducing bacteria, i.e., Desulfobacterium, Desulfococcus and Desulfobacca apparently declined. Several halophile genera, Vibrio, Marinobacter, Pseudomonas, Prochlorococcus, Pediococcus and Thiobacillus predominated finally in the microbiota. The enriched microbiota was capable of removing a maximum of 1000 mg/L sulfide within 12 h with 10% inoculum at pH 7.0, 20–30 °C. After immobilized, the microbiota presented excellent resistance to impact and could completely remove 600 mg/L sulfide in 12 h. Moreover, the immobilized microbiota recovered well even recycled for five times. In conclusion, the immobilized sulfide-removing microbiota showed a quite promising application for biological restoring of sulfide-rich aquaculture environment. - Highlights: • A sulfide-oxidizing microbiota successfully enriched from aquaculture sediment. • Microbiota dominated by Vibrio, Marinobacter, Pseudomonas and Thiobacillus spp. • Sulfide-oxidizing microbiota removed sulfide at an average rate of 100 mg/(L·h). • Immobilized microbiota removed over 85% of sulfide even recycled for five times.

  20. Kinetic studies of sulfide mineral oxidation and xanthate adsorption

    Science.gov (United States)

    Mendiratta, Neeraj K.

    2000-10-01

    Sulfide minerals are a major source of metals; however, certain sulfide minerals, such as pyrite and pyrrhotite, are less desirable. Froth flotation is a commonly used separation technique, which requires the use of several reagents to float and depress different sulfide minerals. Xanthate, a thiol collector, has gained immense usage in sulfide minerals flotation. However, some sulfides are naturally hydrophobic and may float without a collector. Iron sulfides, such as pyrite and pyrrhotite, are few of the most abundant minerals, yet economically insignificant. Their existence with other sulfide minerals leads to an inefficient separation process as well as environmental problems, such as acid mine drainage during mining and processing and SO 2 emissions during smelting process. A part of the present study is focused on understanding their behavior, which leads to undesired flotation and difficulties in separation. The major reasons for the undesired flotation are attributed to the collectorless hydrophobicity and the activation with heavy metal ions. To better understand the collectorless hydrophobicity of pyrite, Electrochemical Impedance Spectroscopy (EIS) of freshly fractured pyrite electrodes was used to study the oxidation and reduction of the mineral. The EIS results showed that the rate of reaction increases with oxidation and reduction. At moderate oxidizing potentials, the rate of reaction is too slow to replenish hydrophilic iron species leaving hydrophobic sulfur species on the surface. However, at higher potentials, iron species are replaced fast enough to depress its flotation. Effects of pH and polishing were also explored using EIS. Besides collectorless hydrophobicity, the activation of pyrrhotite with nickel ions and interaction with xanthate ions makes the separation more difficult. DETA and SO2 are commonly used as pyrrhotite depressants; however, the mechanism is not very well understood. Contact angle measurements, cyclic voltammetry and Tafel

  1. Sulfate Reduction at Low Ph To Remediate Acid Mine Drainage

    NARCIS (Netherlands)

    Sánchez-Andrea, I.; Sanz, J.L.; Bijmans, M.F.M.; Stams, A.J.M.

    2014-01-01

    Industrial activities and the natural oxidation of metallic sulfide-ores produce sulfate-rich waters with low pH and high heavy metals content, generally termed acid mine drainage (AMD). This is of great environmental concern as some heavy metals are highly toxic. Within a number of possibilities,

  2. Impacts of Four SO2 Oxidation Pathways on Wintertime Sulfate Concentrations

    Science.gov (United States)

    Sarwar, G.; Fahey, K.; Zhang, Y.; Kang, D.; Mathur, R.; Xing, J.; Wei, C.; Cheng, Y.

    2017-12-01

    Air quality models tend to under-estimate winter-time sulfate concentrations compared to observed data. Such under-estimations are particularly acute in China where very high concentrations of sulfate have been measured. Sulfate is produced by oxidation of sulfur dioxide (SO2) in gas-phase by hydroxyl radical and in aqueous-phase by hydrogen peroxide, ozone, etc. and most air quality models employ such typical reactions. Several additional SO2 oxidation pathways have recently been proposed. Heterogeneous reaction on dust has been suggested to be an important sink for SO2. Oxidation of SO2 on fine particles in presence of nitrogen dioxide (NO2) and ammonia (NH3) at high relative humidity has been implicated for sulfate formation in Chinese haze and London fog. Reactive nitrogen chemistry in aerosol water has also been suggested to produce winter-time sulfate in China. Specifically, high aerosol water can trap SO2 which can be subsequently oxidized by NO2 to form sulfate. Aqueous-phase (in-cloud) oxidation of SO2 by NO2 can also produce sulfate. Here, we use the hemispheric Community Multiscale Air Quality (CMAQ) modeling system to examine the potential impacts of these SO2 oxidation pathways on sulfate formation. We use anthropogenic emissions from the Emissions Database for Global Atmospheric Research and biogenic emissions from Global Emissions InitiAtive. We performed simulations without and with these SO2 oxidation pathways for October-December of 2014 using meteorological fields obtained from the Weather Research and Forecasting model. The standard CMAQ model contains one gas-phase chemical reaction and five aqueous-phase chemical reactions for SO2 oxidation. We implement four additional SO2 oxidation pathways into the CMAQ model. Our preliminary results suggest that the dust chemistry enhances mean sulfate over parts of China and Middle-East, the in-cloud SO2 oxidation by NO2 enhances sulfate over parts of western Europe, oxidation of SO2 by NO2 and NH3 on

  3. Giant hydrogen sulfide plume in the oxygen minimum zone off Peru supports chemolithoautotrophy.

    Directory of Open Access Journals (Sweden)

    Harald Schunck

    Full Text Available In Eastern Boundary Upwelling Systems nutrient-rich waters are transported to the ocean surface, fuelling high photoautotrophic primary production. Subsequent heterotrophic decomposition of the produced biomass increases the oxygen-depletion at intermediate water depths, which can result in the formation of oxygen minimum zones (OMZ. OMZs can sporadically accumulate hydrogen sulfide (H2S, which is toxic to most multicellular organisms and has been implicated in massive fish kills. During a cruise to the OMZ off Peru in January 2009 we found a sulfidic plume in continental shelf waters, covering an area >5500 km(2, which contained ∼2.2×10(4 tons of H2S. This was the first time that H2S was measured in the Peruvian OMZ and with ∼440 km(3 the largest plume ever reported for oceanic waters. We assessed the phylogenetic and functional diversity of the inhabiting microbial community by high-throughput sequencing of DNA and RNA, while its metabolic activity was determined with rate measurements of carbon fixation and nitrogen transformation processes. The waters were dominated by several distinct γ-, δ- and ε-proteobacterial taxa associated with either sulfur oxidation or sulfate reduction. Our results suggest that these chemolithoautotrophic bacteria utilized several oxidants (oxygen, nitrate, nitrite, nitric oxide and nitrous oxide to detoxify the sulfidic waters well below the oxic surface. The chemolithoautotrophic activity at our sampling site led to high rates of dark carbon fixation. Assuming that these chemolithoautotrophic rates were maintained throughout the sulfidic waters, they could be representing as much as ∼30% of the photoautotrophic carbon fixation. Postulated changes such as eutrophication and global warming, which lead to an expansion and intensification of OMZs, might also increase the frequency of sulfidic waters. We suggest that the chemolithoautotrophically fixed carbon may be involved in a negative feedback loop that

  4. Variability of Fe isotope compositions of hydrothermal sulfides and oxidation products at mid-ocean ridges

    Science.gov (United States)

    Li, Xiaohu; Wang, Jianqiang; Chu, Fengyou; Wang, Hao; Li, Zhenggang; Yu, Xing; Bi, Dongwei; He, Yongsheng

    2018-04-01

    Significant Fe isotopic fractionation occurs during the precipitation and oxidative weathering of modern seafloor hydrothermal sulfides, which has an important impact on the cycling of Fe isotopes in the ocean. This study reports the Fe-isotope compositions of whole-rock sulfides and single-mineral pyrite collected from hydrothermal fields at the South Mid-Atlantic Ridge (SMAR) and the East Pacific Rise (EPR) and discusses the impacts of precipitation and late-stage oxidative weathering of sulfide minerals on Fe isotopic fractionation. The results show large variation in the Fe-isotope compositions of the sulfides from the different hydrothermal fields on the mid-oceanic ridges, indicating that relatively significant isotope fractionation occurs during the sulfide precipitation and oxidative weathering processes. The Fe-isotope compositions of the sulfides from the study area at the SMAR vary across a relatively small range, with an average value of 0.01‰. This Fe-isotope composition is similar to the Fe-isotope composition of mid-oceanic ridge basalt, which suggests that Fe was mainly leached from basalt. In contrast, the Fe-isotope composition of the sulfides from the study area at the EPR are significantly enriched in light Fe isotopes (average value - 1.63‰), mainly due to the kinetic fractionation during the rapid precipitation process of hydrothermal sulfide. In addition, the pyrite from different hydrothermal fields is enriched in light Fe isotopes, which is consistent with the phenomenon in which light Fe isotopes are preferentially enriched during the precipitation of pyrite. The red oxides have the heaviest Fe-isotope compositions (up to 0.80‰), indicating that heavy Fe isotopes are preferentially enriched in the oxidation product during the late-stage oxidation process. The data obtained from this study and previous studies show a significant difference between the Fe-isotope compositions of the sulfides from the SMAR and EPR. The relatively heavy

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

    Science.gov (United States)

    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 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 results provide new empirical data that should allow for more precise quantitative constraints on atmospheric pO2 based on the sedimentary rock record. 1Anbar, A.D. et al., 2007. Science, 317, i. 5846: 1903-1906. 2Williamson & Rimstidt, 1994. Geochim. et Cosmochim

  6. Methanol as electron donor for thermophilic biological sulfate and sulfite reduction

    OpenAIRE

    Weijma, J.

    2000-01-01

    Sulfur oxyanions (e.g. sulfate, sulfite) can be removed from aqueous waste- and process streams by biological reduction with a suitable electron donor to sulfide, followed by partial chemical or biological oxidation of sulfide to elemental sulfur. The aim of the research described in this thesis was to make this biological process more broadly applicable for desulfurization of flue-gases and ground- and wastewaters by using the cheap chemical methanol as electron donor for the reduct...

  7. Galvanic interpretation of self-potential signals associated withmicrobial sulfate-reduction

    Energy Technology Data Exchange (ETDEWEB)

    Williams, Kenneth H.; Hubbard, Susan S.; Banfield, Jillian F.

    2007-05-02

    We have evaluated the usefulness of the self-potential (SP)geophysical method to track the onset and location of microbialsulfate-reduction in saturated sediments during organic carbon amendment.Following stimulation of sulfate-reducing bacteria (SRB) by addition oflactate, anomalous voltages exceeding 600 mV correlated in space and timewith the accumulation of dissolved sulfide. Abiotic experiments in whichthe sulfide concentration at the measurement electrode was systematicallyvaried showed a positive correlation between the magnitude of the SPanomaly and differences in the half-cell potential associated with themeasurement and reference electrodes. Thus, we infer that the SPanomaliesresulted from electrochemical differences that developedbetween sulfide-rich regions and areas having higher oxidation potential.In neither experiment did generation of an SP anomaly require thepresence of an in situ electronic conductor, as is required by othermodels. These findings emphasize the importance of incorporation ofelectrochemical effects at electrode surfaces in interpretation of SPdata from geophysical studies. We conclude that SP measurements provide aminimally invasive means for monitoring stimulated sulfate-reductionwithin saturated sediments.

  8. Effect of pre-oxidation on high temperature sulfidation behavior of FeCr and FeCrAl alloys

    Directory of Open Access Journals (Sweden)

    Pillis Marina Fuser

    2004-01-01

    Full Text Available High temperature corrosion of structural alloys in sulfur bearing environments is many orders of magnitude higher than in oxidizing environments. Efforts to increase sulfidation resistance of these alloys include addition of alloying elements. Aluminum additions to iron-chromium alloys bring about increase in sulfidation resistance. This paper reports the effect of pre-oxidation on the sulfidation behavior of Fe-20Cr and Fe-20Cr-5Al alloys in H2-2% H2S environment at 800 °C. The surfaces of sulfidized specimens were also examined. Pre-oxidation of the two alloys results in an incubation period during subsequent sulfidation. After this incubation period, the Fe-20Cr alloy showed sulfidation behavior similar to that when the alloy was not pre-oxidized. The incubation period during sulfidation of the Fe-20Cr-5Al alloy was significantly longer, over 45 h, compared to 2 h for the Al free alloy. Based on the microscopic and gravimetric data a mechanism for sulfidation of these alloys with pre-oxidation has been proposed.

  9. Ionic liquid-modified metal sulfides/graphene oxide nanocomposites for photoelectric conversion

    International Nuclear Information System (INIS)

    Zhang, Yu; Zhang, Yù; Pei, Qi; Feng, Ting; Mao, Hui; Zhang, Wei; Wu, Shuyao; Liu, Daliang; Wang, Hongyu; Song, Xi-Ming

    2015-01-01

    Graphical abstract: - Highlights: • Metal sulfide (CdS, ZnS, Ag 2 S)/GO nanocomposites were prepared by electrostatic adherence. • Ionic liquid was used to link the metal sulfide and GO in the electrostatic adherence process. • The as-prepared samples showed enhanced photocurrent and highly efficient photocatalytic activity under visible light irradiation. - Abstract: Ionic liquid-modified metal sulfides/graphene oxide nanocomposites are prepared via a facile electrostatic adsorption. Ionic liquid (IL) is firstly used as surface modifier and structure-directing agent of metal sulfide (MS) crystallization process, obtaining ionic liquid modified-MS (IL-MS) nanoparticles with positive charges on surface. IL-MS/GO is obtained by electrostatic adherence between positively charged IL-MS and negatively charged graphene oxide (GO). The as-prepared sample shows enhanced photocurrent and highly efficient photocatalytic activity under visible light irradiation, indicating IL-MS/GO nanocomposites greatly promoted the separation of photogenerated electron–hole pairs

  10. Effect of Sulfide Removal on Sulfate Reduction at pH 5 in a Hydrogen fed Gas-Lift Bioreactor

    NARCIS (Netherlands)

    Bijmans, M.F.M.; Dopson, M.; Lens, P.N.L.; Buisman, C.J.N.

    2008-01-01

    UNCORRECTED PROOF J. Microbiol. Biotechnol. (2007), 17(4), ¿ Effect of Sulfide Removal on Sulfate Reduction at pH 5 in a Hydrogen fed Gas-Lift Bioreactor Bijmans, Martijn F. M.1*, Mark Dopson2, Frederick Ennin1, Piet N. L. Lens1, and Cees J. N. Buisman1 1Sub Department of Environmental Technology,

  11. Source Of Hydrogen Sulfide To Sulfidic Spring And Watershed Ecosystems In Northern Sierra De Chiapas, Mexico Based On Sulfur And Carbon Isotopes

    Science.gov (United States)

    Rosales Lagarde, L.; Boston, P. J.; Campbell, A.

    2013-12-01

    At least four watersheds in northern Sierra de Chiapas, Mexico are fed by conspicuous karst sulfide-rich springs. The toxic hydrogen sulfide (H2S) in these springs nurtures rich ecosystems including especially adapted microorganisms, invertebrates and fish. Sulfur and carbon isotopic analysis of various chemical species in the spring water are integrated within their hydrogeologic context to evaluate the hydrogen sulfide source. Constraining the H2S origin can also increase the understanding of this compound effect in the quality of the nearby hydrocarbon reservoirs, and the extent to which its oxidation to sulfuric acid increases carbonate dissolution and steel corrosion in surface structures. The SO42-/H2S ratio in the spring water varies from 70,000 to 2 meq/L thus sulfate is the dominant species in the groundwater system. This sulfate is mainly produced from anhydrite dissolution based on its isotopic signature. The Δ SO42--H2S range of 16 spring water samples (30-50 ‰) is similar to the values determined by Goldhaber & Kaplan (1975) and Canfield (2001) for low rates of bacterial sulfate reduction suggesting that this is the most important mechanism producing H2S. Although the carbon isotopes do not constrain the nature of the organic matter participating in this reaction, this material likely comes from depth, perhaps as hydrocarbons, due to the apparent stability of the system. The organic matter availability and reactivity probably control the progress of sulfate reduction. The subsurface environments identified in the area also have different sulfur isotopic values. The heavier residual sulfate isotopic value in the Northern brackish springs (δ34S SO42- ≥ 18 ‰) compared to the Southern springs (δ34S SO42- ~18 ‰) suggests sulfate reduction is particularly enhanced in the former, probably by contribution of organic matter associated with oil produced water. In comparison, the composition of the Southern aquifer is mainly influenced by halite

  12. Abundance and Diversity of Denitrifying and Anammox Bacteria in Seasonally Hypoxic and Sulfidic Sediments of the Saline Lake Grevelingen

    Science.gov (United States)

    Lipsewers, Yvonne A.; Hopmans, Ellen C.; Meysman, Filip J. R.; Sinninghe Damsté, Jaap S.; Villanueva, Laura

    2016-01-01

    Denitrifying and anammox bacteria are involved in the nitrogen cycling in marine sediments but the environmental factors that regulate the relative importance of these processes are not well constrained. Here, we evaluated the abundance, diversity, and potential activity of denitrifying, anammox, and sulfide-dependent denitrifying bacteria in the sediments of the seasonally hypoxic saline Lake Grevelingen, known to harbor an active microbial community involved in sulfur oxidation pathways. Depth distributions of 16S rRNA gene, nirS gene of denitrifying and anammox bacteria, aprA gene of sulfur-oxidizing and sulfate-reducing bacteria, and ladderane lipids of anammox bacteria were studied in sediments impacted by seasonally hypoxic bottom waters. Samples were collected down to 5 cm depth (1 cm resolution) at three different locations before (March) and during summer hypoxia (August). The abundance of denitrifying bacteria did not vary despite of differences in oxygen and sulfide availability in the sediments, whereas anammox bacteria were more abundant in the summer hypoxia but in those sediments with lower sulfide concentrations. The potential activity of denitrifying and anammox bacteria as well as of sulfur-oxidizing, including sulfide-dependent denitrifiers and sulfate-reducing bacteria, was potentially inhibited by the competition for nitrate and nitrite with cable and/or Beggiatoa-like bacteria in March and by the accumulation of sulfide in the summer hypoxia. The simultaneous presence and activity of organoheterotrophic denitrifying bacteria, sulfide-dependent denitrifiers, and anammox bacteria suggests a tight network of bacteria coupling carbon-, nitrogen-, and sulfur cycling in Lake Grevelingen sediments. PMID:27812355

  13. Abundance and diversity of denitrifying and anammox bacteria in seasonally hypoxic and sulfidic sediments of the saline Lake Grevelingen

    Directory of Open Access Journals (Sweden)

    Yvonne A. Lipsewers

    2016-10-01

    Full Text Available Denitrifying and anammox bacteria are involved in the nitrogen cycling in marine sediments but the environmental factors that regulate the relative importance of these processes are not well constrained. Here, we evaluated the abundance, diversity and potential activity of denitrifying, anammox, and sulfide-dependent denitrifying bacteria in the sediments of the seasonally hypoxic saline Lake Grevelingen, known to harbor an active microbial community involved in sulfur oxidation pathways. Depth distributions of 16S rRNA gene, nirS gene of denitrifying and anammox bacteria, aprA gene of sulfur-oxidizing and sulfate-reducing bacteria, and ladderane lipids of anammox bacteria were studied in sediments impacted by seasonally hypoxic bottom waters. Samples were collected down to 5 cm depth (1 cm resolution at three different locations before (March and during summer hypoxia (August. The abundance of denitrifying bacteria did not vary despite of differences in oxygen and sulfide availability in the sediments, whereas anammox bacteria were more abundant in the summer hypoxia but in those sediments with lower sulfide concentrations. The potential activity of denitrifying and anammox bacteria as well as of sulfur-oxidizing, including sulfide-dependent denitrifiers and sulfate-reducing bacteria, was potentially inhibited by the competition for nitrate and nitrite with cable and/or Beggiatoa-like bacteria in March and by the accumulation of sulfide in the summer hypoxia. The simultaneous presence and activity of organoheterotrophic denitrifying bacteria, sulfide-dependent denitrifiers and anammox bacteria suggests a tight network of bacteria coupling carbon-, nitrogen- and sulfur cycling in Lake Grevelingen sediments.

  14. Metagenome-based metabolic reconstruction reveals the ecophysiological function of Epsilonproteobacteria in a hydrocarbon-contaminated sulfidic aquifer

    Directory of Open Access Journals (Sweden)

    Andreas Hardy Keller

    2015-12-01

    Full Text Available The population genome of an uncultured bacterium assigned to the Campylobacterales (Epsilonproteobacteria was reconstructed from a metagenome dataset obtained by whole-genome shotgun pyrosequencing. Genomic DNA was extracted from a sulfate-reducing, m-xylene-mineralizing enrichment culture isolated from groundwater of a benzene-contaminated sulfidic aquifer. The identical epsilonproteobacterial phylotype has previously been detected in toluene- or benzene-mineralizing, sulfate-reducing consortia enriched from the same site. Previous stable isotope probing experiments with 13C6-labeled benzene suggested that this phylotype assimilates benzene-derived carbon in a syntrophic benzene-mineralizing consortium that uses sulfate as terminal electron acceptor. However, the type of energy metabolism and the ecophysiological function of this epsilonproteobacterium within aromatic hydrocarbon-degrading consortia and in the sulfidic aquifer are poorly understood.Annotation of the epsilonproteobacterial population genome suggests that the bacterium plays a key role in sulfur cycling as indicated by the presence of a sqr gene encoding a sulfide quinone oxidoreductase and psr genes encoding a polysulfide reductase. It may gain energy by using sulfide or hydrogen/formate as electron donors. Polysulfide, fumarate, as well as oxygen are potential electron acceptors. Auto- or mixotrophic carbon metabolism seems plausible since a complete reductive citric acid cycle was detected. Thus the bacterium can thrive in pristine groundwater as well as in hydrocarbon-contaminated aquifers. In hydrocarbon-contaminated sulfidic habitats, the epsilonproteobacterium may generate energy by coupling the oxidation of hydrogen or formate and highly abundant sulfide with the reduction of fumarate and/or polysulfide, accompanied by efficient assimilation of acetate produced during fermentation or incomplete oxidation of hydrocarbons. The highly efficient assimilation of acetate was

  15. Metagenome-Based Metabolic Reconstruction Reveals the Ecophysiological Function of Epsilonproteobacteria in a Hydrocarbon-Contaminated Sulfidic Aquifer.

    Science.gov (United States)

    Keller, Andreas H; Schleinitz, Kathleen M; Starke, Robert; Bertilsson, Stefan; Vogt, Carsten; Kleinsteuber, Sabine

    2015-01-01

    The population genome of an uncultured bacterium assigned to the Campylobacterales (Epsilonproteobacteria) was reconstructed from a metagenome dataset obtained by whole-genome shotgun pyrosequencing. Genomic DNA was extracted from a sulfate-reducing, m-xylene-mineralizing enrichment culture isolated from groundwater of a benzene-contaminated sulfidic aquifer. The identical epsilonproteobacterial phylotype has previously been detected in toluene- or benzene-mineralizing, sulfate-reducing consortia enriched from the same site. Previous stable isotope probing (SIP) experiments with (13)C6-labeled benzene suggested that this phylotype assimilates benzene-derived carbon in a syntrophic benzene-mineralizing consortium that uses sulfate as terminal electron acceptor. However, the type of energy metabolism and the ecophysiological function of this epsilonproteobacterium within aromatic hydrocarbon-degrading consortia and in the sulfidic aquifer are poorly understood. Annotation of the epsilonproteobacterial population genome suggests that the bacterium plays a key role in sulfur cycling as indicated by the presence of an sqr gene encoding a sulfide quinone oxidoreductase and psr genes encoding a polysulfide reductase. It may gain energy by using sulfide or hydrogen/formate as electron donors. Polysulfide, fumarate, as well as oxygen are potential electron acceptors. Auto- or mixotrophic carbon metabolism seems plausible since a complete reductive citric acid cycle was detected. Thus the bacterium can thrive in pristine groundwater as well as in hydrocarbon-contaminated aquifers. In hydrocarbon-contaminated sulfidic habitats, the epsilonproteobacterium may generate energy by coupling the oxidation of hydrogen or formate and highly abundant sulfide with the reduction of fumarate and/or polysulfide, accompanied by efficient assimilation of acetate produced during fermentation or incomplete oxidation of hydrocarbons. The highly efficient assimilation of acetate was recently

  16. Relationship between microbial sulfate reduction rates and sulfur isotopic fractionation

    Science.gov (United States)

    Matsu'Ura, F.

    2009-12-01

    Sulfate reduction is one of the common processes to obtain energy for certain types of microorganisms.They use hydrogen gas or organic substrates as electron donor and sulfates as electron acceptor, and reduce sulfates to sulfides. Sulfate reducing microbes extend across domains Archea and Bacteria, and are believed to be one of the earliest forms of terrestrial life (Shen 2004). The origin of 34S-depleted (light) sulfide sulfur, especially δ34S vials, which contain 40ml of liquid culture media slightly modified from DSMZ #63 medium.Excess amount of Fe (II) is added to the DSMZ#63 medium to precipitate sulfide as iron sulfide. The vials were incubated at 25°C, 30°C, and 37°C, respectively. 21 vials were used for one temperature and sulfide and sulfate was collected from each three glass vials at every 12 hours from 72 hours to 144 hours after start of incubation. The sulfide was precipitated as iron sulfide and the sulfate was precipitated as barite. Sulfur isotope compositions of sulfate and sulfide were measured by standard method using Delta Plus mass-spectrometer. [Results and Discussion] The fractionation between sulfide and sulfate ranged from 2.7 to 11.0. The fractionation values varied among the different incubation temperature and growth phase of D. desulfuricans. The maximum fractionation values of three incubation temperatures were 9.9, 11.0, and 9.7, for 25 °C, 30°C, and 37°C, respectively. These results were different from standard model and Canfield et al. (2006). I could not find the clear correlation between ∂34S values and incubation temperatures in this experiment. The measured fractionation values during the incubation varied with incubation stage. The fractionation values clearly increased with incubation time at every temperature, and at 25°C ∂34S value was 3.6 at the 72h and it increased to 7.9 at 144 hours. This indicated the difference of sulfate reduction rate due to the growth phase of SRB. In the early logarithmic growth phase

  17. Treatment of antimony mine drainage: challenges and opportunities with special emphasis on mineral adsorption and sulfate reducing bacteria.

    Science.gov (United States)

    Li, Yongchao; Hu, Xiaoxian; Ren, Bozhi

    2016-01-01

    The present article summarizes antimony mine distribution, antimony mine drainage generation and environmental impacts, and critically analyses the remediation approach with special emphasis on iron oxidizing bacteria and sulfate reducing bacteria. Most recent research focuses on readily available low-cost adsorbents, such as minerals, wastes, and biosorbents. It is found that iron oxides prepared by chemical methods present superior adsorption ability for Sb(III) and Sb(V). However, this process is more costly and iron oxide activity can be inhibited by plenty of sulfate in antimony mine drainage. In the presence of sulfate reducing bacteria, sulfate can be reduced to sulfide and form Sb(2)S(3) precipitates. However, dissolved oxygen and lack of nutrient source in antimony mine drainage inhibit sulfate reducing bacteria activity. Biogenetic iron oxide minerals from iron corrosion by iron-oxidizing bacteria may prove promising for antimony adsorption, while the micro-environment generated from iron corrosion by iron oxidizing bacteria may provide better growth conditions for symbiotic sulfate reducing bacteria. Finally, based on biogenetic iron oxide adsorption and sulfate reducing bacteria followed by precipitation, the paper suggests an alternative treatment for antimony mine drainage that deserves exploration.

  18. Understanding the kinetics of sulfate reduction in brines by hydrogen: Progress report

    International Nuclear Information System (INIS)

    Strachan, D.M.

    1988-07-01

    Experiments were conducted with mixtures of hydrogen gas and each of PBB1 and PBB3 brines to examine the reduction kinetics of sulfate in high ionic strength solutions. Results from the experiments with brines showed that the kinetics of sulfate reduction is slower in high ionic strength solutions than the kinetics in low ionic strength solutions. However, the kinetic mechanism does not seem to alter the slow kinetics, but the addition of much larger quantities of sulfide, about 40 mM, does accelerate the reduction of sulfate. Since the proposed reaction mechanism for the reduction of sulfate by hydrogen gas involves the reaction of sulfide with sulfate, slow initial kinetics in the absence of sulfide is understandable, but also implies an unknown rate-limiting reaction. Precipitation of calcium sulfate(s) and calcium sulfide may limit the sulfide and sulfate concentrations to low values. The coexistence of anhydrite and oldhamite may indicate a part of the Ca-S-H 2 O that has not yet been investigated. 6 refs., 4 figs., 3 tabs

  19. Quantifying heavy metals sequestration by sulfate-reducing bacteria in an acid mine drainage-contaminated wetland

    Directory of Open Access Journals (Sweden)

    John W Moreau

    2013-03-01

    Full Text Available Bioremediation strategies that depend on bacterial sulfate reduction for heavy metals remediation harness the reactivity of these metals with biogenic aqueous sulfide. Quantitative knowledge of the degree to which specific toxic metals are partitioned into various sulfide, oxide, or other phases is important for predicting the long-term mobility of these metals under environmental conditions. Here we report the quantitative partitioning into sedimentary biogenic sulfides of a suite of metals and metalloids associated with acid mine drainage contamination of a natural estuarine wetland for over a century.

  20. Corrosion of metals and alloys in sulfate melts at 750 C

    Science.gov (United States)

    Misra, A. K.

    1986-01-01

    The corrosion of Ni, Co, Ni-10Cr, Co-21Cr, and IN738 was studied at 750 C in the presence of molten sulfate mixtures (Na2SO4-Li2SO4 and Na2SO4-CoSO4) and in an atmosphere consisting of O2 + 0.12 percent SO2-SO3. The corrosion was observed to be similar for both Na2SO4-Li2SO4 and Na2SO4-CoSO4 melts. The corrosion of Ni and Co took place by the formation of a mixed oxide plus sulfide scale, very similar to the corrosion in SO2 or SO3 alone. The initial stage for the corrosion of Ni-10Cr involved the formation of a thick NiO + Ni3S2 duplex scale, and Cr sulfide was formed during the later stages. A pitting type of morphology was observed for both Co-21Cr and IN738. The pit was Cr sulfide at the beginning, and subsequently the sulfides oxidized to Cr2O3. A base-metal oxide layer was present above the pit, and this was observed to be formed very early in the corrosion process. A mechanism is proposed to explain this. In general, the formation of sulfides appears to be the primary mode of degradation in mixed sulfide melts.

  1. Anaerobic oxidation of methane and sulfate reduction along the Chilean continental margin

    DEFF Research Database (Denmark)

    Treude, T.; Niggemann, J.; Kallmeyer, J.

    2005-01-01

    of AOM and SR activity, methane, sulfate, sulfide, pH, total chlorins, and a variety of other geochemical parameters. Depth-integrated rates of AOM within the SMT were between 7 and 1124 mmol m(-2) a(-1), effectively removing methane below the sediment-water interface. Single measurements revealed AOM...... with high organic input, to analyze the impact of AOM on the methane budget, and to determine the contribution of AOM to SR within the sulfate-methane transition zone (SMT). Furthermore, we investigated the formation of authigenic carbonates correlated with AOM. We determined the vertical distribution...

  2. The origin and isotopic composition of dissolved sulfide in groundwater from carbonate aquifers in Florida and Texas

    International Nuclear Information System (INIS)

    Rye, R.O.; Back, W.; Hanshaw, B.B.; Rightmire, C.T.; Pearson, F.J. Jr.

    1981-01-01

    The delta 34 S values of dissolved sulfide and the sulfur isotope fractionations between dissolved sulfide and sulfate species in Floridan ground water generally correlate with dissolved sulfate concentrations which are related to flow patterns and residence time within the aquifer. The dissolved sulfide derives from the slow in situ biogenic reduction of sulfate dissolved from sedimentary gypsum in the aquifer. In areas where the water is oldest, the dissolved sulfide has apparently attained isotopic equilibrium with the dissolved sulfate at the temperature of the system. This approach to equilibrium reflects an extremely slow reduction rate of the dissolved sulfate by bacteria; this slow rate probably results from very low concentrations of organic matter in the aquifer. In the reducing part of the Edwards aquifer, Texas, there is a general down-gradient increase in both dissolved sulfide and sulfate concentrations, but neither the delta 34 S values of sulfide nor the sulfide-sulfate isotope fractionation correlates with the ground-water flow pattern. The dissolved sulfide species appear to be derived primarily from biogenic reduction of sulfate ions whose source is gypsum dissolution although upgradient diffusion of H 2 S gas from deeper oil field brines may be important in places. (author)

  3. Anaerobic oxidation of methane coupled to thiosulfate reduction in a biotrickling filter.

    Science.gov (United States)

    Cassarini, Chiara; Rene, Eldon R; Bhattarai, Susma; Esposito, Giovanni; Lens, Piet N L

    2017-09-01

    Microorganisms from an anaerobic methane oxidizing sediment were enriched with methane gas as the substrate in a biotrickling filter (BTF) using thiosulfate as electron acceptor for 213days. Thiosulfate disproportionation to sulfate and sulfide were the dominating sulfur conversion process in the BTF and the sulfide production rate was 0.5mmoll -1 day -1 . A specific group of sulfate reducing bacteria (SRB), belonging to the Desulforsarcina/Desulfococcus group, was enriched in the BTF. The BTF biomass showed maximum sulfate reduction rate (0.38mmoll -1 day -1 ) with methane as sole electron donor, measured in the absence of thiosulfate in the BTF. Therefore, a BTF fed with thiosulfate as electron acceptor can be used to enrich SRB of the DSS group and activate the inoculum for anaerobic oxidation of methane coupled to sulfate reduction. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

    International Nuclear Information System (INIS)

    Natesan, K.

    1988-01-01

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

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

    NARCIS (Netherlands)

    Rao, A.M.F.; Malkin, S.Y.; Hidalgo-Martinez, S.; Meysman, Filip

    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

  6. Periodate Oxidation for Sulfated Glycosaminoglycans, with Special Reference to the Position of Extra Sulfate Groups in Chondroitin Polysulfates, Chondroitin Sulfate D and Chondroitin Sulfate K

    OpenAIRE

    Seno, Nobuko; Murakami, Keiko; Shibusawa, Haru

    1981-01-01

    The optimum conditions for periodate oxidation of sulfated disaccharides were investigated to determine the position of extra sulfate groups on the saturated disulfated disaccharides obtained from chondroitin polysulfates, chondroitin sulfates D and K. Under the conditions: 2mM saturated disulfated disaccharide with 20mM sodium periodate at 37°in the dark, the uronic acid residue in the disulfated disaccharide from chondroitin sulfate D was rapidly and completely destroyed, whereas that in th...

  7. Thermodynamics and Kinetics of Sulfide Oxidation by Oxygen: A Look at Inorganically Controlled Reactions and Biologically Mediated Processes in the Environment

    Science.gov (United States)

    Luther, George W.; Findlay, Alyssa J.; MacDonald, Daniel J.; Owings, Shannon M.; Hanson, Thomas E.; Beinart, Roxanne A.; Girguis, Peter R.

    2011-01-01

    The thermodynamics for the first electron transfer step for sulfide and oxygen indicates that the reaction is unfavorable as unstable superoxide and bisulfide radical ions would need to be produced. However, a two-electron transfer is favorable as stable S(0) and peroxide would be formed, but the partially filled orbitals in oxygen that accept electrons prevent rapid kinetics. Abiotic sulfide oxidation kinetics improve when reduced iron and/or manganese are oxidized by oxygen to form oxidized metals which in turn oxidize sulfide. Biological sulfur oxidation relies on enzymes that have evolved to overcome these kinetic constraints to affect rapid sulfide oxidation. Here we review the available thermodynamic and kinetic data for H2S and HS• as well as O2, reactive oxygen species, nitrate, nitrite, and NOx species. We also present new kinetic data for abiotic sulfide oxidation with oxygen in trace metal clean solutions that constrain abiotic rates of sulfide oxidation in metal free solution and agree with the kinetic and thermodynamic calculations. Moreover, we present experimental data that give insight on rates of chemolithotrophic and photolithotrophic sulfide oxidation in the environment. We demonstrate that both anaerobic photolithotrophic and aerobic chemolithotrophic sulfide oxidation rates are three or more orders of magnitude higher than abiotic rates suggesting that in most environments biotic sulfide oxidation rates will far exceed abiotic rates due to the thermodynamic and kinetic constraints discussed in the first section of the paper. Such data reshape our thinking about the biotic and abiotic contributions to sulfide oxidation in the environment. PMID:21833317

  8. Sulfate reduction and methanogenesis at a freshwater

    DEFF Research Database (Denmark)

    Iversen, Vibeke Margrethe Nyvang; Andersen, Martin Søgaard; Jakobsen, Rasmus

    The freshwater-seawater interface was studied in a ~9-m thick anaerobic aquifer located in marine sand and gravel with thin peat lenses. Very limited amounts of iron-oxides are present. Consequently, the dominating redox processes are sulfate reduction and methanogenesis, and the groundwater...... is enriched in dissolved sulfide, methane and bicarbonate. Under normal conditions the seawater-freshwater interface is found at a depth of 4 m at the coastline and reaches the bottom of the aquifer 40 m inland. However, occasional flooding of the area occurs, introducing sulfate to the aquifer. Groundwater...... chemistry was studied in a 120 m transect perpendicular to the coast. Cores were taken for radiotracer rate measurements of sulfate reduction and methanogenesis. In the saline part of the aquifer 35 m inland, sulfate reduction was the dominant process with rates of 0.1-10 mM/year. In the freshwater part 100...

  9. Structural and Mechanistic Insights into Hemoglobin-catalyzed Hydrogen Sulfide Oxidation and the Fate of Polysulfide Products

    Energy Technology Data Exchange (ETDEWEB)

    Vitvitsky, Victor; Yadav, Pramod K.; An, Sojin; Seravalli, Javier; Cho, Uhn-Soo; Banerjee, Ruma (Michigan-Med); (UNL)

    2017-02-17

    Hydrogen sulfide is a cardioprotective signaling molecule but is toxic at elevated concentrations. Red blood cells can synthesize H2S but, lacking organelles, cannot dispose of H2S via the mitochondrial sulfide oxidation pathway. We have recently shown that at high sulfide concentrations, ferric hemoglobin oxidizes H2S to a mixture of thiosulfate and iron-bound polysulfides in which the latter species predominates. Here, we report the crystal structure of human hemoglobin containing low spin ferric sulfide, the first intermediate in heme-catalyzed sulfide oxidation. The structure provides molecular insights into why sulfide is susceptible to oxidation in human hemoglobin but is stabilized against it in HbI, a specialized sulfide-carrying hemoglobin from a mollusk adapted to life in a sulfide-rich environment. We have also captured a second sulfide bound at a postulated ligand entry/exit site in the α-subunit of hemoglobin, which, to the best of our knowledge, represents the first direct evidence for this site being used to access the heme iron. Hydrodisulfide, a postulated intermediate at the junction between thiosulfate and polysulfide formation, coordinates ferric hemoglobin and, in the presence of air, generated thiosulfate. At low sulfide/heme iron ratios, the product distribution between thiosulfate and iron-bound polysulfides was approximately equal. The iron-bound polysulfides were unstable at physiological glutathione concentrations and were reduced with concomitant formation of glutathione persulfide, glutathione disulfide, and H2S. Hence, although polysulfides are unlikely to be stable in the reducing intracellular milieu, glutathione persulfide could serve as a persulfide donor for protein persulfidation, a posttranslational modification by which H2S is postulated to signal.

  10. Hydrogen sulfide generation in shipboard oily-water waste. Part 3. Ship factors

    Energy Technology Data Exchange (ETDEWEB)

    Hodgeman, D.K.; Fletcher, L.E.; Upsher, F.J.

    1995-04-01

    The chemical and microbiological composition of bilge-water in ships of the Royal Australian Navy has been investigated in relation to the formation of hydrogen sulfide by sulfate-reducing bacteria. Sulfate-reducing bacteria were found in most ships in populations up to 800,000 per mL. Sulfate in the wastes is provided by sea-water. Sea-water constitutes up to 60% (median 20%) of the wastes analysed. Evidence for generation of hydrogen sulfide in the ships was found directly as sulfide or indirectly as depressed sulfate concentrations. The low levels of sulfide found in bilge-water from machinery spaces suggested the ventilation systems were effectively removing the gas from the working area. The effect of storage of the wastes under conditions which simulated the oily- water holding tanks of ships were also investigated. Some wastes were found to produce large quantities of hydrogen sulfide on storage. The wastes that failed to produce hydrogen sulfide were investigated to identify any specific nutritional deficiencies. Some organic substances present in bilge-water, such as lactate or biodegradable cleaning agents, and phosphate strongly influenced the generation of hydrogen sulfide in stored oily-water wastes.

  11. Artificial electron acceptors decouple archaeal methane oxidation from sulfate reduction.

    Science.gov (United States)

    Scheller, Silvan; Yu, Hang; Chadwick, Grayson L; McGlynn, Shawn E; Orphan, Victoria J

    2016-02-12

    The oxidation of methane with sulfate is an important microbial metabolism in the global carbon cycle. In marine methane seeps, this process is mediated by consortia of anaerobic methanotrophic archaea (ANME) that live in syntrophy with sulfate-reducing bacteria (SRB). The underlying interdependencies within this uncultured symbiotic partnership are poorly understood. We used a combination of rate measurements and single-cell stable isotope probing to demonstrate that ANME in deep-sea sediments can be catabolically and anabolically decoupled from their syntrophic SRB partners using soluble artificial oxidants. The ANME still sustain high rates of methane oxidation in the absence of sulfate as the terminal oxidant, lending support to the hypothesis that interspecies extracellular electron transfer is the syntrophic mechanism for the anaerobic oxidation of methane. Copyright © 2016, American Association for the Advancement of Science.

  12. Determination of kinetics and stoichiometry of chemical sulfide oxidation in wastewater of sewer networks

    DEFF Research Database (Denmark)

    Nielsen, Asbjørn Haaning; Vollertsen, Jes; Hvitved-Jacobsen, Thorkild

    2003-01-01

    A method for determination of kinetics and stoichiometry of chemical sulfide oxidation by dissolved oxygen (DO) in wastewater is presented. The method was particularly developed to investigate chemical sulfide oxidation in wastewater of sewer networks at low DO concentrations. The method is based...... be considered constant during the course of the experiments although intermediates accumulated. This was explained by an apparent slow oxidation rate of the intermediates. The method was capable of determining kinetics and stoichiometry of chemical sulfide oxidation at DO concentrations lower than 1 g of O2 m...... on continuous measurement of the reactants allowing the kinetics to be determined at varying reactant concentrations during the course of the experiment. The kinetics determined was simulated by a rate equation. The precision of the method was assessed in terms of the standard deviation of the kinetic...

  13. Early diagenesis in the sediments of the Congo deep-sea fan dominated by massive terrigenous deposits: Part III - Sulfate- and methane- based microbial processes

    Science.gov (United States)

    Pastor, L.; Toffin, L.; Decker, C.; Olu, K.; Cathalot, C.; Lesongeur, F.; Caprais, J.-C.; Bessette, S.; Brandily, C.; Taillefert, M.; Rabouille, C.

    2017-08-01

    Geochemical profiles (SO42-, H2S, CH4, δ13CH4) and phylogenetic diversity of Archaea and Bacteria from two oceanographic cruises dedicated to the lobes sediments of the Congo deep-sea fan are presented in this paper. In this area, organic-rich turbidites reach 5000 m and allow the establishment of patchy cold-seep-like habitats including microbial mats, reduced sediments, and vesicomyid bivalves assemblages. These bivalves live in endosymbiosis with sulfur-oxidizing bacteria and use sulfides to perform chemosynthesis. In these habitats, unlike classical abyssal sediments, anoxic processes are dominant. Total oxygen uptake fluxes and methane fluxes measured with benthic chambers are in the same range as those of active cold-seep environments, and oxygen is mainly used for reoxidation of reduced compounds, especially in bacterial mats and reduced sediments. High concentrations of methane and sulfate co-exist in the upper 20 cm of sediments, and evidence indicates that sulfate-reducing microorganisms and methanogens co-occur in the shallow layers of these sediments. Simultaneously, anaerobic oxidation of methane (AOM) with sulfate as the electron acceptor is evidenced by the presence of ANMEs (ANaerobic MEthanotroph). Dissolved sulfide produced through the reduction of sulfate is reoxidized through several pathways depending on the habitat. These pathways include vesicomyid bivalves uptake (adults or juveniles in the bacterial mats habitats), reoxidation by oxygen or iron phases within the reduced sediment, or reoxidation by microbial mats. Sulfide uptake rates by vesicomyids measured in sulfide-rich sea water (90±18 mmol S m-2 d-1) were similar to sulfide production rates obtained by modelling the sulfate profile with different bioirrigation constants, highlighting the major control of vesicomyids on sulfur cycle in their habitats.

  14. Pyritization processes and greigite formation in the advancing sulfidization front in the Upper Pleistocene sediments of the Black Sea

    DEFF Research Database (Denmark)

    Neretin, LN; Bottcher, ME; Jørgensen, BB

    2004-01-01

    Pyritization in late Pleistocene sediments of the Black Sea is driven by sulfide formed during anaerobic methane oxidation. A sulfidization front is formed by the opposing gradients of sulfide and dissolved iron. The sulfidization processes are controlled by the diffusion flux of sulfide from above...... and by the solid reactive iron content. Two processes of diffusion-limited pyrite formation were identified. The first process includes pyrite precipitation with the accumulation of iron sulfide precursors with the average chemical composition of FeSn (n = 1.10-1.29), including greigite. Elemental sulfur...... and polysulfides, formed from H,S by a reductive dissolution of Fe(Ill)-containing minerals, serve as intermediates to convert iron sulfides into pyrite. In the second process, a "direct" pyrite precipitation occurs through prolonged exposure of iron-containing minerals to dissolved sulfide. Methane-driven sulfate...

  15. Mercury mobilization and speciation linked to bacterial iron oxide and sulfate reduction: A column study to mimic reactive transfer in an anoxic aquifer.

    Science.gov (United States)

    Hellal, Jennifer; Guédron, Stéphane; Huguet, Lucie; Schäfer, Jörg; Laperche, Valérie; Joulian, Catherine; Lanceleur, Laurent; Burnol, André; Ghestem, Jean-Philippe; Garrido, Francis; Battaglia-Brunet, Fabienne

    2015-09-01

    Mercury (Hg) mobility and speciation in subsurface aquifers is directly linked to its surrounding geochemical and microbial environment. The role of bacteria on Hg speciation (i.e., methylation, demethylation and reduction) is well documented, however little data is available on their impact on Hg mobility. The aim of this study was to test if (i) Hg mobility is due to either direct iron oxide reduction by iron reducing bacteria (IRB) or indirect iron reduction by sulfide produced by sulfate reducing bacteria (SRB), and (ii) to investigate its subsequent fate and speciation. Experiments were carried out in an original column setup combining geochemical and microbiological approaches that mimic an aquifer including an interface of iron-rich and iron depleted zones. Two identical glass columns containing iron oxides spiked with Hg(II) were submitted to (i) direct iron reduction by IRB and (ii) to indirect iron reduction by sulfides produced by SRB. Results show that in both columns Hg was leached and methylated during the height of bacterial activity. In the column where IRB are dominant, Hg methylation and leaching from the column was directly correlated to bacterial iron reduction (i.e., Fe(II) release). In opposition, when SRB are dominant, produced sulfide induced indirect iron oxide reduction and rapid adsorption of leached Hg (or produced methylmercury) on neoformed iron sulfides (e.g., Mackinawite) or its precipitation as HgS. At the end of the SRB column experiment, when iron-oxide reduction was complete, filtered Hg and Fe concentrations increased at the outlet suggesting a leaching of Hg bound to FeS colloids that may be a dominant mechanism of Hg transport in aquifer environments. These experimental results highlight different biogeochemical mechanisms that can occur in stratified sub-surface aquifers where bacterial activities play a major role on Hg mobility and changes in speciation. Copyright © 2015 Elsevier B.V. All rights reserved.

  16. The investigation on physico-chemical conditions of sulfides and sulfates based on petrographic and sulfur - oxygen stable isotope studies from the Darreh-Zar porphyry copper deposit, Kerman

    Directory of Open Access Journals (Sweden)

    Anis Parsapoor

    2014-04-01

    Full Text Available The Darreh-Zar porphyry copper deposit, located in the Urumieh – Dokhtar magmatic belt, lies about 10 km southeast of Sar-Cheshmeh porphyry copper deposit. The ore body with hydrothermally altered zones including potassic, chlorite-sericite, sericite, argillic and propylitic all related to the Darreh-Zar porphyry stock intruded the Eocene volcanic rocks. Pyrite, chalcopyrite, molybdenite, with different textures as disseminated and veinlet, are the major sulfide minerals and chalcocite and covellite are considered as the secondary minerals. Sulfur isotopic composition of the sulfates and sulfides studied fall on the magmatic values. Two different origins may be suggested for the gypsums studied: 1- hydration of anhydrite and 2- oxidation of pyrite during supergene enrichment. The stable isotopic data calculated on couple minerals (pyrite-anhydrite point to the formation temperature of about 485-515οC for the fluids involved in mineralization. The fluid responsible for mineralization suggests magmatic sources for all sulfide phases and reduced aqueous sulfur species. Isotopic zoning, based on the δ34S pyrite values, divided the area into the east and the west parts with negative and positive correlation against the depth, respectively. Also, a negative correlation is observed between the Cu and the δ34S in the eastern portion of the area.

  17. Enrichment of sulfate reducing anaerobic methane oxidizing community dominated by ANME-1 from Ginsburg Mud Volcano (Gulf of Cadiz) sediment in a biotrickling filter.

    Science.gov (United States)

    Bhattarai, Susma; Cassarini, Chiara; Rene, Eldon R; Zhang, Yu; Esposito, Giovanni; Lens, Piet N L

    2018-07-01

    This study was performed to enrich anaerobic methane-oxidizing archaea (ANME) present in sediment from the Ginsburg Mud Volcano (Gulf of Cadiz) in a polyurethane foam packed biotrickling filter (BTF). The BTF was operated at 20 (±2) °C, ambient pressure with continuous supply of methane for 248 days. Sulfate reduction with simultaneous sulfide production (accumulating ∼7 mM) after 200 days of BTF operation evidenced anaerobic oxidation of methane (AOM) coupled to sulfate reduction. High-throughput sequence analysis of 16S rRNA genes showed that after 248 days of BTF operation, the ANME clades enriched to more than 50% of the archaeal sequences, including ANME-1b (40.3%) and ANME-2 (10.0%). Enrichment of the AOM community was beneficial to Desulfobacteraceae, which increased from 0.2% to 1.8%. Both the inoculum and the BTF enrichment contained large populations of anaerobic sulfur oxidizing bacteria, suggesting extensive sulfur cycling in the BTF. Copyright © 2018 Elsevier Ltd. All rights reserved.

  18. Use of biogenic sulfide for ZnS precipitation

    NARCIS (Netherlands)

    Esposito, G.; Veeken, A.; Weijma, J.; Lens, P.N.L.

    2006-01-01

    A 600 ml continuously stirred tank reactor was used to assess the performance of a zinc sulfide precipitation process using a biogenic sulfide solution (the effluent of a sulfate-reducing bioreactor) as sulfide source. In all experiments, a proportional-integral (PI) control algorithm was used to

  19. Transformation of iron sulfide to greigite by nitrite produced by oil field bacteria.

    Science.gov (United States)

    Lin, Shiping; Krause, Federico; Voordouw, Gerrit

    2009-05-01

    Nitrate, injected into oil fields, can oxidize sulfide formed by sulfate-reducing bacteria (SRB) through the action of nitrate-reducing sulfide-oxidizing bacteria (NR-SOB). When reservoir rock contains siderite (FeCO(3)), the sulfide formed is immobilized as iron sulfide minerals, e.g. mackinawite (FeS). The aim of our study was to determine the extent to which oil field NR-SOB can oxidize or transform FeS. Because no NR-SOB capable of growth with FeS were isolated, the well-characterized oil field isolate Sulfurimonas sp. strain CVO was used. When strain CVO was presented with a mixture of chemically formed FeS and dissolved sulfide (HS(-)), it only oxidized the HS(-). The FeS remained acid soluble and non-magnetic indicating that it was not transformed. In contrast, when the FeS was formed by adding FeCl(2) to a culture of SRB which gradually produced sulfide, precipitating FeS, and to which strain CVO and nitrate were subsequently added, transformation of the FeS to a magnetic, less acid-soluble form was observed. X-ray diffraction and energy-dispersive spectrometry indicated the transformed mineral to be greigite (Fe(3)S(4)). Addition of nitrite to cultures of SRB, containing microbially formed FeS, was similarly effective. Nitrite reacts chemically with HS(-) to form polysulfide and sulfur (S(0)), which then transforms SRB-formed FeS to greigite, possibly via a sulfur addition pathway (3FeS + S(0) --> Fe(3)S(4)). Further chemical transformation to pyrite (FeS(2)) is expected at higher temperatures (>60 degrees C). Hence, nitrate injection into oil fields may lead to NR-SOB-mediated and chemical mineral transformations, increasing the sulfide-binding capacity of reservoir rock. Because of mineral volume decreases, these transformations may also increase reservoir injectivity.

  20. Importance of sulfate radical anion formation and chemistry in heterogeneous OH oxidation of sodium methyl sulfate, the smallest organosulfate

    Science.gov (United States)

    Chung Kwong, Kai; Chim, Man Mei; Davies, James F.; Wilson, Kevin R.; Nin Chan, Man

    2018-02-01

    Organosulfates are important organosulfur compounds present in atmospheric particles. While the abundance, composition, and formation mechanisms of organosulfates have been extensively investigated, it remains unclear how they transform and evolve throughout their atmospheric lifetime. To acquire a fundamental understanding of how organosulfates chemically transform in the atmosphere, this work investigates the heterogeneous OH radical-initiated oxidation of sodium methyl sulfate (CH3SO4Na) droplets, the smallest organosulfate detected in atmospheric particles, using an aerosol flow tube reactor at a high relative humidity (RH) of 85 %. Aerosol mass spectra measured by a soft atmospheric pressure ionization source (direct analysis in real time, DART) coupled with a high-resolution mass spectrometer showed that neither functionalization nor fragmentation products are detected. Instead, the ion signal intensity of the bisulfate ion (HSO4-) has been found to increase significantly after OH oxidation. We postulate that sodium methyl sulfate tends to fragment into a formaldehyde (CH2O) and a sulfate radical anion (SO4 ṡ -) upon OH oxidation. The formaldehyde is likely partitioned back to the gas phase due to its high volatility. The sulfate radical anion, similar to OH radical, can abstract a hydrogen atom from neighboring sodium methyl sulfate to form the bisulfate ion, contributing to the secondary chemistry. Kinetic measurements show that the heterogeneous OH reaction rate constant, k, is (3.79 ± 0.19) × 10-13 cm3 molecule-1 s-1 with an effective OH uptake coefficient, γeff, of 0.17 ± 0.03. While about 40 % of sodium methyl sulfate is being oxidized at the maximum OH exposure (1.27 × 1012 molecule cm-3 s), only a 3 % decrease in particle diameter is observed. This can be attributed to a small fraction of particle mass lost via the formation and volatilization of formaldehyde. Overall, we firstly demonstrate that the heterogeneous OH oxidation of an

  1. Sulfur cycling in contaminated aquifers: What can we learn from oxygen isotopes in sulfate? (Invited)

    Science.gov (United States)

    Knoeller, K.; Vogt, C.; Hoth, N.

    2009-12-01

    abandoned lignite mine. Due to the heterogeneous isotopic composition of the sulfate source (oxidation of sedimentary sulfide), sulfur isotopes alone are inappropriate for the recognition of BSR. Only the application of oxygen isotopes in sulfate provides clear evidence for the activity of sulfate reducing bacteria. However, the obtained small θ value indicates a significant influence of sulfide re-oxidation. In the second example we applied the dual isotope system to investigate the relevance of BSR for natural biodegradation in an aquifer contaminated with BTEX. Isotope fractionation parameters were determined in column experiments operated under near in situ conditions. The differences between field derived and experimental fractionation parameters revealed essential information on the occurrence of sulfur transformations competing with the actual biodegradation reactions. Most important of those processes is the re-oxidation of reduced sulfur species consuming electron acceptors that would be relevant for contaminant oxidation.

  2. Rock magnetic properties in the sulfate reduction zone in IODP 350 Hole 1437B, Izu Bonin rear arc: preliminary results

    Science.gov (United States)

    Musgrave, R. J.; Kars, M. A. C.; Kodama, K.

    2014-12-01

    During the northern Spring 2014 (April-May), IODP Expedition 350 drilled a 1806.5 m deep hole at Site U1437 in the Izu-Bonin rear arc, in order to understand, among other objectives, the compositional evolution of the arc since the Miocene and track the missing half of the subduction factory. The good recovery of mostly fine grained sediments at this site enables a high resolution paleomagnetic and rock magnetic study. Particularly, variations in magnetic properties and mineralogy are well documented. The onboard magnetostratigraphy established from the study of the archive halves highlighted remagnetized intervals that produced "ghost" repetitions of geomagnetic reversals ~10's meters below their actual stratigraphic position in specific intervals. Onboard paleo- and rock magnetic analyses showed that remagnetization is probably due to a chemical remanence carried by iron sulfides (putatively identified as greigite). The rock magnetic parameters, SIRM/k and the S-ratio are consistent with the presence of ferromagnetic iron sulfides in Site U1437. A mixture of iron oxides and iron sulfides was found within the sulfate reduction zone, which was identified by onboard pore water analyses at ~50-60 meters below sea floor (mbsf) by a minimum in sulfate (~5 mM) coupled with a maximum in alkalinity. Below 50 mbsf, the sulfate content increases up to ~29 mM at ~460 mbsf. The particular downhole profile of the sulfate content in Site U1437 is probably triggered by fluid circulation. Evolution of sulfate content, pyritization process and fluid circulation are closely linked. Onshore research is focusing on further downhole characterization of the iron sulfides including their abundance, grain size and composition. Routine magnetic properties (NRM, magnetic susceptibility) and rock magnetic analyses at high resolution (every ~20-50 cm), including hysteresis properties and low temperature magnetic measurements, have been conducted on about 400 discrete samples in the first 200

  3. Sulfate Reduction and Thiosulfate Transformations in a Cyanobacterial Mat during a Diel Oxygen Cycle

    DEFF Research Database (Denmark)

    JØRGENSEN, BB

    1994-01-01

    Bacterial sulfate reduction and transformations of thiosulfate were studied with radiotracers in a Microcoleus chthono-plastes-dominated microbial mat growing in a hypersaline pond at the Red Sea. The study showed how a diel cycle of oxygen evolution affected respiration by sulfate-reducing bacte......Bacterial sulfate reduction and transformations of thiosulfate were studied with radiotracers in a Microcoleus chthono-plastes-dominated microbial mat growing in a hypersaline pond at the Red Sea. The study showed how a diel cycle of oxygen evolution affected respiration by sulfate......-reducing bacteria and the metabolism of thiosulfate through oxidative and reductive pathways. Sulfate reduction occurred in both oxic and anoxic layers of the mat and varied diurnally, apparently according to temperature rather than to oxygen. Time course experiments showed that the radiotracer method...... underestimated sulfate reduction in the oxic zone due to rapid reoxidation of the produced sulfide. Extremely high reduction rates of up to 10 mu mol cm(-3) d(-1) were measured just below the euphotic zone. Although thiosulfate was simultaneously oxidized, reduced and disproportionated by bacteria in all layers...

  4. Importance of sulfate radical anion formation and chemistry in heterogeneous OH oxidation of sodium methyl sulfate, the smallest organosulfate

    Directory of Open Access Journals (Sweden)

    K. C. Kwong

    2018-02-01

    Full Text Available Organosulfates are important organosulfur compounds present in atmospheric particles. While the abundance, composition, and formation mechanisms of organosulfates have been extensively investigated, it remains unclear how they transform and evolve throughout their atmospheric lifetime. To acquire a fundamental understanding of how organosulfates chemically transform in the atmosphere, this work investigates the heterogeneous OH radical-initiated oxidation of sodium methyl sulfate (CH3SO4Na droplets, the smallest organosulfate detected in atmospheric particles, using an aerosol flow tube reactor at a high relative humidity (RH of 85 %. Aerosol mass spectra measured by a soft atmospheric pressure ionization source (direct analysis in real time, DART coupled with a high-resolution mass spectrometer showed that neither functionalization nor fragmentation products are detected. Instead, the ion signal intensity of the bisulfate ion (HSO4− has been found to increase significantly after OH oxidation. We postulate that sodium methyl sulfate tends to fragment into a formaldehyde (CH2O and a sulfate radical anion (SO4 ⋅ − upon OH oxidation. The formaldehyde is likely partitioned back to the gas phase due to its high volatility. The sulfate radical anion, similar to OH radical, can abstract a hydrogen atom from neighboring sodium methyl sulfate to form the bisulfate ion, contributing to the secondary chemistry. Kinetic measurements show that the heterogeneous OH reaction rate constant, k, is (3.79 ± 0.19  ×  10−13 cm3 molecule−1 s−1 with an effective OH uptake coefficient, γeff, of 0.17 ± 0.03. While about 40 % of sodium methyl sulfate is being oxidized at the maximum OH exposure (1.27  ×  1012 molecule cm−3 s, only a 3 % decrease in particle diameter is observed. This can be attributed to a small fraction of particle mass lost via the formation and volatilization of formaldehyde. Overall, we

  5. Effect of Nitrogen Oxides on Elemental Mercury Removal by Nanosized Mineral Sulfide.

    Science.gov (United States)

    Li, Hailong; Zhu, Lei; Wang, Jun; Li, Liqing; Lee, Po-Heng; Feng, Yong; Shih, Kaimin

    2017-08-01

    Because of its large surface area, nanosized zinc sulfide (Nano-ZnS) has been demonstrated in a previous study to be efficient for removal of elemental mercury (Hg 0 ) from coal combustion flue gas. The excellent mercury adsorption performance of Nano-ZnS was found to be insusceptible to water vapor, sulfur dioxide, and hydrogen chloride. However, nitrogen oxides (NO X ) apparently inhibited mercury removal by Nano-ZnS; this finding was unlike those of many studies on the promotional effect of NO X on Hg 0 removal by other sorbents. The negative effect of NO X on Hg 0 adsorption over Nano-ZnS was systematically investigated in this study. Two mechanisms were identified as primarily responsible for the inhibitive effect of NO X on Hg 0 adsorption over Nano-ZnS: (1) active sulfur sites on Nano-ZnS were oxidized to inactive sulfate by NO X ; and (2) the chemisorbed mercury, i.e., HgS, was reduced to Hg 0 by NO X . This new insight into the role of NO X in Hg 0 adsorption over Nano-ZnS can help to optimize operating conditions, maximize Hg 0 adsorption, and facilitate the application of Nano-ZnS as a superior alternative to activated carbon for Hg 0 removal using existing particulate matter control devices in power plants.

  6. Transition-Metal-Free Highly Efficient Aerobic Oxidation of Sulfides to Sulfoxides under Mild Conditions

    Directory of Open Access Journals (Sweden)

    Hua Zhang

    2009-12-01

    Full Text Available A highly efficient transition-metal-free catalytic system Br2/NaNO2/H2O has been developed for a robust and economic acid-free aerobic oxidation of sulfides. It is noteworthy that the sulfide function reacts under mild conditions without over-oxidation to sulfone. The role of NaNO2as an efficient NO equivalent for the activation of molecular oxygen was identified. Under the optimal conditions, a broad range of sulfide substrates were converted into their corresponding sulfoxides in high yields by molecular oxygen. The present catalytic system utilizes cheap and readily available agents as the catalysts, exhibits high selectivity for sulfoxide products and releases only innocuous water as the by-products.

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

    International Nuclear Information System (INIS)

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

    1993-01-01

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

  8. Cadmium solubility in paddy soils: Effects of soil oxidation, metal sulfides and competitive ions

    Energy Technology Data Exchange (ETDEWEB)

    Livera, Jennifer de, E-mail: Jennifer.deLivera@adelaide.edu.au [Soil Science, School of Agriculture Food and Wine, Waite Research Institute, University of Adelaide, Adelaide, SA (Australia); McLaughlin, Mike J. [Soil Science, School of Agriculture Food and Wine, Waite Research Institute, University of Adelaide, Adelaide, SA (Australia); CSIRO Land and Water, Environmental Biogeochemistry Program, Sustainable Agriculture Flagship, Adelaide, SA (Australia); Hettiarachchi, Ganga M. [CSIRO Land and Water, Environmental Biogeochemistry Program, Sustainable Agriculture Flagship, Adelaide, SA (Australia); Department of Agronomy, Kansas state University, Manhattan, KS (United States); Kirby, Jason K. [CSIRO Land and Water, Environmental Biogeochemistry Program, Sustainable Agriculture Flagship, Adelaide, SA (Australia); CSIRO Land and Water, Environmental Biogeochemistry Program, Water for a Healthy Country Flagship, Adelaide, SA (Australia); Beak, Douglas G. [CSIRO Land and Water, Environmental Biogeochemistry Program, Sustainable Agriculture Flagship, Adelaide, SA (Australia)

    2011-03-15

    Cadmium (Cd) is a non-essential element for human nutrition and is an agricultural soil contaminant. Cadmium solubility in paddy soils affects Cd accumulation in the grain of rice. This is a human health risk, exacerbated by the fact that rice grains are deficient in iron (Fe) and zinc (Zn) for human nutrition. To find ways of limiting this potential risk, we investigated factors influencing Cd solubility relative to Fe and Zn during pre-harvest drainage of paddy soils, in which soil oxidation is accompanied by the grain-filling stage of rice growth. This was simulated in temperature-controlled 'reaction cell' experiments by first excluding oxygen to incubate soil suspensions anaerobically, then inducing aerobic conditions. In treatments without sulfur addition, the ratios of Cd:Fe and Cd:Zn in solution increased during the aerobic phase while Cd concentrations were unaffected and the Fe and Zn concentrations decreased. However, in treatments with added sulfur (as sulfate), up to 34 % of sulfur (S) was precipitated as sulfide minerals during the anaerobic phase and the Cd:Fe and Cd:Zn ratios in solution during the aerobic phase were lower than for treatments without S addition. When S was added, Cd solubility decreased whereas Fe and Zn were unaffected. When soil was spiked with Zn the Cd:Zn ratio was lower in solution during the aerobic phase, due to higher Zn concentrations. Decreased Cd:Fe and Cd:Zn ratios during the grain filling stage could potentially limit Cd enrichment in paddy rice grain due to competitive ion effects for root uptake. - Research Highlights: {yields} Cd:Fe and Cd:Zn ratios increase in paddy soil solution during oxidation. {yields} Cd:Fe and Cd:Zn ratios increase because Fe and Zn concentrations decrease. {yields} Cd concentrations do not change during oxidation. {yields} Cd:Fe and Cd:Zn ratios in solution decrease when Zn is added to soil. {yields} Metal sulfide precipitation lowers Cd:Fe and Cd:Zn ratios in soil solution.

  9. Sulfide Intrusion and Detoxification in the Seagrass Zostera marina

    DEFF Research Database (Denmark)

    Hasler-Sheetal, Harald; Holmer, Marianne

    2015-01-01

    Gaseous sulfide intrusion into seagrasses growing in sulfidic sediments causes little or no harm to the plant, indicating the presence of an unknown sulfide tolerance or detoxification mechanism. We assessed such mechanism in the seagrass Zostera marina in the laboratory and in the field...... as sulfate throughout the plant. We conclude that avoidance of sulfide exposure by reoxidation of sulfide in the rhizosphere or aerenchyma and tolerance of sulfide intrusion by incorporation of sulfur in the plant are likely major survival strategies of seagrasses in sulfidic sediments....

  10. Sulfate cooling effects on climate through in-cloud oxidation of anthropogenic SO2

    International Nuclear Information System (INIS)

    Lelieveld, J.; Heintzenberg, J.

    1992-01-01

    Anthropogenic SO 2 emissions may exert a significant cooling effect on climate in the Northern Hemisphere through backscattering of solar radiation by sulfate particles. Earlier estimates of the sulfate climate forcing were based on a limited number of sulfate-scattering correlation measurements from which a high sulfate-scattering efficiency was derived. Model results suggest that cloud processing of air is the underlying mechanism. aqueous phase oxidation of SO 2 into sulfate and the subsequent release of the dry aerosol by cloud evaporation render sulfate a much more efficient scatterer than through gas-phase SO 2 oxidation

  11. LIGNOCELLULOSE NANOCOMPOSITE CONTAINING COPPER SULFIDE

    Directory of Open Access Journals (Sweden)

    Sanchi Nenkova

    2011-04-01

    Full Text Available Copper sulfide-containing lignocellulose nanocomposites with improved electroconductivity were obtained. Two methods for preparing the copper sulfide lignocellulose nanocomposites were developed. An optimization of the parameters for obtaining of the nanocomposites with respect to obtaining improved electroconductivity, economy, and lower quantities and concentration of copper and sulfur ions in waste waters was conducted. The mechanisms and schemes of delaying and subsequent connection of copper sulfides in the lignocellulosic matrix were investigated. The modification with a system of 2 components: cupric sulfate pentahydrate (CuSO4. 5H2O and sodium thiosulfate pentahydrate (Na2S2O3.5H2O for wood fibers is preferred. Optimal parameters were established for the process: 40 % of the reduction system; hydromodule M=1:6; and ratio of cupric sulfate pentahydrate:sodium thiosulfate pentahydrate = 1:2. The coordinative connection of copper ions with oxygen atoms of cellulose OH groups and aromatic nucleus in lignin macromolecule was observed.

  12. Seawater sulfate reduction and sulfur isotope fractionation in basaltic systems: interaction of seawater with fayalite and magnetite at 200-3500C

    International Nuclear Information System (INIS)

    Shanks, W.C. III; Bischoff, J.L.; Rosenbauer, R.J.

    1981-01-01

    Sulfate reduction during seawater reaction with fayalite and with magnetite was rapid at 350 0 C, producing equilibrium assemblages of talc-pyrite-hematite-magnetite at low water/rock ratios and talc-pyrite-hematite-anhydrite at higher water/rock ratios. At 250 0 C, seawater reacting with fayalite produced detectable amounts of dissolved H 2 S. At 200 0 C, dissolved H 2 S was not detected, even after 219 days. Reaction stoichiometry indicates that sulfate reduction requires large amounts of H + , which, in subseafloor hydrothermal systems is provided by Mg metasomatism. Seawater contains sufficient Mg to supply all the H + necessary for quantitative reduction of seawater sulfate. Systematics of sulfur isotopes in the 250 and 350 0 C experiments indicate that isotopic equilibrium is reached and can be modeled as a Rayleigh distillation process. Isotopic composition of hydrothermally produced H 2 S in natural systems is strongly dependent upon the seawater/basalt ratio in the geothermal system, which controls the relative sulfide contributions from the two important sulfur sources, seawater sulfate and sulfide phases in basalt. Anhydrite precipitation during geothermal heating severely limits sulfate ingress into high temperature interaction zones. Quantitative sulfate reduction can thus be accomplished without producing strongly oxidized rocks and resultant sulfide sulfur isotope values represent a mixture of seawater and basaltic sulfur. (author)

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

    Science.gov (United States)

    Nason, Peter; Johnson, Raymond H; Neuschütz, Clara; Alakangas, Lena; Öhlander, Björn

    2014-02-28

    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 0.2m 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 0.6m 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 0.3m 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. Copyright © 2014 Elsevier B.V. All rights reserved.

  14. Acid Sulfate Alteration on Mars

    Science.gov (United States)

    Ming, D. W.; Morris, R. V.

    2016-01-01

    aqueous formation of sulfate-bearing phases under acidic conditions on the surface of Mars including (1) sulfuric acid weathering of basaltic materials; (2) oxidative weathering of ultramafic igneous rocks containing sulfides; (3) acid fog weathering of basaltic materials, and (4) near-neutral pH subsurface solutions rich in Fe2(+) that were rapidly oxidized to Fe3(+), which produced excess acidity as iron was oxidized on exposure to O2 or photo-oxidized by ultraviolet radiation at the martian surface. Next, we briefly describe evidence for these hypothesis.

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

    Energy Technology Data Exchange (ETDEWEB)

    Mitchell, Joshua K.; Arcibar-Orozco, Javier A.; Bandosz, Teresa J., E-mail: tbandosz@ccny.cuny.edu

    2016-12-30

    Highlights: • Microporous zirconium-cerium (hydr) oxides were synthetized. • Ce presence narrowed the band gap of the materials. • The samples showed a high efficiency for removal of CEES vapors. • 1,2-Bis (ethyl thio) ethane and ethyl vinyl sulfide were the main reaction products. • 5% (Ce/Zr mol) addition of cerium oxide results in the best performing material. - Abstract: Highly porous cerium oxide modified Zr(OH){sub 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 (CeO{sub 2}) and hydroxide (Zr(OH){sub 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.

  16. A batch assay to measure microbial hydrogen sulfide production from sulfur-containing solid wastes

    International Nuclear Information System (INIS)

    Sun, Mei; Sun, Wenjie; Barlaz, Morton A.

    2016-01-01

    Large volumes of sulfur-containing wastes enter municipal solid waste landfills each year. Under the anaerobic conditions that prevail in landfills, oxidized forms of sulfur, primarily sulfate, are converted to sulfide. Hydrogen sulfide (H 2 S) is corrosive to landfill gas collection and treatment systems, and its presence in landfill gas often necessitates the installation of expensive removal systems. For landfill operators to understand the cost of managing sulfur-containing wastes, an estimate of the H 2 S production potential is needed. The objective of this study was to develop and demonstrate a biochemical sulfide potential (BSP) test to measure the amount of H 2 S produced by different types of sulfur-containing wastes in a relatively fast (30 days) and inexpensive (125 mL serum bottles) batch assay. This study confirmed the toxic effect of H 2 S on both sulfate reduction and methane production in batch systems, and demonstrated that removing accumulated H 2 S by base adsorption was effective for mitigating inhibition. H 2 S production potentials of coal combustion fly ash, flue gas desulfurization residual, municipal solid waste combustion ash, and construction and demolition waste were determined in BSP assays. After 30 days of incubation, most of the sulfate in the wastes was converted to gaseous or aqueous phase sulfide, with BSPs ranging from 0.8 to 58.8 mL H 2 S/g waste, depending on the chemical composition of the samples. Selected samples contained solid phase sulfide which contributed to the measured H 2 S yield. A 60 day incubation in selected samples resulted in 39–86% additional sulfide production. H 2 S production measured in BSP assays was compared with that measured in simulated landfill reactors and that calculated from chemical analyses. H 2 S production in BSP assays and in reactors was lower than the stoichiometric values calculated from chemical composition for all wastes tested, demonstrating the importance of assays to estimate the

  17. Trace methane oxidation and the methane dependency of sulfate reduction in anaerobic granular sludge

    KAUST Repository

    Meulepas, Roel J.W.

    2010-05-01

    This study investigates the oxidation of labeled methane (CH4) and the CH4 dependence of sulfate reduction in three types of anaerobic granular sludge. In all samples, 13C-labeled CH4 was anaerobically oxidized to 13C-labeled CO2, while net endogenous CH4 production was observed. Labeled-CH4 oxidation rates followed CH4 production rates, and the presence of sulfate hampered both labeled-CH4 oxidation and methanogenesis. Labeled-CH4 oxidation was therefore linked to methanogenesis. This process is referred to as trace CH4 oxidation and has been demonstrated in methanogenic pure cultures. This study shows that the ratio between labeled-CH4 oxidation and methanogenesis is positively affected by the CH4 partial pressure and that this ratio is in methanogenic granular sludge more than 40 times higher than that in pure cultures of methanogens. The CH4 partial pressure also positively affected sulfate reduction and negatively affected methanogenesis: a repression of methanogenesis at elevated CH4 partial pressures confers an advantage to sulfate reducers that compete with methanogens for common substrates, formed from endogenous material. The oxidation of labeled CH 4 and the CH4 dependence of sulfate reduction are thus not necessarily evidence of anaerobic oxidation of CH4 coupled to sulfate reduction. © 2010 Federation of European Microbiological Societies.

  18. Oxygen isotope evidence for sorption of molecular oxygen to pyrite surface sites and incorporation into sulfate in oxidation experiments

    International Nuclear Information System (INIS)

    Tichomirowa, Marion; Junghans, Manuela

    2009-01-01

    Experiments were conducted to investigate (i) the rate of O-isotope exchange between SO 4 and water molecules at low pH and surface temperatures typical for conditions of acid mine drainage (AMD) and (ii) the O- and S-isotope composition of sulfates produced by pyrite oxidation under closed and open conditions (limited and free access of atmospheric O 2 ) to identify the O source/s in sulfide oxidation (water or atmospheric molecular O 2 ) and to better understand the pyrite oxidation pathway. An O-isotope exchange between SO 4 and water was observed over a pH range of 0-2 only at 50 deg. C, whereas no exchange occurred at lower temperatures over a period of 8 a. The calculated half-time of the exchange rate for 50 deg. C (pH = 0 and 1) is in good agreement with former experimental data for higher and lower temperatures and excludes the possibility of isotope exchange for typical AMD conditions (T ≤ 25 deg. C, pH ≥ 3) for decades. Pyrite oxidation experiments revealed two dependencies of the O-isotope composition of dissolved sulfates: O-isotope values decreased with longer duration of experiments and increasing grain size of pyrite. Both changes are interpreted as evidence for chemisorption of molecular O 2 to pyrite surface sites. The sorption of molecular O 2 is important at initial oxidation stages and more abundant in finer grained pyrite fractions and leads to its incorporation in the produced SO 4 . The calculated bulk contribution of atmospheric O 2 in the dissolved SO 4 reached up to 50% during initial oxidation stages (first 5 days, pH 2, fine-grained pyrite fraction) and decreased to less than 20% after about 100 days. Based on the direct incorporation of molecular O 2 in the early-formed sulfates, chemisorption and electron transfer of molecular O 2 on S sites of the pyrite surface are proposed, in addition to chemisorption on Fe sites. After about 10 days, the O of all newly-formed sulfates originates only from water, indicating direct interaction

  19. Oxidation study of the synthetic sulfides molybdenite (MoS2) and covellite (CuS) by acidithiobacillus ferrooxidants using respirometric experiments

    International Nuclear Information System (INIS)

    Francisco Junior, Wilmo E.; Universidade Estadual Paulista; Bevilaqua, Denise; Garcia Junior, Oswaldo

    2009-01-01

    This paper analyses the oxidation of covellite and molybdenite by Acidithiobacillus ferrooxidans strain LR using respirometric experiments. The results showed that both sulfides were oxidized by A. ferrooxidans, however, the covellite oxidation was much higher than molybdenite. Regarding the kinetic oxidation, the findings revealed that just molybdenite oxidation followed the classical Michaelis-Menten kinetic. It is probably associated with the pathway which these sulfides react to chemistry-bacterial attack, what is influenced by its electronic structures. Besides, experiments conducted in the presence of Fe 3+ did not indicate alterations in molybdenite oxidation. Thus, ferric ions seem not to be essential to the sulfide oxidations. (author)

  20. Reactive Transport Modeling Investigation of High Dissolved Sulfide Concentrations in Sedimentary Basin Rocks

    Science.gov (United States)

    Xie, M.; Mayer, U. K.; MacQuarrie, K. T. B.

    2017-12-01

    Water with total dissolved sulfide in excess of 1 mmol L-1is widely found in groundwater at intermediate depths in sedimentary basins, including regions of the Michigan basin in southeastern Ontario, Canada. Conversely, at deeper and shallower depths, relatively low total dissolved sulfide concentrations have been reported. The mechanisms responsible for the occurrence of these brackish sulfide-containing waters are not fully understood. Anaerobic microbial sulfate reduction is a common process resulting in the formation of high sulfide concentrations. Sulfate reduction rates depend on many factors including the concentration of sulfate, the abundance of organic substances, redox conditions, temperature, salinity and the species of sulfate reducing bacteria (SRB). A sedimentary basin-specific conceptual model considering the effect of salinity on the rate of sulfate reduction was developed and implemented in the reactive transport model MIN3P-THCm. Generic 2D basin-scale simulations were undertaken to provide a potential explanation for the dissolved sulfide distribution observed in the Michigan basin. The model is 440 km in the horizontal dimension and 4 km in depth, and contains fourteen sedimentary rock units including shales, sandstones, limestones, dolostone and evaporites. The main processes considered are non-isothermal density dependent flow, kinetically-controlled mineral dissolution/precipitation and its feedback on hydraulic properties, cation exchange, redox reactions, biogenic sulfate reduction, and hydromechanical coupling due to glaciation-deglaciation events. Two scenarios were investigated focusing on conditions during an interglacial period and the transient evolution during a glaciation-deglaciation cycle. Inter-glaciation simulations illustrate that the presence of high salinity brines strongly suppress biogenic sulfate reduction. The transient simulations show that glaciation-deglaciation cycles can have an impact on the maximum depth of

  1. Sulfidation/oxidation resistant alloys

    International Nuclear Information System (INIS)

    Smith, G.D.; Tassen, C.S.

    1989-01-01

    The patent describes a nickel-base, high chromium alloy. It is characterized by excellent resistance to sulfidation and oxidation at elevated temperatures as high as 2000 degrees F. (1093 degrees C.) and higher, a stress-rupture life of about 200 hours or more at a temperature at least as high as 1800 degrees F. (990:0083 degrees C.) and under a stress of 2000 psi, good tensile strength and good ductility both at room and elevated temperature. The alloy consists essentially of about 27 to 35% chromium, about 2.5 to 5% aluminum, about 2.5 to about 6% iron, 0.5 to 2.5% columbium, up to 0.1% carbon, up to 1% each of titanium and zirconium, up to 0.05% cerium, up to 0.05% yttrium, up to 1% silicon, up to 1% manganese, and the balance nickel

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

    Science.gov (United States)

    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.

  3. Evaluation of biological hydrogen sulfide oxidation coupled with two-stage upflow filtration for groundwater treatment.

    Science.gov (United States)

    Levine, Audrey D; Raymer, Blake J; Jahn, Johna

    2004-01-01

    Hydrogen sulfide in groundwater can be oxidized by aerobic bacteria to form elemental sulfur and biomass. While this treatment approach is effective for conversion of hydrogen sulfide, it is important to have adequate control of the biomass exiting the biological treatment system to prevent release of elemental sulfur into the distribution system. Pilot scale tests were conducted on a Florida groundwater to evaluate the use of two-stage upflow filtration downstream of biological sulfur oxidation. The combined biological and filtration process was capable of excellent removal of hydrogen sulfide and associated turbidity. Additional benefits of this treatment approach include elimination of odor generation, reduction of chlorine demand, and improved stability of the finished water.

  4. Enrichment and cultivation of a sulfide-oxidizing bacteria consortium for its deploying in full-scale biogas desulfurization

    International Nuclear Information System (INIS)

    González Sánchez, Armando; Flores Márquez, Trinidad Eliseo; Revah, Sergio; Morgan Sagastume, Juan Manuel

    2014-01-01

    Operational experiences and strategies to get suitable chemolithoautotrophic sulfide-oxidizing biomass from activated sludge wastewater treatment plant for its deploying in a full-scale biogas desulfurization plant are described. An economic nutrient source was applied to foster microbial selection and rapid growth. Respirometry was implemented on full-scale installations to monitor the ability of the specialized bacteria consortium to oxidize reduced sulfur i.e. H 2 S. During the deployment in the full-scale desulfurization reactor, intermittent sulfide feed from biogas scrubbing was performed to accelerate the startup the desulfurization process. - Highlights: • A simple method for reaching high amounts of specialized sulfide-oxidizing bacterial consortium from activated sludge was developed. • The full-scale desulfurization process can be continuously monitored by respirometry allowing fast decision making if problems arise. • The dissolved sulfide concentration was estimated with an empirical correlation between measurements of ORP, dissolved oxygen and pH

  5. Localized sulfate-reducing zones in a coastal plain aquifer

    Science.gov (United States)

    Brown, C.J.; Coates, J.D.; Schoonen, M.A.A.

    1999-01-01

    High concentrations of dissolved iron in ground water of coastal plain or alluvial aquifers contribute to the biofouling of public supply wells for which treatment and remediation is costly. Many of these aquifers, however, contain zones in which microbial sulfate reduction and the associated precipitation of iron-sulfide minerals decreases iron mobility. The principal water-bearing aquifer (Magothy Aquifer of Cretaceous age) in Suffolk County, New York, contains localized sulfate-reducing zones in and near lignite deposits, which generally are associated with clay lenses. Microbial analyses of core samples amended with [14C]-acetate indicate that microbial sulfate reduction is the predominant terminal-electron-accepting process (TEAP) in poorly permeable, lignite-rich sediments at shallow depths and near the ground water divide. The sulfate-reducing zones are characterized by abundant lignite and iron-sulfide minerals, low concentrations of Fe(III) oxyhydroxides, and by proximity to clay lenses that contain pore water with relatively high concentrations of sulfate and dissolved organic carbon. The low permeability of these zones and, hence, the long residence time of ground water within them, permit the preservation and (or) allow the formation of iron-sulfide minerals, including pyrite and marcasite. Both sulfate-reducing bacteria (SRB) and iron-reducing bacteria (IRB) are present beneath and beyond the shallow sulfate-reducing zones. A unique Fe(III)-reducing organism, MD-612, was found in core sediments from a depth of 187 m near the southern shore of Long Island. The distribution of poorly permeable, lignite-rich, sulfate-reducing zones with decreased iron concentration is varied within the principal aquifer and accounts for the observed distribution of dissolved sulfate, iron, and iron sulfides in the aquifer. Locating such zones for the placement of production wells would be difficult, however, because these zones are of limited aerial extent.

  6. Interpreting isotopic analyses of microbial sulfate reduction in oil reservoirs

    Science.gov (United States)

    Hubbard, C. G.; Engelbrektson, A. L.; Druhan, J. L.; Cheng, Y.; Li, L.; Ajo Franklin, J. B.; Coates, J. D.; Conrad, M. E.

    2013-12-01

    Microbial sulfate reduction in oil reservoirs is often associated with secondary production of oil where seawater (28 mM sulfate) is commonly injected to maintain reservoir pressure and displace oil. The hydrogen sulfide produced can cause a suite of operating problems including corrosion of infrastructure, health exposure risks and additional processing costs. We propose that monitoring of the sulfur and oxygen isotopes of sulfate can be used as early indicators that microbial sulfate reduction is occurring, as this process is well known to cause substantial isotopic fractionation. This approach relies on the idea that reactions with reservoir (iron) minerals can remove dissolved sulfide, thereby delaying the transport of the sulfide through the reservoir relative to the sulfate in the injected water. Changes in the sulfate isotopes due to microbial sulfate reduction may therefore be measurable in the produced water before sulfide is detected. However, turning this approach into a predictive tool requires (i) an understanding of appropriate fractionation factors for oil reservoirs, (ii) incorporation of isotopic data into reservoir flow and reactive transport models. We present here the results of preliminary batch experiments aimed at determining fractionation factors using relevant electron donors (e.g. crude oil and volatile fatty acids), reservoir microbial communities and reservoir environmental conditions (pressure, temperature). We further explore modeling options for integrating isotope data and discuss whether single fractionation factors are appropriate to model complex environments with dynamic hydrology, geochemistry, temperature and microbiology gradients.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  8. Isotope effects associated with the anaerobic oxidation of sulfide by the purple photosynthetic bacterium, Chromatium vinosum

    International Nuclear Information System (INIS)

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

    1984-01-01

    Small inverse isotope effects of 1-3 per thousand were consistently observed for the oxidation of sulfide to elemental sulfur during anaerobic photometabolism by Chromatium vinosum. The inverse fractionation can be accounted for by an equilibrium isotope effect between H 2 S and HS - , and may indicate that C. vinosum (and other photosynthetic bacteria) utilizes H 2 S rather than HS - as the substrate during sulfide oxidation. (Auth.)

  9. Organic-inorganic hybrid polyionic liquid based polyoxometalate as nano porous material for selective oxidation of sulfides

    Science.gov (United States)

    Rafiee, Ezzat; Shahebrahimi, Shabnam

    2017-07-01

    Organic-inorganic hybrid nano porous materials based on poly(ionic liquid)-polyoxometalate (PIL-POM) were reported. These hybrid materials were synthesized by the reaction of 4-vinyl pyridine with 1,3-propanesultone, followed by the polymerization and also sulfonate-functionalized cross-linked poly(4-vinylpyridine) and combining these polymers with H5PMo10V2O40 (PMo10V2). Activity of prepared PIL-PMo10V2 hybrids were investigated as catalysts for oxidation of sulfides with H2O2 as oxidant. For understanding catalytic activities of the PIL-PMo10V2 hybrids in oxidation of sulfides, effect of catalyst composition, substrate, and reaction conditions were studied. The results show that the PIL-PMo10V2 hybrids are active as selective heterogeneous catalysts for oxidation of sulfides and can be recovered and reused. The catalyst was characterized by FT-IR, TGA-DSC, XRD, SEM/EDX, BET, CV and zeta potential measurement. Also, average molecular weight of prepared catalysts were measured.

  10. Anaerobic methane oxidation rates at the sulfate-methane transition in marine sediments from Kattegat and Skagerrak (Denmark)

    International Nuclear Information System (INIS)

    Iversen, N.; Jorgensen, B.B.

    1985-01-01

    Concomitant radiotracer measurements were made of in situ rates of sulfate reduction and anaerobic methane oxidation in 2-3-m-long sediment cores. Methane accumulated to high concentrations (> 1 mM CH 4 ) only below the sulfate zone, at 1 m or deeper in the sediment. Sulfate reduction showed a broad maximum below the sediment surface and a smaller, narrow maximum at the sulfate-methane transition. Methane oxidation was low (0.002-0.1 nmol CH 4 cm -3 d -1 ) throughout the sulfate zone and showed a sharp maximum at the sulfate-methane transition, coinciding with the sulfate reduction maximum. Total anaerobic methane oxidation at two stations was 0.83 and 1.16 mmol CH 4 m -2 d -1 , of which 96% was confined to the sulfate-methane transition. All the methane that was calculated to diffuse up into the sulfate-methane transition was oxidized in this zone. The methane oxidation was equivalent to 10% of the electron donor requirement for the total measured sulfate reduction. A third station showed high sulfate concentrations at all depths sampled and the total methane oxidation was only 0.013 mmol m -2 d -1 . From direct measurements of rates, concentration gradients, and diffusion coefficients, simple calculations were made of sulfate and methane fluxes and of methane production rates

  11. Role of sulfate reduction and methane production by organic carbon degradation ineutrophic fjord sediments (Limfjorden, Denmark)

    DEFF Research Database (Denmark)

    Jørgensen, Bo Barker; Parkes, R. John

    2010-01-01

    , accompanied by peaks in sulfide (4-6 mmol L21) and high dissolved inorganic carbon (30-50 mmol L21). Pore-water acetate concentrations were 2-10 mmol L21. 14C-acetate was oxidized to 14CO2 in the sulfate zone and reduced to 14CH4 at and below the SMT. CO2 reduction was the predominant pathway....... A comparison of the burial flux of organic carbon below the sulfate zone and the returning flux of methane indicated that the diffusion modeling of pore-water sulfate strongly underestimated in situ SRRs, whereas the 35S data may have overestimated the rates at depth. Modeled and measured SRR could...

  12. Control of malodorous hydrogen sulfide compounds using microbial fuel cell.

    Science.gov (United States)

    Eaktasang, Numfon; Min, Hyeong-Sik; Kang, Christina; Kim, Han S

    2013-10-01

    In this study, a microbial fuel cell (MFC) was used to control malodorous hydrogen sulfide compounds generated from domestic wastewaters. The electricity production demonstrated a distinct pattern of a two-step increase during 170 h of system run: the first maximum current density was 118.6 ± 7.2 mA m⁻² followed by a rebound of current density increase, reaching the second maximum of 176.8 ± 9.4 mA m⁻². The behaviors of the redox potential and the sulfate level in the anode compartment indicated that the microbial production of hydrogen sulfide compounds was suppressed in the first stage, and the hydrogen sulfide compounds generated from the system were removed effectively as a result of their electrochemical oxidation, which contributed to the additional electricity production in the second stage. This was also directly supported by sulfur deposits formed on the anode surface, which was confirmed by analyses on those solids using a scanning electron microscope equipped with energy dispersive X-ray spectroscopy as well as an elemental analyzer. To this end, the overall reduction efficiencies for HS⁻ and H₂S(g) were as high as 67.5 and 96.4 %, respectively. The correlations among current density, redox potential, and sulfate level supported the idea that the electricity signal generated in the MFC can be utilized as a potential indicator of malodor control for the domestic wastewater system.

  13. Toxicity of sulfide to early life stages of wild rice (Zizania palustris).

    Science.gov (United States)

    Fort, Douglas J; Todhunter, Kevin; Fort, Troy D; Mathis, Michael B; Walker, Rachel; Hansel, Mike; Hall, Scott; Richards, Robin; Anderson, Kurt

    2017-08-01

    The sensitivity of wild rice (Zizania palustris) to sulfide is not well understood. Because sulfate in surface waters is reduced to sulfide by anaerobic bacteria in sediments and historical information indicated that 10 mg/L sulfate in Minnesota (USA) surface water reduced Z. palustris abundance, the Minnesota Pollution Control Agency established 10 mg/L sulfate as a water quality criterion in 1973. A 21-d daily-renewal hydroponic study was conducted to evaluate sulfide toxicity to wild rice and the potential mitigation of sulfide toxicity by iron (Fe). The hydroponic design used hypoxic test media for seed and root exposure and aerobic headspace for the vegetative portion of the plant. Test concentrations were 0.3, 1.6, 3.1, 7.8, and 12.5 mg/L sulfide in test media with 0.8, 2.8, and 10.8 mg/L total Fe used to evaluate the impact of iron on sulfide toxicity. Visual assessments (i.e., no plants harvested) of seed activation, mesocotyl emergence, seedling survival, and phytoxicity were conducted 10 d after dark-phase exposure. Each treatment was also evaluated for time to 30% emergence (ET30), total plant biomass, root and shoot lengths, and signs of phytotoxicity at study conclusion (21 d). The results indicate that exposure of developing wild rice to sulfide at ≥3.1 mg sulfide/L in the presence of 0.8 mg/L Fe reduced mesocotyl emergence. Sulfide toxicity was mitigated by the addition of Fe at 2.8 mg/L and 10.8 mg/L relative to the control value of 0.8 mg Fe/L, demonstrating the importance of iron in mitigating sulfide toxicity to wild rice. Ultimately, determination of site-specific sulfate criteria taking into account factors that alter toxicity, including sediment Fe and organic carbon, are necessary. Environ Toxicol Chem 2017;36:2217-2226. © 2017 SETAC. © 2017 SETAC.

  14. Enhanced sulfidation xanthate flotation of malachite using ammonium ions as activator

    OpenAIRE

    Dandan Wu; Wenhui Ma; Yingbo Mao; Jiushuai Deng; Shuming Wen

    2017-01-01

    In this study, ammonium ion was used to enhance the sulfidation flotation of malachite. The effect of ammonium ion on the sulfidation flotation of malachite was investigated using microflotation test, inductively coupled plasma (ICP) analysis, zeta potential measurements, and scanning electron microscope analysis (SEM). The results of microflotation test show that the addition of sodium sulfide and ammonium sulfate resulted in better sulfidation than the addition of sodium sulfide alone. The ...

  15. Pyrolytically grown indium sulfide sensitized zinc oxide nanowires for solar water splitting

    Energy Technology Data Exchange (ETDEWEB)

    Komurcu, Pelin; Can, Emre Kaan; Aydin, Erkan; Semiz, Levent [Micro and Nanotechnology Graduate Program, TOBB University of Economics and Technology, 06560 Ankara (Turkey); Gurol, Alp Eren; Alkan, Fatma Merve [Department of Materials Science and Nanotechnology Engineering, TOBB University of Economics and Technology, 06560 Ankara (Turkey); Sankir, Mehmet; Sankir, Nurdan Demirci [Micro and Nanotechnology Graduate Program, TOBB University of Economics and Technology, 06560 Ankara (Turkey); Department of Materials Science and Nanotechnology Engineering, TOBB University of Economics and Technology, 06560 Ankara (Turkey)

    2015-11-15

    Zinc oxide (ZnO) nanowires, sensitized with spray pyrolyzed indium sulfide, were obtained by chemical bath deposition. The XRD analysis indicated dominant evolution of hexagonal ZnO phase. Significant gain in photoelectrochemical current using ZnO nanowires is largely accountable to enhancement of the visible light absorption and the formation of heterostructure. The maximum photoconversion efficiency of 2.77% was calculated for the indium sulfide sensitized ZnO nanowire photoelectrodes. (copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  16. Optimizing substrate for sulfate-reducing bacteria

    International Nuclear Information System (INIS)

    Chang, L.K.; Updegraff, D.M.; Wildeman, T.R.

    1991-01-01

    Microbial sulfate reduction followed by sulfide precipitation effectively removes heavy metals from wastewaters. The substrate in the anaerobic zone in a constructed wetland can be designed to emphasize this removal process. This group of bacteria requires CH 2 O, P, N, and SO 4 =, reducing conditions, and pH range of 5-9 (pH=7 is optimum). The objective of this study was to find an inexpensive source of nutrients that would give the best initial production of sulfide and make a good wetland substrate. All tested materials contain sufficient P and N; mine drainage provides sulfate. Thus, tests focused on finding organic material that provides the proper nutrients and does not cause the culture to fall below pH of 5. Among chemical nutrients, sodium lactate combined with (NH 4 ) 2 HPO 4 were the only compounds that produced sulfide after 11 days. Among complex nutrients, only cow manure produced sulfide after 26 days. Among complex carbohydrates, cracked corn and raw rice produced sulfide after 10 days. Most substrates failed to produce sulfide because anaerobic fermentation reduced the pH below 5. Presently, cracked corn is the best candidate for a substrate. Five grams of cow manure produced 0.14 millimole of sulfide whereas 0.1 g of cracked corn produced 0.22 millimole

  17. Hydrous Ferric Oxides in Sediment Catalyze Formation of Reactive Oxygen Species during Sulfide Oxidation

    Directory of Open Access Journals (Sweden)

    Sarah A. Murphy

    2016-11-01

    Full Text Available Abstract: This article describes the formation of reactive oxygen species as a result of the oxidation of dissolved sulfide by Fe(III-containing sediments suspended in oxygenated seawater over the pH range 7.00 and 8.25. Sediment samples were obtained from across the coastal littoral zone in South Carolina, US, at locations from the beach edge to the forested edge of a Spartina dominated estuarine salt marsh and suspended in aerated seawater. Reactive oxygen species (superoxide and hydrogen peroxide production was initiated in sediment suspensions by the addition of sodium bisulfide. The subsequent loss of HS-, formation of Fe(II (as indicated by Ferrozine, and superoxide and hydrogen peroxide were monitored over time. The concentration of superoxide rose from the baseline and then persisted at an apparent steady state concentration of approximately 500 nanomolar at pH 8.25 and 200 nanomolar at pH 7.00 respectively until >97% hydrogen sulfide was consumed. Measured superoxide was used to predict hydrogen peroxide yield based on superoxide dismutation. Dismutation alone quantitatively predicted hydrogen peroxide formation at pH 8.25 but over predicted hydrogen peroxide formation at pH 7 by a factor of approximately 102. Experiments conducted with episodic spikes of added hydrogen peroxide indicated rapid hydrogen peroxide consumption could account for its apparent low instantaneous yield, presumably the result of its reaction with Fe(II species, polysulfides or bisulfite. All sediment samples were characterized for total Fe, Cu, Mn, Ni, Co and hydrous ferric oxide by acid extraction followed by mass spectrometric or spectroscopic characterization. Sediments with the highest loadings of hydrous ferric oxide were the only sediments that produced significant dissolved Fe(II species or ROS as a result of sulfide exposure.

  18. THE WEATHERING OF A SULFIDE OREBODY: SPECIATION AND FATE OF SOME POTENTIAL CONTAMINANTS

    Energy Technology Data Exchange (ETDEWEB)

    Courtin-Nomade, Alexandra; Grosbois, Cecile; Marcus, Matthew A.; Fakra, Sirine C.; Beny, Jean Michel; Foster, Andrea L.

    2010-07-16

    Various potentially toxic trace elements such as As, Cu, Pb and Zn have been remobilized by the weathering of a sulfide orebody that was only partially mined at Leona Heights, California. As a result, this body has both natural and anthropogenically modified weathering profiles only 500 m apart. The orebody is located in a heavily urbanized area in suburban Oakland, and directly affects water quality in at least one stream by producing acidic conditions and relatively high concentrations of dissolved elements (e.g., {approx}500 mg/L Cu, {approx}3700 mg/L Zn). Micrometric-scale mineralogical investigations were performed on the authigenic metal-bearing phases (less than 10 {mu}m in size) using electron-probe micro-analysis (EPMA), micro-Raman, micro X-ray absorption spectroscopy (mXAS), scanning X-ray diffraction (mSXRD) and scanning X-ray fluorescence (mSXRF) mapping techniques. Those measurements were coupled with classical mineralogical laboratory techniques, X-ray diffraction (XRD) and scanning electron microscopy (SEM). Authigenic metal-bearing phases identified are mainly sulfates (jarosite, epsomite, schwertmannite), Fe (oxy-)hydroxides (goethite, hematite and poorly crystalline Fe products) and poorly crystalline Mn (hydr-)oxides. Sulfates and Fe (oxy-)hydroxides are the two main secondary products at both sites, whereas Mn (hydr-) oxides were only observed in the samples from the non-mining site. In these samples, the various trace elements show different affinities for Fe or Mn compounds. Lead is preferentially associated with Mn (hydr-)oxides and As with Fe (oxy-)hydroxides or sulfates. Copper association with Mn and Fe phases is questionable, and the results obtained rather indicate that Cu is present as individual Cu-rich grains (Cu hydroxides). Some ochreous precipitates were found at both sites and correspond to a mixture of schwertmannite, goethite and jarosite containing some potentially toxic trace elements such as Cu, Pb and Zn. According to the

  19. A batch assay to measure microbial hydrogen sulfide production from sulfur-containing solid wastes

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Mei, E-mail: msun8@uncc.edu [Department of Civil, Construction, and Environmental Engineering, North Carolina State University, Campus Box 7908, Raleigh, NC (United States); Sun, Wenjie, E-mail: wsun@smu.edu [Department of Civil, Construction, and Environmental Engineering, North Carolina State University, Campus Box 7908, Raleigh, NC (United States); Department of Civil and Environmental Engineering, Southern Methodist University, PO Box 750340, Dallas, TX (United States); Barlaz, Morton A., E-mail: barlaz@ncsu.edu [Department of Civil, Construction, and Environmental Engineering, North Carolina State University, Campus Box 7908, Raleigh, NC (United States)

    2016-05-01

    Large volumes of sulfur-containing wastes enter municipal solid waste landfills each year. Under the anaerobic conditions that prevail in landfills, oxidized forms of sulfur, primarily sulfate, are converted to sulfide. Hydrogen sulfide (H{sub 2}S) is corrosive to landfill gas collection and treatment systems, and its presence in landfill gas often necessitates the installation of expensive removal systems. For landfill operators to understand the cost of managing sulfur-containing wastes, an estimate of the H{sub 2}S production potential is needed. The objective of this study was to develop and demonstrate a biochemical sulfide potential (BSP) test to measure the amount of H{sub 2}S produced by different types of sulfur-containing wastes in a relatively fast (30 days) and inexpensive (125 mL serum bottles) batch assay. This study confirmed the toxic effect of H{sub 2}S on both sulfate reduction and methane production in batch systems, and demonstrated that removing accumulated H{sub 2}S by base adsorption was effective for mitigating inhibition. H{sub 2}S production potentials of coal combustion fly ash, flue gas desulfurization residual, municipal solid waste combustion ash, and construction and demolition waste were determined in BSP assays. After 30 days of incubation, most of the sulfate in the wastes was converted to gaseous or aqueous phase sulfide, with BSPs ranging from 0.8 to 58.8 mL H{sub 2}S/g waste, depending on the chemical composition of the samples. Selected samples contained solid phase sulfide which contributed to the measured H{sub 2}S yield. A 60 day incubation in selected samples resulted in 39–86% additional sulfide production. H{sub 2}S production measured in BSP assays was compared with that measured in simulated landfill reactors and that calculated from chemical analyses. H{sub 2}S production in BSP assays and in reactors was lower than the stoichiometric values calculated from chemical composition for all wastes tested, demonstrating

  20. Methane Migration and Its Influence on Sulfate Reduction in the Good Weather Ridge Region, South China Sea Continental Margin Sediments

    Directory of Open Access Journals (Sweden)

    Saulwood Lin

    2006-01-01

    Full Text Available Bacteria sulfate reduction is a major pathway for organic carbon oxidation in marine sediments. Upward diffusion of methane from gas hydrate deep in the sedimentary strata might be another important source of carbon for sulfate reducing bacteria and subsequently induce higher rates of sulfate reduction in sediments. Since abundant gas may migrate upward to the surface as a result of tectonic activity occurring in the accretionary wedge, this study investigates the effect of methane migration on the sulfate reduction process in continental margin sediments offshore southwestern Taiwan. Piston and gravity core samples were taken in order to evaluate vertical and spatial variations of sulfate and methane. Pore water sulfate, sulfide, methane, sediment pyrite, and organic carbon were extracted and analyzed.

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

    Science.gov (United States)

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

  2. Sulfur isotope study of a modern intertidal environment, and the interpretation of ancient sulfides

    International Nuclear Information System (INIS)

    Chambers, L.A.

    1982-01-01

    Extensive sulfur isotope distribution data for sulfides precipitated in an intertidal environment show no distinctive features when compared with isotope values for other marine, sedimentary sulfides. The fractionation ranges from α = 1.030 to α = 1.048. The pattern is characteristic for a system essentially open to sulfate, and isotope analyses of interstitial sulfates are corroborative. A population of sulfate-reducing bacteria of the order of 10 9 organisms per cc of interstitial water is indicated. Seasonal variation of the isotope distribution reflects a transient sulfide composition and a bacterial population in which the fractionation effect is indirectly controlled by temperature. The data presented for this modern shallow water environment are at variance with an earlier assessment of isotopic distributions in ancient sulfides which linked shallow water environments with limited fractionation (α =< 1.025) in a closed system. (author)

  3. Sulfur isotope study of a modern intertidal environment, and the interpretation of ancient sulfides

    Energy Technology Data Exchange (ETDEWEB)

    Chambers, L.A. (Baas Becking Geobiological Lab., Canberra City (Australia))

    1982-05-01

    Extensive sulfur isotope distribution data for sulfides precipitated in an intertidal environment show no distinctive features when compared with isotope values for other marine, sedimentary sulfides. The fractionation ranges from ..cap alpha.. = 1.030 to ..cap alpha.. = 1.048. The pattern is characteristic for a system essentially open to sulfate, and isotope analyses of interstitial sulfates are corroborative. A population of sulfate-reducing bacteria of the order of 10/sup 9/ organisms per cc of interstitial water is indicated. Seasonal variation of the isotope distribution reflects a transient sulfide composition and a bacterial population in which the fractionation effect is indirectly controlled by temperature. The data presented for this modern shallow water environment are at variance with an earlier assessment of isotopic distributions in ancient sulfides which linked shallow water environments with limited fractionation (..cap alpha.. =< 1.025) in a closed system.

  4. 34S and 18O in dissolved sulfate as tracers of hydrogeochemical evolution of the Triassic carbonate aquifer exposed to intense groundwater exploitation (Olkusz-Zawiercie region, southern Poland)

    International Nuclear Information System (INIS)

    Samborska, Katarzyna; Halas, Stanislaw

    2010-01-01

    Research highlights: → Groundwater table rebound in aquifer containing sulfide ore. → Degradation of water quality causes by the significant increase in sulfate concentrations. → Isotopic examinations of sulfate and sulfate concentrations along flow path. → Sulfate concentrations as a result of binary mixing of sources (sulfide and evaporate). → Changes in isotopic composition of sulfide in extended vadose zone. - Abstract: The objective of this study was to determine the sources of SO 4 2- in groundwater of the Olkusz-Zawiercie Major Groundwater Body. The quality of groundwater was relatively good in the past, but fluctuations of the water table level have caused degradation of water quality. Variations in the water table level and the formation of the depression cone have resulted from both groundwater withdrawal and Zn-Pb mine dewatering. As a result within the extended vadose zone of the aquifer, weathering of pyrite and accompanying sulfides has taken place. Since 1992 the water table has risen and this process has been associated with an increase in concentrations of SO 4 2- , Ca and Mg. At the same time, the pH has decreased and periodically high Fe concentrations have been detected. High concentrations of Mg and Sr have been observed and, since gypsum layers are known to be present, a de-dolomitisation process has been hypothesized. The PHREEQC program for Windows was used to estimate saturation indices for calcite, dolomite, gypsum and epsomite. Isotopic data for SO 4 2- dissolved in the groundwater and archival data on isotopic composition of ore sulfides were used to solve the isotope balance equation and to estimate the fraction of dissolved SO 4 2- that originated from pyrite oxidation and gypsum dissolution. The results have shown that dissolution of pyrite oxidation products has a significant influence on chemical composition of groundwater, especially in the southern part of the cone of depression. By solving the additional, combined mass

  5. Influence of process variables on biooxidation of ferrous sulfate by an indigenous Acidithiobacillus ferrooxidans. Part I: Flask experiments

    Energy Technology Data Exchange (ETDEWEB)

    S.M. Mousavi; S. Yaghmaei; F. Salimi; A. Jafari [Sharif University of Technology, Tehran (Iran). Department of Chemical and Petroleum Engineering

    2006-12-15

    Biological oxidation of ferrous sulfate by Acidithiobacillus ferrooxidans has proved to be a significant step in the bioleaching of sulfide minerals and the treatment of acid mine drainage. The same bioreaction also has beneficial applications in the desulphurization of coal and removal of hydrogen sulfide from gaseous effluents. In this research, the effects of some process variables such as pH, temperature, elemental sulfur, amount of initial ferrous and magnesium ions on oxidation of ferrous sulfate by a native A. ferrooxidans, which was isolated from a chalcopyrite concentrate, were investigated. All experiments carried out in shake flasks at 33{sup o}C that was obtained as optimum temperature for the specific bacterial growth rate. The optimum range of pH for the maximum growth of the cells and effective biooxidation of ferrous sulfate varied from 2 to 2.3. The maximum biooxidation rate was achieved 1.2 g/L h in a culture initially containing 20.2 g/L Fe{sup 2+}. Mg{sup 2+} from 20 mg/L to 120 mg/L did not have any effect on the efficiency of the process, while the presence of elemental sulfur had negative effect on the biooxidation. 16 refs., 8 figs.

  6. Effect of hydraulic retention time on metal precipitation in sulfate reducing inverse fluidized bed reactors

    KAUST Repository

    Villa-Gómez, Denys Kristalia

    2014-02-13

    BACKGROUND: Metal sulfide recovery in sulfate reducing bioreactors is a challenge due to the formation of small precipitates with poor settling properties. The size of the metal sulfide precipitates with the change in operational parameters such as pH, sulfide concentration and reactor configuration has been previously studied. The effect of the hydraulic retention time (HRT) on the metal precipitate characteristics such as particle size for settling has not yet been addressed. RESULTS: The change in size of the metal (Cu, Zn, Pb and Cd) sulfide precipitates as a function of the HRT was studied in two sulfate reducing inversed fluidized bed (IFB) reactors operating at different chemical oxygen demand concentrations to produce high and low sulfide concentrations. The decrease of the HRT from 24 to 9h in both IFB reactors affected the contact time of the precipitates formed, thus making differences in aggregation and particle growth regardless of the differences in sulfide concentration. Further HRT decrease to 4.5h affected the sulfate reducing activity for sulfide production and hence, the supersaturation level and solid phase speciation. Metal sulfide precipitates affected the sulfate reducing activity and community in the biofilm, probably because of the stronger local supersaturation causing metal sulfides accumulation in the biofilm. CONCLUSIONS: This study shows that the HRT is an important factor determining the size and thus the settling rate of the metal sulfides formed in bioreactors.

  7. A simple and reliable method reducing sulfate to sulfide for multiple sulfur isotope analysis.

    Science.gov (United States)

    Geng, Lei; Savarino, Joel; Savarino, Clara A; Caillon, Nicolas; Cartigny, Pierre; Hattori, Shohei; Ishino, Sakiko; Yoshida, Naohiro

    2018-02-28

    Precise analysis of four sulfur isotopes of sulfate in geological and environmental samples provides the means to extract unique information in wide geological contexts. Reduction of sulfate to sulfide is the first step to access such information. The conventional reduction method suffers from a cumbersome distillation system, long reaction time and large volume of the reducing solution. We present a new and simple method enabling the process of multiple samples at one time with a much reduced volume of reducing solution. One mL of reducing solution made of HI and NaH 2 PO 2 was added to a septum glass tube with dry sulfate. The tube was heated at 124°C and the produced H 2 S was purged with inert gas (He or N 2 ) through gas-washing tubes and then collected by NaOH solution. The collected H 2 S was converted into Ag 2 S by adding AgNO 3 solution and the co-precipitated Ag 2 O was removed by adding a few drops of concentrated HNO 3 . Within 2-3 h, a 100% yield was observed for samples with 0.2-2.5 μmol Na 2 SO 4 . The reduction rate was much slower for BaSO 4 and a complete reduction was not observed. International sulfur reference materials, NBS-127, SO-5 and SO-6, were processed with this method, and the measured against accepted δ 34 S values yielded a linear regression line which had a slope of 0.99 ± 0.01 and a R 2 value of 0.998. The new methodology is easy to handle and allows us to process multiple samples at a time. It has also demonstrated good reproducibility in terms of H 2 S yield and for further isotope analysis. It is thus a good alternative to the conventional manual method, especially when processing samples with limited amount of sulfate available. © 2017 The Authors. Rapid Communications in Mass Spectrometry Pubished by John Wiley & Sons Ltd.

  8. Microbial Diversity in Sulfate-Reducing Marine Sediment Enrichment Cultures Associated with Anaerobic Biotransformation of Coastal Stockpiled Phosphogypsum (Sfax, Tunisia

    Directory of Open Access Journals (Sweden)

    Hana Zouch

    2017-08-01

    Full Text Available Anaerobic biotechnology using sulfate-reducing bacteria (SRB is a promising alternative for reducing long-term stockpiling of phosphogypsum (PG, an acidic (pH ~3 by-product of the phosphate fertilizer industries containing high amounts of sulfate. The main objective of this study was to evaluate, for the first time, the diversity and ability of anaerobic marine microorganisms to convert sulfate from PG into sulfide, in order to look for marine SRB of biotechnological interest. A series of sulfate-reducing enrichment cultures were performed using different electron donors (i.e., acetate, formate, or lactate and sulfate sources (i.e., sodium sulfate or PG as electron acceptors. Significant sulfide production was observed from enrichment cultures inoculated with marine sediments, collected near the effluent discharge point of a Tunisian fertilizer industry (Sfax, Tunisia. Sulfate sources impacted sulfide production rates from marine sediments as well as the diversity of SRB species belonging to Deltaproteobacteria. When PG was used as sulfate source, Desulfovibrio species dominated microbial communities of marine sediments, while Desulfobacter species were mainly detected using sodium sulfate. Sulfide production was also affected depending on the electron donor used, with the highest production obtained using formate. In contrast, low sulfide production (acetate-containing cultures was associated with an increase in the population of Firmicutes. These results suggested that marine Desulfovibrio species, to be further isolated, are potential candidates for bioremediation of PG by immobilizing metals and metalloids thanks to sulfide production by these SRB.

  9. Microbial contributions to coupled arsenic and sulfur cycling in the acid-sulfide hot spring Champagne Pool, New Zealand

    Directory of Open Access Journals (Sweden)

    Katrin eHug

    2014-11-01

    Full Text Available Acid-sulfide hot springs are analogs of early Earth geothermal systems where microbial metal(loid resistance likely first evolved. Arsenic is a metalloid enriched in the acid-sulfide hot spring Champagne Pool (Waiotapu, New Zealand. Arsenic speciation in Champagne Pool follows reaction paths not yet fully understood with respect to biotic contributions and coupling to biogeochemical sulfur cycling. Here we present quantitative arsenic speciation from Champagne Pool, finding arsenite dominant in the pool, rim and outflow channel (55-75% total arsenic, and dithio- and trithioarsenates ubiquitously present as 18-25% total arsenic. In the outflow channel, dimethylmonothioarsenate comprised ≤9% total arsenic, while on the outflow terrace thioarsenates were present at 55% total arsenic. We also quantified sulfide, thiosulfate, sulfate and elemental sulfur, finding sulfide and sulfate as major species in the pool and outflow terrace, respectively. Elemental sulfur reached a maximum at the terrace. Phylogenetic analysis of 16S rRNA genes from metagenomic sequencing revealed the dominance of Sulfurihydrogenibium at all sites and an increased archaeal population at the rim and outflow channel. Several phylotypes were found closely related to known sulfur- and sulfide-oxidizers, as well as sulfur- and sulfate-reducers. Bioinformatic analysis revealed genes underpinning sulfur redox transformations, consistent with sulfur speciation data, and illustrating a microbial role in sulfur-dependent transformation of arsenite to thioarsenate. Metagenomic analysis also revealed genes encoding for arsenate reductase at all sites, reflecting the ubiquity of thioarsenate and a need for microbial arsenate resistance despite anoxic conditions. Absence of the arsenite oxidase gene, aio, at all sites suggests prioritization of arsenite detoxification over coupling to energy conservation. Finally, detection of methyl arsenic in the outflow channel, in conjunction with

  10. An Exploratory Study on the Pathways of Cr (VI) Reduction in Sulfate-reducing Up-flow Anaerobic Sludge Bed (UASB) Reactor.

    Science.gov (United States)

    Qian, Jin; Wei, Li; Liu, Rulong; Jiang, Feng; Hao, Xiaodi; Chen, Guang-Hao

    2016-03-29

    Electroplating wastewater contains both Cr (VI) and sulfate. So Cr (VI) removal under sulfate-rich condition is quite complicated. This study mainly investigates the pathways for Cr (VI) removal under biological sulfate-reducing condition in the up-flow anaerobic sludge bed (UASB) reactor. Two potential pathways are found for the removal of Cr (VI). The first one is the sulfidogenesis-induced Cr (VI) reduction pathway (for 90% Cr (VI) removal), in which Cr (VI) is reduced by sulfide generated from biological reduction of sulfate. The second one leads to direct reduction of Cr (VI) which is utilized by bacteria as the electron acceptor (for 10% Cr (VI) removal). Batch test results confirmed that sulfide was oxidized to elemental sulfur instead of sulfate during Cr (VI) reduction. The produced extracellular polymeric substances (EPS) provided protection to the microbes, resulting in effective removal of Cr (VI). Sulfate-reducing bacteria (SRB) genera accounted for 11.1% of the total bacterial community; thus they could be the major organisms mediating the sulfidogenesis-induced reduction of Cr (VI). In addition, chromate-utilizing genera (e.g. Microbacterium) were also detected, which were possibly responsible for the direct reduction of Cr (VI) using organics as the electron donor and Cr (VI) as the electron acceptor.

  11. An Exploratory Study on the Pathways of Cr (VI) Reduction in Sulfate-reducing Up-flow Anaerobic Sludge Bed (UASB) Reactor

    Science.gov (United States)

    Qian, Jin; Wei, Li; Liu, Rulong; Jiang, Feng; Hao, Xiaodi; Chen, Guang-Hao

    2016-01-01

    Electroplating wastewater contains both Cr (VI) and sulfate. So Cr (VI) removal under sulfate-rich condition is quite complicated. This study mainly investigates the pathways for Cr (VI) removal under biological sulfate-reducing condition in the up-flow anaerobic sludge bed (UASB) reactor. Two potential pathways are found for the removal of Cr (VI). The first one is the sulfidogenesis-induced Cr (VI) reduction pathway (for 90% Cr (VI) removal), in which Cr (VI) is reduced by sulfide generated from biological reduction of sulfate. The second one leads to direct reduction of Cr (VI) which is utilized by bacteria as the electron acceptor (for 10% Cr (VI) removal). Batch test results confirmed that sulfide was oxidized to elemental sulfur instead of sulfate during Cr (VI) reduction. The produced extracellular polymeric substances (EPS) provided protection to the microbes, resulting in effective removal of Cr (VI). Sulfate-reducing bacteria (SRB) genera accounted for 11.1% of the total bacterial community; thus they could be the major organisms mediating the sulfidogenesis-induced reduction of Cr (VI). In addition, chromate-utilizing genera (e.g. Microbacterium) were also detected, which were possibly responsible for the direct reduction of Cr (VI) using organics as the electron donor and Cr (VI) as the electron acceptor. PMID:27021522

  12. An Exploratory Study on the Pathways of Cr (VI) Reduction in Sulfate-reducing Up-flow Anaerobic Sludge Bed (UASB) Reactor

    Science.gov (United States)

    Qian, Jin; Wei, Li; Liu, Rulong; Jiang, Feng; Hao, Xiaodi; Chen, Guang-Hao

    2016-03-01

    Electroplating wastewater contains both Cr (VI) and sulfate. So Cr (VI) removal under sulfate-rich condition is quite complicated. This study mainly investigates the pathways for Cr (VI) removal under biological sulfate-reducing condition in the up-flow anaerobic sludge bed (UASB) reactor. Two potential pathways are found for the removal of Cr (VI). The first one is the sulfidogenesis-induced Cr (VI) reduction pathway (for 90% Cr (VI) removal), in which Cr (VI) is reduced by sulfide generated from biological reduction of sulfate. The second one leads to direct reduction of Cr (VI) which is utilized by bacteria as the electron acceptor (for 10% Cr (VI) removal). Batch test results confirmed that sulfide was oxidized to elemental sulfur instead of sulfate during Cr (VI) reduction. The produced extracellular polymeric substances (EPS) provided protection to the microbes, resulting in effective removal of Cr (VI). Sulfate-reducing bacteria (SRB) genera accounted for 11.1% of the total bacterial community; thus they could be the major organisms mediating the sulfidogenesis-induced reduction of Cr (VI). In addition, chromate-utilizing genera (e.g. Microbacterium) were also detected, which were possibly responsible for the direct reduction of Cr (VI) using organics as the electron donor and Cr (VI) as the electron acceptor.

  13. Role of aqueous sulfide and sulfate-reducing bacteria in the kinetics and mechanisms of the reduction of uranyl ion

    International Nuclear Information System (INIS)

    Mohagheghi, A.

    1985-01-01

    Formation of sedimentary rock-hosted uranium ore deposits is thought to have resulted from the reduction by aqueous sulfide species of relatively soluble uranyl ion (U(VI)) to insoluble uranium(IV) oxides and silicates. The origin of this H 2 S in such deposits can be either biogenic or abiogenic. Therefore, the kinetics and mechanism of uranyl ion reduction by aqueous sulfide, and the effect of several key variables on the reduction process in non-bacterial (sterile) systems was studied. The role of both pure and mixed cultures of sulfate-reducing bacteria on the reduction process was also investigated. In sterile systems the reduction reaction generally occurred by a two step reaction sequence. Uranium(V) (as UO 2 + ) and U(IV) (as UO 2 the mineral uraninite) were the intermediate and final products, respectively. The initial concentration of uranyl ion required for reaction initiation had a minimum value of 0.8 ppm at pH 7, and was higher at pH values less than or greater than 7. An induction period was observed in all experiments. No reduction was observed after 8 hours at pH 8. Although increasing ionic strength increased the length of the induction period, it also increased the rate of the reduction of UO 2 + in the second step. No reaction was observed under any experimental conditions with initial UO 2 2+ concentration less than 0.1 ppm, which is thought to be typical for ore forming solutions. However, by absorbing uranyl ion onto kaolinite, the reduction by H 2 S occurred at lower UO 2 2+ concentrations (∼ 0.1 ppm) in that in the homogeneous system. Thus, adsorption may play a significant role in the reduction and therefore in the formation of ore deposits

  14. SULFATE RADICAL-BASED ADVANCED OXIDATION PROCESSES- ACS MEETING

    Science.gov (United States)

    This paper will present an overview of sulfate radical-based advanced oxidation technologies for the destruction of environmentally toxic chemicals in wastewater, industrial water, groundwater and sources of water supply. The paper will include fundamental aspects of the generati...

  15. In situ recovery of copper from sulfide ore bodies following nuclear fracturing

    Energy Technology Data Exchange (ETDEWEB)

    Rosenbaum, Joe B; McKinney, W A [Salt Lake City Metallurgy Research Center, Bureau of Mines, US Department of the Interior, Salt Lake City, UT (United States)

    1970-05-15

    Leaching now yields about 12 percent of the Nation's annual new copper production. About 200,000 tons of copper a year is being won by heap and vat leaching of ore, dump leaching of waste, and in-place leaching of caved underground workings. Although in-place leaching was practiced as long ago as the 15th century, it is little used and contributes only a few percent of the total leach copper production. Current technology in this area is exemplified by practice at the Miami, Ariz., mine of the Miami Copper Co. Despite its limited use, the concept of extracting copper by in-place leaching without physically mining and transporting the ore continues to present intriguing cost saving possibilities. Project SLOOP has been proposed as an experiment to test the feasibility of nuclear fracturing and acid leaching the oxidized portion of a deep ore body near Safford, Ariz. However, the bulk of the copper in deep ore deposits occurs as sulfide minerals that are not easily soluble in acid solutions. This paper explores the concept of in-place leaching of nuclear fractured, deeply buried copper sulfide deposits. On the assumption that fracturing of rock and solution injection and collection would be feasible, an assessment is made of solution systems that might be employed for the different copper sulfide minerals in porphyry ore bodies. These include the conventional ferric sulfate-sulfuric acid systems and combinations of sulfide mineral oxidants and different acids. (author)

  16. In situ recovery of copper from sulfide ore bodies following nuclear fracturing

    International Nuclear Information System (INIS)

    Rosenbaum, Joe B.; McKinney, W.A.

    1970-01-01

    Leaching now yields about 12 percent of the Nation's annual new copper production. About 200,000 tons of copper a year is being won by heap and vat leaching of ore, dump leaching of waste, and in-place leaching of caved underground workings. Although in-place leaching was practiced as long ago as the 15th century, it is little used and contributes only a few percent of the total leach copper production. Current technology in this area is exemplified by practice at the Miami, Ariz., mine of the Miami Copper Co. Despite its limited use, the concept of extracting copper by in-place leaching without physically mining and transporting the ore continues to present intriguing cost saving possibilities. Project SLOOP has been proposed as an experiment to test the feasibility of nuclear fracturing and acid leaching the oxidized portion of a deep ore body near Safford, Ariz. However, the bulk of the copper in deep ore deposits occurs as sulfide minerals that are not easily soluble in acid solutions. This paper explores the concept of in-place leaching of nuclear fractured, deeply buried copper sulfide deposits. On the assumption that fracturing of rock and solution injection and collection would be feasible, an assessment is made of solution systems that might be employed for the different copper sulfide minerals in porphyry ore bodies. These include the conventional ferric sulfate-sulfuric acid systems and combinations of sulfide mineral oxidants and different acids. (author)

  17. Anaerobic oxidation of methane by sulfate in hypersaline groundwater of the Dead Sea aquifer

    Science.gov (United States)

    Avrahamov, N; Antler, G; Yechieli, Y; Gavrieli, I; Joye, S B; Saxton, M; Turchyn, A V; Sivan, O

    2014-01-01

    Geochemical and microbial evidence points to anaerobic oxidation of methane (AOM) likely coupled with bacterial sulfate reduction in the hypersaline groundwater of the Dead Sea (DS) alluvial aquifer. Groundwater was sampled from nine boreholes drilled along the Arugot alluvial fan next to the DS. The groundwater samples were highly saline (up to 6300 mm chlorine), anoxic, and contained methane. A mass balance calculation demonstrates that the very low δ13CDIC in this groundwater is due to anaerobic methane oxidation. Sulfate depletion coincident with isotope enrichment of sulfur and oxygen isotopes in the sulfate suggests that sulfate reduction is associated with this AOM. DNA extraction and 16S amplicon sequencing were used to explore the microbial community present and were found to be microbial composition indicative of bacterial sulfate reducers associated with anaerobic methanotrophic archaea (ANME) driving AOM. The net sulfate reduction seems to be primarily controlled by the salinity and the available methane and is substantially lower as salinity increases (2.5 mm sulfate removal at 3000 mm chlorine but only 0.5 mm sulfate removal at 6300 mm chlorine). Low overall sulfur isotope fractionation observed (34ε = 17 ± 3.5‰) hints at high rates of sulfate reduction, as has been previously suggested for sulfate reduction coupled with methane oxidation. The new results demonstrate the presence of sulfate-driven AOM in terrestrial hypersaline systems and expand our understanding of how microbial life is sustained under the challenging conditions of an extremely hypersaline environment. PMID:25039851

  18. Inhibition of sulfate reduction in paddy soils

    Energy Technology Data Exchange (ETDEWEB)

    Vamos, R

    1958-12-13

    The hydrogen sulfide formed in waterlogged soils is a serious problem in rice cultivation. It inhibits the uptake of water and nutrients and may even cause root-rot. Results can best be obtained by preventing the formation of hydrogen sulfide. It is formed mainly by reduction of sulfate for which the cellulose-butyric acid fermentation provides the hydrogen source. Addition of ammonium or potassium nitrate prevents the formation of H/sub 2/S. The hydrogen produced by butyric acid fermentation is used to reduce nitrate and consequently cannot be utilized by the sulfate-reducing bacteria as a source of energy. 6 references.

  19. Microbial contributions to coupled arsenic and sulfur cycling in the acid-sulfide hot spring Champagne Pool, New Zealand.

    Science.gov (United States)

    Hug, Katrin; Maher, William A; Stott, Matthew B; Krikowa, Frank; Foster, Simon; Moreau, John W

    2014-01-01

    Acid-sulfide hot springs are analogs of early Earth geothermal systems where microbial metal(loid) resistance likely first evolved. Arsenic is a metalloid enriched in the acid-sulfide hot spring Champagne Pool (Waiotapu, New Zealand). Arsenic speciation in Champagne Pool follows reaction paths not yet fully understood with respect to biotic contributions and coupling to biogeochemical sulfur cycling. Here we present quantitative arsenic speciation from Champagne Pool, finding arsenite dominant in the pool, rim and outflow channel (55-75% total arsenic), and dithio- and trithioarsenates ubiquitously present as 18-25% total arsenic. In the outflow channel, dimethylmonothioarsenate comprised ≤9% total arsenic, while on the outflow terrace thioarsenates were present at 55% total arsenic. We also quantified sulfide, thiosulfate, sulfate and elemental sulfur, finding sulfide and sulfate as major species in the pool and outflow terrace, respectively. Elemental sulfur concentration reached a maximum at the terrace. Phylogenetic analysis of 16S rRNA genes from metagenomic sequencing revealed the dominance of Sulfurihydrogenibium at all sites and an increased archaeal population at the rim and outflow channel. Several phylotypes were found closely related to known sulfur- and sulfide-oxidizers, as well as sulfur- and sulfate-reducers. Bioinformatic analysis revealed genes underpinning sulfur redox transformations, consistent with sulfur speciation data, and illustrating a microbial role in sulfur-dependent transformation of arsenite to thioarsenate. Metagenomic analysis also revealed genes encoding for arsenate reductase at all sites, reflecting the ubiquity of thioarsenate and a need for microbial arsenate resistance despite anoxic conditions. Absence of the arsenite oxidase gene, aio, at all sites suggests prioritization of arsenite detoxification over coupling to energy conservation. Finally, detection of methyl arsenic in the outflow channel, in conjunction with

  20. Using Thermodynamics to Predict the Outcomes of Nitrate-Based Oil Reservoir Souring Control Interventions

    Directory of Open Access Journals (Sweden)

    Jan Dolfing

    2017-12-01

    Full Text Available Souring is the undesirable production of hydrogen sulfide (H2S in oil reservoirs by sulfate-reducing bacteria (SRB. Souring is a common problem during secondary oil recovery via water flooding, especially when seawater with its high sulfate concentration is introduced. Nitrate injection into these oil reservoirs can prevent and remediate souring by stimulating nitrate-reducing bacteria (NRB. Two conceptually different mechanisms for NRB-facilitated souring control have been proposed: nitrate-sulfate competition for electron donors (oil-derived organics or H2 and nitrate driven sulfide oxidation. Thermodynamics can facilitate predictions about which nitrate-driven mechanism is most likely to occur in different scenarios. From a thermodynamic perspective the question “Which reaction yields more energy, nitrate driven oxidation of sulfide or nitrate driven oxidation of organic compounds?” can be rephrased as: “Is acetate driven sulfate reduction to sulfide exergonic or endergonic?” Our analysis indicates that under conditions encountered in oil fields, sulfate driven oxidation of acetate (or other SRB organic electron donors is always more favorable than sulfide oxidation to sulfate. That predicts that organotrophic NRB that oxidize acetate would outcompete lithotrophic NRB that oxidize sulfide. However, sulfide oxidation to elemental sulfur is different. At low acetate HS− oxidation is more favorable than acetate oxidation. Incomplete oxidation of sulfide to S0 is likely to occur when nitrate levels are low, and is favored by low temperatures; conditions that can be encountered at oil field above-ground facilities where intermediate sulfur compounds like S0 may cause corrosion. These findings have implications for reservoir management strategies and for assessing the success and progress of nitrate-based souring control strategies and the attendant risks of corrosion associated with souring and nitrate injection.

  1. Leaching of strontium sulfide from produced clinker in conversion furnace

    International Nuclear Information System (INIS)

    Ghorbanian, S. A.; Salehpour, A. R.; Radpour, S. R.

    2009-01-01

    Iran is rich in mineral resources one of which is mineral Celestine. Basing on current estimations, the capacity of mineral Celestine is over two million tons, 75-95% of which is strontium sulfate. However; in industries such as Color cathode Ray Tubes, pyrochemical processes, ceramics, paint production, zinc purification processes; strontium sulfate is not a direct feed, rather it is largely consumed in the form of strontium carbonate. Two conventional methods are used to produce strontium carbonate from the sulfate; that is direct reaction and black ash methods. Strontium sulfide, as an intermediate component has a key role in black ash process including strontium sulfate reduction by coke, hence producing and leaching the strontium sulfide by hot water. Finally the reaction of strontium sulfate with sodium carbonate lead to strontium carbonate. In this paper, a system was designed to analyze and optimize the process parameters of strontium sulfide production which is less expensive and available solvent in water. Fundamentally, when strontium sulfide becomes in contact with strontium sulfate; Sr(SH) 2 , and Sr(OH) 2 , are produced. The solubility of strontium sulfide depends on water temperature and the maximum solubility achieved at 90 d egree C . The results showed that in the experimental scale, at water to SrS ratio of 6; they sediment for 45 minutes at 95 d egree C in five operational stages; the separation of 95 and 97.1 percent of imported SrS is possible in effluent of fourth and fifth stages, respectively. Thus; four leaching stages could be recommended for pilot scale plants. Also, the results show that at water to SrS ratio of 8, 40 minutes sedimentation at 85-95 d egree C in one operational stage, the separation of 95 percent separation of inputted SrS, is possible. Solvent leaching process is continued till no smell of sulfur components is felt. It could be used as a key role to determine the number of leaching stages in experiments. Finally, the

  2. Effect of sulfide concentration on the location of the metal precipitates in inversed fluidized bed reactors

    Energy Technology Data Exchange (ETDEWEB)

    Villa-Gomez, D., E-mail: d.villagomez@unesco-ihe.org [Core Pollution Prevention and Control, UNESCO-IHE, Institute for Water Education, PO Box 3015, 2601 DA Delft (Netherlands); Ababneh, H.; Papirio, S.; Rousseau, D.P.L.; Lens, P.N.L. [Core Pollution Prevention and Control, UNESCO-IHE, Institute for Water Education, PO Box 3015, 2601 DA Delft (Netherlands)

    2011-08-15

    Highlights: {yields} Sulfide concentration governs the location of metal precipitates in sulfate reducing bioreactors. {yields} High dissolved sulfide induces metal precipitation in the bulk liquid as fines. {yields} Low dissolved sulfide concentrations yield local supersaturation and thus metal precipitation in the biofilm. -- Abstract: The effect of the sulfide concentration on the location of the metal precipitates within sulfate-reducing inversed fluidized bed (IFB) reactors was evaluated. Two mesophilic IFB reactors were operated for over 100 days at the same operational conditions, but with different chemical oxygen demand (COD) to SO{sub 4}{sup 2-} ratio (5 and 1, respectively). After a start up phase, 10 mg/L of Cu, Pb, Cd and Zn each were added to the influent. The sulfide concentration in one IFB reactor reached 648 mg/L, while it reached only 59 mg/L in the other one. In the high sulfide IFB reactor, the precipitated metals were mainly located in the bulk liquid (as fines), whereas in the low sulfide IFB reactor the metal preciptiates were mainly present in the biofilm. The latter can be explained by local supersaturation due to sulfide production in the biofilm. This paper demonstrates that the sulfide concentration needs to be controlled in sulfate reducing IFB reactors to steer the location of the metal precipitates for recovery.

  3. Sulfidation behavior of Fe20Cr alloys

    International Nuclear Information System (INIS)

    Pillis, Marina Fuser

    2001-01-01

    Alloys for use in high temperature environments rely on the formation of an oxide layer for their protection. Normally, these protective oxides are Cr 2 O 3 , Al 2 O 3 and, some times, SiO 2 . Many industrial gaseous environments contain sulfur. Sulfides, formed in the presence of sulfur are thermodynamically less stable, have lower melting points and deviate much more stoichiometrically, compared to the corresponding oxides. The mechanism of sulfidation of various metals is as yet not clear, in spite of the concerted efforts during the last decade. To help address this situation, the sulfidation behavior of Fe20Cr has been studied as a function of compositional modifications and surface state of the alloy. The alloys Fe20Cr, Fe20Cr0.7Y, Fe20Cr5Al and Fe20Cr5Al0.6Y were prepared and three sets of sulfidation tests were carried out. In the first set, the alloys were sulfidized at 700 deg C and 800 deg C for 10h. In the second set, the alloys were pre-oxidized at 1000 deg C and then sulfidized at 800 deg C for up to 45h. In the third set of tests, the initial stages of sulfidation of the alloys was studied. All the tests were carried out in a thermobalance, in flowing H 2 /2%H 2 S, and the sulfidation behavior determined as mass change per unit area. Scanning electron microscopy coupled to energy dispersive spectroscopy and X-ray diffraction analysis were used to characterize the reaction products. The addition of Y and Al increased sulfidation resistance of Fe20Cr. The addition of Y altered the species that diffused predominantly during sulfide growth. It changed from predominant cationic diffusion to predominant anionic diffusion. The addition of Al caused an even greater increase in sulfidation resistance of Fe20Cr, with the parabolic rate constant decreasing by three orders of magnitude. Y addition to the FeCrAl alloy did not cause any appreciable alteration in sulfidation resistance. Pre-oxidation of the FeCrAl and FeCrAlY alloys resulted in an extended

  4. Toluidine blue-sodium lauryl ether sulfate complexes : Influence of ethylene oxide length

    NARCIS (Netherlands)

    Vleugels, L.F.W.; Féat, A.; Voets, I.K.; Tuinier, R.

    2017-01-01

    Sodium Lauryl Ether Sulfates (SLES) are an increasingly important and versatile type of surfactants. The complexation between ortho-Toluidine blue (TBO) and a homologous series of SLES, including Sodium Lauryl Sulfate (SDS) without Ethylene Oxide (EO), has been investigated using visible

  5. Methanol utilizing Desulfotomaculum species utilizes hydrogen in a methanol-fed sulfate-reducing bioreactor.

    Science.gov (United States)

    Balk, Melike; Weijma, Jan; Goorissen, Heleen P; Ronteltap, Mariska; Hansen, Theo A; Stams, Alfons J M

    2007-01-01

    A sulfate-reducing bacterium, strain WW1, was isolated from a thermophilic bioreactor operated at 65 degrees C with methanol as sole energy source in the presence of sulfate. Growth of strain WW1 on methanol or acetate was inhibited at a sulfide concentration of 200 mg l(-1), while on H2/CO2, no apparent inhibition occurred up to a concentration of 500 mg l(-1). When strain WW1 was co-cultured under the same conditions with the methanol-utilizing, non-sulfate-reducing bacteria, Thermotoga lettingae and Moorella mulderi, both originating from the same bioreactor, growth and sulfide formation were observed up to 430 mg l(-1). These results indicated that in the co-cultures, a major part of the electron flow was directed from methanol via H2/CO2 to the reduction of sulfate to sulfide. Besides methanol, acetate, and hydrogen, strain WW1 was also able to use formate, malate, fumarate, propionate, succinate, butyrate, ethanol, propanol, butanol, isobutanol, with concomitant reduction of sulfate to sulfide. In the absence of sulfate, strain WW1 grew only on pyruvate and lactate. On the basis of 16S rRNA analysis, strain WW1 was most closely related to Desulfotomaculum thermocisternum and Desulfotomaculum australicum. However, physiological properties of strain WW1 differed in some aspects from those of the two related bacteria.

  6. Bioflotation of sulfide minerals with Acidithiobacillus ferrooxidans in relation to copper activation and surface oxidation.

    Science.gov (United States)

    Pecina-Treviño, E T; Ramos-Escobedo, G T; Gallegos-Acevedo, P M; López-Saucedo, F J; Orrantia-Borunda, E

    2012-09-01

    Surface oxidation of sulfides and copper (Cu) activation are 2 of the main processes that determine the efficiency of flotation. The present study was developed with the intention to ascertain the role of the phenomena in the biomodification of sulfides by Acidithiobacillus ferrooxidans culture (cells and growth media) and their impact in bioflotation. Surface characteristics of chalcopyrite, sphalerite, and pyrrhotite, alone and in mixtures, after interaction with A. ferrooxidans were evaluated. Chalcopyrite floatability was increased substantially by biomodification, while bacteria depressed pyrrhotite floatability, favoring separation. The results showed that elemental sulfur concentration increased because of the oxidation generated by bacterial cells, the effect is intensified by the Fe(III) left in the culture and by galvanic contact. Acidithiobacillus ferrooxidans culture affects the Cu activation of sphalerite. The implications of elemental sulfur concentration and Cu activation of sphalerite are key factors that must be considered for the future development of sulfide bioflotation processes, since the depressive effect of cells could be counteracted by elemental sulfur generation.

  7. Durable regenerable sorbent pellets for removal of hydrogen sulfide coal gas

    Science.gov (United States)

    Siriwardane, Ranjani V.

    1999-01-01

    Pellets for removing hydrogen sulfide from a coal gasification stream at an elevated temperature are prepared in durable form, usable over repeated cycles of absorption and regeneration. The pellets include a material reactive with hydrogen sulfide, in particular zinc oxide, a binder, and an inert material, in particular calcium sulfate (drierite), having a particle size substantially larger than other components of the pellets. A second inert material and a promoter may also be included. Preparation of the pellets may be carried out by dry, solid-state mixing of components, moistening the mixture, and agglomerating it into pellets, followed by drying and calcining. Pellet size is selected, depending on the type of reaction bed for which the pellets are intended. The use of inert material with a large particle size provides a stable pellet structure with increased porosity, enabling effective gas contact and prolonged mechanical durability.

  8. Hydrogen sulfide-powered solid oxide fuel cells

    Science.gov (United States)

    Liu, Man

    2004-12-01

    The potential utilization of hydrogen sulfide as fuel in solid oxide fuel cells has been investigated using an oxide-ion conducting YSZ electrolyte and different kinds of anode catalysts at operating temperatures in the range of 700--900°C and at atmospheric pressure. This technology offers an economically attractive alternative to present methods for removing toxic and corrosive H2S gas from sour gas streams and a promising approach for cogenerating electrical energy and useful chemicals. The primary objective of the present research was to find active and stable anode materials. Fuel cell experimental results showed that platinum was a good electrocatalyst for the conversion of H2S, but the Pt/YSZ interface was physically unstable due to the reversible formation and decomposition of PtS in H 2S streams at elevated temperatures. Moreover, instability of the Pt/YSZ interface was accelerated significantly by electrochemical reactions, and ultimately led to the detachment of the Pt anode from the electrolyte. It has been shown that an interlayer of TiO2 stabilized the Pt anode on YSZ electrolyte, thereby prolonging cell lifetime. However, the current output for a fuel cell using Pt/TiO2 as anode was not improved compared to using Pt alone. It was therefore necessary to investigate novel anode systems for H 2S-air SOFCs. New anode catalysts comprising composite metal sulfides were developed. These catalysts exhibited good electrical conductivity and better catalytic activity than Pt. In contrast to MoS2 alone, composite catalysts (M-Mo-S, M = Fe, Co, Ni) were not volatile and had superior stability. However, when used for extended periods of time, detachment of Pt current collecting film from anodes comprising metal sulfides alone resulted in a large increase in contact resistance and reduction in cell performance. Consequently, a systematic investigation was conducted to identify alternative electronic conductors for use with M-Mo-S catalysts. Anode catalysts

  9. Biogenic uraninite precipitation and its reoxidation by iron(III) (hydr)oxides: A reaction modeling approach

    Science.gov (United States)

    Spycher, Nicolas F.; Issarangkun, Montarat; Stewart, Brandy D.; Sevinç Şengör, S.; Belding, Eileen; Ginn, Tim R.; Peyton, Brent M.; Sani, Rajesh K.

    2011-08-01

    One option for immobilizing uranium present in subsurface contaminated groundwater is in situ bioremediation, whereby dissimilatory metal-reducing bacteria and/or sulfate-reducing bacteria are stimulated to catalyze the reduction of soluble U(VI) and precipitate it as uraninite (UO 2). This is typically accomplished by amending groundwater with an organic electron donor. It has been shown, however, that once the electron donor is entirely consumed, Fe(III) (hydr)oxides can reoxidize biogenically produced UO 2, thus potentially impeding cleanup efforts. On the basis of published experiments showing that such reoxidation takes place even under highly reducing conditions (e.g., sulfate-reducing conditions), thermodynamic and kinetic constraints affecting this reoxidation are examined using multicomponent biogeochemical simulations, with particular focus on the role of sulfide and Fe(II) in solution. The solubility of UO 2 and Fe(III) (hydr)oxides are presented, and the effect of nanoscale particle size on stability is discussed. Thermodynamically, sulfide is preferentially oxidized by Fe(III) (hydr)oxides, compared to biogenic UO 2, and for this reason the relative rates of sulfide and UO 2 oxidation play a key role on whether or not UO 2 reoxidizes. The amount of Fe(II) in solution is another important factor, with the precipitation of Fe(II) minerals lowering the Fe +2 activity in solution and increasing the potential for both sulfide and UO 2 reoxidation. The greater (and unintuitive) UO 2 reoxidation by hematite compared to ferrihydrite previously reported in some experiments can be explained by the exhaustion of this mineral from reaction with sulfide. Simulations also confirm previous studies suggesting that carbonate produced by the degradation of organic electron donors used for bioreduction may significantly increase the potential for UO 2 reoxidation through formation of uranyl carbonate aqueous complexes.

  10. The fate of sulfate in acidified pig slurry during storage and following application to cropped soil

    DEFF Research Database (Denmark)

    Eriksen, Jørgen; Sørensen, Peter; Elsgaard, Lars

    2008-01-01

    -available sulfate form. Microbial sulfate reduction during storage of acidified pig slurry was limited, presumably due to initial pH effects and a limitation in the availability of easily degradable organic matter. Sulfide accumulation was observed during storage but the sulfide levels in acidified slurry did...

  11. Distribution of iron- and sulfate-reducing bacteria across a coastal acid sulfate soil (CASS environment: implications for passive bioremediation by tidal inundation

    Directory of Open Access Journals (Sweden)

    Yu-Chen eLing

    2015-07-01

    Full Text Available Coastal acid sulfate soils (CASS constitute a serious and global environmental problem. Oxidation of iron sulfide minerals exposed to air generates sulfuric acid with consequently negative impacts on coastal and estuarine ecosystems. Tidal inundation represents one current treatment strategy for CASS, with the aim of neutralizing acidity by triggering microbial iron- and sulfate-reduction and inducing the precipitation of iron-sulfides. Although well-known functional guilds of bacteria drive these processes, their distributions within CASS environments, as well as their relationships to tidal cycling and the availability of nutrients and electron acceptors, are poorly understood. These factors will determine the long-term efficacy of passive CASS remediation strategies. Here we studied microbial community structure and functional guild distribution in sediment cores obtained from ten depths ranging from 0-20 cm in three sites located in the supra-, inter- and sub-tidal segments, respectively, of a CASS-affected salt marsh (East Trinity, Cairns, Australia. Whole community 16S rRNA gene diversity within each site was assessed by 454 pyrotag sequencing and bioinformatic analyses in the context of local hydrological, geochemical and lithological factors. The results illustrate spatial overlap, or close association, of iron- and sulfate-reducing bacteria in an environment rich in organic matter and controlled by parameters such as acidity, redox potential, degree of water saturation, and mineralization. The observed spatial distribution implies the need for empirical understanding of the timing, relative to tidal cycling, of various terminal electron-accepting processes that control acid generation and biogeochemical iron and sulfur cycling.

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

    Directory of Open Access Journals (Sweden)

    Patrick S. Michael

    2015-08-01

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

  13. CO2-SO3-rich (carbonate-sulfate) melt/fluids in the lithosphere beneath El Hierro, Canary Islands.

    Science.gov (United States)

    Oglialoro, E.; Ferrando, S.; Malaspina, N.; Villa, I. M.; Frezzotti, M. L.

    2015-12-01

    Mantle xenoliths from the island of El Hierro, the youngest of the Canary Islands, have been studied to characterize fluxes of carbon in the lithosphere of an OIB volcanism region. Fifteen xenoliths (4-10 cm in diameter) were collected in a rift lava flow (15-41 ka) at a new xenolith locality in El Julan cliff (S-SW of the island). Peridotites consist of protogranular to porphyroblastic spinel harzburgites, lherzolites, and subordinate dunites. One spinel clinopyroxenite, and one olivine-websterite were also analyzed. Ultramafic xenoliths were classified as HEXO (harzburgite and dunite with exsolved orthopyroxene), HLCO (harzburgite and lherzolite containing orthopyroxene without visible exsolution lamellae), and HTR (transitional harzburgite with exsolved orthopyroxene porphyroclasts, and poikilitic orthopyroxene) following [1]. While HLCO and HTR peridotites contain mostly CO2 fluid inclusions, HEXO peridotites preserve an early association of melt/fluid inclusions containing dominantly carbonate/sulfate/silicate glass, evolving to carbonate/sulfate/phosphate/spinel aggregates, with exsolved CO2 (± carbonates, anhydrite and H2O). Chemical and Raman analyses identify dolomite, Mg-calcite, anhydrite, sulfohalite [Na6(SO4)2FCl] (± other anhydrous and hydrous alkali-sulfates), apatite, and Cr-spinel in the inclusions. Sulfides are noticeably absent. The microstructure and chemical composition of the metasomatic fluids indicate that the peridotites were infiltrated by a carbonate-sulfate-silicate melt/fluid enriched in CO2, H2O, and P. A mantle origin for this fluid is supported by high densities of CO2inclusions (> 1g/cm3), determined by Raman microspectroscopy and cross-checked by microthermometry. Consequently, El Julan peridotites provide the first evidence for liberating oxidized C and S fluxes from the Earth lithosphere in an OIB source region, and suggest that oxidation of sulfide to sulfate can occur during small-degree partial melting of the upper mantle

  14. Treatment of acid rock drainage using a sulfate-reducing bioreactor with zero-valent iron

    Energy Technology Data Exchange (ETDEWEB)

    Ayala-Parra, Pedro; Sierra-Alvarez, Reyes; Field, James A., E-mail: jimfield@email.arizona.edu

    2016-05-05

    Highlights: • Electron donor from zero-valent iron (ZVI) drives sulfate reduction to sulfide. • Sulfide converts soluble heavy metals into sulfide minerals. • Excess sulfide is sequestered by iron preventing discharge. • Corrosion of ZVI consumes acidity in acid rock drainage. • ZVI as reactive material outlasted limestone in removing heavy metals. - Abstract: This study assessed the bioremediation of acid rock drainage (ARD) in flow-through columns testing zero-valent iron (ZVI) for the first time as the sole exogenous electron donor to drive sulfate-reducing bacteria in permeable reactive barriers. Columns containing ZVI, limestone or a mixture of both materials were inoculated with an anaerobic mixed culture and fed a synthetic ARD containing sulfuric acid and heavy metals (initially copper, and later also cadmium and lead). ZVI significantly enhanced sulfate reduction and the heavy metals were extensively removed (>99.7%). Solid-phase analyses showed that heavy metals were precipitated with biogenic sulfide in the columns packed with ZVI. Excess sulfide was sequestered by iron, preventing the discharge of dissolved sulfide. In the absence of ZVI, heavy metals were also significantly removed (>99.8%) due to precipitation with hydroxide and carbonate ions released from the limestone. Vertical-profiles of heavy metals in the columns packing, at the end of the experiment, demonstrated that the ZVI columns still had excess capacity to remove heavy metals, while the capacity of the limestone control column was approaching saturation. The ZVI provided conditions that enhanced sulfate reduction and generated alkalinity. Collectively, the results demonstrate an innovative passive ARD remediation process using ZVI as sole electron-donor.

  15. Treatment of acid rock drainage using a sulfate-reducing bioreactor with zero-valent iron

    International Nuclear Information System (INIS)

    Ayala-Parra, Pedro; Sierra-Alvarez, Reyes; Field, James A.

    2016-01-01

    Highlights: • Electron donor from zero-valent iron (ZVI) drives sulfate reduction to sulfide. • Sulfide converts soluble heavy metals into sulfide minerals. • Excess sulfide is sequestered by iron preventing discharge. • Corrosion of ZVI consumes acidity in acid rock drainage. • ZVI as reactive material outlasted limestone in removing heavy metals. - Abstract: This study assessed the bioremediation of acid rock drainage (ARD) in flow-through columns testing zero-valent iron (ZVI) for the first time as the sole exogenous electron donor to drive sulfate-reducing bacteria in permeable reactive barriers. Columns containing ZVI, limestone or a mixture of both materials were inoculated with an anaerobic mixed culture and fed a synthetic ARD containing sulfuric acid and heavy metals (initially copper, and later also cadmium and lead). ZVI significantly enhanced sulfate reduction and the heavy metals were extensively removed (>99.7%). Solid-phase analyses showed that heavy metals were precipitated with biogenic sulfide in the columns packed with ZVI. Excess sulfide was sequestered by iron, preventing the discharge of dissolved sulfide. In the absence of ZVI, heavy metals were also significantly removed (>99.8%) due to precipitation with hydroxide and carbonate ions released from the limestone. Vertical-profiles of heavy metals in the columns packing, at the end of the experiment, demonstrated that the ZVI columns still had excess capacity to remove heavy metals, while the capacity of the limestone control column was approaching saturation. The ZVI provided conditions that enhanced sulfate reduction and generated alkalinity. Collectively, the results demonstrate an innovative passive ARD remediation process using ZVI as sole electron-donor.

  16. Remediation of Acid Mine Drainage with Sulfate Reducing Bacteria

    Science.gov (United States)

    Hauri, James F.; Schaider, Laurel A.

    2009-01-01

    Sulfate reducing bacteria have been shown to be effective at treating acid mine drainage through sulfide production and subsequent precipitation of metal sulfides. In this laboratory experiment for undergraduate environmental chemistry courses, students design and implement a set of bioreactors to remediate acid mine drainage and explain observed…

  17. Electrochemical oxidation of iron and alkalinity generation for efficient sulfide control in sewers.

    Science.gov (United States)

    Lin, Hui-Wen; Kustermans, Caroline; Vaiopoulou, Eleni; Prévoteau, Antonin; Rabaey, Korneel; Yuan, Zhiguo; Pikaar, Ilje

    2017-07-01

    The addition of iron salts is one of the most commonly used dosing strategies for sulfide control in sewers. However, iron salts decrease the sewage pH which not only reduces the effectiveness of sulfide precipitation but also enhances the release of residual sulfide to the sewer atmosphere. Equally important, concentrated iron salt solutions are corrosive and their frequent transport, handling, and on-site storage often come with Occupational Health and Safety (OH&S) concerns. Here, we experimentally demonstrated a novel sulfide control approach using electrochemical systems with parallel placed iron electrodes. This enabled combining anodic dissolved iron species release with cathodic hydroxyl anion production, which alleviates all the aforementioned concerns. A long-term experiment was successfully carried out achieving an average sulfide removal efficiency of 95.4 ± 4.4% at low voltage input of 2.90 ± 0.54 V over the course of 8 weeks. This electrochemical method was demonstrated to successfully achieve efficient sulfide control. In addition, it increases the sewage pH, thereby overcoming the drawbacks associated with the pH decrease in the case of conventional iron salt dosing. Ferrous ions were produced at an overall coulombic efficiency (CE) of 98.2 ± 1.2%, whereas oxygen evolution and direct sulfide oxidation were not observed. Short-term experiments showed that increasing either inter-electrode gap or current density increased the cell voltage associated with the increase in the ohmic drop of the system. Overall, this study highlights the practical potential of in-situ generation of dissolved iron species and simultaneous hydroxyl anion generation for efficient sulfide control in sewers. Copyright © 2017 Elsevier Ltd. All rights reserved.

  18. Durable regenerable sorbent pellets for removal of hydrogen sulfide from coal gas

    Science.gov (United States)

    Siriwardane, Ranjani V.

    1997-01-01

    Pellets for removing hydrogen sulfide from a coal gasification stream at an elevated temperature are prepared in durable form usable over repeated cycles of absorption and regeneration. The pellets include a material reactive with hydrogen sulfide, in particular zinc oxide, a binder, and an inert material, in particular calcium sulfate (drierite), having a particle size substantially larger than other components of the pellets. A second inert material and a promoter may also be included. Preparation of the pellets may be carried out by dry, solid-state mixing of components, moistening the mixture, and agglomerating it into pellets, followed by drying and calcining. Pellet size is selected, depending on the type of reaction bed for which the pellets are intended. The use of inert material with a large particle size provides a stable pellet structure with increased porosity, enabling effective gas contact and prolonged mechanical durability.

  19. Synthesis and characterization of titanium oxide/bismuth sulfide nanorods for solar cells applications

    International Nuclear Information System (INIS)

    Solis, M.; Rincon, M. E.

    2008-01-01

    In the present work is showed the synthesis and characterization of titanium oxide/bismuth sulfide nanowires hetero-junctions for solar cells applications. Conductive glass substrates (Corning 25 x 75 mm) were coated with a thin layer of sol-gel TiO2 and used as substrates for the subsequent deposition of bismuth sulfide nanorods (BN). TiO2 films (∼400 nm) were deposited with a semiautomatic immersion system with controlled immersion/withdraw velocity, using titanium isopropoxide as the titania precursor [1]. For BN synthesis and deposition, the solvo-thermal method was used, introducing air annealed TiO2-substrates in the autoclave. The typical bilayer TiO2/BN hetero-junction was 600 nm thick. The synthesized materials (powders and films) were characterized by X-Ray Diffraction, Scanning Electron Microscopy, and UV-Visible Spectroscopy. Anatase was the crystalline phase of TiO2, while bismuth sulfide nanotubes show a diffraction pattern characteristic of bismuthinite distorted by the preferential growth of some planes [2-4]. The optoelectronic characterization of TiO2/NB hetero-junctions was compared with hetero-junctions obtained by sensitizing TiO2 with chemically deposited bismuth sulfide films. Bismuth sulfide nanowires are 2µm long and 70nm wide (aspect ratio L/D = 43), while chemically deposited bismuth sulfide have L/D = 1, therefore the effect of particle size evaluation and geometry in the photosensitization phenomena will be discussed in the context of new materials for solar-cells applications. (Full text)

  20. Environmental geochemistry of a Kuroko-type massive sulfide deposit at the abandoned Valzinco mine, Virginia, USA

    Energy Technology Data Exchange (ETDEWEB)

    Seal, Robert R. [US Geological Survey, 954 National Center, Reston, VA 20192 (United States)], E-mail: rseal@usgs.gov; Hammarstrom, Jane M.; Johnson, Adam N.; Piatak, Nadine M.; Wandless, Gregory A. [US Geological Survey, 954 National Center, Reston, VA 20192 (United States)

    2008-02-15

    The abandoned Valzinco mine, which worked a steeply dipping Kuroko-type massive sulfide deposit in the Virginia Au-pyrite belt, contributed significant metal-laden acid-mine drainage to the Knight's Branch watershed. The host rocks were dominated by metamorphosed felsic volcanic rocks, which offered limited acid-neutralizing potential. The ores were dominated by pyrite, sphalerite, galena, and chalcopyrite, which represented significant acid-generating potential. Acid-base accounting and leaching studies of flotation tailings - the dominant mine waste at the site - indicated that they were acid generating and therefore, should have liberated significant quantities of metals to solution. Field studies of mine drainage from the site confirmed that mine drainage and the impacted stream waters had pH values from 1.1 to 6.4 and exceeded aquatic ecosystem toxicity limits for Fe, Al, Cd, Cu, Pb and Zn. Stable isotope studies of water, dissolved SO{sub 4}{sup 2-}, and primary and secondary sulfate and sulfide minerals indicated that two distinct sulfide oxidation pathways were operative at the site: one dominated by Fe(III) as the oxidant, and another by molecular O{sub 2} as the oxidant. Reaction-path modeling suggested that geochemical interactions between tailings and waters approached a steady state within about a year. Both leaching studies and geochemical reaction-path modeling provided reasonable predictions of the mine-drainage chemistry.

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

    Science.gov (United States)

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

    2016-12-01

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

  2. Remediation of Sulfidic Wastewater by Aeration in the Presence of Ultrasonic Vibration

    Directory of Open Access Journals (Sweden)

    F. Ahmad

    2018-06-01

    Full Text Available In the current study, the aerial oxidation of sodium sulfide in the presence of ultrasonic vibration is investigated. Sulfide analysis was carried out by the methylene blue method. Sodium sulfide is oxidized to elemental sulfur in the presence of ultrasonic vibration. The influence of air flow rate, initial sodium sulfide concentration and ultrasonic vibration intensity on the oxidation of sodium sulfide was investigated. The rate law equation regarding the oxidation of sulfide was determined from the experimental data. The order of reaction with respect to sulfide and oxygen was found to be 0.36 and 0.67 respectively. The overall reaction followed nearly first order kinetics.

  3. Guar Gum Stimulates Biogenic Sulfide Production at Elevated Pressures: Implications for Shale Gas Extraction

    Science.gov (United States)

    Nixon, Sophie L.; Walker, Leanne; Streets, Matthew D. T.; Eden, Bob; Boothman, Christopher; Taylor, Kevin G.; Lloyd, Jonathan R.

    2017-01-01

    Biogenic sulfide production is a common problem in the oil industry, and can lead to costly hydrocarbon processing and corrosion of extraction infrastructure. The same phenomenon has recently been identified in shale gas extraction by hydraulic fracturing, and organic additives in fracturing fluid have been hypothesized to stimulate this process. Constraining the relative effects of the numerous organic additives on microbial metabolism in situ is, however, extremely challenging. Using a bespoke bioreactor system we sought to assess the potential for guar gum, the most commonly used gelling agent in fracturing fluids, to stimulate biogenic sulfide production by sulfate-reducing microorganisms at elevated pressure. Two pressurized bioreactors were fed with either sulfate-amended freshwater medium, or low-sulfate natural surface water, in addition to guar gum (0.05 w/v%) and an inoculum of sulfate-reducing bacteria for a period of 77 days. Sulfide production was observed in both bioreactors, even when the sulfate concentration was low. Analysis of 16S rRNA gene sequences indicate that heterotrophic bacteria closely associated with the genera Brevundimonas and Acinetobacter became enriched early in the bioreactor experiments, followed by an increase in relative abundance of 16S rRNA genes associated with sulfate-reducing bacteria (Desulfosporosinus and Desulfobacteraceae) at later time points. Results demonstrate that guar gum can stimulate acid- and sulfide-producing microorganisms at elevated pressure, and may have implications for the potential role in microbially induced corrosion during hydraulic fracturing operations. Key differences between experimental and in situ conditions are discussed, as well as additional sources of carbon and energy for biogenic sulfide production during shale gas extraction. Our laboratory approach can be tailored to better simulate deep subsurface conditions in order to probe the role of other fracturing fluid additives and downhole

  4. Guar Gum Stimulates Biogenic Sulfide Production at Elevated Pressures: Implications for Shale Gas Extraction.

    Science.gov (United States)

    Nixon, Sophie L; Walker, Leanne; Streets, Matthew D T; Eden, Bob; Boothman, Christopher; Taylor, Kevin G; Lloyd, Jonathan R

    2017-01-01

    Biogenic sulfide production is a common problem in the oil industry, and can lead to costly hydrocarbon processing and corrosion of extraction infrastructure. The same phenomenon has recently been identified in shale gas extraction by hydraulic fracturing, and organic additives in fracturing fluid have been hypothesized to stimulate this process. Constraining the relative effects of the numerous organic additives on microbial metabolism in situ is, however, extremely challenging. Using a bespoke bioreactor system we sought to assess the potential for guar gum, the most commonly used gelling agent in fracturing fluids, to stimulate biogenic sulfide production by sulfate-reducing microorganisms at elevated pressure. Two pressurized bioreactors were fed with either sulfate-amended freshwater medium, or low-sulfate natural surface water, in addition to guar gum (0.05 w/v%) and an inoculum of sulfate-reducing bacteria for a period of 77 days. Sulfide production was observed in both bioreactors, even when the sulfate concentration was low. Analysis of 16S rRNA gene sequences indicate that heterotrophic bacteria closely associated with the genera Brevundimonas and Acinetobacter became enriched early in the bioreactor experiments, followed by an increase in relative abundance of 16S rRNA genes associated with sulfate-reducing bacteria ( Desulfosporosinus and Desulfobacteraceae) at later time points. Results demonstrate that guar gum can stimulate acid- and sulfide-producing microorganisms at elevated pressure, and may have implications for the potential role in microbially induced corrosion during hydraulic fracturing operations. Key differences between experimental and in situ conditions are discussed, as well as additional sources of carbon and energy for biogenic sulfide production during shale gas extraction. Our laboratory approach can be tailored to better simulate deep subsurface conditions in order to probe the role of other fracturing fluid additives and downhole

  5. A model for the description of oxidation in sulfidic waste rock dumps

    International Nuclear Information System (INIS)

    Bennett, J. W.; Pantelis, G.; Ritchie, A.I.M.; Stepanyants, Y.A.

    2000-03-01

    Basic mathematical equations which describe the processes of sulfide oxidation and gas and water transport in waste rock dumps are presented and discussed. The governing equations account for gas and water flow, vaporisation and condensation with latent heat effects, heat transport and mass balance. Gas, water and solid phases are assumed to be in local thermal equilibrium at all times. Air is approximated as an ideal three-component gas. Different semi-empirical relationships between physical values are used: Darcy's law for fluid flow, ideal gas law, the Van Genuchten formula for the relationship between degree of water saturation and pressure head, Mualem's formula for the relative hydraulic conductivity as a function of pressure head, etc. Some important global quantities, such as the fraction of sulfide sulfur oxidised and the global oxidation rate, are defined and considered as functions of time. The full set of equations is collected and presented in explicit form, convenient for further numerical modelling. The glossary of some technical terms and the table of definitions of the main parameters as well as their units and characteristic values are given

  6. Characterizing the effect of carbon steel exposure in sulfide containing solutions to microbially induced corrosion

    Energy Technology Data Exchange (ETDEWEB)

    Sherar, B.W.A. [Department of Chemistry, University of Western Ontario, London, ON, N6A 5B7 (Canada); Power, I.M. [Department of Earth Sciences, University of Western Ontario, London, ON, N6A 5B7 (Canada); Keech, P.G.; Mitlin, S. [Department of Chemistry, University of Western Ontario, London, ON, N6A 5B7 (Canada); Southam, G. [Department of Earth Sciences, University of Western Ontario, London, ON, N6A 5B7 (Canada); Shoesmith, D.W., E-mail: dwshoesm@uwo.c [Department of Chemistry, University of Western Ontario, London, ON, N6A 5B7 (Canada)

    2011-03-15

    Research highlights: Compares inorganic sulfide and sulfate reducing bacteria (SRB) on steel corrosion. Mackinawite was the dominant iron sulfide phase. SRBs can form nanowires, presumably grown to acquire energy. - Abstract: This article compares the electrochemical effects induced by inorganic sulfide and sulfate reducing bacteria on the corrosion of carbon steel - a subject of concern for pipelines. Biological microcosms, containing varying concentrations of bioorganic content, were studied to investigate changes to the morphology of biofilms and corrosion product deposits. Raman analysis indicated mackinawite (FeS{sub 1-x}) was the dominant iron sulfide phase grown both abiotically and biotically. A fascinating feature of biological media, void of an organic electron donor, was the formation of putative nanowires that may be grown to acquire energy from carbon steel by promoting the measured cathodic reaction.

  7. Properties of protective oxide scales containing cerium on Incoloy 800H in oxidizing and sulfidizing environments. I. Constant-extension-rate study of mechanical properties

    NARCIS (Netherlands)

    Haanappel, V.A.C.; Fransen, T.; Geerdink, Bert; Gellings, P.J.

    1988-01-01

    The mechanical properties of ceramic coatings containing cerium oxide, prepared by the sol-gel method and used to protect Incoloy 800H against aggressive environments, are reported. Deformation and cracking behavior in oxidizing and sulfidizing environments has been investigated by

  8. Microbial fuel cell based on electroactive sulfate-reducing biofilm

    International Nuclear Information System (INIS)

    Angelov, Anatoliy; Bratkova, Svetlana; Loukanov, Alexandre

    2013-01-01

    Highlights: ► Regulation and management of electricity generation by variation of residence time. ► Design of microbial fuel cell based on electroactive biofilm on zeolite. ► Engineering solution for removing of the obtained elemental sulfur. - abstract: A two chambered laboratory scale microbial fuel cell (MFC) has been developed, based on natural sulfate-reducing bacterium consortium in electroactive biofilm on zeolite. The MFC utilizes potassium ferricyanide in the cathode chamber as an electron acceptor that derives electrons from the obtained in anode chamber H 2 S. The molecular oxygen is finally used as a terminal electron acceptor at cathode compartment. The generated power density was 0.68 W m −2 with current density of 3.2 A m −2 at 150 Ω electrode resistivity. The hydrogen sulfide itself is produced by microbial dissimilative sulfate reduction process by utilizing various organic substrates. Finally, elemental sulfur was identified as the predominant final oxidation product in the anode chamber. It was removed from MFC through medium circulation and gathering in an external tank. This report reveals dependence relationship between the progress of general electrochemical parameters and bacterial sulfate-reduction rate. The presented MFC design can be used for simultaneous sulfate purification of mining drainage wastewater and generation of renewable electricity

  9. Sulfate Adsorption on Iron Nanocomposites on Graphene Oxide and Activated Carbon Beds

    Directory of Open Access Journals (Sweden)

    Rezvan Birooni

    2017-01-01

    Full Text Available This study is an experimental investigation of sulfate removal efficiency using iron nanocomposites on graphene oxide and activated carbon beds. The graphene oxide used was synthesized according to the Hummer method during which process graphene oxide and activated carbon were added. The effects of various parameters including adsorbent content, pH, and contact time on adsorption were investigated. Furthermore, the data were subjected to kinetic studies. Results revealed that the highest absorption rates of 84% and 62% were achieved for iron on the graphene oxide and activated carbon beds, respectively, when 0.06 g of the adsorbent was used at pH =11 over a contact time of 9 hours. It was also found that the kinetic pseudo-second-order model best fit the data. Finally, the results indicated that the two environmentally-friendly adsorbents have a good potential for removing sulfate from aqueous solutions.

  10. Spectral induced polarization and electrodic potential monitoring of microbially mediated iron sulfide transformations

    Energy Technology Data Exchange (ETDEWEB)

    Hubbard, Susan; Personna, Y.R.; Ntarlagiannis, D.; Slater, L.; Yee, N.; O' Brien, M.; Hubbard, S.

    2008-02-15

    Stimulated sulfate-reduction is a bioremediation technique utilized for the sequestration of heavy metals in the subsurface.We performed laboratory column experiments to investigate the geoelectrical response of iron sulfide transformations by Desulfo vibriovulgaris. Two geoelectrical methods, (1) spectral induced polarization (SIP), and (2) electrodic potential measurements, were investigated. Aqueous geochemistry (sulfate, lactate, sulfide, and acetate), observations of precipitates (identified from electron microscopy as iron sulfide), and electrodic potentials on bisulfide ion (HS) sensitive silver-silver chloride (Ag-AgCl) electrodes (630 mV) were diagnostic of induced transitions between an aerobic iron sulfide forming conditions and aerobic conditions promoting iron sulfide dissolution. The SIP data showed 10m rad anomalies during iron sulfide mineralization accompanying microbial activity under an anaerobic transition. These anomalies disappeared during iron sulfide dissolution under the subsequent aerobic transition. SIP model parameters based on a Cole-Cole relaxation model of the polarization at the mineral-fluid interface were converted to (1) estimated biomineral surface area to pore volume (Sp), and (2) an equivalent polarizable sphere diameter (d) controlling the relaxation time. The temporal variation in these model parameters is consistent with filling and emptying of pores by iron sulfide biofilms, as the system transitions between anaerobic (pore filling) and aerobic (pore emptying) conditions. The results suggest that combined SIP and electrodic potential measurements might be used to monitor spatiotemporal variability in microbial iron sulfide transformations in the field.

  11. Hypochlorous acid turn-on boron dipyrromethene probe based on oxidation of methyl phenyl sulfide

    International Nuclear Information System (INIS)

    Liu, Shi-Rong; Vedamalai, Mani; Wu, Shu-Pao

    2013-01-01

    Graphical abstract: -- Highlights: •A BODIPY-based green fluorescent probe for sensing HOCl was developed. •The probe utilizes HOCl-promoted oxidation of methyl phenyl sulfide to produce a proportional fluorescence response to the concentration of HOCl. •Confocal fluorescence microscopy imaging of RAW264.7 cells demonstrated that the HCS probe might have application in the investigation of HOCl roles in biological systems. -- Abstract: A boron dipyrromethene (BODIPY)-based fluorometric probe, HCS, has been successfully developed for the highly sensitive and selective detection of hypochlorous acid (HOCl). The probe is based on the specific HOCl-promoted oxidation of methyl phenyl sulfide. The reaction is accompanied by a 160-fold increase in the fluorescent quantum yield (from 0.003 to 0.480). The fluorescent turn-on mechanism is accomplished by suppression of photoinduced electron transfer (PET) from the methyl phenyl sulfide group to BODIPY. The fluorescence intensity of the reaction between HOCl and HCS shows a good linearity in the HOCl concentration range 1–10 μM. The detection limit is 23.7 nM (S/N = 3). In addition, confocal fluorescence microscopy imaging using RAW264.7 macrophages demonstrates that the HCS probe could be an efficient fluorescent detector for HOCl in living cells

  12. Hypochlorous acid turn-on boron dipyrromethene probe based on oxidation of methyl phenyl sulfide

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Shi-Rong; Vedamalai, Mani; Wu, Shu-Pao, E-mail: spwu@mail.nctu.edu.tw

    2013-10-24

    Graphical abstract: -- Highlights: •A BODIPY-based green fluorescent probe for sensing HOCl was developed. •The probe utilizes HOCl-promoted oxidation of methyl phenyl sulfide to produce a proportional fluorescence response to the concentration of HOCl. •Confocal fluorescence microscopy imaging of RAW264.7 cells demonstrated that the HCS probe might have application in the investigation of HOCl roles in biological systems. -- Abstract: A boron dipyrromethene (BODIPY)-based fluorometric probe, HCS, has been successfully developed for the highly sensitive and selective detection of hypochlorous acid (HOCl). The probe is based on the specific HOCl-promoted oxidation of methyl phenyl sulfide. The reaction is accompanied by a 160-fold increase in the fluorescent quantum yield (from 0.003 to 0.480). The fluorescent turn-on mechanism is accomplished by suppression of photoinduced electron transfer (PET) from the methyl phenyl sulfide group to BODIPY. The fluorescence intensity of the reaction between HOCl and HCS shows a good linearity in the HOCl concentration range 1–10 μM. The detection limit is 23.7 nM (S/N = 3). In addition, confocal fluorescence microscopy imaging using RAW264.7 macrophages demonstrates that the HCS probe could be an efficient fluorescent detector for HOCl in living cells.

  13. Dimethyl sulfide: Less important than long-range transport as a source of sulfate to the remote tropical Pacific marine boundary layer

    Science.gov (United States)

    Simpson, Rebecca M. C.; Howell, Steven G.; Blomquist, Byron W.; Clarke, Antony D.; Huebert, Barry J.

    2014-07-01

    During the Pacific Atmospheric Sulfur Experiment (PASE), dimethyl sulfide (DMS) was not the principal source of non-sea salt sulfate (NSS) mass in the remote marine boundary layer (MBL), according to an Eulerian sulfur budget based on observations of chemical concentrations from the NCAR C-130 in relatively dry, subsiding regions of the tropical Pacific. Our three (DMS, SO2, and NSS) monthly-average budgets are mutually consistent. The PASE-average DMS emission was 3.0 ± 0.5μmol m-2 d-1 (our budget "units"). SO2 sources include DMS + OH (1.4 ± 0.4 units, assuming 75% of reacted DMS forms SO2) and entrainment from the free troposphere (FT) (0.8 ± 0.2 units). Clouds were the most important chemical reactors for SO2 (-1.0 ± 0.5 units). SO2 loss terms also include divergence (-0.9 ± 0.3 units), dry deposition (-0.5 ± 0.2 units), and OH + SO2 (-0.22 ± 0.05 units). The total SO2 loss balanced the SO2 source. We assume that no SO2 was lost to ozone oxidation on sea salt particles; we found negligible NSS on particles from 2.6 μm (the sea salt mass peak) to 10 μm diameter. Fine-particle NSS sources include in-cloud oxidation of SO2 by H2O2 (1.0 ± 0.5 units), OH + SO2 (0.19 ± 0.05 units), and entrainment (1.1 ± 0.3 units in clean conditions; twice that when continental pollution is present). NSS sources balance NSS loss to divergence. Only about one fourth of emitted DMS becomes NSS. FT entrainment supplied two thirds and DMS oxidation produced one third of MBL NSS, rather similar source terms.

  14. Sulfate Reduction at pH 4.0 for Treatment of Process and Wastewaters

    NARCIS (Netherlands)

    Bijmans, M.F.M.; Vries, de E.; Yang, C.H.; Buisman, C.J.N.; Lens, P.N.L.; Dopson, M.

    2010-01-01

    Acidic industrial process and wastewaters often contain high sulfate and metal concentrations and their direct biological treatment is thus far not possible as biological processes at pH <5 have been neglected. Sulfate-reducing bacteria convert sulfate to sulfide that can subsequently be used to

  15. Effect of growth conditions on microbial activity and iron-sulfide production by Desulfovibrio vulgaris

    International Nuclear Information System (INIS)

    Zhou, Chen; Vannela, Raveender; Hayes, Kim F.; Rittmann, Bruce E.

    2014-01-01

    Highlights: • Extended incubation time to 16 days allowed significant FeS crystallization. • A weakly acidic pH greatly enhanced particle growth of mackinawite. • Microbial metabolism of different donors systematically altered the ambient pH. • Greater sulfide accumulation stimulated mackinawite transformation to greigite. - Abstract: Sulfate-reducing bacteria (SRB) can produce iron sulfide (FeS) solids with mineralogical characteristics that may be beneficial for a variety of biogeochemical applications, such as long-term immobilization of uranium. In this study, the growth and metabolism of Desulfovibrio vulgaris, one of the best-studied SRB species, were comprehensively monitored in batch studies, and the biogenic FeS solids were characterized by X-ray diffraction. Controlling the pH by varying the initial pH, the iron-to-sulfate ratio, or the electron donor – affected the growth of D. vulgaris and strongly influenced the formation and growth of FeS solids. In particular, lower pH (from initial conditions or a decrease caused by less sulfate reduction, FeS precipitation, or using pyruvate as the electron donor) produced larger-sized mackinawite (Fe 1+x S). Greater accumulation of free sulfide, from more sulfate reduction by D. vulgaris, also led to larger-sized mackinawite and particularly stimulated mackinawite transformation to greigite (Fe 3 S 4 ) when the free sulfide concentration was 29.3 mM. Furthermore, sufficient free Fe 2+ led to the additional formation of vivianite [Fe 3 (PO 4 ) 2 ·8(H 2 O)]. Thus, microbially relevant conditions (initial pH, choice of electron donor, and excess or deficiency of sulfide) are tools to generate biogenic FeS solids of different characteristics

  16. Acid Sulfate Alteration in Gusev Crater, Mars

    Science.gov (United States)

    Morris, R. V.; Ming, D. W.; Catalano, J. G.

    2016-01-01

    dust. The Moessbauer parameters are not definitive for mineralogical speciation (other than octahedrally-coordinated Fe(3+) but are consistent with a schwertmannite-like phase (i.e., a nanophase ferric oxide). The high oxidation state and values of Moessbauer parameters (center shift and quadrupole splitting) for the high-SO3 samples imply ferric sulfate (i.e., oxidized sulfur), although the hydration state cannot be constrained. In no case is there an excess of SO3 over available cations (i.e., no evidence for elemental sulfur), and Fe sulfide (pyrite) has been detected in only one Gusev sample. The presence of both high-SiO2 (and low total iron and SO3) and high SO3 (and high total iron as ferric sulfate) can be accommodated by a two-step geochemical model developed with the Geochemist's Workbench. (1) Step 1 is anoxic acid sulfate leaching of Martian basalt at high water-to rock ratios (greater than 70). The result is a high-SiO2 residue0, and anoxic conditions are required to solubilize Fe as Fe(2+). (2) Step 2 is the oxic precipitation of sulfate salts from the leachate. Oxic conditions are required to produce the high concentrations of ferric sulfate with minor Mg-sulfates and no detectable Fe(2+)-sulfates.

  17. Optimization of biological sulfide removal in a CSTR bioreactor.

    Science.gov (United States)

    Roosta, Aliakbar; Jahanmiri, Abdolhossein; Mowla, Dariush; Niazi, Ali; Sotoodeh, Hamidreza

    2012-08-01

    In this study, biological sulfide removal from natural gas in a continuous bioreactor is investigated for estimation of the optimal operational parameters. According to the carried out reactions, sulfide can be converted to elemental sulfur, sulfate, thiosulfate, and polysulfide, of which elemental sulfur is the desired product. A mathematical model is developed and was used for investigation of the effect of various parameters on elemental sulfur selectivity. The results of the simulation show that elemental sulfur selectivity is a function of dissolved oxygen, sulfide load, pH, and concentration of bacteria. Optimal parameter values are calculated for maximum elemental sulfur selectivity by using genetic algorithm as an adaptive heuristic search. In the optimal conditions, 87.76% of sulfide loaded to the bioreactor is converted to elemental sulfur.

  18. Algae as an electron donor promoting sulfate reduction for the bioremediation of acid rock drainage

    Energy Technology Data Exchange (ETDEWEB)

    Ayala-Parra, Pedro; Sierra-Alvarez, Reyes; Field, Jim A., E-mail: jimfield@email.arizona.edu

    2016-11-05

    Highlights: • Algal biomass can serve as an electron donor to drive reduction of sulfate to sulfide. • Biogenic sulfide precipitates Cu{sup 2+} as stable sulfide mineral. • Cu{sup +2} removal in sulfidogenic bioreactors amended with algal biomass exceeded 99.5%. • Acidity in synthetic acid rock drainage was consumed by sulfate reduction. - Abstract: This study assessed bioremediation of acid rock drainage in simulated permeable reactive barriers (PRB) using algae, Chlorella sorokiniana, as the sole electron donor for sulfate-reducing bacteria. Lipid extracted algae (LEA), the residues of biodiesel production, were compared with whole cell algae (WCA) as an electron donor to promote sulfate-reducing activity. Inoculated columns containing anaerobic granular sludge were fed a synthetic medium containing H{sub 2}SO{sub 4} and Cu{sup 2+}. Sulfate, sulfide, Cu{sup 2+} and pH were monitored throughout the experiment of 123 d. Cu recovered in the column packing at the end of the experiment was evaluated using sequential extraction. Both WCA and LEA promoted 80% of sulfate removal (12.7 mg SO{sub 4}{sup 2−} d{sup −1}) enabling near complete Cu removal (>99.5%) and alkalinity generation raising the effluent pH to 6.5. No noteworthy sulfate reduction, alkalinity formation and Cu{sup 2+} removal were observed in the endogenous control. In algae amended-columns, Cu{sup 2+} was precipitated with biogenic H{sub 2}S produced by sulfate reduction. Formation of CuS was evidenced by sequential extraction and X-ray diffraction. LEA and WCA provided similar levels of electron donor based on the COD balance. The results demonstrate an innovative passive remediation system using residual algae biomass from the biodiesel industry.

  19. Hydrogen sulfide in plants: from dissipation of excess sulfur to signaling molecule.

    Science.gov (United States)

    Calderwood, Alexander; Kopriva, Stanislav

    2014-09-15

    Sulfur is essential in all organisms for the synthesis of amino acids cysteine and methionine and as an active component of numerous co-factors and prosthetic groups. However, only plants, algae, fungi, and some prokaryotes are capable of using the abundant inorganic source of sulfur, sulfate. Plants take sulfate up, reduce it, and assimilate into organic compounds with cysteine being the first product of the pathway and a donor of reduced sulfur for synthesis of other S-containing compounds. Cysteine is formed in a reaction between sulfide, derived from reduction of sulfite and an activated amino acid acceptor, O-acetylserine. Sulfide is thus an important intermediate in sulfur metabolism, but numerous other functions in plants has been revealed. Hydrogen sulfide can serve as an alternative source of sulfur for plants, which may be significant in anaerobic conditions of waterlogged soils. On the other hand, emissions of hydrogen sulfide have been detected from many plant species. Since the amount of H2S discharged correlated with sulfate supply to the plants, the emissions were considered a mechanism for dissipation of excess sulfur. Significant hydrogen sulfide emissions were also observed in plants infected with pathogens, particularly with fungi. H2S thus seems to be part of the widely discussed sulfur-induced-resistance/sulfur-enhanced-defense. Recently, however, more evidence has emerged for a role for H2S in regulation and signaling. Sulfide stabilizes the cysteine synthase complex, increasing so the synthesis of its acceptor O-acetylserine. H2S has been implicating in regulation of plant stress response, particularly draught stress. There are more and more examples of processes regulated by H2S in plants being discovered, and hydrogen sulfide is emerging as an important signaling molecule, similar to its role in the animal and human world. How similar the functions, and homeostasis of H2S are in these diverse organisms, however, remains to be elucidated

  20. Ferrous sulfate, but not iron polymaltose complex, aggravates local and systemic inflammation and oxidative stress in dextran sodium sulfate-induced colitis in rats

    Directory of Open Access Journals (Sweden)

    Toblli JE

    2015-05-01

    Full Text Available Jorge E Toblli, Gabriel Cao, Margarita Angerosa Laboratory of Experimental Medicine, Hospital Alemán, School of Medicine, University of Buenos Aires, Buenos Aires, Argentina Background and aims: Iron deficiency is common in inflammatory bowel disease, yet oral iron therapy may worsen the disease symptoms and increase systemic and local oxidative stress. The aim of this study was to compare the effects of oral ferrous sulfate and iron polymaltose complex on inflammatory and oxidative stress markers in colitic rats.Methods: Animals were divided into four groups with ten animals each. Rats of three groups received dextran sodium sulfate to induce colitis and animals of two of these groups received 5 mg iron/kg of body weight a day, as ferrous sulfate or iron polymaltose complex, for 7 days. Gross colon anatomy, histology of colon and liver, stainings of L-ferritin, Prussian blue, hepcidin, tumor necrosis factor-α, and interleukin-6, as well serum levels of liver enzymes, inflammatory markers, and iron markers, were assessed.Results: Body weight, gross anatomy, crypt injury and inflammation scores, inflammatory parameters in liver and colon, as well as serum and liver hepcidin levels were not significantly different between colitic animals without iron treatment and colitic animals treated with iron polymaltose complex. In contrast, ferrous sulfate treatment caused significant worsening of these parameters. As opposed to ferrous sulfate, iron polymaltose complex caused less or no additional oxidative stress in the colon and liver compared to colitic animals without iron treatment.Conclusion: Iron polymaltose complex had negligible effects on colonic tissue erosion, local or systemic oxidative stress, and local or systemic inflammation, even at high therapeutic doses, and may thus represent a valuable oral treatment of iron deficiency in inflammatory bowel disease. Keywords: preclinical, oral iron treatment, tolerability, colonic tissue erosion

  1. Replacive sulfide formation in anhydrite chimneys from the Pacmanus hydrothermal field, Papua New Guinea

    Science.gov (United States)

    Los, Catharina; Bach, Wolfgang; Plümper, Oliver

    2016-04-01

    Hydrothermal flow within the oceanic crust is an important process for the exchange of energy and mass between the lithosphere, hydrosphere and biosphere. Infiltrated seawater heats up and interacts with wall rock, causing mineral replacement reactions. These play a large role in the formation of ore deposits; at the discharge zone, a hot, acidic and metal-rich potential ore fluid exits the crust. It mixes with seawater and forms chimneys, built up of sulfate minerals such as anhydrite (CaSO4), which are subsequently replaced by sulfide minerals. Sulfide formation is related to fluid pathways, defined by cracks and pores in the sulfate chimney. Over time, these systems might develop into massive sulfide deposits. The big question is then: how is sulfate-sulfide replacement related to the evolution of rock porosity? To address this question, sulfide-bearing anhydrite chimneys from the Pacmanus hydrothermal field (Manus Basin, Papua New Guinea) were studied using X-ray tomography, EMPA, FIB-SEM and -TEM. The apparently massive anhydrite turns out highly porous on the micro scale, with sulfide minerals in anhydrite cleavage planes and along grain boundaries. The size of the sulfide grains relates to the pores they grew into, suggesting a tight coupling between dissolution (porosity generation) and growth of replacive minerals. Some of the sulfide grains are hollow and apparently used the dissolving anhydrite as a substrate to start growth in a pore. Another mode of sulfide development is aggregates of euhedral pyrite cores surrounded by colloform chalcopyrite. This occurrence implies that fluid pathways have remained open for some time to allow several stages of precipitation during fluid evolution. To start the replacement and to keep it going, porosity generation is crucial. Our samples show that dissolution of anhydrite occurred along pathways where fluid could enter, such as cleavage planes and grain boundaries. It appears that fluids ascending within the inner

  2. Metal and acidity fluxes controlled by precipitation/dissolution cycles of sulfate salts in an anthropogenic mine aquifer.

    Science.gov (United States)

    Cánovas, C R; Macías, F; Pérez-López, R

    2016-05-01

    Underground mine drainages are extremely difficult to study due to the lack of information about the flow path and source proximity in relation to the outflow adit. Geochemical processes controlling metals and acidity fluxes in a complex anthropogenic mine aquifer in SW Spain during the dry and rainy season were investigated by geochemical and statistical tools. High concentrations of acidity, sulfate, metals and metalloids (e.g. Fe, Cu, Zn, As, Cd, Ni, Co) were observed due to intense sulfide oxidation processes. The high residence time inside the anthropogenic aquifer, around 40days, caused the release of significant quantities of metals linked to host rocks (e.g. Al, Ca, Ge, Li, Mg, REE). The most outstanding characteristic of the acid mine drainage (AMD) outflows is the existence of higher Fe/SO4 molar ratios than those theoretical of pyrite (0.50) during most of the monitored period, due to a fire which occurred in 1949 and remained active for decades. Permanent and temporal retention mechanisms of acidity and metals were observed in the galleries. Once released from sulfide oxidation, Pb and As are sorbed on Fe oxyhydroxysulfate or precipitated as low solubility minerals (i.e. anglesite) inside the galleries. The precipitation of evaporitic sulfate salts during the dry season and the subsequent re-dissolution after rainfall control the fluxes of acidity and main metals (i.e. Fe, Mg, Al) from this anthropogenic aquifer. Some elements, such as Cd, Cu, Ni, REE and Zn, are retained in highly soluble sulfate salts while other elements, such as Ge, Pb and Sc, have a lower response to washout processes due to its incorporation in less soluble sulfate salts. In this way, metal concentration during the washout processes would be controlled by the proportion and solubility of each type of evaporitic sulfate salt stored during the dry season. The recovery of metals of economic interest contained in the AMD could help to self-finance the remediation of these waters in

  3. Microbial sulfate reduction and metal attenuation in pH 4 acid mine water

    Directory of Open Access Journals (Sweden)

    Alpers Charles N

    2007-10-01

    Full Text Available Abstract Sediments recovered from the flooded mine workings of the Penn Mine, a Cu-Zn mine abandoned since the early 1960s, were cultured for anaerobic bacteria over a range of pH (4.0 to 7.5. The molecular biology of sediments and cultures was studied to determine whether sulfate-reducing bacteria (SRB were active in moderately acidic conditions present in the underground mine workings. Here we document multiple, independent analyses and show evidence that sulfate reduction and associated metal attenuation are occurring in the pH-4 mine environment. Water-chemistry analyses of the mine water reveal: (1 preferential complexation and precipitation by H2S of Cu and Cd, relative to Zn; (2 stable isotope ratios of 34S/32S and 18O/16O in dissolved SO4 that are 2–3 ‰ heavier in the mine water, relative to those in surface waters; (3 reduction/oxidation conditions and dissolved gas concentrations consistent with conditions to support anaerobic processes such as sulfate reduction. Scanning electron microscope (SEM analyses of sediment show 1.5-micrometer, spherical ZnS precipitates. Phospholipid fatty acid (PLFA and denaturing gradient gel electrophoresis (DGGE analyses of Penn Mine sediment show a high biomass level with a moderately diverse community structure composed primarily of iron- and sulfate-reducing bacteria. Cultures of sediment from the mine produced dissolved sulfide at pH values near 7 and near 4, forming precipitates of either iron sulfide or elemental sulfur. DGGE coupled with sequence and phylogenetic analysis of 16S rDNA gene segments showed populations of Desulfosporosinus and Desulfitobacterium in Penn Mine sediment and laboratory cultures.

  4. Microbial sulfate reduction and metal attenuation in pH 4 acid mine water

    Science.gov (United States)

    Church, C.D.; Wilkin, R.T.; Alpers, Charles N.; Rye, R.O.; Blaine, R.B.

    2007-01-01

    Sediments recovered from the flooded mine workings of the Penn Mine, a Cu-Zn mine abandoned since the early 1960s, were cultured for anaerobic bacteria over a range of pH (4.0 to 7.5). The molecular biology of sediments and cultures was studied to determine whether sulfate-reducing bacteria (SRB) were active in moderately acidic conditions present in the underground mine workings. Here we document multiple, independent analyses and show evidence that sulfate reduction and associated metal attenuation are occurring in the pH-4 mine environment. Water-chemistry analyses of the mine water reveal: (1) preferential complexation and precipitation by H2S of Cu and Cd, relative to Zn; (2) stable isotope ratios of 34S/32S and 18O/16O in dissolved SO4 that are 2-3 ??? heavier in the mine water, relative to those in surface waters; (3) reduction/oxidation conditions and dissolved gas concentrations consistent with conditions to support anaerobic processes such as sulfate reduction. Scanning electron microscope (SEM) analyses of sediment show 1.5-micrometer, spherical ZnS precipitates. Phospholipid fatty acid (PLFA) and denaturing gradient gel electrophoresis (DGGE) analyses of Penn Mine sediment show a high biomass level with a moderately diverse community structure composed primarily of iron- and sulfate-reducing bacteria. Cultures of sediment from the mine produced dissolved sulfide at pH values near 7 and near 4, forming precipitates of either iron sulfide or elemental sulfur. DGGE coupled with sequence and phylogenetic analysis of 16S rDNA gene segments showed populations of Desulfosporosinus and Desulfitobacterium in Penn Mine sediment and laboratory cultures. ?? 2007 Church et al; licensee BioMed Central Ltd.

  5. Role of dissimilatory sulfate reduction in wetlands constructed for acid coal mine drainage (AMD) treatment. Master's thesis

    International Nuclear Information System (INIS)

    Taddeo, F.J.

    1991-01-01

    Five constructed wetlands with different organic substrates were exposed to the same quantity/quality of acid mine drainage (AMD). During the 16-month exposure to AMD, all wetlands accumulated S in the forms of organic and reduced inorganic S and Fe in the form of iron sulfides. Iron sulfide and probably most of the organic S(C-bonded S) accumulation were end products of bacterial dissimilatory sulfate reduction. Results of study support the notion that sulfate reduction and accumulation of Fe sulfides contribute to Fe retention in wetlands exposed to AMD. Detailed information is provided

  6. Quantification and isotopic analysis of intracellular sulfur metabolites in the dissimilatory sulfate reduction pathway

    Science.gov (United States)

    Sim, Min Sub; Paris, Guillaume; Adkins, Jess F.; Orphan, Victoria J.; Sessions, Alex L.

    2017-06-01

    Microbial sulfate reduction exhibits a normal isotope effect, leaving unreacted sulfate enriched in 34S and producing sulfide that is depleted in 34S. However, the magnitude of sulfur isotope fractionation is quite variable. The resulting changes in sulfur isotope abundance have been used to trace microbial sulfate reduction in modern and ancient ecosystems, but the intracellular mechanism(s) underlying the wide range of fractionations remains unclear. Here we report the concentrations and isotopic ratios of sulfur metabolites in the dissimilatory sulfate reduction pathway of Desulfovibrio alaskensis. Intracellular sulfate and APS levels change depending on the growth phase, peaking at the end of exponential phase, while sulfite accumulates in the cell during stationary phase. During exponential growth, intracellular sulfate and APS are strongly enriched in 34S. The fractionation between internal and external sulfate is up to 49‰, while at the same time that between external sulfate and sulfide is just a few permil. We interpret this pattern to indicate that enzymatic fractionations remain large but the net fractionation between sulfate and sulfide is muted by the closed-system limitation of intracellular sulfate. This 'reservoir effect' diminishes upon cessation of exponential phase growth, allowing the expression of larger net sulfur isotope fractionations. Thus, the relative rates of sulfate exchange across the membrane versus intracellular sulfate reduction should govern the overall (net) fractionation that is expressed. A strong reservoir effect due to vigorous sulfate reduction might be responsible for the well-established inverse correlation between sulfur isotope fractionation and the cell-specific rate of sulfate reduction, while at the same time intraspecies differences in sulfate uptake and/or exchange rates could account for the significant scatter in this relationship. Our approach, together with ongoing investigations of the kinetic isotope

  7. Hydrogen production through microheterogeneous photocatalysis of hydrogen sulfide cleavage. The thiosulfate cycle

    Energy Technology Data Exchange (ETDEWEB)

    Borgarello, E; Serpone, N; Graetzel, M; Pelizzetti, E

    1985-01-01

    Cleavage of hydrogen sulfide into hydrogen and sulfur occurs in alkaline aqueous CdS dispersions under visible light illumination. Small quantities of a noble metal catalyst (RuO/sub 2/) loaded onto 'naked' CdS particles markedly improve the yield of hydrogen formation. The effect of RuO/sub 2/ is ascribed to catalysis of electron transfer to proton. Simultaneous and efficient photogeneration of hydrogen and thiosulfate occurs in CdS dispersions containing both sulfite and bisulfide (or sulfide) ions. Electron transfer from the conduction band of CdS to that of TiO/sub 2/ particles occurs in alkaline suspensions containing these HS/sup -/ ions and has been exploited to improve the performance of a system achieving decomposition of H/sub 2/S by visible light. Equally important is a recent finding that the performance of a system containing 'naked' CdS in combination with RuO/sub 2/-loaded TiO/sub 2/ particles is far better than that of CdS/RuO/sub 2/ alone. Additionally, conduction band electrons produced by bandgap excitation of TiO/sub 2/ particles efficiently reduce thiosulfate to sulfide and sulfite. The valence band process in alklaine TiO/sub 2/ dispersions is thought to involve oxidation of S/sub 2/O/sub 3//sup 2 -/ to tetrathionate, S/sub 4/O/sub 6//sup 2 -/, which quantitatively dismutates into sulfite and thiosulfate. The photodriven disproportionation of thiosulfate into sulfide and sulfate is of great interest in systems that photochemically cleave hydrogen sulfide into hydrogen and sulfur. (author).

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

    Energy Technology Data Exchange (ETDEWEB)

    Natesan, K. (Argonne National Lab., IL (USA)); Baxter, D.J. (Argonne National Lab., IL (USA) INCO Alloy Ltd., Hereford, England (UK))

    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.

  9. Measurement of chemical leaching potential of sulfate from landfill disposed sulfate containing wastes.

    Science.gov (United States)

    Sun, Wenjie; Barlaz, Morton A

    2015-02-01

    A number of sulfate-containing wastes are disposed in municipal solid wastes (MSW) landfills including residues from coal, wood, and MSW combustion, and construction and demolition (C&D) waste. Under anaerobic conditions that dominate landfills, the sulfate can be reduced to hydrogen sulfide which is problematic for several reasons including its low odor threshold, toxicity, and corrosive nature. The overall objective of this study was to evaluate existing protocols for the quantification of total leachable sulfate from solid samples and to compare their effectiveness and efficiency with a new protocol described in this study. Methods compared include two existing acid extraction protocols commonly used in the U.S., a pH neutral protocol that requires multiple changes of the leaching solution, and a new acid extraction method. The new acid extraction method was shown to be simple and effective to measure the leaching potential of sulfate from a range of landfill disposed sulfate-containing wastes. However, the acid extraction methods do not distinguish between sulfate and other forms of sulfur and are thus most useful when sulfate is the only form of sulfur present. Copyright © 2014 Elsevier Ltd. All rights reserved.

  10. Aerobic transformation of cadmium through metal sulfide biosynthesis in photosynthetic microorganisms.

    Science.gov (United States)

    Edwards, Chad D; Beatty, Joseph C; Loiselle, Jacqueline B R; Vlassov, Katya A; Lefebvre, Daniel D

    2013-07-15

    Cadmium is a non-essential metal that is toxic because of its interference with essential metals such as iron, calcium and zinc causing numerous detrimental metabolic and cellular effects. The amount of this metal in the environment has increased dramatically since the advent of the industrial age as a result of mining activities, the use of fertilizers and sewage sludge in farming, and discharges from manufacturing activities. The metal bioremediation utility of phototrophic microbes has been demonstrated through their ability to detoxify Hg(II) into HgS under aerobic conditions. Metal sulfides are generally very insoluble and therefore, biologically unavailable. When Cd(II) was exposed to cells it was bioconverted into CdS by the green alga Chlamydomonas reinhardtii, the red alga Cyanidioschyzon merolae, and the cyanobacterium, Synechoccocus leopoliensis. Supplementation of the two eukaryotic algae with extra sulfate, but not sulfite or cysteine, increased their cadmium tolerances as well as their abilities to produce CdS, indicating an involvement of sulfate assimilation in the detoxification process. However, the combined activities of extracted serine acetyl-transferase (SAT) and O-acetylserine(thiol)lyase (OASTL) used to monitor sulfate assimilation, was not significantly elevated during cell treatments that favored sulfide biosynthesis. It is possible that the prolonged incubation of the experiments occurring over two days could have compensated for the low rates of sulfate assimilation. This was also the case for S. leopoliensis where sulfite and cysteine as well as sulfate supplementation enhanced CdS synthesis. In general, conditions that increased cadmium sulfide production also resulted in elevated cysteine desulfhydrase activities, strongly suggesting that cysteine is the direct source of sulfur for CdS synthesis. Cadmium(II) tolerance and CdS formation were significantly enhanced by sulfate supplementation, thus indicating that algae and cyanobacteria

  11. Isolation and characterization of a mesophilic heavy-metals-tolerant sulfate-reducing bacterium Desulfomicrobium sp. from an enrichment culture using phosphogypsum as a sulfate source

    International Nuclear Information System (INIS)

    Azabou, Samia; Mechichi, Tahar; Patel, Bharat K.C.; Sayadi, Sami

    2007-01-01

    A sulfate-reducing bacterium, was isolated from a 6 month trained enrichment culture in an anaerobic media containing phosphogypsum as a sulfate source, and, designated strain SA2. Cells of strain SA2 were rod-shaped, did not form spores and stained Gram-negative. Phylogenetic analysis of the 16S rRNA gene sequence of the isolate revealed that it was related to members of the genus Desulfomicrobium (average sequence similarity of 98%) with Desulfomicrobium baculatum being the most closely related (sequence similarity of 99%). Strain SA2 used thiosulfate, sulfate, sulfite and elemental sulfur as electron acceptors and produced sulfide. Strain SA2 reduced sulfate contained in 1-20 g/L phosphogypsum to sulfide with reduction of sulfate contained in 2 g/L phosphogypsum being the optimum concentration. Strain SA2 grew with metalloid, halogenated and non-metal ions present in phosphogypsum and with added high concentrations of heavy metals (125 ppm Zn and 100 ppm Ni, W, Li and Al). The relative order for the inhibitory metal concentrations, based on the IC 50 values, was Cu, Te > Cd > Fe, Co, Mn > F, Se > Ni, Al, Li > Zn

  12. Sorption of chromium(III) and chromium(VI) on lead sulfide

    International Nuclear Information System (INIS)

    Music, S.

    1985-01-01

    The sorption of chromium(III) and chromium(VI) on lead sulfide was investigated in dependence on pH, time of sorption, and on the concnetrations of sorbate and sorbent. The mechanisms of the sorption of Crsup(3+) and CrOsub(4)sup(2-) traces on lead sulfide are discussed; a difference between CrOsub(4)sup(2-) sorption on PbS and α-Fesub(2)Osub(3) was found. Sulfates and molybdates affect the removal of chromates from aqueous solutions. Lead sulfide carrier prepared in this work was also used for the preconcentration of chromium(III) and chromium(VI) from tap water. (author)

  13. Reduction of sulfate by hydrogen in natural systems: A literature review: Salt Repository Project

    International Nuclear Information System (INIS)

    Mahoney, J.J.; Strachan, D.M.

    1988-01-01

    The results of this literature search indicate that the reduction of sulfate by hydrogen gas can occur in nature, but that temperature appears to be a key factor in the rate of this reaction. At temperatures below 200/degree/C, the key factor in the rate of reaction appears to be extremely slow. At low pH the rate of reaction is faster than at high pH. The solution composition also influences the reaction rate; the most recent research available (Yanisagawa 1983) suggests that the concentration of sulfide in solution influences the rate of this reaction. The reduction reaction appears to proceed through a thiosulfate intermediate, so the presence and distribution of other sulfur species will influence the reaction rate. If the reaction mechanism proposed by Yanisagawa is correct, then higher concentrations of sulfide will result in faster rates of sulfate reduction. In conclusion, the reduction of sulfate by hydrogen to form significant amounts of sulfide is a function of temperature, sulfate and sulfide concentrations, pH, and solution composition. The rate of this reaction appears to be very slow under the conditions anticipated in this repository, but given the length of time required to maintain the integrity of the containers (300 to 1000 years) and the unusual solution compositions present, a better understanding of the reaction mechanism is needed. 16 refs., 1 tab

  14. Influence of Water Salinity on Air Purification from Hydrogen Sulfide

    Directory of Open Access Journals (Sweden)

    Leybovych L.I.

    2015-12-01

    Full Text Available Mathematical modeling of «sliding» water drop motion in the air flow was performed in software package FlowVision. The result of mathematical modeling of water motion in a droplet with diameter 100 microns at the «sliding» velocity of 15 m/s is shown. It is established that hydrogen sulfide oxidation occurs at the surface of phases contact. The schematic diagram of the experimental setup for studying air purification from hydrogen sulfide is shown. The results of the experimental research of hydrogen sulfide oxidation by tap and distilled water are presented. The dependence determining the share of hydrogen sulfide oxidized at the surface of phases contact from the dimensionless initial concentration of hydrogen sulfide in the air has been obtained.

  15. Large scale disposal of waste sulfur: From sulfide fuels to sulfate sequestration

    International Nuclear Information System (INIS)

    Rappold, T.A.; Lackner, K.S.

    2010-01-01

    Petroleum industries produce more byproduct sulfur than the market can absorb. As a consequence, most sulfur mines around the world have closed down, large stocks of yellow sulfur have piled up near remote operations, and growing amounts of toxic H 2 S are disposed of in the subsurface. Unless sulfur demand drastically increases or thorough disposal practices are developed, byproduct sulfur will persist as a chemical waste problem on the scale of 10 7 tons per year. We review industrial practices, salient sulfur chemistry, and the geochemical cycle to develop sulfur management concepts at the appropriate scale. We contend that the environmentally responsible disposal of sulfur would involve conversion to sulfuric acid followed by chemical neutralization with equivalent amounts of base, which common alkaline rocks can supply cheaply. The resulting sulfate salts are benign and suitable for brine injection underground or release to the ocean, where they would cause minimal disturbance to ecosystems. Sequestration costs can be recouped by taking advantage of the fuel-grade thermal energy released in the process of oxidizing reduced compounds and sequestering the products. Sulfate sequestration can eliminate stockpiles and avert the proliferation of enriched H 2 S stores underground while providing plenty of carbon-free energy to hydrocarbon processing.

  16. Effect of hydraulic retention time on metal precipitation in sulfate reducing inverse fluidized bed reactors

    KAUST Repository

    Villa-Gó mez, Denys Kristalia; Enright, Anne Marie; Rini, Eki Listya; Buttice, Audrey L.; Kramer, Herman J M; Lens, Piet Nl L

    2014-01-01

    BACKGROUND: Metal sulfide recovery in sulfate reducing bioreactors is a challenge due to the formation of small precipitates with poor settling properties. The size of the metal sulfide precipitates with the change in operational parameters

  17. Carbon isotope fractionation by sulfate-reducing bacteria using different pathways for the oxidation of acetate.

    Science.gov (United States)

    Goevert, Dennis; Conrad, Ralf

    2008-11-01

    Acetate is a key intermediate in the anaerobic degradation of organic matter. In anoxic environments, available acetate is a competitive substrate for sulfate-reducing bacteria (SRB) and methane-producing archaea. Little is known about the fractionation of carbon isotopes by sulfate reducers. Therefore, we determined carbon isotope compositions in cultures of three acetate-utilizing SRB, Desulfobacter postgatei, Desulfobacter hydrogenophilus, and Desulfobacca acetoxidans. We found that these species showed strong differences in their isotope enrichment factors (epsilon) of acetate. During the consumption of acetate and sulfate, acetate was enriched in 13C by 19.3% per hundred in Desulfobacca acetoxidans. By contrast, both D. postgatei and D. hydrogenophilus showed a slight depletion of 13C resulting in epsilon(ac)-values of 1.8 and 1.5% per hundred, respectively. We suggest that the different isotope fractionation is due to the different metabolic pathways for acetate oxidation. The strongly fractionating Desulfobacca acetoxidans uses the acetyl-CoA/carbon monoxide dehydrogenase pathway, which is also used by acetoclastic methanogens that show a similar fractionation of acetate (epsilon(ac) = -21 to -27% per hundred). In contrast, Desulfobacter spp. oxidize acetate to CO2 via the tricarboxylic acid (TCA) cycle and apparently did not discriminate against 13C. Our results suggestthat carbon isotope fractionation in environments with sulfate reduction will strongly depend on the composition of the sulfate-reducing bacterial community oxidizing acetate.

  18. Enhanced sulfidation xanthate flotation of malachite using ammonium ions as activator.

    Science.gov (United States)

    Wu, Dandan; Ma, Wenhui; Mao, Yingbo; Deng, Jiushuai; Wen, Shuming

    2017-05-18

    In this study, ammonium ion was used to enhance the sulfidation flotation of malachite. The effect of ammonium ion on the sulfidation flotation of malachite was investigated using microflotation test, inductively coupled plasma (ICP) analysis, zeta potential measurements, and scanning electron microscope analysis (SEM). The results of microflotation test show that the addition of sodium sulfide and ammonium sulfate resulted in better sulfidation than the addition of sodium sulfide alone. The results of ICP analysis indicate that the dissolution of enhanced sulfurized malachite surface is significantly decreased. Zeta potential measurements indicate that a smaller isoelectric point value and a large number of copper-sulfide films formed on the malachite surface by enhancing sulfidation resulted in a large amount of sodium butyl xanthate absorbed onto the enhanced sulfurized malachite surface. EDS semi-quantitative analysis and XPS analysis show that malachite was easily sulfurized by sodium sulfide with ammonium ion. These results show that the addition of ammonium ion plays a significant role in the sulfidation of malachite and results in improved flotation performance.

  19. The nitrogen cycle in anaerobic methanotrophic mats of the Black Sea is linked to sulfate reduction and biomass decomposition.

    Science.gov (United States)

    Siegert, Michael; Taubert, Martin; Seifert, Jana; von Bergen-Tomm, Martin; Basen, Mirko; Bastida, Felipe; Gehre, Matthias; Richnow, Hans-Hermann; Krüger, Martin

    2013-11-01

    Anaerobic methanotrophic (ANME) mats host methane-oxidizing archaea and sulfate-reducing prokaryotes. Little is known about the nitrogen cycle in these communities. Here, we link the anaerobic oxidation of methane (AOM) to the nitrogen cycle in microbial mats of the Black Sea by using stable isotope probing. We used four different (15)N-labeled sources of nitrogen: dinitrogen, nitrate, nitrite and ammonium. We estimated the nitrogen incorporation rates into the total biomass and the methyl coenzyme M reductase (MCR). Dinitrogen played an insignificant role as nitrogen source. Assimilatory and dissimilatory nitrate reduction occurred. High rates of nitrate reduction to dinitrogen were stimulated by methane and sulfate, suggesting that oxidation of reduced sulfur compounds such as sulfides was necessary for AOM with nitrate as electron acceptor. Nitrate reduction to dinitrogen occurred also in the absence of methane as electron donor but at six times slower rates. Dissimilatory nitrate reduction to ammonium was independent of AOM. Ammonium was used for biomass synthesis under all conditions. The pivotal enzyme in AOM coupled to sulfate reduction, MCR, was synthesized from nitrate and ammonium. Results show that AOM coupled to sulfate reduction along with biomass decomposition drive the nitrogen cycle in the ANME mats of the Black Sea and that MCR enzymes are involved in this process. © 2013 Federation of European Microbiological Societies. Published by John Wiley & Sons Ltd. All rights reserved.

  20. Sulfide oxidation and acid mine drainage formation within two active tailings impoundments in the Golden Quadrangle of the Apuseni Mountains, Romania.

    Science.gov (United States)

    Sima, Mihaela; Dold, Bernhard; Frei, Linda; Senila, Marin; Balteanu, Dan; Zobrist, Jurg

    2011-05-30

    Sulfidic mine tailings have to be classified as one of the major source of hazardous materials leading to water contamination. This study highlights the processes leading to sulfide oxidation and acid mine drainage (AMD) formation in the active stage of two tailings impoundments located in the southern part of the Apuseni Mountains, in Romania, a well-known region for its long-term gold-silver and metal mining activity. Sampling was undertaken when both impoundments were still in operation in order to assess their actual stage of oxidation and long-term behavior in terms of the potential for acid mine drainage generation. Both tailings have high potential for AMD formation (2.5 and 3.7 wt.% of pyrite equivalent, respectively) with lesser amount of carbonates (5.6 and 3.6 wt.% of calcite equivalent) as neutralization potential (ABA=-55.6 and -85.1 tCaCO(3)/1000 t ) and showed clear signs of sulfide oxidation yet during operation. Sequential extraction results indicate a stronger enrichment and mobility of elements in the oxidized tailings: Fe as Fe(III) oxy-hydroxides and oxides (transformation from sulfide minerals, leaching in oxidation zone), Ca mainly in water soluble and exchangeable form where gypsum and calcite are dissolved and higher mobility of Cu for Ribita and Pb for Mialu. Two processes leading to the formation of mine drainage at this stage could be highlighted (1) a neutral Fe(II) plume forming in the impoundment with ferrihydrite precipitation at its outcrop and (2) acid mine drainage seeping in the unsaturated zone of the active dam, leading to the formation of schwertmannite at its outcrop. Copyright © 2011 Elsevier B.V. All rights reserved.

  1. Significant role of organic sulfur in supporting sedimentary sulfate reduction in low-sulfate environments

    Science.gov (United States)

    Fakhraee, Mojtaba; Li, Jiying; Katsev, Sergei

    2017-09-01

    Dissimilatory sulfate reduction (DSR) is a major carbon mineralization pathway in aquatic sediments, soils, and groundwater, which regulates the production of hydrogen sulfide and the mobilization rates of biologically important elements such as phosphorus and mercury. It has been widely assumed that water-column sulfate is the main sulfur source to fuel this reaction in sediments. While this assumption may be justified in high-sulfate environments such as modern seawater, we argue that in low-sulfate environments mineralization of organic sulfur compounds can be an important source of sulfate. Using a reaction-transport model, we investigate the production of sulfate from sulfur-containing organic matter for a range of environments. The results show that in low sulfate environments (50%) of sulfate reduction. In well-oxygenated systems, porewater sulfate profiles often exhibit sub-interface peaks so that sulfate fluxes are directed out of the sediment. Our measurements in Lake Superior, the world's largest lake, corroborate this conclusion: offshore sediments act as sources rather than sinks of sulfate for the water column, and sediment DSR is supported entirely by the in-sediment production of sulfate. Sulfate reduction rates are correlated to the depth of oxygen penetration and strongly regulated by the supply of reactive organic matter; rate co-regulation by sulfate availability becomes appreciable below 500 μM level. The results indicate the need to consider the mineralization of organic sulfur in the biogeochemical cycling in low-sulfate environments, including several of the world's largest freshwater bodies, deep subsurface, and possibly the sulfate-poor oceans of the Early Earth.

  2. Effect of sulfide, selenite and mercuric mercury on the growth and methylation capacity of the sulfate reducing bacterium Desulfovibrio desulfuricans

    Energy Technology Data Exchange (ETDEWEB)

    Truong, Hoang-Yen T. [Department of Biology, Laurentian University, Sudbury, Ontario, Canada P3E 2C6 (Canada); Department of Chemistry and Biochemistry, Laurentian University, Sudbury, Ontario, Canada P3E 2C6 (Canada); Chen, Yu-Wei [Department of Chemistry and Biochemistry, Laurentian University, Sudbury, Ontario, Canada P3E 2C6 (Canada); Belzile, Nelson, E-mail: nbelzile@laurentian.ca [Department of Chemistry and Biochemistry, Laurentian University, Sudbury, Ontario, Canada P3E 2C6 (Canada); Cooperative Freshwater Ecology Unit, Laurentian University, Sudbury, Ontario, Canada P3E 2C6 (Canada)

    2013-04-01

    Cultures of the sulfate reducing bacteria Desulfovibrio desulfuricans were grown under anoxic conditions to study the effect of added sulfide, selenite and mercuric ions. A chemical trap consisting in a CuSO{sub 4} solution was used to control the poisoning effect induced by the bacterial production of hydrogen sulfide via the precipitation of CuS. Following the addition of Hg{sup 2+}, the formation of methylmercury (MeHg) was correlated to bacterial proliferation with most of MeHg found in the culture medium. A large fraction (50–80%) of added Hg{sup 2+} to a culture ended up in a solid phase (Hg{sup 0} and likely HgS) limiting its bioavailability to cells with elemental Hg representing ∼ 40% of the solid. Following the addition of selenite, a small fraction was converted into Se(0) inside the cells and, even though the conversion to this selenium species increased with the increase of added selenite, it never reached more than 49% of the added amount. The formation of volatile dimethylselenide is suggested as another detoxification mechanism. In cultures containing both added selenite and mercuric ions, elemental forms of the two compounds were still produced and the increase of selenium in the residual fraction of the culture suggests the formation of mercuric selenite limiting the bioavailability of both elements to cells. - Highlights: ► Detoxification mechanisms of D. desulfuricans were studied in presence of added sulfide, selenite and mercuric ions. ► The poisoning effect of H{sub 2}S added to or generated by cultures of D. desulfuricans can be controlled with a chemical trap. ► The addition of selenite to cultures triggered the formation of elemental Se and other forms of volatile and non-volatile Se. ► The addition of mercuric ions to cultures led to the production of methylmercury, volatile Hg and solid mercuric sulfide. ► With both Se and Hg added to cultures, fractionation of species in solid and liquid phases suggests the formation of HgSe.

  3. Air oxidation of aqueous sodium sulfide solutions with coal fly ash

    Energy Technology Data Exchange (ETDEWEB)

    Mallik, D; Chaudhuri, S K [Southern Illinois University, Carbondale, IL (United States). Dept. of Mining Engineering

    1999-02-01

    The paper investigated the potential of coal fly ash as a catalyst in the air oxidation of aqueous sodium sulfide (Na{sub 2}S) solutions in the temperature range of 303-333 K. The rate of oxidation was found to be independent of the initial concentration of Na{sub 2}S in the range of 5.80 x 10{sup -2} - 28.45 x 10{sup -2} kmol/m{sup 3}. The effects of fly ash loading, source of fly ash, speed of agitation, air flow rate, fly ash particle size were also studied. Experimental results suggested a film-diffusion controlled reaction mechanism. The deactivation of the catalytic effect of fly ash was found to be less than 31% even after five repeated uses.

  4. Influence of pipe material and surfaces on sulfide related odor and corrosion in sewers.

    Science.gov (United States)

    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. Solid-solution partitioning and thionation of diphenylarsinic acid in a flooded soil under the impact of sulfate and iron reduction

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Meng [Key Laboratory of Coastal Environmental Processes and Ecological Remediation, Yantai Institute of Coastal Zone Research, Chinese Academy of Sciences, Yantai 264003 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Tu, Chen [Key Laboratory of Coastal Environmental Processes and Ecological Remediation, Yantai Institute of Coastal Zone Research, Chinese Academy of Sciences, Yantai 264003 (China); Hu, Xuefeng; Zhang, Haibo [Key Laboratory of Coastal Environmental Processes and Ecological Remediation, Yantai Institute of Coastal Zone Research, Chinese Academy of Sciences, Yantai 264003 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Zhang, Lijuan [Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800 (China); Wei, Jing [Key Laboratory of Coastal Environmental Processes and Ecological Remediation, Yantai Institute of Coastal Zone Research, Chinese Academy of Sciences, Yantai 264003 (China); Li, Yuan [Key Laboratory of Coastal Environmental Processes and Ecological Remediation, Yantai Institute of Coastal Zone Research, Chinese Academy of Sciences, Yantai 264003 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Luo, Yongming, E-mail: ymluo@yic.ac.cn [Key Laboratory of Coastal Environmental Processes and Ecological Remediation, Yantai Institute of Coastal Zone Research, Chinese Academy of Sciences, Yantai 264003 (China); Key Laboratory of Soil Environment and Pollution Remediation, Institute of Soil Science, Chinese Academy of Sciences, Nanjing 210008 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Christie, Peter [Key Laboratory of Soil Environment and Pollution Remediation, Institute of Soil Science, Chinese Academy of Sciences, Nanjing 210008 (China)

    2016-11-01

    Diphenylarsinic acid (DPAA) is a major organic arsenic (As) compound derived from abandoned chemical weapons. The solid-solution partitioning and transformation of DPAA in flooded soils are poorly understood but are of great concern. The identification of the mechanisms responsible for the mobilization and transformation of DPAA may help to develop effective remediation strategies. Here, soil and Fe mineral incubation experiments were carried out to elucidate the partitioning and transformation of DPAA in anoxic (without addition of sulfate or sodium lactate) and sulfide (with the addition of sulfate and sodium lactate) soil and to examine the impact of sulfate and Fe(III) reduction on these processes. Results show that DPAA was more effectively mobilized and thionated in sulfide soil than in anoxic soil. At the initial incubation stages (0–4 weeks), 6.7–74.5% of the total DPAA in sulfide soil was mobilized likely by sorption competition with sodium lactate. At later incubation stage (4–8 weeks), DPAA was almost completely released into the solution likely due to the near-complete Fe(III) reduction. Scanning transmission X-ray microscopy (STXM) results provide further direct evidence of elevated DPAA release coupled with Fe(III) reduction in sulfide environments. The total DPAA fraction decreased significantly to 24.5% after two weeks and reached 3.4% after eight weeks in sulfide soil, whereas no obvious elimination of DPAA occurred in anoxic soil at the initial two weeks and the total DPAA fraction decreased to 10.9% after eight weeks. This can be explained in part by the enhanced mobilization of DPAA and sulfate reduction in sulfide soil compared with anoxic soil. These results suggest that under flooded soil conditions, Fe(III) and sulfate reduction significantly promote DPAA mobilization and thionation, respectively, and we suggest that it is essential to consider both sulfate and Fe(III) reduction to further our understanding of the environmental fate of

  6. Mechanisms and Effectivity of Sulfate Reducing Bioreactors ...

    Science.gov (United States)

    Mining-influenced water (MIW) is the main environmental challenges associated with the mining industry. Passive MIW remediation can be achieved through microbial activity in sulfate-reducing bioreactors (SRBRs), but their actual removal rates depend on different factors, one of which is the substrate composition. Chitinous materials have demonstrated high metal removal rates, particularly for the two recalcitrant MIW contaminants Zn and Mn, but their removal mechanisms need further study. We studied Cd, Fe, Zn, and Mn removal in bioactive and abiotic SRBRs to elucidate the metal removal mechanisms and the differences in metal and sulfate removal rates using a chitinous material as substrate. We found that sulfate-reducing bacteria are effective in increasing metal and sulfate removal rates and duration of operation in SRBRs, and that the main mechanism involved was metal precipitation as sulfides. The solid residues provided evidence of the presence of sulfides in the bioactive column, more specifically ZnS, according to XPS analysis. The feasibility of passive treatments with a chitinous substrate could be an important option for MIW remediation. Mining influenced water (MIW) remediation is still one of the top priorities for the agency because it addresses the most important environmental problem associated with the mining industry and that affects thousands of communities in the U.S. and worldwide. In this paper, the MIW bioremediation mechanisms are studied

  7. Hydrogen sulfide and nitric oxide metabolites in the blood of free-ranging brown bears and their potential roles in hibernation

    DEFF Research Database (Denmark)

    Revsbech, Inge G; Shen, Xinggui; Chakravarti, Ritu

    2014-01-01

    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...

  8. Biogeochemistry of an iron-rich hypersaline microbial mat (Camargue, France).

    Science.gov (United States)

    Wieland, A; Zopfi, J; Benthien, M; Kühl, M

    2005-01-01

    In situ microsensor measurements were combined with biogeochemical methods to determine oxygen, sulfur, and carbon cycling in microbial mats growing in a solar saltern (Salin-de-Giraud, France). Sulfate reduction rates closely followed the daily temperature changes and were highest during the day at 25 degrees C and lowest during the night at 11 degrees C, most probably fueled by direct substrate interactions between cyanobacteria and sulfate-reducing bacteria. Sulfate reduction was the major mineralization process during the night and the contribution of aerobic respiration to nighttime DIC production decreased. This decrease of aerobic respiration led to an increasing contribution of sulfide (and iron) oxidation to nighttime O2 consumption. A peak of elemental sulfur in a layer of high sulfate reduction at low sulfide concentration underneath the oxic zone indicated anoxygenic photosynthesis and/or sulfide oxidation by iron, which strongly contributed to sulfide consumption. We found a significant internal carbon cycling in the mat, and sulfate reduction directly supplied DIC for photosynthesis. The mats were characterized by a high iron content of 56 micromol Fe cm(-3), and iron cycling strongly controlled the sulfur cycle in the mat. This included sulfide precipitation resulting in high FeS contents with depth, and reactions of iron oxides with sulfide, especially after sunset, leading to a pronounced gap between oxygen and sulfide gradients and an unusual persistence of a pH peak in the uppermost mat layer until midnight.

  9. Friction behaviour of anodic oxide film on aluminum impregnated with molybdenum sulfide compounds

    Energy Technology Data Exchange (ETDEWEB)

    Maejima, M.; Saruwatari, K. [Fujikura Ltd., Tokyo (Japan); Takaya, M. [Faculty of Engineering, Chiba Institute of Technology 17-1, Tsudanuma 2-Chome, 275-0016, Narasino-shi Chiba (Japan)

    2000-10-23

    In order to improve the lubricity and wear resistance of aluminum anodic oxide films, it is necessary to ensure the film layers are dense to prevent cracking, and to harden the films as well as reduce the shear stress of the film surfaces. From this view point, lubricious, hard anodic oxide films have been studied in the past, but fully satisfactory results have yet to be realized. In this paper, we report on our study of the re-anodizing of anodic oxide film in an aqueous solution of (NH)MoS. Molybdenum sulfide and compounds filled the 20-nm diameter pores of the film, creating internal stress which compressed the film, suppressing the occurrence of cracks and reducing the friction coefficient. (orig.)

  10. Experimental and theoretical studies of the reaction of the OH radical with alkyl sulfides: 3. Kinetics and mechanism of the OH initiated oxidation of dimethyl, dipropyl, and dibutyl sulfides: reactivity trends in the alkyl sulfides and development of a predictive expression for the reaction of OH with DMS.

    Science.gov (United States)

    Williams, M B; Campuzano-Jost, P; Hynes, A J; Pounds, A J

    2009-06-18

    A pulsed laser photolysis-pulsed laser-induced fluorescence technique has been employed to measure rate coefficients for the OH-initiated oxidation of dimethyl sulfide (DMS), its deuterated analog (DMS-d(6)), dipropyl sulfide (DPS), and dibutyl sulfide (DBS). Effective rate coefficients have been measured as a function of the partial pressure of O(2) over the temperature range of 240-295 K and at 200 and 600 Torr total pressure. We report the first observations of an O(2) enhancement in the effective rate coefficients for the reactions of OH with DPS and DBS. All observations are consistent with oxidation proceeding via a two-channel oxidation mechanism involving abstraction and addition channels. Structures and thermochemistry of the DPSOH and DBSOH adducts were calculated. Calculated bond strengths of adducts increase with alkyl substitution but are comparable to that of the DMSOH adduct and are consistent with experimental observations. Reactivity trends across the series of alkyl sulfide (C(2)-C(8)) reactions are analyzed. All reactions proceed via a two-channel mechanism involving either an H-atom abstraction or the formation of an OH adduct that can then react with O(2). Measurements presented in this work, in conjunction with previous measurements, have been used to develop a predictive expression for the OH-initiated oxidation of DMS. This expression is based on the elementary rate coefficients in the two-channel mechanism. The expression can calculate the effective rate coefficient for the reaction of OH with DMS over the range of 200-300 K, 0-760 Torr, and 0-100% partial pressure of O(2). This expression expands on previously published work but is applicable to DMS oxidation throughout the troposphere.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2001-05-17

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

  12. Nitrogen, carbon, and sulfur metabolism in natural Thioploca samples

    DEFF Research Database (Denmark)

    Otte, S.; Kuenen, JG; Nielsen, LP

    1999-01-01

    in combination with (15)N compounds and mass spectrometry and found that these Thioploca samples produce ammonium at a rate of 1 nmol min(-1) mg of protein(-1). Controls showed no significant activity. Sulfate was shown to be the end product of sulfide oxidation and was observed at a rate of 2 to 3 nmol min(-1......) mg of protein(-1). The ammonium and sulfate production rates were not influenced by the addition of sulfide, suggesting that sulfide is first oxidized to elemental sulfur, and in a second independent step elemental sulfur is oxidized to sulfate. The average sulfide oxidation rate measured was 5 nmol......]acetate incorporation was 0.4 nmol min(-1) mg of protein(-1), which is equal to the CO(2) fixation rate, and no (14)CO(2) production was detected. These results suggest that Thioploca species are facultative chemolithoautotrophs capable of mixotrophic growth. Microautoradiography confirmed that Thioploca cells...

  13. Trace methane oxidation and the methane dependency of sulfate reduction in anaerobic granular sludge

    KAUST Repository

    Meulepas, Roel J.W.; Jagersma, Christian G.; Zhang, Yu; Petrillo, Michele; Cai, Hengzhe; Buisman, Cees J.N.; Stams, Alfons J.M.; Lens, Piet N.L.

    2010-01-01

    This study investigates the oxidation of labeled methane (CH4) and the CH4 dependence of sulfate reduction in three types of anaerobic granular sludge. In all samples, 13C-labeled CH4 was anaerobically oxidized to 13C-labeled CO2, while net

  14. Eutrophication, microbial-sulfate reduction and mass extinctions

    DEFF Research Database (Denmark)

    Schobben, Martin; Stebbins, Alan; Ghaderi, Abbas

    2016-01-01

    to the Earth system, notably, the biogeochemical sulfur and carbon cycle. This climate warming feedback produces large-scale eutrophication on the continental shelf, which, in turn, expands oxygen minimum zones by increased respiration, which can turn to a sulfidic state by increased microbial-sulfate...

  15. Effect of methanogenic substrates on anaerobic oxidation of methane and sulfate reduction by an anaerobic methanotrophic enrichment.

    KAUST Repository

    Meulepas, Roel J W; Jagersma, Christian G; Khadem, Ahmad F; Stams, Alfons J M; Lens, Piet N L

    2010-01-01

    Anaerobic oxidation of methane (AOM) coupled to sulfate reduction (SR) is assumed to be a syntrophic process, in which methanotrophic archaea produce an interspecies electron carrier (IEC), which is subsequently utilized by sulfate-reducing bacteria

  16. 34S/32S fractionation in sulfur cycles catalyzed by anaerobic bacteria

    Science.gov (United States)

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

    1988-01-01

    Stable isotopic distributions in the sulfur cycle were studied with pure and mixed cultures of the anaerobic bacteria, Chlorobium vibrioforme and Desulfovibrio vulgaris. D. vulgaris and C. vibrioforme can catalyze three reactions constituting a complete anaerobic sulfur cycle: reduction of sulfate to sulfide (D. vulgaris), oxidation of sulfide to elemental sulfur (C. vibrioforme), and oxidation of sulfur to sulfate (C. vibrioforme). In all experiments, the first and last reactions favored concentration of the light 32S isotope in products (isotopic fractionation factor epsilon = -7.2 and -1.7%, respectively), whereas oxidation of sulfide favored concentration of the heavy 34S isotope in products (epsilon = +1.7%). Experimental results and model calculations suggest that elemental sulfur enriched in 34S versus sulfide may be a biogeochemical marker for the presence of sulfide-oxidizing bacteria in modern and ancient environments.

  17. Synergistic reaction between SO2 and NO2 on mineral oxides: a potential formation pathway of sulfate aerosol.

    Science.gov (United States)

    Liu, Chang; Ma, Qingxin; Liu, Yongchun; Ma, Jinzhu; He, Hong

    2012-02-07

    Sulfate is one of the most important aerosols in the atmosphere. A new sulfate formation pathway via synergistic reactions between SO(2) and NO(2) on mineral oxides was proposed. The heterogeneous reactions of SO(2) and NO(2) on CaO, α-Fe(2)O(3), ZnO, MgO, α-Al(2)O(3), TiO(2), and SiO(2) were investigated by in situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (in situ DRIFTS) at ambient temperature. Formation of sulfate from adsorbed SO(2) was promoted by the coexisting NO(2), while surface N(2)O(4) was observed as the crucial oxidant for the oxidation of surface sulfite. This process was significantly promoted by the presence of O(2). The synergistic effect between SO(2) and NO(2) was not observed on other mineral particles (such as CaCO(3) and CaSO(4)) probably due to the lack of the surface reactive oxygen sites. The synergistic reaction between SO(2) and NO(2) on mineral oxides resulted in the formation of internal mixtures of sulfate, nitrate, and mineral oxides. The change of mixture state will affect the physicochemical properties of atmospheric particles and therefore further influence their environmental and climate effects.

  18. INVESTIGATIONS ON BIOCHEMICAL PURIFICATION OF GROUND WATER FROM HYDROGEN SULFIDE

    Directory of Open Access Journals (Sweden)

    Yu. P. Sedlukho

    2015-01-01

    Full Text Available The paper considers problems and features of biochemical removal of hydrogen sulfide from ground water. The analysis of existing methods for purification of ground water from hydrogen sulfide has been given in the paper. The paper has established shortcomings of physical and chemical purification of ground water. While using aeration methods for removal of hydrogen sulfide formation of colloidal sulfur that gives muddiness and opalescence to water occurs due to partial chemical air oxidation. In addition to this violation of sulfide-carbonate equilibrium taking place in the process of aeration due to desorption of H2S and CO2, often leads to clogging of degasifier nozzles with formed CaCO3 that causes serious operational problems. Chemical methods require relatively large flow of complex reagent facilities, storage facilities and transportation costs.In terms of hydrogen sulfide ground water purification the greatest interest is given to the biochemical method. Factors deterring widespread application of the biochemical method is its insufficient previous investigation and necessity to execute special research in order to determine optimal process parameters while purifying groundwater of a particular water supply source. Biochemical methods for oxidation of sulfur compounds are based on natural biological processes that ensure natural sulfur cycle. S. Vinogradsky has established a two-stage mechanism for oxidation of hydrogen sulfide with sulfur bacteria (Beggiatoa. The first stage presupposes oxidation of hydrogen sulphide to elemental sulfur which is accumulating in the cytoplasm in the form of globules. During the second stage sulfur bacteria begin to oxidize intracellular sulfur to sulfuric acid due to shortage of hydrogen sulfide.The paper provides the results of technological tests of large-scale pilot plants for biochemical purification of groundwater from hydrogen sulfide in semi-industrial conditions. Dependences of water quality

  19. Biological sulfate removal from gypsum contaminated construction and demolition debris.

    Science.gov (United States)

    Kijjanapanich, Pimluck; Annachhatre, Ajit P; Esposito, Giovanni; van Hullebusch, Eric D; Lens, Piet N L

    2013-12-15

    Construction and demolition debris (CDD) contains high levels of sulfate that can cause detrimental environmental impacts when disposed without adequate treatment. In landfills, sulfate can be converted to hydrogen sulfide under anaerobic conditions. CDD can thus cause health impacts or odor problems to landfill employees and surrounding residents. Reduction of the sulfate content of CDD is an option to overcome these problems. This study aimed at developing a biological sulfate removal system to reduce the sulfate content of gypsum contaminated CDD in order to decrease the amount of solid waste, to improve the quality of CDD waste for recycling purposes and to recover sulfur from CDD. The treatment leached out the gypsum contained in CDD by water in a leaching column. The sulfate loaded leachate was then treated in a biological sulfate reducing Upflow Anaerobic Sludge Blanket (UASB) reactor to convert the sulfate to sulfide. The UASB reactor was operated at 23 ± 3 °C with a hydraulic retention time and upflow velocity of 15.5 h and 0.1 m h(-1), respectively while ethanol was added as electron donor at a final organic loading rate of 3.46 g COD L(-1) reactor d(-1). The CDD leachate had a pH of 8-9 and sulfate dissolution rates of 526.4 and 609.8 mg L(-1) d(-1) were achieved in CDD gypsum and CDD sand, respectively. Besides, it was observed that the gypsum dissolution was the rate limiting step for the biological treatment of CDD. The sulfate removal efficiency of the system stabilized at around 85%, enabling the reuse of the UASB effluent for the leaching step, proving the versatility of the bioreactor for practical applications. Copyright © 2013 Elsevier Ltd. All rights reserved.

  20. Hydrogen sulfide release from dairy manure storages containing gypsum bedding

    Science.gov (United States)

    Recycled gypsum products can provide a cost-effective bedding alternative for dairy producers. Manufacturers report reduced odors, moisture and bacteria in the stall environment when compared to traditional bedding. Gypsum provides a sulfate source that can be converted to hydrogen sulfide under ana...

  1. Process for scavenging hydrogen sulfide from hydrocarbon gases

    International Nuclear Information System (INIS)

    Fox, I.

    1981-01-01

    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 2 O 3 containing a crystalline phase of Fe 2 O 3 , Fe 3 O 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

  2. Technetium Reduction and Permanent Sequestration by Abiotic and Biotic Formation of Low-Solubility Sulfide Mineral Phases

    Energy Technology Data Exchange (ETDEWEB)

    Tratnyek, Paul G. [Oregon Health & Science Univ., Beaverton, OR (United States); Tebo, Bradley M. [Oregon Health & Science Univ., Beaverton, OR (United States); Fan, Dimin [Oregon Health & Science Univ., Beaverton, OR (United States); Anitori, Roberto [Oregon Health & Science Univ., Beaverton, OR (United States); Szecsody, Jim [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Jansik, Danielle [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2015-11-14

    One way to minimize the mobility of the TcVII oxyanion pertechnetate (TcO4-) is to effect reduction under sulfidogenic conditions (generated abiotically by Fe0 or biotically) to form TcSx, which is significantly slower to oxidize than TcIVO2. In sediment systems, TcSx and other precipitates may oxidize more slowly due to oxygen diffusion limitations to these low permeability precipitate zones. In addition, the TcO4- reduction rate may be more rapid in the presence of sediment because of additional reductive surface phases. This project aims to provide a fundamental understanding of the feasibility of immobilization of TcO4- as TcSx in the vadose zone or groundwater by application nano zero-valent iron (nZVI), and sulfide or sulfate. Biotic batch experiments have used the sulfate-reducing bacterium (SRB) Desulfotomaculum reducens. The iron sulfide mineral mackinawite was generated under these conditions, while vivianite was formed in nZVI only controls. The sulfide/bacteria-containing system consistently reduced aqueous pertechnetate rapidly (> 95% in the first hour), a rate similar to that for the sulfide-free, nZVI only system. Reduced Tc (aged for 3 months) generated in both SRB/nZVI systems was highly resistant to reoxidation. In reduced samples, Tc was found associated with solid phases containing Fe and S (D. reducens/nZVI) or Fe (nZVI only). Experiments using D. reducens without nZVI provided some additional insights. Firstly, stationary phase cultures were able to slowly reduce pertechnetate. Secondly, addition of pertechnetate at the beginning of cell growth (lag phase) resulted in a faster rate of Tc reduction, possibly indicating a direct (e.g. enzymatic) role for D. reducens in Tc reduction. Abiotic batch experiments were conducted with Na2S as the sulfide source. Pertechnetate reduction was

  3. Surficial weathering of iron sulfide mine tailings under semi-arid climate.

    Science.gov (United States)

    Hayes, Sarah M; Root, Robert A; Perdrial, Nicolas; Maier, Raina; Chorover, Jon

    2014-09-15

    Mine wastes introduce anthropogenic weathering profiles to the critical zone that often remain unvegetated for decades after mining cessation. As such, they are vulnerable to wind and water dispersion of particulate matter to adjacent ecosystems and residential communities. In sulfide-rich ore tailings, propagation to depth of the oxidative weathering front controls the depth-variation in speciation of major and trace elements. Despite the prevalence of surficial mine waste deposits in arid regions of the globe, few prior studies have been conducted to resolve the near-surface profile of sulfide ore tailings weathered under semi-arid climate. We investigated relations between gossan oxidative reaction-front propagation and the molecular speciation of iron and sulfur in tailings subjected to weathering under semi-arid climate at an EPA Superfund Site in semi-arid central Arizona (USA). Here we report a multi-method data set combining wet chemical and synchrotron-based X-ray diffraction (XRD) and X-ray absorption near-edge spectroscopy (XANES) methods to resolve the tight coupling of iron (Fe) and sulfur (S) geochemical changes in the top 2 m of tailings. Despite nearly invariant Fe and S concentration with depth (130-140 and 100-120 g kg -1 , respectively), a sharp redox gradient and distinct morphological change was observed within the top 0.5 m, associated with a progressive oxidative alteration of ferrous sulfides to (oxyhydr)oxides and (hydroxy)sulfates. Transformation is nearly complete in surficial samples. Trends in molecular-scale alteration were co-located with a decrease in pH from 7.3 to 2.3, and shifts in Fe and S lability as measured via chemical extraction. Initial weathering products, ferrihydrite and gypsum, transform to schwertmannite, then jarosite-group minerals with an accompanying decrease in pH. Interestingly, thermodynamically stable phases such as goethite and hematite were not detected in any samples, but ferrihydrite was observed even in

  4. Surficial weathering of iron sulfide mine tailings under semi-arid climate

    Science.gov (United States)

    Hayes, Sarah M.; Root, Robert A.; Perdrial, Nicolas; Maier, Raina M.; Chorover, Jon

    2014-09-01

    Mine wastes introduce anthropogenic weathering profiles to the critical zone that often remain unvegetated for decades after mining cessation. As such, they are vulnerable to wind and water dispersion of particulate matter to adjacent ecosystems and residential communities. In sulfide-rich ore tailings, propagation to depth of the oxidative weathering front controls the depth-variation in speciation of major and trace elements. Despite the prevalence of surficial mine waste deposits in arid regions of the globe, few prior studies have been conducted to resolve the near-surface profile of sulfide ore tailings weathered under semi-arid climate. We investigated relations between gossan oxidative reaction-front propagation and the molecular speciation of iron and sulfur in tailings subjected to weathering in a semi-arid climate at an EPA Superfund Site in central Arizona (USA). Here we report a multi-method data set combining wet chemical and synchrotron-based X-ray diffraction (XRD) and X-ray absorption near-edge spectroscopy (XANES) methods to resolve the tight coupling of iron (Fe) and sulfur (S) geochemical changes in the top 2 m of tailings. Despite nearly invariant Fe and S concentration with depth (130-140 and 100-120 g kg-1, respectively), a sharp redox gradient and distinct morphological change was observed within the top 0.5 m, associated with a progressive oxidative alteration of ferrous sulfides to (oxyhydr)oxides and (hydroxy)sulfates. Transformation is nearly complete in surficial samples. Trends in molecular-scale alteration were co-located with a decrease in pH from 7.3 to 2.3, and shifts in Fe and S lability as measured via chemical extraction. Initial weathering products, ferrihydrite and gypsum, transform to schwertmannite, then jarosite-group minerals with an accompanying decrease in pH. Interestingly, thermodynamically stable phases such as goethite and hematite were not detected in any samples, but ferrihydrite was observed even in samples with

  5. Biotic and a-biotic Mn and Fe cycling in deep sediments across a gradient of sulfate reduction rates along the California margin

    Science.gov (United States)

    Schneider-Mor, A.; Steefel, C.; Maher, K.

    2011-12-01

    The coupling between the biological and a-biotic processes controlling trace metals in deep marine sediments are not well understood, although the fluxes of elements and trace metals across the sediment-water interface can be a major contribution to ocean water. Four marine sediment profiles (ODP leg 167 sites 1011, 1017, 1018 and 1020)were examined to evaluate and quantify the biotic and abiotic reaction networks and fluxes that occur in deep marine sediments. We compared biogeochemical processes across a gradient of sulfate reduction (SR) rates with the objective of studying the processes that control these rates and how they affect major elements as well as trace metal redistribution. The rates of sulfate reduction, methanogenesis and anaerobic methane oxidation (AMO) were constrained using a multicomponent reactive transport model (CrunchFlow). Constraints for the model include: sediment and pore water concentrations, as well as %CaCO3, %biogenic silica, wt% carbon and δ13C of total organic carbon (TOC), particulate organic matter (POC) and mineral associated carbon (MAC). The sites are distinguished by the depth of AMO: a shallow zone is observed at sites 1018 (9 to 19 meters composite depth (mcd)) and 1017 (19 to 30 mcd), while deeper zones occur at sites 1011 (56 to 76 mcd) and 1020 (101 to 116 mcd). Sulfate reduction rates at the shallow AMO sites are on the order 1x10-16 mol/L/yr, much faster than rates in the deeper zone sulfate reduction (1-3x10-17 mol/L/yr), as expected. The dissolved metal ion concentrations varied between the sites, with Fe (0.01-7 μM) and Mn (0.01-57 μM) concentrations highest at Site 1020 and lowest at site 1017. The highest Fe and Mn concentrations occurred at various depths, and were not directly correlated with the rates of sulfate reduction and the maximum alkalinity values. The main processes that control cycling of Fe are the production of sulfide from sulfate reduction and the distribution of Fe-oxides. The Mn distribution

  6. Occurrence and distribution of color and hydrogen sulfide in water of the principal artesian aquifers in the Valdosta area, Georgia

    Science.gov (United States)

    Krause, Richard E.

    1976-01-01

    Hydrogen sulfide and color occur in objectionable amounts in ground water from the principal artesian aquifer in the Valdosta , Ga., area. Generally, water from wells south of Valdosta is high in hydrogen sulfide; water from wells north of the city is high in color. Water with high sulfate is likely to be a problem in wells deeper than about 540 ft. Heavy pumpage concentrated in a small area may cause high-sulfate water to migrate vertically upward into shallower wells. (Woodard-USGS)

  7. Effect of nitric oxide and hydrogen sulfide on radiation sensitivity of spores of Bacillus megaterium in suspension

    Energy Technology Data Exchange (ETDEWEB)

    Russell, C

    1966-01-01

    The effect of nitric oxide on the sensitivity to radiation of spores of B. megaterium in water suspension is similar to that seen in vegetative cells of E. coli. The spores are less sensitive in the presence of hydrogen sulfide. 11 references, 1 figure.

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

    Energy Technology Data Exchange (ETDEWEB)

    Chamberland, A M; Gauthier, J M

    1977-01-01

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

  9. An advanced modeling study on the impacts and atmospheric implications of multiphase dimethyl sulfide chemistry

    Science.gov (United States)

    Hoffmann, Erik Hans; Tilgner, Andreas; Schrödner, Roland; Bräuer, Peter; Wolke, Ralf; Herrmann, Hartmut

    2016-01-01

    Oceans dominate emissions of dimethyl sulfide (DMS), the major natural sulfur source. DMS is important for the formation of non-sea salt sulfate (nss-SO42−) aerosols and secondary particulate matter over oceans and thus, significantly influence global climate. The mechanism of DMS oxidation has accordingly been investigated in several different model studies in the past. However, these studies had restricted oxidation mechanisms that mostly underrepresented important aqueous-phase chemical processes. These neglected but highly effective processes strongly impact direct product yields of DMS oxidation, thereby affecting the climatic influence of aerosols. To address these shortfalls, an extensive multiphase DMS chemistry mechanism, the Chemical Aqueous Phase Radical Mechanism DMS Module 1.0, was developed and used in detailed model investigations of multiphase DMS chemistry in the marine boundary layer. The performed model studies confirmed the importance of aqueous-phase chemistry for the fate of DMS and its oxidation products. Aqueous-phase processes significantly reduce the yield of sulfur dioxide and increase that of methyl sulfonic acid (MSA), which is needed to close the gap between modeled and measured MSA concentrations. Finally, the simulations imply that multiphase DMS oxidation produces equal amounts of MSA and sulfate, a result that has significant implications for nss-SO42− aerosol formation, cloud condensation nuclei concentration, and cloud albedo over oceans. Our findings show the deficiencies of parameterizations currently used in higher-scale models, which only treat gas-phase chemistry. Overall, this study shows that treatment of DMS chemistry in both gas and aqueous phases is essential to improve the accuracy of model predictions. PMID:27688763

  10. Kinetic comparison of microbial assemblages for the anaerobic treatment of wastewater with high sulfate and heavy metal contents.

    Science.gov (United States)

    Sinbuathong, Nusara; Sirirote, Pramote; Liengcharernsit, Winai; Khaodhiar, Sutha; Watts, Daniel J

    2009-01-01

    Mixed-microbial assemblages enriched from a septic tank, coastal sediment samples, the digester sludge of a brewery wastewater treatment plant and acidic sulfate soil samples were compared on the basis of growth rate, waste and sulfate reduction rate under sulfate reducing conditions at 30 degrees C. The specific growth rate of various cultures was in the range 0.0013-0.0022 hr(-1). Estimates of waste and sulfate reduction rate were obtained by fitting substrate depletion and sulfate reduction data with the Michaelis-Menten equation. The waste reduction rates were in the range 4x10(-8)-1x10(-7) I mg(-1) hr(-1) and generally increased in the presence of copper, likely by copper sulfide precipitation that reduced sulfide and copper toxicity and thus protected the anaerobic microbes. Anaerobic microorganisms from a brewery digester sludge were found to be the most appropriate culture for the treatment of wastewater with high sulfate and heavy metal content due to their growth rate, and waste and sulfate reduction rate.

  11. Remediation of arsenic-contaminated groundwater by in-situ stimulating biogenic precipitation of iron sulfides.

    Science.gov (United States)

    Pi, Kunfu; Wang, Yanxin; Xie, Xianjun; Ma, Teng; Liu, Yaqing; Su, Chunli; Zhu, Yapeng; Wang, Zhiqiang

    2017-02-01

    Severe health problems due to elevated arsenic (As) in groundwater have made it urgent to develop cost-effective technologies for As removal. This field experimental study tested the feasibility of in-situ As immobilization via As incorporation into newly formed biogenic Fe(II) sulfides in a typical As-affected strongly reducing aquifer at the central part of Datong Basin, China. After periodic supply of FeSO 4 into the aquifer for 25 d to stimulate microbial sulfate reduction, dissolved sulfide concentrations increased during the experiment, but the supplied Fe(II) reacted quickly with sulfide to form Fe(II)-sulfides existing majorly as mackinawite as well as a small amount of pyrite-like minerals in sediments, thereby restricting sulfide build-up in groundwater. After the completion of field experiment, groundwater As concentration decreased from an initial average value of 593 μg/L to 159 μg/L, with an overall As removal rate of 73%, and it further declined to 136 μg/L adding the removal rate up to 77% in 30 d after the experiment. The arsenite/As total ratio gradually increased over time, making arsenite to be the predominant species in groundwater residual As. The good correlations between dissolved Fe(II), sulfide and As concentrations, the increased abundance of As in newly-formed Fe sulfides as well as the reactive-transport modeling results all indicate that As could have been adsorbed onto and co-precipitated with Fe(II)-sulfide coatings once microbial sulfate reduction was stimulated after FeSO 4 supply. Under the strongly reducing conditions, sulfide may facilitate arsenate reduction into arsenite and promote As incorporation into pyrite or arsenopyrite. Therefore, the major mechanisms for the in-situ As-contaminated groundwater remediation can be As surface-adsorption on and co-precipitation with Fe(II) sulfides produced during the experimental period. Copyright © 2016. Published by Elsevier Ltd.

  12. Sulfidization of Organic Freshwater Flocs from a Minerotrophic Peatland: Speciation Changes of Iron, Sulfur, and Arsenic.

    Science.gov (United States)

    ThomasArrigo, Laurel K; Mikutta, Christian; Lohmayer, Regina; Planer-Friedrich, Britta; Kretzschmar, Ruben

    2016-04-05

    Iron-rich organic flocs are frequently observed in surface waters of wetlands and show a high affinity for trace metal(loid)s. Under low-flow stream conditions, flocs may settle, become buried, and eventually be subjected to reducing conditions facilitating trace metal(loid) release. In this study, we reacted freshwater flocs (704-1280 mg As/kg) from a minerotrophic peatland (Gola di Lago, Switzerland) with sulfide (5.2 mM, S(-II)spike/Fe = 0.75-1.62 mol/mol) at neutral pH and studied the speciation changes of Fe, S, and As at 25 ± 1 °C over 1 week through a combination of synchrotron X-ray techniques and wet-chemical analyses. Sulfidization of floc ferrihydrite and nanocrystalline lepidocrocite caused the rapid formation of mackinawite (52-81% of Fesolid at day 7) as well as solid-phase associated S(0) and polysulfides. Ferrihydrite was preferentially reduced over lepidocrocite, although neoformation of lepidocrocite from ferrihydrite could not be excluded. Sulfide-reacted flocs contained primarily arsenate (47-72%) which preferentially adsorbed to Fe(III)-(oxyhydr)oxides, despite abundant mackinawite precipitation. At higher S(-II)spike/Fe molar ratios (≥1.0), the formation of an orpiment-like phase accounted for up to 35% of solid-phase As. Despite Fe and As sulfide precipitation and the presence of residual Fe(III)-(oxyhydr)oxides, mobilization of As was recorded in all samples (Asaq = 0.45-7.0 μM at 7 days). Aqueous As speciation analyses documented the formation of thioarsenates contributing up to 33% of Asaq. Our findings show that freshwater flocs from the Gola di Lago peatland may become a source of As under sulfate-reducing conditions and emphasize the pivotal role Fe-rich organic freshwater flocs play in trace metal(loid) cycling in S-rich wetlands characterized by oscillating redox conditions.

  13. Sulfur in serpentinized oceanic peridotites: Serpentinization processes and microbial sulfate reduction

    Science.gov (United States)

    Alt, J.C.; Shanks, Wayne C.

    1998-01-01

    The mineralogy, contents, and isotopic compositions of sulfur in oceanic serpentinites reflect variations in temperatures and fluid fluxes. Serpentinization of serpentinization of Iberian Margin peridotites occurred at low temperatures (???20??-200??C) and high water/rock ratios. Complete serpentinization and consumption of ferrous iron allowed evolution to higher fO2. Microbial reduction of seawater sulfate resulted in addition of low-??34S sulfide (-15 to -43???) and formation of higher-sulfur assemblages that include valleriite and pyrite. The high SO4/total S ratio of Hess Deep serpentinites (0.89) results in an increase of total sulfur and high ??34S of total sulfur (mean ??? 8???). In contrast, Iberian Margin serpentinites gained large amounts of 34S-poor sulfide (mean total S = 3800 ppm), and the high sulfide/total S ratio (0.61) results in a net decrease in ??34S of total sulfur (mean ??? -5???). Thus serpentinization is a net sink for seawater sulfur, but the amount fixed and its isotopic composition vary significantly. Serpentinization may result in uptake of 0.4-14 ?? 1012 g S yr-1 from the oceans, comparable to isotopic exchange in mafic rocks of seafloor hydrothermal systems and approaching global fluxes of riverine sulfate input and sedimentary sulfide output.

  14. EQCM Study of Influence of Anion Nature on Electrochemical Reduction of Bismuth Sulfide in Nickel Plating Solution

    Directory of Open Access Journals (Sweden)

    Loreta TAMAŠAUSKAITĖ-TAMAŠIŪNAITĖ

    2011-03-01

    Full Text Available The influence of anion nature on the reduction of bismuth sulfide film deposited on gold using the successive ionic layer adsorption and reaction method in solutions containing Ni2+ ions has been investigated by electrochemical quartz crystal microbalance combined with cyclic voltammetry and X-ray photoelectron spectroscopy. It has been determined that the reduction of bismuth sulfide film in the nickel plating solution depends on the anion nature: larger cathodic current and mass changes (Dƒ are observed in the solution containing acetate anion as compared to those in the solution containing sulfate anion. As the reduction of bismuth sulfide film in the background solutions depends on the nature of anion, it influences the cathodic reduction of Ni2+ ions prior to OPD of Ni. A greater current and mass change (Dƒ is conditioned by simultaneously occurring reduction of bismuth sulfide film when the film is reduced in the acetate nickel plating electrolyte in contrast to that in the sulfate one.http://dx.doi.org/10.5755/j01.ms.17.1.244

  15. Effect of nitrate addition on the diversity and activity of sulfate-reducing prokaryotes in high-temperature oil production systems

    DEFF Research Database (Denmark)

    Gittel, Antje; Wieczorek, Adam; Sørensen, Ketil

    Sulfate-reducing prokaryotes (SRP) producing hydrogen sulfide cause severe problems like microbial corrosion, souring and plugging in seawater-injected oil production systems. Adding nitrate to the injection water is a possible strategy to control the activity of SRP by favoring the growth of both...... heterotrophic, nitrate-reducing bacteria that outcompete SRP for substrates, and nitrate-reducing, sulfide-oxidizing bacteria (NR-SOB). To assess the effects of nitrate addition, microbial diversity (Bacteria, Archaea) and SRP activity were studied in the production waters of a nitrate-treated and a non...... their potential activity under pipeline (60°C), but not under oil reservoir conditions (80°C), indicating that the troublesome SRP were pipeline-derived. Consistent with the low amount of SRP, no activity could be shown for samples from the nitrate-treated system suggesting that SRP were inhibited by nitrate...

  16. Sulfate reduction and carbon removal during kraft char burning

    Energy Technology Data Exchange (ETDEWEB)

    Waag, K.J.; Frederick, W.J.; Sricharoenchaikul, V [Oregon State Univ., Corvallis, OR (United States). Dept. of Chemical Engineering; Grace, T.M. [T.M. Grace Company, Appleton, WI (United States); Kymalainen, M. [Tampella Power, Tampere (Finland)

    1995-12-31

    An improved mathematical model of char burning during black liquor combustion was described. Enhancements include a proper treatment of CO{sub 2} and H{sub 2}O gasification, reactions between oxygen and combustibles in the boundary layer, and integration of sulfate reduction and sulfide reoxidation into the char burning process. Gasification of char carbon by reaction with H{sub 2}O and CO{sub 2} proved to be the most important means of carbon release under typical recovery furnace conditions. Sulfate reduction was shown to be responsible for only a minor part of the carbon release. Simulations showed that for typical recovery boiler conditions, char burning behavior is independent of oxygen concentration up to the point of carbon depletion. After carbon depletion, sulfide reoxidation occurs at a rate determined by oxygen mass transfer. Process variables that had the biggest effect on char burning behavior were initial black liquor drop diameter and temperature; also there was a direct link between char burnout times and the amount of sulfate reduction. At a given temperature, any variable that shortened the char burnout time resulted in proportionately less reduction. 22 refs., 10 figs., 2 tabs.

  17. Methanol utilizing Desulfotomaculum species utilizes hydrogen in a methanol-fed sulfate-reducing bioreactor

    NARCIS (Netherlands)

    Balk, M.; Weijma, J.; Goorissen, H.P.; Ronteltap, M.; Hansen, T.A.; Stams, A.J.M.

    2007-01-01

    A sulfate-reducing bacterium, strain WW1, was isolated from a thermophilic bioreactor operated at 65 degrees C with methanol as sole energy source in the presence of sulfate. Growth of strain WW1 on methanol or acetate was inhibited at a sulfide concentration of 200 mg l(-1), while on H-2/CO2, no

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

    Directory of Open Access Journals (Sweden)

    Natascha Riedinger

    2017-05-01

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

  19. Raman spectroscopy of efflorescent sulfate salts from Iron Mountain Mine Superfund Site, California

    Science.gov (United States)

    Sobron, Pablo; Alpers, Charles N.

    2013-01-01

    The Iron Mountain Mine Superfund Site near Redding, California, is a massive sulfide ore deposit that was mined for iron, silver, gold, copper, zinc, and pyrite intermittently for nearly 100 years. As a result, both water and air reached the sulfide deposits deep within the mountain, producing acid mine drainage consisting of sulfuric acid and heavy metals from the ore. Particularly, the drainage water from the Richmond Mine at Iron Mountain is among the most acidic waters naturally found on Earth. The mineralogy at Iron Mountain can serve as a proxy for understanding sulfate formation on Mars. Selected sulfate efflorescent salts from Iron Mountain, formed from extremely acidic waters via drainage from sulfide mining, have been characterized by means of Raman spectroscopy. Gypsum, ferricopiapite, copiapite, melanterite, coquimbite, and voltaite are found within the samples. This work has implications for Mars mineralogical and geochemical investigations as well as for terrestrial environmental investigations related to acid mine drainage contamination.

  20. Raman spectroscopy of efflorescent sulfate salts from Iron Mountain Mine Superfund Site, California.

    Science.gov (United States)

    Sobron, Pablo; Alpers, Charles N

    2013-03-01

    The Iron Mountain Mine Superfund Site near Redding, California, is a massive sulfide ore deposit that was mined for iron, silver, gold, copper, zinc, and pyrite intermittently for nearly 100 years. As a result, both water and air reached the sulfide deposits deep within the mountain, producing acid mine drainage consisting of sulfuric acid and heavy metals from the ore. Particularly, the drainage water from the Richmond Mine at Iron Mountain is among the most acidic waters naturally found on Earth. The mineralogy at Iron Mountain can serve as a proxy for understanding sulfate formation on Mars. Selected sulfate efflorescent salts from Iron Mountain, formed from extremely acidic waters via drainage from sulfide mining, have been characterized by means of Raman spectroscopy. Gypsum, ferricopiapite, copiapite, melanterite, coquimbite, and voltaite are found within the samples. This work has implications for Mars mineralogical and geochemical investigations as well as for terrestrial environmental investigations related to acid mine drainage contamination.

  1. Sulfide intrusion in seagrasses assessed by stable sulfur isotopes—a synthesis of current results

    DEFF Research Database (Denmark)

    Holmer, Marianne; Hasler-Sheetal, Harald

    2014-01-01

    of sedimentary sulfide in the plant increases, and accumulation of elemental sulfur (S0) inside the plant with δ34S values similar to the sedimentary sulfide suggests that S0 is an important reoxidation product of the sedimentary sulfide. The accumulation of S0 can, however, not account for the increase...... in sulfur in the tissue, and other sulfur containing compounds such as thiols, organic sulfur, and sulfate contribute to the accumulated sulfur pool. Experimental studies with seagrasses exposed to environmental and biological stressors show decreasing δ34S in the tissues along with reduction in growth...

  2. Uranium accumulation in modern and ancient Fe-oxide sediments: Examples from the Ashadze-2 hydrothermal sulfide field (Mid-Atlantic Ridge) and Yubileynoe massive sulfide deposit (South Urals, Russia)

    Science.gov (United States)

    Ayupova, N. R.; Melekestseva, I. Yu.; Maslennikov, V. V.; Tseluyko, A. S.; Blinov, I. A.; Beltenev, V. E.

    2018-05-01

    Fe-oxyhydroxide sediments (gossans) from the Ashadze-2 hydrothermal sulfide field (Mid-Atlantic Ridge) and hematite-carbonate-quartz rocks (gossanites) from the Yubileynoe Cu-Zn VHMS deposit (South Urals) are characterized by anomalously high U contents (up to 352 ppm and 73 ppm, respectively). In gossans from the Ashadze-2 hydrothermal sulfide field, rare isometric anhedral uraninite grains (up to 2 μm) with outer P- and Ca-rich rims, and numerous smaller (<1 μm) grains, occur in Fe-oxyhydroxides and sepiolite, associated with pyrite, isocubanite, chalcopyrite, galena, atacamite and halite. In gossanites from the Yubileynoe deposit, numerous uraninite particles (<3 μm) are associated with apatite, V-rich Mg-chlorite, micro-nodules of pyrite, Se-bearing galena, hessite and acanthite in a hematite-carbonate-quartz matrix. Small (1-3 μm) round grains of uraninite, which locally coalesce to large grains up to 10 μm in size, are associated with authigenic chalcopyrite. The similar diagenetic processes of U accumulation in modern and ancient Fe-oxyhydroxide sediments were the result of U fixation from seawater during the oxidation of sulfide minerals. Uraninite in gossanites was mainly deposited from diagenetic pore fluids, which circulated in the sulfide-hyaloclast-carbonate sediments.

  3. The Importance of Microbial Iron Sulfide Oxidation for Nitrate Depletion in Anoxic Danish Sediments

    DEFF Research Database (Denmark)

    Vaclavkova, Sarka; Jacobsen, Ole Stig; Jørgensen, Christian Juncher

    2014-01-01

    of organic carbon in the sediment. An apparent salinity limitation to MISON was observed in the most brackish environment. Addition of high surface area synthetically precipitated iron sulfide (FeS x ) to the aquifer sediment with the lowest natural FeS x reactivity increased both the relative fraction of NO......Nitrate (NO3 −) reduction processes are important for depleting the NO3 − load from agricultural source areas before the discharge water reaches surface waters or groundwater aquifers. In this study, we experimentally demonstrate the co-occurrence of microbial iron sulfide oxidation by NO3 − (MISON......) and other NO3 −-depleting processes in a range of contrasting sediment types: sandy groundwater aquifer, non-managed minerotrophic freshwater peat and two brackish muddy sediments. Approximately 1/3 of the net NO3 − reduction was caused by MISON in three of the four environments despite the presence...

  4. Preparation of ammonium sulfate, calcium oxide and rare earth concentrate from phospho-gypsum

    International Nuclear Information System (INIS)

    Andrianov, A.M.; Rusin, N.F.; Dejneka, G.F.; Zinchenko, T.A.; Burova, T.I.

    1978-01-01

    A technological scheme is proposed which gives ammonium sulfate, purified (from admixtures of silicon, iron, titanium, aluminium) calcium oxide with direct yield of calcium 91% and rare-earth concentrate, containing 5.6% of Ln 2 O 3 with direct yield of 99.5%

  5. A Cryptic Sulfur Cycle in Oxygen-Minimum-Zone Waters off the Chilean Coast

    OpenAIRE

    Canfield, D. E.; Thamdrup, B.; De Brabandere, L.; Dalsgaard, T.; Revsbech, N. P.; Ulloa, O.; Stewart, Frank J.; DeLong, Edward Francis

    2010-01-01

    Nitrogen cycling is normally thought to dominate the biogeochemistry and microbial ecology of oxygen-minimum zones in marine environments. Through a combination of molecular techniques and process rate measurements, we showed that both sulfate reduction and sulfide oxidation contribute to energy flux and elemental cycling in oxygen-free waters off the coast of northern Chile. These processes may have been overlooked because in nature, the sulfide produced by sulfate reduction immediately oxid...

  6. Microbial Community Structure and Functions in Ethanol-Fed Sulfate Removal Bioreactors for Treatment of Mine Water

    Directory of Open Access Journals (Sweden)

    Malin Bomberg

    2017-09-01

    Full Text Available Sulfate-rich mine water must be treated before it is released into natural water bodies. We tested ethanol as substrate in bioreactors designed for biological sulfate removal from mine water containing up to 9 g L−1 sulfate, using granular sludge from an industrial waste water treatment plant as inoculum. The pH, redox potential, and sulfate and sulfide concentrations were measured twice a week over a maximum of 171 days. The microbial communities in the bioreactors were characterized by qPCR and high throughput amplicon sequencing. The pH in the bioreactors fluctuated between 5.0 and 7.7 with the highest amount of up to 50% sulfate removed measured around pH 6. Dissimilatory sulfate reducing bacteria (SRB constituted only between 1% and 15% of the bacterial communities. Predicted bacterial metagenomes indicated a high prevalence of assimilatory sulfate reduction proceeding to formation of l-cystein and acetate, assimilatory and dissimilatory nitrate reduction, denitrification, and oxidation of ethanol to acetaldehyde with further conversion to ethanolamine, but not to acetate. Despite efforts to maintain optimal conditions for biological sulfate reduction in the bioreactors, only a small part of the microorganisms were SRB. The microbial communities were highly diverse, containing bacteria, archaea, and fungi, all of which affected the overall microbial processes in the bioreactors. While it is important to monitor specific physicochemical parameters in bioreactors, molecular assessment of the microbial communities may serve as a tool to identify biological factors affecting bioreactor functions and to optimize physicochemical attributes for ideal bioreactor performance.

  7. Iron-sulfide crystals in probe deposits

    DEFF Research Database (Denmark)

    Laursen, Karin; Frandsen, Flemming

    1998-01-01

    Iron-sulfides were observed in deposits collected on a probe inserted at the top of the furnace of a coal-fired power station in Denmark. The chemical composition of the iron-sulfides is equivalent to pyrrhotite (FeS). The pyrrhotites are present as crystals and, based on the shape of the crystals......: (1) impact of low viscous droplets of iron sulfide; and (2) sulfur diffusion. Previous research on the influence of pyrite on slagging focused on the decomposition of pyrite into pyrrhotite and especially on the oxidation stage of this product during impact on the heat transfer surfaces...

  8. Distinguishing iron-reducing from sulfate-reducing conditions

    Science.gov (United States)

    Chapelle, F.H.; Bradley, P.M.; Thomas, M.A.; McMahon, P.B.

    2009-01-01

    Ground water systems dominated by iron- or sulfate-reducing conditions may be distinguished by observing concentrations of dissolved iron (Fe2+) and sulfide (sum of H2S, HS-, and S= species and denoted here as "H2S"). This approach is based on the observation that concentrations of Fe2+ and H2S in ground water systems tend to be inversely related according to a hyperbolic function. That is, when Fe2+ concentrations are high, H2S concentrations tend to be low and vice versa. This relation partly reflects the rapid reaction kinetics of Fe2+ with H2S to produce relatively insoluble ferrous sulfides (FeS). This relation also reflects competition for organic substrates between the iron- and the sulfate-reducing microorganisms that catalyze the production of Fe2+ and H 2S. These solubility and microbial constraints operate in tandem, resulting in the observed hyperbolic relation between Fe2+ and H 2S concentrations. Concentrations of redox indicators, including dissolved hydrogen (H2) measured in a shallow aquifer in Hanahan, South Carolina, suggest that if the Fe2+/H2S mass ratio (units of mg/L) exceeded 10, the screened interval being tapped was consistently iron reducing (H2 ???0.2 to 0.8 nM). Conversely, if the Fe 2+/H2S ratio was less than 0.30, consistent sulfate-reducing (H2 ???1 to 5 nM) conditions were observed over time. Concomitantly high Fe2+ and H2S concentrations were associated with H2 concentrations that varied between 0.2 and 5.0 nM over time, suggesting mixing of water from adjacent iron- and sulfate-reducing zones or concomitant iron and sulfate reduction under nonelectron donor-limited conditions. These observations suggest that Fe2+/H2S mass ratios may provide useful information concerning the occurrence and distribution of iron and sulfate reduction in ground water systems. ?? 2009 National Ground Water Association.

  9. Potential of nitrate addition to control the activity of sulfate-reducing prokaryotes in high-temperature oil production systems - a comparative study on a nitrate-treated and an untreated system

    DEFF Research Database (Denmark)

    Gittel, Antje; Sørensen, Ketil; Skovhus, Torben L.

    Sulfate-reducing prokaryotes (SRP) cause severe problems like microbial corrosion and reservoir souring in seawater-injected oil production systems. Adding nitrate to the injection water is applied to control SRP activity by favoring the growth of heterotrophic, nitrate-reducing bacteria (h......NRB) and nitrate-reducing, sulfide-oxidizing bacteria (NR-SOB). Microbial diversity, abundance of Bacteria, Archaea and sulfate-reducing prokaryotes (SRP) and the potential activity of SRP were studied in production water samples from a nitrate-treated and an untreated system. The reservoirs and the produced water......) and Desulfotomaculum (system with nitrate). In samples from the untreated site, the presence of active SRP was supported by demonstrating their activity (incubations with 35S-sulfate) and growth in batch cultures at pipeline temperature. No SRP activity was detected at reservoir temperature and in samples from...

  10. Cobalt sulfide aerogel prepared by anion exchange method with enhanced pseudocapacitive and water oxidation performances

    Science.gov (United States)

    Gao, Qiuyue; Shi, Zhenyu; Xue, Kaiming; Ye, Ziran; Hong, Zhanglian; Yu, Xinyao; Zhi, Mingjia

    2018-05-01

    This work introduces the anion exchange method into the sol-gel process for the first time to prepare a metal sulfide aerogel. A porous Co9S8 aerogel with a high surface area (274.2 m2 g‑1) and large pore volume (0.87 cm3 g‑1) has been successfully prepared by exchanging cobalt citrate wet gel in thioacetamide and subsequently drying in supercritical ethanol. Such a Co9S8 aerogel shows enhanced supercapacitive performance and catalytic activity toward oxygen evolution reaction (OER) compared to its oxide aerogel counterpart. High specific capacitance (950 F g‑1 at 1 A g‑1), good rate capability (74.3% capacitance retention from 1 to 20 A g‑1) and low onset overpotential for OER (220 mV) were observed. The results demonstrated here have implications in preparing various sulfide chalcogels.

  11. Immunological detection of enzymes for sulfate reduction in anaerobic methane-oxidizing consortia.

    Science.gov (United States)

    Milucka, Jana; Widdel, Friedrich; Shima, Seigo

    2013-05-01

    Anaerobic oxidation of methane (AOM) coupled to sulfate reduction (SR) at marine gas seeps is performed by archaeal-bacterial consortia that have so far not been cultivated in axenic binary or pure cultures. Knowledge about possible biochemical reactions in AOM consortia is based on metagenomic retrieval of genes related to those in archaeal methanogenesis and bacterial sulfate reduction, and identification of a few catabolic enzymes in protein extracts. Whereas the possible enzyme for methane activation (a variant of methyl-coenzyme M reductase, Mcr) was shown to be harboured by the archaea, enzymes for sulfate activation and reduction have not been localized so far. We adopted a novel approach of fluorescent immunolabelling on semi-thin (0.3-0.5 μm) cryosections to localize two enzymes of the SR pathway, adenylyl : sulfate transferase (Sat; ATP sulfurylase) and dissimilatory sulfite reductase (Dsr) in microbial consortia from Black Sea methane seeps. Both Sat and Dsr were exclusively found in an abundant microbial morphotype (c. 50% of all cells), which was tentatively identified as Desulfosarcina/Desulfococcus-related bacteria. These results show that ANME-2 archaea in the Black Sea AOM consortia did not express bacterial enzymes of the canonical sulfate reduction pathway and thus, in contrast to previous suggestions, most likely cannot perform canonical sulfate reduction. Moreover, our results show that fluorescent immunolabelling on semi-thin cryosections which to our knowledge has been so far only applied on cell tissues, is a powerful tool for intracellular protein detection in natural microbial associations. © 2012 Society for Applied Microbiology and Blackwell Publishing Ltd.

  12. Community structure and activity of sulfate-reducing bacteria in an intertidal surface sediment: a multi-method approach

    DEFF Research Database (Denmark)

    Llobet-Brossa, E.; Rabus, R.; Böttcher, M.

    2002-01-01

    by the presence of acid-volatile sulfides (AVS, essentially iron monosulfide). Stable sulfur isotope discrimination between dissolved sulfate and AVS was dominated by sulfate reduction. The diversity of SRB was studied using denaturant gradient gel electrophoresis of 16S rDNA, phospholipid fatty acid analysis...

  13. Synthesis of Copper Sulfide Nanoparticles Using Biogenic H2S Produced by a Low-pH Sulfidogenic Bioreactor

    Directory of Open Access Journals (Sweden)

    Camila Colipai

    2018-01-01

    Full Text Available The application of acidophilic sulfate-reducing bacteria (SRB for the treatment of acidic mine water has been recently developed to integrate mine water remediation and selective biomineralization. The use of biogenic hydrogen sulfide (H2S produced from the dissimilatory reduction of sulfate to fabricate valuable products such as metallic sulfide nanoparticles has potential applications in green chemistry. Here we report on the operation of a low-pH sulfidogenic bioreactor, inoculated with an anaerobic sediment obtained from an acid river in northern Chile, to recover copper via the production of copper sulfide nanoparticles using biogenic H2S. The laboratory-scale system was operated as a continuous flow mode for up to 100 days and the bioreactor pH was maintained by the automatic addition of a pH 2.2 influent liquor to compensate for protons consumed by biosulfidogenesis. The “clean” copper sulfide nanoparticles, produced in a two-step process using bacterially generated sulfide, were examined using transmission electron microscopy, dynamic light scattering, energy dispersive (X-ray spectroscopy and UV-Vis spectroscopy. The results demonstrated a uniform nanoparticle size distribution with an average diameter of less than 50 nm. Overall, we demonstrated the production of biogenic H2S using a system designed for the treatment of acid mine water that holds potential for large-scale abiotic synthesis of copper sulfide nanoparticles.

  14. Electron Spectroscopy Studies of Iron, Iron Sulfides and Supported Iron Surfaces: Chemisorption of Simple Gases.

    Science.gov (United States)

    Lee, Yiu Chung

    EELS was used to investigate the chemisorption of oxygen and carbon on iron. The EELS spectra of oxidized iron show characteristic features with strong enhancement of the interband transitions involving the Fe 3d band (4.6 and 7.5 eV) and moderate enhancement of the M(,2,3) transition doublet (54.4 and 58.2 eV). The changes in the electron energy loss structures with an overlayer of graphitic or carbidic carbon were investigated. The adsorption and growth of iron on Ni(100) has been studied using the combined techniques of LEED and EELS. Initially iron grows by a layer-by-layer mechanism for the first few layers. High iron coverages result in the observation of complex LEED patterns with satellites around the main (1 x 1) diffraction sports. This is due to the formation of b.c.c. Fe(110) crystallites arranged in domains with different orientations. EELS studies show the presence of three stages in the growth of iron on Ni(100): low-coverage, film-like and bulk-like. Auger and EELS were used to study the iron sulfide (FeS(,2), Fe(,7)S(,8) and FeS) surfaces. A characteristic M(,2,3) VV Auger doublet with a separation of 5.0 eV was observed on the sulfides. An assignment of the electron energy loss peaks was made based on the energy dependence of the loss peaks and previous photoemission results. The effect of argon ion bombardment was studied. Peaks with strong iron and sulfur character were observed. Heating the damaged sulfides results in reconstruction of the sulfide surfaces. The reactions of the sulfides with simple gases, such as H(,2), CO, CH(,4), C(,2)H(,4), NH(,3) and O(,2) were also studied. Using XPS, the chemisorption of SO(,2) on CaO(100) has been studied. The chemical state of sulfur has been identified as that of sulfate. The kinetics of SO(,2) chemisorption on CaO are discussed. The binding states of Fe and Na on CaO were determined to be Fe('2+) and Na('+) respectively. At low Fe or Na coverages (< 0.5 ML), there is a large increase in the rate of

  15. Preparation of transition metal sulfide nanoparticles via hydrothermal route

    International Nuclear Information System (INIS)

    Fei-Ling, P.; Chin-Hua, C.; Sarani Zakaria; Tze-Khong, L.; Mohd Ambar Yarmo; Nay-Ming, H.

    2010-01-01

    Nano sized copper sulfide, iron sulfide and molybdenum sulfide were successfully synthesised via a simple hydrothermal method. Sodium thiosulfate pentahydrate (Na 2 S 2 O 3 ·5H 2 O) and hydroxylamine sulfate ((H 3 NO) 2 ·H 2 SO 4 ) were used as the starting materials and reacted with the transition metal source at 200 degree Celsius for 90 min. The products were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and Fourier transform infrared spectroscopy (FTIR). Spherical shape CuS and FeS 2 nanoparticles with high crystallinity were successfully produced. The transmission electron micrographs revealed the well-dispersibility of the produced nanoparticles. Scanning electron micrograph showed the MoS 2 nanoparticles possessed a spherical shape with sheet-like structure covering on the outer surface of the particles. (author)

  16. Tillage and water management for riceland productivity in acid sulfate soils of the Mekong delta, Vietnam.

    NARCIS (Netherlands)

    Minh, L.Q.; Tuong, T.P.; Mensvoort, van M.E.F.; Bouma, J.

    1997-01-01

    Acid sulfate soils are characterized by low pH and high concentrations of aluminum, sulfate, iron and hydrogen sulfide. Removal of at least part of these substances is a prerequisite for land use, at least in severely acid soils. In this study, the effectiveness of harrowing and flushing with

  17. Selective production of hydrogen peroxide and oxidation of hydrogen sulfide in an unbiased solar photoelectrochemical cell

    DEFF Research Database (Denmark)

    Zong, Xu; Chen, Hongjun; Seger, Brian

    2014-01-01

    A solar-to-chemical conversion process is demonstrated using a photoelectrochemical cell without external bias for selective oxidation of hydrogen sulfide (H2S) to produce hydrogen peroxide (H2O2) and sulfur (S). The process integrates two redox couples anthraquinone/anthrahydroquinone and I−/I3......−, and conceptually illustrates the remediation of a waste product for producing valuable chemicals....

  18. Synthesis of zinc sulfide by chemical vapor deposition using an organometallic precursor: Di-tertiary-butyl-disulfide

    International Nuclear Information System (INIS)

    Vasekar, Parag; Dhakal, Tara; Ganta, Lakshmikanth; Vanhart, Daniel; Desu, Seshu

    2012-01-01

    Zinc sulfide has gained popularity in the last few years as a cadmium-free heterojunction partner for thin film solar cells and is seen as a good replacement for cadmium sulfide due to better blue photon response and non-toxicity. In this work, zinc sulfide films are prepared using an organic sulfur source. We report a simple and repeatable process for development of zinc sulfide using a cost-effective and less hazardous organic sulfur source. The development of zinc sulfide has been studied on zinc oxide-coated glass where the zinc oxide is converted into zinc sulfide. Zinc oxide grown by atomic layer deposition as well as commercially available zinc oxide-coated glass was used. The zinc sulfide synthesis has been studied and the films are characterized using scanning electron microscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and a UV–VIS spectrophotometer. XRD, XPS and optical characterization confirm the zinc sulfide phase formation. - Highlights: ► Synthesis of ZnS using a less-hazardous precursor, di-tertiary-butyl-disulfide. ► ZnS process optimized for two types of ZnO films. ► Preliminary results for a solar cell show an efficiency of 1.09%.

  19. Effect of pH buffering capacity and sources of dietary sulfur on rumen fermentation, sulfide production, methane production, sulfate reducing bacteria, and total Archaea in in vitro rumen cultures.

    Science.gov (United States)

    Wu, Hao; Meng, Qingxiang; Yu, Zhongtang

    2015-06-01

    The effects of three types of dietary sulfur on in vitro fermentation characteristics, sulfide production, methane production, and microbial populations at two different buffer capacities were examined using in vitro rumen cultures. Addition of dry distilled grain with soluble (DDGS) generally decreased total gas production, degradation of dry matter and neutral detergent fiber, and concentration of total volatile fatty acids, while increasing ammonia concentration. High buffering capacity alleviated these adverse effects on fermentation. Increased sulfur content resulted in decreased methane emission, but total Archaea population was not changed significantly. The population of sulfate reducing bacteria was increased in a sulfur type-dependent manner. These results suggest that types of dietary sulfur and buffering capacity can affect rumen fermentation and sulfide production. Diet buffering capacity, and probably alkalinity, may be increased to alleviate some of the adverse effects associated with feeding DDGS at high levels. Copyright © 2015 Elsevier Ltd. All rights reserved.

  20. Sulfide Generation by Dominant Halanaerobium Microorganisms in Hydraulically Fractured Shales

    Energy Technology Data Exchange (ETDEWEB)

    Booker, Anne E.; Borton, Mikayla A.; Daly, Rebecca A.; Welch, Susan A.; Nicora, Carrie D.; Hoyt, David W.; Wilson, Travis; Purvine, Samuel O.; Wolfe, Richard A.; Sharma, Shikha; Mouser, Paula J.; Cole, David R.; Lipton, Mary S.; Wrighton, Kelly C.; Wilkins, Michael J.; McMahon, Katherine

    2017-07-05

    research demonstrates that dominant microbial populations in these subsurface ecosystems contain the conserved capacity for the reduction of thiosulfate to sulfide and that this process is likely occurring in the environment. Sulfide generation (also known as “souring”) is considered deleterious in the oil and gas industry because of both toxicity issues and impacts on corrosion of the subsurface infrastructure. Critically, the capacity for sulfide generation via reduction of sulfate was not detected in our data sets. Given that current industry wellhead tests for sulfidogenesis target canonical sulfate-reducing microorganisms, these data suggest that new approaches to the detection of sulfide-producing microorganisms may be necessary.

  1. Processes affecting δ34S and δ18O values of dissolved sulfate in alluvium along the Canadian River, central Oklahoma, USA

    Science.gov (United States)

    Tuttle, Michele L.W.; Breit, George N.; Cozzarelli, Isabelle M.

    2009-01-01

    The δ34S and δ18O values for dissolved sulfate in groundwater are commonly used in aquifer studies to identify sulfate reservoirs and describe biogeochemical processes. The utility of these data, however, often is compromised by mixing of sulfate sources within reservoirs and isotope fractionation during sulfur redox cycling. Our study shows that, after all potential sulfate sources are identified and isotopically characterized, the δ34SSO4 and δ18OSO4 values differentiate processes such as sulfate-source mixing, sulfide oxidation, barite dissolution, and organosulfur decomposition. During bacterial reduction of sulfate, the values reflect kinetic sulfur isotope fractionation and exchange of oxygen isotopes between sulfate and water. Detailed analysis of the chemistry (Cl and SO4 concentrations) and isotopic composition (δ2HH2Oand δ18OH2O) of groundwater in an alluvial aquifer in Central Oklahoma, USA allowed the identification of five distinct end members that supply water to the aquifer (regional groundwater flowing into the study area, river water, leachate from a closed landfill that operated within the site, rain, and surface runoff). The δ34SSO4 and δ18OSO4 values in each end member differentiated three sources of sulfate: sulfate dissolved from Early to Late Permian rocks within the drainage basin (δ34SSO4 = 8–12‰ and δ18OSO4 = 10‰), iron sulfides oxidized by molecular oxygen during low water-table levels (δ34SSO4 = − 16‰ and δ18OSO4 = 10‰), and organosulfur compounds (predominately ester sulfates) from decomposition of vegetation on the surface and from landfill trash buried in the alluvium (δ34SSO4 = 8‰ and δ18OSO4 = 6‰). During bacterial reduction of these sulfate sources, similar isotope fractionation processes are recorded in the parallel trends of increasing δ34SSO4 and δ18OSO4 values. When extensive reduction occurs, the kinetic sulfur isotope fractionation (estimated by εH2S–SO4 = − 23

  2. A Cryptic Sulfur Cycle in Oxygen-Minimum-Zone Waters off the Chilean Coast

    Science.gov (United States)

    Canfield, Don E.; Stewart, Frank J.; Thamdrup, Bo; De Brabandere, Loreto; Dalsgaard, Tage; Delong, Edward F.; Revsbech, Niels Peter; Ulloa, Osvaldo

    2010-12-01

    Nitrogen cycling is normally thought to dominate the biogeochemistry and microbial ecology of oxygen-minimum zones in marine environments. Through a combination of molecular techniques and process rate measurements, we showed that both sulfate reduction and sulfide oxidation contribute to energy flux and elemental cycling in oxygen-free waters off the coast of northern Chile. These processes may have been overlooked because in nature, the sulfide produced by sulfate reduction immediately oxidizes back to sulfate. This cryptic sulfur cycle is linked to anammox and other nitrogen cycling processes, suggesting that it may influence biogeochemical cycling in the global ocean.

  3. Luminescent hybrid lanthanide sulfates and lanthanide sulfonate-carboxylates with 1,10-phenanthroline involving in-situ oxidation of 2-mercaptonbenzoic acid

    International Nuclear Information System (INIS)

    Zhong, Jie-Cen; Wan, Fang; Sun, Yan-Qiong; Chen, Yi-Ping

    2015-01-01

    A series of lanthanide sulfates and lanthanide sulfonate-carboxylates, [Ln 2 (phen) 2 (SO 4 ) 3 (H 2 O) 2 ] n (I:Ln=Nd(1a), Sm(1b), Eu(1c), phen=1,10-phenanthroline) and [Ln(phen)(2-SBA)(BZA)] n (II: Ln=Sm(2a), Eu(2b), Dy(2c), 2-SBA=2-sulfobenzoate, BZA=benzoate) have been hydrothermally synthesized from lanthanide oxide, 2-mercaptonbenzoic acid with phen as auxiliary ligand and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectra, TG analyses and luminescence spectroscopy. Interestingly, SO 4 2− anions in I came from the in situ deep oxidation of thiol groups of 2-mercaptonbenzoic acid while 2-sulfobenzoate and benzoate ligands in II from the middle oxidation and desulfuration reactions of 2-mercaptonbenzoic acid. Compounds I are organic–inorganic hybrid lanthanide sulfates, which have rare one-dimensional column-like structures. Complexes II are binuclear lanthanide sulfonate-carboxylates with 2-sulfobenzoate and benzoate as bridges and 1,10-phenanthroline as terminal. Photoluminescence studies reveal that complexes I and II exhibit strong lanthanide characteristic emission bands in the solid state at room temperature. - Graphical abstract: Lanthanide sulfates and lanthanide sulfonate-carboxylates have been hydrothermally synthesized. Interestingly, sulfate anions, 2-sulfobenzoate and benzoate ligands came from the in situ oxidation and desulfuration reactions of 2-mercaptonbenzoic acid. - Highlights: • In situ oxidation and desulfuration reactions of 2-mercaptonbenzoic acid. • The organic–inorganic hybrid lanthanide sulfates with one-dimensional column-like structure. • The dinuclear lanthanide sulfonate-carboxylates. • The emission spectra exhibit the characteristic transition of 5 D 0 → 7 F J (J=0–4) of the Eu(III)

  4. Contribution to the study of the role of sulfate-reducing bacteria in bio-corrosion phenomenon

    International Nuclear Information System (INIS)

    Chatelus, C.

    1987-11-01

    By their metabolic activities of hydrogen consumption and of sulfides production, the sulfate-reducing bacteria are the main bacteria responsible of the metallic corrosion phenomena in the absence of oxygen. A physiological and enzymatic study of some Desulfovibrio has contributed to the understanding of the role of these bacteria in the anaerobic bio-corrosion phenomena. Desulfovibrio (D.) vulgaris in organic medium, after having oxidized the lactate, consumes the hydrogen formed by the electrochemical reaction of iron dissolution. The Desulfovibrio can be responsible either of a corrosion by a direct contact with the metal in using the H 2 layer formed at its surface, (bacteria are then adsorbed at the surface because of an iron sulfide crystalline lattice), or of a distant corrosion in consuming the dissolved or gaseous hydrogen. As their hydrogenases can be stable in time independently of the cellular structure (D. vulparis) and active at high temperatures (to 70 C - 75 C) (D. baculatus), these bacteria can act in conditions incompatible with the viability of cells but compatible with the enzymatic expression. A study in terms of temperature has shown that inside the mesophilic group of the Desulfovibrio, the behaviour towards this parameter is specific to each bacteria, that accounts for the permanent presence of the representatives of this population in sites where the temperature variations are important. A change of some degrees Celsius can induce modifications in the yields of bacteria growth and by a consequence in variations in the corrosion intensity. Moreover, sulfate D. multispirans can reduce with specific velocities of different growth, the nitrate, the nitrite and the fumarate. Some sulfato-reducing could then adapt themselves to the variations of concentrations in electron acceptors and metabolize the oxidized substances used as biocides too. The choice of an electron acceptor rather than another do not depend uniquely of the specificity of the

  5. Solid-state ionics: Studies of lithium-conducting sulfide glasses and a superconducting oxide compound

    International Nuclear Information System (INIS)

    Ahn, Byung Tae.

    1989-01-01

    The first part of this work studies lithium-conducting sulfide glasses for battery applications, while the second part studies the thermodynamic properties of a superconducting oxide compound by using an oxide electrolyte. Lithium conducting glasses based on the SiS 2 -Li 2 S system are possible solid electrolytes for high-energy-density lithium batteries. The foremost requirement for solid electrolytes is that they should have high ionic conductivities. Unfortunately, most crystalline lithium conductors have low ionic conductivities at room temperature. However, glass ionic conductors show higher ionic conductivities than do crystalline forms of the same material. In addition to higher ionic conductivities, glasses appear to have several advantages over crystalline materials. These advantages include isotropic conductivity, absence of grain boundary effects, ease of glass forming, and the potential for a wide range of stability to oxidizing and reducing conditions. Using pyrolitic graphite-coated quartz ampoules, new ternary compounds and glasses in the SiS 2 -Li 2 S system were prepared. Several techniques were used to characterize the materials: powder x-ray diffraction, differential thermal analysis, differential scanning calorimetry, and AC impedance spectroscopy. The measured lithium conductivity of the sulfide glasses was one of the highest among the known solid lithium conductors. Measuring the equilibrium open circuit voltages assisted in determining the electrochemical stabilities of the ternary compounds and glasses with respect to pure Li. A solid-state ionic technique called oxygen coulometric titration was used to measure the thermodynamic stability, the oxygen stoichiometry, and the effects of the oxygen stoichiometry, and the effects of the oxygen stoichiometry and the cooling rate on superconductivity of the YBa 2 Cu 3 O 7-x compound were investigated

  6. Hydrogen sulfide oxidation in novel Horizontal-Flow Biofilm Reactors dominated by an Acidithiobacillus and a Thiobacillus species.

    Science.gov (United States)

    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.

  7. Sulfate-reducing bacteria influence the nucleation and growth of mackinawite and greigite

    Science.gov (United States)

    Picard, Aude; Gartman, Amy; Clarke, David R.; Girguis, Peter R.

    2018-01-01

    Sedimentary iron sulfide minerals play a key role in maintaining the oxygenation of Earth's atmosphere over geological timescales; they also record critical geochemical information that can be used to reconstruct paleo-environments. On modern Earth, sedimentary iron sulfide mineral formation takes places in low-temperature environments and requires the production of free sulfide by sulfate-reducing microorganisms (SRM) under anoxic conditions. Yet, most of our knowledge on the properties and formation pathways of iron sulfide minerals, including pyrite, derives from experimental studies performed in abiotic conditions, and as such the role of biotic processes in the formation of sedimentary iron sulfide minerals is poorly understood. Here we investigate the role of SRM in the nucleation and growth of iron sulfide minerals in laboratory experiments. We set out to test the hypothesis that SRM can influence Fe-S mineralization in ways other than providing sulfide through the comparison of the physical properties of iron sulfide minerals precipitated in the presence and in the absence of the sulfate-reducing bacterium Desulfovibrio hydrothermalis AM13 under well-controlled conditions. X-ray diffraction and microscopy analyses reveal that iron sulfide minerals produced in the presence of SRM exhibit unique morphology and aggregate differently than abiotic minerals formed in media without cells. Specifically, mackinawite growth is favored in the presence of both live and dead SRM, when compared to the abiotic treatments tested. The cell surface of live and dead SRM, and the extracellular polymers produced by live cells, provide templates for the nucleation of mackinawite and favor mineral growth. The morphology of minerals is however different when live and dead cells are provided. The transformation of greigite from mackinawite occurred after several months of incubation only in the presence of live SRM, suggesting that SRM might accelerate the kinetics of greigite

  8. Adaptation of cyanobacteria to the sulfide-rich microenvironment of black band disease of coral.

    Science.gov (United States)

    Myers, Jamie L; Richardson, Laurie L

    2009-02-01

    Black band disease (BBD) is a cyanobacteria-dominated microbial mat that migrates across living coral colonies lysing coral tissue and leaving behind exposed coral skeleton. The mat is sulfide-rich due to the presence of sulfate-reducing bacteria, integral members of the BBD microbial community, and the sulfide they produce is lethal to corals. The effect of sulfide, normally toxic to cyanobacteria, on the photosynthetic capabilities of five BBD cyanobacterial isolates of the genera Geitlerinema (3), Leptolyngbya (1), and Oscillatoria (1) and six non-BBD cyanobacteria of the genera Leptolyngbya (3), Pseudanabaena (2), and Phormidium (1) was examined. Photosynthetic experiments were performed by measuring the photoincorporation of [(14)C] NaHCO(3) under the following conditions: (1) aerobic (no sulfide), (2) anaerobic with 0.5 mM sulfide, and (3) anaerobic with 0.5 mM sulfide and 10 microM 3-(3',4'-dichlorophenyl)-1,1-dimethylurea (DCMU). All five BBD cyanobacterial isolates tolerated sulfide by conducting sulfide-resistant oxygenic photosynthesis. Five of the non-BBD cyanobacterial isolates did not tolerate sulfide, although one Pseudanabaena isolate continued to photosynthesize in the presence of sulfide at a considerably reduced rate. None of the isolates conducted anoxygenic photosynthesis with sulfide as an electron donor. This is the first report on the physiology of a culture of Oscillatoria sp. found globally in BBD.

  9. Reconciling "Whiffs" of O2 with the Archean MIF S Record: Insights from Sulfide Oxidation Experiments

    Science.gov (United States)

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

    2016-12-01

    The Archean-Proterozoic transition is marked by the first appreciable accumulation of O2 in Earth's oceans and atmosphere at 2.4 billion years ago (Ga). However, this Great Oxidation Event (GOE) is not the first evidence for O2 in Earth's surface environment. Paleoredox proxies preserved in ancient marine shales (Mo, Cr, Re, U) suggest transient episodes of oxidative weathering before the GOE, perhaps as early as 3.0 Ga. One marine shale in particular, the 2.5 Ga Mount McRae Shale of Western Australia, contains a euxinic interval with Mo enrichments up to 50 ppm. This enrichment is classically interpreted as the result of oxidative weathering of sulfides on the continental surface. However, prior weathering models based on experiments suggested that sulfides require large amounts of O2 [>10-4 present atmospheric level (PAL) pO2] to produce this weathering signature, in conflict with estimates of Archean pO2 from non-mass-dependent (NMD) sulfur isotope anomalies (molybdenite from 3 - 700 nM O2 (equivalent at equilibrium to 10-5 - 10-3 PAL) to measure oxidation kinetics as a function of the concentration of dissolved O2. We measured rates by injecting oxygenated water at a steady flow rate and monitoring dissolved O2 concentrations with LUMOS sensors. Our data extend the O2 range explored in pyrite oxidation experiments by three orders of magnitude and provide the first rates for molybdenite oxidation at O2 concentrations potentially analogous to those characteristic of the Archean atmosphere. Our results show that pyrite and molybdenite oxidize significantly more rapidly at lower O2 levels than previously thought. As a result, our revised weathering model demonstrates that the Mo enrichments observed in late Archean marine shales are potentially attainable at extremely low atmospheric pO2 values (e.g., <10-5 PAL), reconciling large sedimentary Mo enrichments with co-occurring NMD sulfur isotope anomalies.

  10. Effects of Wood Pollution on Pore-Water Sulfide Levels and Eelgrass Germination

    Science.gov (United States)

    Ekelem, C.

    2016-02-01

    Historically, sawmills released wood waste onto coastal shorelines throughout the Pacific Northwest of the USA, enriching marine sediments with organic material. The increase in organic carbon boosts the bacterial reduction of sulfate and results in the production of a toxic metabolite, hydrogen sulfide. Hydrogen sulfide is a phytotoxin and can decrease the growth and survival of eelgrass. This is a critical issue since eelgrass, Zostera marina, forms habitat for many species, stabilizes sediment, and plays a role in nutrient cycling and sediment chemistry. The objective of our study was to determine the effects of wood debris on sediment pore-water hydrogen sulfide concentrations and eelgrass germination. To test the impact of wood inputs on sulfide production and seed germination, we conducted a laboratory mesocosm experiment, adding sawdust to marine sediments and measuring the sulfide levels weekly. We subsequently planted seeds in the mesocosms and measured germination rates. Higher concentrations of sawdust led to higher levels of pore-water hydrogen sulfide and drastically slower eelgrass germination rates. Treatments with greater than 10% wood enrichment developed free sulfide concentrations of 0.815 (± 0.427) mM after 118 days, suggesting sediments with greater than 10% wood pollution may have threateningly high pore-water hydrogen sulfide levels. These results can be used to set thresholds for remediation efforts and guide seed distribution in wood polluted areas.

  11. Metal dispersion in groundwater in an area with natural and processed black shale - Nationwide perspective and comparison with acid sulfate soils

    International Nuclear Information System (INIS)

    Lavergren, Ulf; Astroem, Mats E.; Falk, Helena; Bergbaeck, Bo

    2009-01-01

    Black shale is often rich in sulfides and trace elements, and is thus a potential environmental threat in a manner similar to acid sulfate soils and active or abandoned sulfide mines. This study aims at characterising how exposed and processed (mined and burnt) black shale (alum shale) in Degerhamn, SE Sweden, affects the chemistry (Al, As, Ba, Cd, Ca, Cr, Co, Cu, Fe, Pb, Mg, Mn, Mo, Ni, K, Si, Na, Sr, S, U, V and Zn) of the groundwater. There were large variations in groundwater chemistry between nearby sampling points, while the temporal variations generally were small. Acidic groundwater (around pH 4), found in deposits of burnt and carbonate-poor shale where the conditions for sulfide oxidation were favourable, was strongly elevated in Al, U and several chalcophilic metals (Cd, Co, Cu, Ni and Zn). Cadmium and U were also, together with Mo, abundant in many of the near-neutral waters, both in the non-mined black shale bedrock and in the deposits of burnt shale. An extrapolation to a national level suggests that the dispersion of Ni from naturally occurring black shale is similar to that from anthropogenic point sources, while for Cd and As it is assessed to be approximately one tenth of that from point sources. The processed shale was, however, a much larger source of metals than the black shale bedrock itself, showing this material's potential as a massive supplier of metals to the aquatic environment. A comparison of waters in contact with the processed Cambrian-Ordovician black shale in Degerhamn and acid sulfate soils of the region shows that these two sulfide-bearing materials, in many respects very different, delivers basically the same suite of trace elements to the aquatic environment. This has implications for environmental planning and protection in areas where these types of materials exist

  12. Practical considerations of pyrite oxidation control in uranium tailings

    International Nuclear Information System (INIS)

    1984-05-01

    The problems posed by the oxidation of pyrite in uranium tailings include the generation of sulfuric acid and acid sulfate metal salts. These have substantial negative impacts on watercourse biota by themselves, and the lowered pH levels tend to mobilize heavy metals present in the tailings the rate of oxidation of pyrite at lower pH levels is catalyzed by sulfur and iron oxidizing bacteria present in soils. No single clear solution to the problems came from this study. Exclusion of air is a most important preventative of bacterial catalysis of oxidation. Bactericides, chemically breaking the chain of integrated oxidation reactions, maintaining anaerobic conditions, or maintaining a neutral or alkaline pH all reduce the oxidation rate. Removal of pyrite by flotation will reduce but not eliminate the impact of pyrite oxidation. Controlled oxidation of the remaining sulfide in the flotation tails would provide an innocuous tailing so far as acidity generation is concerned

  13. Weathering behavior of mine tailings and waste rock: A surface investigation

    International Nuclear Information System (INIS)

    Domvile, S.J.; Li, M.G.; Sollner, D.D.; Nesbitt, W.

    1994-01-01

    A study focusing on the ion movement in the near surface of sulfide minerals was conducted to better understand the weathering mechanisms of mine waste materials. Tailings and waste rock samples from Canadian mines were subjected to controlled weathering studies using various chemical leachants. Leachates were analyzed for various parameters, and petrographic analyses were conducted on the solid residues. Laboratory oxidation studies of pure pyrrhotite and arsenopyrite were carried out using the surface techniques X-ray photoelectron spectroscopy (XPS) and auger electron spectroscopy (AES). The data derived from the weathering study and the surface techniques were correlated to determine mechanisms of oxidation. Several results were observed during the project: ferric iron constitutes one third of the iron present in pyrrhotite, sulfide oxidation is initiated when rock is blasted, sulfide sulfur is oxidized to di- and poly-sulfides prior to forming sulfates, and significantly more sulfate is produced upon exposure to aqueous environments than to air alone

  14. Selective Sulfidation of Lead Smelter Slag with Sulfur

    Science.gov (United States)

    Han, Junwei; Liu, Wei; Wang, Dawei; Jiao, Fen; Qin, Wenqing

    2016-02-01

    The selective sulfidation of lead smelter slag with sulfur was studied. The effects of temperature, sulfur dosage, carbon, and Na salts additions were investigated based on thermodynamic calculation. The results indicated that more than 96 pct of zinc in the slag could be converted into sulfides. Increasing temperature, sulfur dosage, or Na salts dosage was conducive to the sulfidation of the zinc oxides in the slag. High temperature and excess Na salts would result in the more consumption of carbon and sulfur. Carbon addition not only promoted the selective sulfidation but reduced the sulfur dosage and eliminated the generation of SO2. Iron oxides had a buffering role on the sulfur efficient utilization. The transformation of sphalerite to wurtzite was feasible under reducing condition at high temperature, especially above 1273 K (1000 °C). The growth of ZnS particles largely depended upon the roasting temperature. They were significantly increased when the temperature was above 1273 K (1000 °C), which was attributed to the formation of a liquid phase.

  15. Anoxic sulfide biooxidation using nitrite as electron acceptor

    International Nuclear Information System (INIS)

    Mahmood, Qaisar; Zheng Ping; Cai Jing; Wu Donglei; Hu, Baolan; Li Jinye

    2007-01-01

    Biotechnology can be used to assess the well being of ecosystems, transform pollutants into benign substances, generate biodegradable materials from renewable sources, and develop environmentally safe manufacturing and disposal processes. Simultaneous elimination of sulfide and nitrite from synthetic wastewaters was investigated using a bioreactor. A laboratory scale anoxic sulfide-oxidizing (ASO) reactor was operated for 135 days to evaluate the potential for volumetric loading rates, effect of hydraulic retention time (HRT) and substrate concentration on the process performance. The maximal sulfide and nitrite removal rates were achieved to be 13.82 and 16.311 kg/(m 3 day), respectively, at 0.10 day HRT. The process can endure high sulfide concentrations, as the sulfide removal percentage always remained higher than 88.97% with influent concentration up to 1920 mg/L. Incomplete sulfide oxidation took place due to lower consumed nitrite to sulfide ratios of 0.93. It also tolerated high nitrite concentration up to 2265.25 mg/L. The potential achieved by decreasing HRT at fixed substrate concentration is higher than that by increasing substrate concentration at fixed HRT. The process can bear short HRT of 0.10 day but careful operation is needed. Nitrite conversion was more sensitive to HRT than sulfide conversion when HRT was decreased from 1.50 to 0.08 day. Stoichiometric analyses and results of batch experiments show that major part of sulfide (89-90%) was reduced by nitrite while some autooxidation (10-11%) was resulted from presence of small quantities of dissolved oxygen in the influent wastewater. There was ammonia amassing in considerably high amounts in the bioreactor when the influent nitrite concentration reached above 2265.25 mg/L. High ammonia concentrations (200-550 mg/L) in the bioreactor contributed towards the overall inhibition of the process. Present biotechnology exhibits practical value with a high potential for simultaneous removal of nitrite

  16. Nitrogen release from forest soils containing sulfide-bearing sediments

    Science.gov (United States)

    Maileena Nieminen, Tiina; Merilä, Päivi; Ukonmaanaho, Liisa

    2014-05-01

    Soils containing sediments dominated by metal sulfides cause high acidity and release of heavy metals, when excavated or drained, as the aeration of these sediments causes formation of sulfuric acid. Consequent leaching of acidity and heavy metals can kill tree seedlings and animals such as fish, contaminate water, and corrode concrete and steel. These types of soils are called acid sulfate soils. Their metamorphic equivalents, such as sulfide rich black shales, pose a very similar risk of acidity and metal release to the environment. Until today the main focus in treatment of the acid sulfate soils has been to prevent acidification and metal toxicity to agricultural crop plants, and only limited attention has been paid to the environmental threat caused by the release of acidity and heavy metals to the surrounding water courses. Even less attention is paid on release of major nutrients, such as nitrogen, although these sediments are extremely rich in carbon and nitrogen and present a potentially high microbiological activity. In Europe, the largest cover of acid sulfate soils is found in coastal lowlands of Finland. Estimates of acid sulfate soils in agricultural use range from 1 300 to 3 000 km2, but the area in other land use classes, such as managed peatland forests, is presumably larger. In Finland, 49 500 km2 of peatlands have been drained for forestry, and most of these peatland forests will be at the regeneration stage within 10 to 30 years. As ditch network maintenance is often a prerequisite for a successful establishment of the following tree generation, the effects of maintenance operations on the quality of drainage water should be under special control in peatlands underlain by sulfide-bearing sediments. Therefore, identification of risk areas and effective prevention of acidity and metal release during drain maintenance related soil excavating are great challenges for forestry on coastal lowlands of Finland. The organic and inorganic nitrogen

  17. Oxidation study of the synthetic sulfides molybdenite (MoS{sub 2}) and covellite (CuS) by acidithiobacillus ferrooxidants using respirometric experiments; Estudo da oxidacao dos sulfetos sinteticos molibdenita (MoS2) e covelita (CuS) por Acidithiobacillus ferrooxidans via respirometria celular

    Energy Technology Data Exchange (ETDEWEB)

    Francisco Junior, Wilmo E. [Universidade Federal de Rondonia (UFRO), Porto Velho, RO (Brazil). Dept. de Quimica; Universidade Estadual Paulista (UNESP), Araraquara, SP (Brazil). Inst. de Quimica. Dept. de Bioquimica e Tecnologia Quimica], e-mail: wilmojr@bol.com.br; Bevilaqua, Denise; Garcia Junior, Oswaldo [Universidade Estadual Paulista (UNESP), Araraquara, SP (Brazil). Inst. de Quimica. Dept. de Bioquimica e Tecnologia Quimica

    2009-07-01

    This paper analyses the oxidation of covellite and molybdenite by Acidithiobacillus ferrooxidans strain LR using respirometric experiments. The results showed that both sulfides were oxidized by A. ferrooxidans, however, the covellite oxidation was much higher than molybdenite. Regarding the kinetic oxidation, the findings revealed that just molybdenite oxidation followed the classical Michaelis-Menten kinetic. It is probably associated with the pathway which these sulfides react to chemistry-bacterial attack, what is influenced by its electronic structures. Besides, experiments conducted in the presence of Fe{sup 3+} did not indicate alterations in molybdenite oxidation. Thus, ferric ions seem not to be essential to the sulfide oxidations. (author)

  18. Isotope geochemistry of waters affected by acid mine drainage in old labour sites (SE, Spain).

    Science.gov (United States)

    Pérez-Sirvent, Carmen; Martinez-Sanchez, Maria Jose; Garcia-Lorenzo, Maria Luz; Agudo, Ines; Hernandez-Cordoba, Manuel; Recio, Clemente

    2015-04-01

    The ore deposits of this zone have iron, lead and zinc as the main metal components. Iron is present in oxides, hydroxides, sulfides, sulfates, carbonates, and silicates; lead and zinc occur in sulfides (galena and sphalerite, respectively), carbonates, sulfates, and lead or zinc-bearing (manganese, iron) oxides. Mining started with the Romans and activity peaked in the second half of the 19th century and throughout the 20th century until the 1980's. From 1940 to 1957, mineral concentration was made by froth flotation and, prior to this, by gravimetric techniques. The mining wastes, or tailings, with a very fine particle size were deposited inland (tailings dams) and, since 1957, huge releases were made in directly the sea coast. The objective of this work was to evaluate processes affecting waters from abandoned mine sites by way of stable isotopic analysis, particularly H and O stable isotopes from water and S and O from dissolved sulfates. Several common chemical and physical processes, such as evaporation, water-rock interaction and mixing could alter water isotopic composition. Evaporation, which causes an enrichment in δD and δ18O in the residual water, is an important process in semiarid areas. The results obtained indicate that, for sites near the coast, waters are meteoric, and marine infiltration only takes place in the deepest layers near the shore or if water remains stagnated in sediments with low permeability. The main source of sulfate was the oxidation of sulfides, resulting in the liberation of acid, sulfate and metals. In order to assess the mechanism responsible for sulfide oxidation, the stoichiometric isotope balance model and the general isotope balance model were tested, suggesting that the oxidation via Fe3+ was predominant in the surface, and controlled by A. ferrooxidans, while at depth, sulfate reduction occurred.

  19. Sulfate reduction and methane oxidation activity below the sulfate-methane transition zone in Alaskan Beaufort Sea continental margin sediments: Implications for deep sulfur cycling

    Science.gov (United States)

    Treude, Tina; Krause, Stefan; Maltby, Johanna; Dale, Andrew W.; Coffin, Richard; Hamdan, Leila J.

    2014-11-01

    Two ∼6 m long sediment cores were collected along the ∼300 m isobath on the Alaskan Beaufort Sea continental margin. Both cores showed distinct sulfate-methane transition zones (SMTZ) at 105 and 120 cm below seafloor (cmbsf). Sulfate was not completely depleted below the SMTZ but remained between 30 and 500 μM. Sulfate reduction and anaerobic oxidation of methane (AOM) determined by radiotracer incubations were active throughout the methanogenic zone. Although a mass balance could not explain the source of sulfate below the SMTZ, geochemical profiles and correlation network analyses of biotic and abiotic data suggest a cryptic sulfur cycle involving iron, manganese and barite. Inhibition experiments with molybdate and 2-bromoethanesulfonate (BES) indicated decoupling of sulfate reduction and AOM and competition between sulfate reducers and methanogens for substrates. While correlation network analyses predicted coupling of AOM to iron reduction, the addition of manganese or iron did not stimulate AOM. Since none of the classical archaeal anaerobic methanotrophs (ANME) were abundant, the involvement of unknown or unconventional phylotypes in AOM is conceivable. The resistance of AOM activity to inhibitors implies deviation from conventional enzymatic pathways. This work suggests that the classical redox cascade of electron acceptor utilization based on Gibbs energy yields does not always hold in diffusion-dominated systems, and instead biotic processes may be more strongly coupled to mineralogy.

  20. Corrosion of Iron by Sulfate-Reducing Bacteria: New Views of an Old Problem

    Science.gov (United States)

    Garrelfs, Julia

    2014-01-01

    About a century ago, researchers first recognized a connection between the activity of environmental microorganisms and cases of anaerobic iron corrosion. Since then, such microbially influenced corrosion (MIC) has gained prominence and its technical and economic implications are now widely recognized. Under anoxic conditions (e.g., in oil and gas pipelines), sulfate-reducing bacteria (SRB) are commonly considered the main culprits of MIC. This perception largely stems from three recurrent observations. First, anoxic sulfate-rich environments (e.g., anoxic seawater) are particularly corrosive. Second, SRB and their characteristic corrosion product iron sulfide are ubiquitously associated with anaerobic corrosion damage, and third, no other physiological group produces comparably severe corrosion damage in laboratory-grown pure cultures. However, there remain many open questions as to the underlying mechanisms and their relative contributions to corrosion. On the one hand, SRB damage iron constructions indirectly through a corrosive chemical agent, hydrogen sulfide, formed by the organisms as a dissimilatory product from sulfate reduction with organic compounds or hydrogen (“chemical microbially influenced corrosion”; CMIC). On the other hand, certain SRB can also attack iron via withdrawal of electrons (“electrical microbially influenced corrosion”; EMIC), viz., directly by metabolic coupling. Corrosion of iron by SRB is typically associated with the formation of iron sulfides (FeS) which, paradoxically, may reduce corrosion in some cases while they increase it in others. This brief review traces the historical twists in the perception of SRB-induced corrosion, considering the presently most plausible explanations as well as possible early misconceptions in the understanding of severe corrosion in anoxic, sulfate-rich environments. PMID:24317078

  1. Inhibition of bacterial oxidation of ferrous iron by lead nitrate in sulfate-rich systems.

    Science.gov (United States)

    Wang, Hongmei; Gong, Linfeng; Cravotta, Charles A; Yang, Xiaofen; Tuovinen, Olli H; Dong, Hailiang; Fu, Xiang

    2013-01-15

    Inhibition of bacterial oxidation of ferrous iron (Fe(II)) by Pb(NO(3))(2) was investigated with a mixed culture of Acidithiobacillus ferrooxidans. The culture was incubated at 30 °C in ferrous-sulfate medium amended with 0-24.2 mM Pb(II) added as Pb(NO(3))(2). Anglesite (PbSO(4)) precipitated immediately upon Pb addition and was the only solid phase detected in the abiotic controls. Both anglesite and jarosite (KFe(3)(SO(4))(2)(OH)(6)) were detected in inoculated cultures. Precipitation of anglesite maintained dissolved Pb concentrations at 16.9-17.6 μM regardless of the concentrations of Pb(NO(3))(2) added. Fe(II) oxidation was suppressed by 24.2 mM Pb(NO(3))(2) addition even when anglesite was removed before inoculation. Experiments with 0-48 mM KNO(3) demonstrated that bacterial Fe(II) oxidation decreased as nitrate concentration increased. Therefore, inhibition of Fe(II) oxidation at 24.2 mM Pb(NO(3))(2) addition resulted from nitrate toxicity instead of Pb addition. Geochemical modeling that considered the initial precipitation of anglesite to equilibrium followed by progressive oxidation of Fe(II) and the precipitation of jarosite and an amorphous iron hydroxide phase, without allowing plumbojarosite to precipitate were consistent with the experimental time-series data on Fe(II) oxidation under biotic conditions. Anglesite precipitation in mine tailings and other sulfate-rich systems maintains dissolved Pb concentrations below the toxicity threshold of A. ferrooxidans. Copyright © 2012 Elsevier B.V. All rights reserved.

  2. Nanoporous gold-based microbial biosensor for direct determination of sulfide.

    Science.gov (United States)

    Liu, Zhuang; Ma, Hanyue; Sun, Huihui; Gao, Rui; Liu, Honglei; Wang, Xia; Xu, Ping; Xun, Luying

    2017-12-15

    Environmental pollution caused by sulfide compounds has become a major problem for public health. Hence, there is an urgent need to explore a sensitive, selective, and simple sulfide detection method for environmental monitoring and protection. Here, a novel microbial biosensor was developed using recombinant Escherichia coli BL21 (E. coli BL21) expressing sulfide:quinone oxidoreductase (SQR) for sulfide detection. As an important enzyme involved in the initial step of sulfide metabolism, SQR oxidizes sulfides to polysulfides and transfers electrons to the electron transport chain. Nanoporous gold (NPG) with its unique properties was selected for recombinant E. coli BL21 cells immobilization, and then glassy carbon electrode (GCE) was modified by the resulting E. coli/NPG biocomposites to construct an E. coli/NPG/GCE bioelectrode. Due to the catalytic oxidation properties of NPG for sulfide, the electrochemical reaction of the E. coli/NPG/GCE bioelectrode is attributed to the co-catalysis of SQR and NPG. For sulfide detection, the E. coli/NPG/GCE bioelectrode showed a good linear response ranging from 50μM to 5mM, with a high sensitivity of 18.35μAmM -1 cm -2 and a low detection limit of 2.55μM. The anti-interference ability of the E. coli/NPG/GCE bioelectrode is better than that of enzyme-based inhibitive biosensors. Further, the E. coli/NPG/GCE bioelectrode was successfully applied to the detection of sulfide in wastewater. These unique properties potentially make the E. coli/NPG/GCE bioelectrode an excellent choice for reliable sulfide detection. Copyright © 2017 Elsevier B.V. All rights reserved.

  3. Experimental investigation on thermochemical sulfate reduction in the presence of 1-pentanethiol at 200 and 250 °C: Implications for in situ TSR processes occurring in some MVT deposits

    Science.gov (United States)

    Yuan, Shunda; Ellis, Geoffrey S.; Chou, I-Ming; Burruss, Robert

    2017-01-01

    Organic sulfur compounds are ubiquitous in natural oil and gas fields and moderate-low temperature sulfide ore deposits. Previous studies have shown that organic sulfur compounds are important in enhancing the rates of thermochemical sulfate reduction (TSR) reactions, but the details of these reaction mechanisms remain unclear. In order to assess the extent of sulfate reduction in the presence of labile sulfur species at temperature conditions near to those where TSR occurs in nature, we conducted a series of experiments using the fused silica capillary capsule (FCSS) method. The tested systems containing labile sulfur species are MgSO4 + 1-pentanethiol (C5H11SH) + 1-octene (C8H16), MgSO4 + 1-octene (C8H16), MgSO4 + 1-pentanethiol (C5H11SH), 1-pentanethiol (C5H11SH)+H2O, and MgSO4 + 1-pentanethiol (C5H11SH) + ZnBr2 systems. Our results show that: (1) intermediate oxidized carbon species (ethanol and acetic acid) are formed during TSR simulation experiments when 1-pentanethiol is present; (2) in the presence of ZnBr2, 1-pentanethiol can be oxidized by sulfate to CO2 at 200 °C, which is within the temperature range observed in natural TSR; and (3) the precipitation of sulfide minerals may significantly promote the rate of TSR, indicating that the rates of in situ TSR reactions in ore deposits could be much faster than previously thought. This may be important for understanding the possibility of in situ TSR as a mechanism for the precipitation of metal sulfides in some ore deposits. These findings provide important experimental evidence for understanding the role of organic sulfur compounds in TSR reactions and the pathway of TSR reactions initiated by organic sulfur compounds under natural conditions.

  4. Reactions of calcium orthosilicate and barium zirconate with oxides and sulfates of various elements

    Science.gov (United States)

    Zaplatynsky, I.

    1979-01-01

    Calcium orthosilicate and barium zirconate were evaluated as the insulation layer of thermal barrier coatings for air cooled gas turbine components. Their reactions with various oxides and sulfates were studied at 1100 C and 1300 C for times ranging up to 400 and 200 hours, respectively. These oxides and sulfates represent potential impurities or additives in gas turbine fuels and in turbine combustion air, as well as elements of potential bond coat alloys. The phase compositions of the reaction products were determined by X-ray diffraction analysis. BaZrO3 and 2CaO-SiO2 both reacted with P2O5, V2O5, Cr2O3, Al2O3, and SiO2. In addition, 2CaO-SiO2 reacted with Na2O, BaO, MgO, and CoO and BaZrO3 reacted with Fe2O3.

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

    Science.gov (United States)

    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 (H 2 S) 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 H 2 S (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.

  6. Characterization of the sulfate uptake and assimilation pathway from Xanthomonas citri - targets for bacterial growth inhibitors

    Energy Technology Data Exchange (ETDEWEB)

    Tambascia, C.; Balan, A. [Laboratorio Nacional de Biociencias - LNBIO, Campinas, SP (Brazil)

    2012-07-01

    Full text: Microorganisms require sulfur for growth and obtain it either for inorganic sulfate or organosulfur compounds. ATP-Binding Cassete (SulT family) or major facilitator superfamily-type (SulP) transporters are responsible for the sulfate transport into the cell. In Xanthomonas citri, the phytopathogenic bacterium that causes the canker citrus disease, there are no reports related to the importance of these transporters during in vitro or in vivo infection. We identified in X. citri genome all the genes that belong to the well-characterized cys regulon from Escherichia coli and Salmonella typhimurium, which includes three ABC transporters and all the enzymes necessary for sulfate oxide reduction to sulfide and cysteine. Once these genes have been shown to be extremely important for bacteria growth and development in different environments, we chose the sbpcysWUA and cysDNCHIJG operons, which encodes the ABC inorganic sulfate ABC transporter and all the enzymes necessary for conversion of sulfate in cysteine, respectively. As a step for crystallization trials and resolution of their tridimensional structures, the referred genes were amplified and cloned into the cloning vector pGEM T-easy. In addition, using bioinformatics tools and molecular modeling we characterized all the protein functions as well as built tridimensional models of their structure for determination of the active sites. The importance of each protein is discussed aiming the discovery of a good target for development of inhibitors that could block the bacterium growth. (author)

  7. Characterization of the sulfate uptake and assimilation pathway from Xanthomonas citri - targets for bacterial growth inhibitors

    International Nuclear Information System (INIS)

    Tambascia, C.; Balan, A.

    2012-01-01

    Full text: Microorganisms require sulfur for growth and obtain it either for inorganic sulfate or organosulfur compounds. ATP-Binding Cassete (SulT family) or major facilitator superfamily-type (SulP) transporters are responsible for the sulfate transport into the cell. In Xanthomonas citri, the phytopathogenic bacterium that causes the canker citrus disease, there are no reports related to the importance of these transporters during in vitro or in vivo infection. We identified in X. citri genome all the genes that belong to the well-characterized cys regulon from Escherichia coli and Salmonella typhimurium, which includes three ABC transporters and all the enzymes necessary for sulfate oxide reduction to sulfide and cysteine. Once these genes have been shown to be extremely important for bacteria growth and development in different environments, we chose the sbpcysWUA and cysDNCHIJG operons, which encodes the ABC inorganic sulfate ABC transporter and all the enzymes necessary for conversion of sulfate in cysteine, respectively. As a step for crystallization trials and resolution of their tridimensional structures, the referred genes were amplified and cloned into the cloning vector pGEM T-easy. In addition, using bioinformatics tools and molecular modeling we characterized all the protein functions as well as built tridimensional models of their structure for determination of the active sites. The importance of each protein is discussed aiming the discovery of a good target for development of inhibitors that could block the bacterium growth. (author)

  8. Development of novel and sensitive methods for the determination of sulfide in aqueous samples by hydrogen sulfide generation-inductively coupled plasma-atomic emission spectroscopy.

    Science.gov (United States)

    Colon, M; Todolí, J L; Hidalgo, M; Iglesias, M

    2008-02-25

    Two new, simple and accurate methods for the determination of sulfide (S(2-)) at low levels (microgL(-1)) in aqueous samples were developed. The generation of hydrogen sulfide (H(2)S) took place in a coil where sulfide reacted with hydrochloric acid. The resulting H(2)S was then introduced as a vapor into an inductively coupled plasma-atomic emission spectrometer (ICP-AES) and sulfur emission intensity was measured at 180.669nm. In comparison to when aqueous sulfide was introduced, the introduction of sulfur as H(2)S enhanced the sulfur signal emission. By setting a gas separator at the end of the reaction coil, reduced sulfur species in the form of H(2)S were removed from the water matrix, thus, interferences could be avoided. Alternatively, the gas separator was replaced by a nebulizer/spray chamber combination to introduce the sample matrix and reagents into the plasma. This methodology allowed the determination of both sulfide and sulfate in aqueous samples. For both methods the linear response was found to range from 5microgL(-1) to 25mgL(-1) of sulfide. Detection limits of 5microgL(-1) and 6microgL(-1) were obtained with and without the gas separator, respectively. These new methods were evaluated by comparison to the standard potentiometric method and were successfully applied to the analysis of reduced sulfur species in environmental waters.

  9. Development of novel and sensitive methods for the determination of sulfide in aqueous samples by hydrogen sulfide generation-inductively coupled plasma-atomic emission spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Colon, M. [Department of Chemistry, University of Girona, Campus Montilivi, 17071 Girona (Spain); Departamento de Quimica Analitica, Nutricion y Bromatologia, University of Alicante, 03080 Alicante (Spain); Todoli, J.L. [Departamento de Quimica Analitica, Nutricion y Bromatologia, University of Alicante, 03080 Alicante (Spain); Hidalgo, M. [Department of Chemistry, University of Girona, Campus Montilivi, 17071 Girona (Spain); Iglesias, M. [Department of Chemistry, University of Girona, Campus Montilivi, 17071 Girona (Spain)], E-mail: monica.iglesias@udg.es

    2008-02-25

    Two new, simple and accurate methods for the determination of sulfide (S{sup 2-}) at low levels ({mu}g L{sup -1}) in aqueous samples were developed. The generation of hydrogen sulfide (H{sub 2}S) took place in a coil where sulfide reacted with hydrochloric acid. The resulting H{sub 2}S was then introduced as a vapor into an inductively coupled plasma-atomic emission spectrometer (ICP-AES) and sulfur emission intensity was measured at 180.669 nm. In comparison to when aqueous sulfide was introduced, the introduction of sulfur as H{sub 2}S enhanced the sulfur signal emission. By setting a gas separator at the end of the reaction coil, reduced sulfur species in the form of H{sub 2}S were removed from the water matrix, thus, interferences could be avoided. Alternatively, the gas separator was replaced by a nebulizer/spray chamber combination to introduce the sample matrix and reagents into the plasma. This methodology allowed the determination of both sulfide and sulfate in aqueous samples. For both methods the linear response was found to range from 5 {mu}g L{sup -1} to 25 mg L{sup -1} of sulfide. Detection limits of 5 {mu}g L{sup -1} and 6 {mu}g L{sup -1} were obtained with and without the gas separator, respectively. These new methods were evaluated by comparison to the standard potentiometric method and were successfully applied to the analysis of reduced sulfur species in environmental waters.

  10. Heterogeneous reactions of carbonyl sulfide on mineral oxides: mechanism and kinetics study

    Directory of Open Access Journals (Sweden)

    Y. Liu

    2010-11-01

    Full Text Available The heterogeneous reactions of carbonyl sulfide (OCS on the typical mineral oxides in the mineral dust particles were investigated using a Knudsen cell flow reactor and a diffuse reflectance UV-vis spectroscopy. The reaction pathway for OCS on mineral dust was identified based on the gaseous products and surface species. The hydrolysis of OCS and succeeding oxidation of intermediate products readily took place on α-Al2O3, MgO, and CaO. Reversible and irreversible adsorption of OCS were observed on α-Fe2O3 and ZnO, respectively, whereas no apparent uptake of OCS by SiO2 and TiO2 was observed. The reactivity of OCS on these oxides depends on both the basicity of oxides and the decomposition reactivity of oxides for H2S. Based on the individual uptake coefficients and chemical composition of authentic mineral dust, the uptake coefficient (γBET of mineral dust was estimated to be in the range of 3.84×10−7–2.86×10−8. The global flux of OCS due to heterogeneous reactions and adsorption on mineral dust was estimated at 0.13–0.29 Tg yr−1, which is comparable to the annual flux of OCS for its reaction with ·OH.

  11. Reduction of produced elementary sulfur in denitrifying sulfide removal process.

    Science.gov (United States)

    Zhou, Xu; Liu, Lihong; Chen, Chuan; Ren, Nanqi; Wang, Aijie; Lee, Duu-Jong

    2011-05-01

    Denitrifying sulfide removal (DSR) processes simultaneously convert sulfide, nitrate, and chemical oxygen demand from industrial wastewater into elemental sulfur, dinitrogen gas, and carbon dioxide, respectively. The failure of a DSR process is signaled by high concentrations of sulfide in reactor effluent. Conventionally, DSR reactor failure is blamed for overcompetition for heterotroph to autotroph communities. This study indicates that the elementary sulfur produced by oxidizing sulfide that is a recoverable resource from sulfide-laden wastewaters can be reduced back to sulfide by sulfur-reducing Methanobacterium sp. The Methanobacterium sp. was stimulated with excess organic carbon (acetate) when nitrite was completely consumed by heterotrophic denitrifiers. Adjusting hydraulic retention time of a DSR reactor when nitrite is completely consumed provides an additional control variable for maximizing DSR performance.

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

    Science.gov (United States)

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

    2017-12-01

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

  13. Technetium behavior in sulfide and ferrous iron solutions

    International Nuclear Information System (INIS)

    Lee, S.Y.; Bondietti, E.A.

    1982-01-01

    Pertechnetate oxyanion ( 99 TcO 4- ), a potentially mobile species in leachate from a breached radioactive waste repository, was removed from a brine solution by precipitation with sulfide, iron, and ferrous sulfide at environmental pH's. Maghemite (ν-Fe 2 O 3 ) and geothite (α-FeOOH) were the dominant minerals in the precipitate obtained from the TcO 4- -ferrous iron reaction. The observation of small particle size and poor crystallinity of the minerals formed in the presence of Tc suggested that the Tc was incorporated into the mineral structure after reduction to a lower valence state. Amorphous ferrous sulfide, an initial phase precipitating in the TcO 4- -ferrous iron-sulfide reaction, was transformed to goethite and hematite (α-Fe 2 O 3 ) on aging. The black precipitate obtained from the TcO 4- -sulfide reaction was poorly crystallized technetium sulfide (Tc 2 S 7 ) which was insoluble in both acid and alkaline solution in the absence of strong oxidents. The results suggested that ferrous- and/or sulfide-bearing groundwaters and minerals in host rocks or backfill barriers could reduce the mobility of Tc through the formation of less-soluble Tc-bearing iron and/or sulfide minerals

  14. Biologically-induced precipitation of sphalerite-wurtzite nanoparticles by sulfate-reducing bacteria: implications for acid mine drainage treatment.

    Science.gov (United States)

    Castillo, Julio; Pérez-López, Rafael; Caraballo, Manuel A; Nieto, José M; Martins, Mónica; Costa, M Clara; Olías, Manuel; Cerón, Juan C; Tucoulou, Rémi

    2012-04-15

    Several experiments were conducted to evaluate zinc-tolerance of sulfate-reducing bacteria (SRB) obtained from three environmental samples, two inocula from sulfide-mining districts and another inoculum from a wastewater treatment plant. The populations of SRB resisted zinc concentrations of 260 mg/L for 42 days in a sulfate-rich medium. During the experiments, sulfate was reduced to sulfide and concentrations in solution decreased. Zinc concentrations also decreased from 260 mg/L to values below detection limit. Both decreases were consistent with the precipitation of newly-formed sphalerite and wurtzite, two polymorphs of ZnS, forming <2.5-μm-diameter spherical aggregates identified by microscopy and synchrotron-μ-XRD. Sulfate and zinc are present in high concentrations in acid mine drainage (AMD) even after passive treatments based on limestone dissolution. The implementation of a SRB-based zinc removal step in these systems could completely reduce the mobility of all metals, which would improve the quality of stream sediments, water and soils in AMD-affected landscapes. Copyright © 2012 Elsevier B.V. All rights reserved.

  15. Recent findings on sinks for sulfide in gravity sewer networks

    DEFF Research Database (Denmark)

    Nielsen, Asbjørn Haaning; Hvitved-Jacobsen, Thorkild; Vollertsen, Jes

    2006-01-01

    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...

  16. Ferrous Iron Oxidation by Thiobacillus ferrooxidans: Inhibition with Benzoic Acid, Sorbic Acid, and Sodium Lauryl Sulfate

    OpenAIRE

    Onysko, Steven J.; Kleinmann, Robert L. P.; Erickson, Patricia M.

    1984-01-01

    Benzoic acid, sorbic acid, and sodium lauryl sulfate at low concentrations (5 to 10 mg/liter) each effectively inhibited bacterial oxidation of ferrous iron in batch cultures of Thiobacillus ferrooxidans. The rate of chemical oxidation of ferrous iron in low-pH, sterile batch reactors was not substantially affected at the tested concentrations (5 to 50 mg/liter) of any of the compounds.

  17. Partitioning of metals in a degraded acid sulfate soil landscape: influence of tidal re-inundation.

    Science.gov (United States)

    Claff, Salirian R; Sullivan, Leigh A; Burton, Edward D; Bush, Richard T; Johnston, Scott G

    2011-11-01

    The oxidation and acidification of sulfidic soil materials results in the re-partitioning of metals, generally to more mobile forms. In this study, we examine the partitioning of Fe, Cr, Cu, Mn, Ni and Zn in the acidified surface soil (0-0.1 m) and the unoxidised sub-soil materials (1.3-1.5 m) of an acid sulfate soil landscape. Metal partitioning at this acidic site was then compared to an adjacent site that was previously acidified, but has since been remediated by tidal re-inundation. Differences in metal partitioning were determined using an optimised six-step sequential extraction procedure which targets the "labile", "acid-soluble", "organic", "crystalline oxide", "pyritic" and "residual" fractions. The surficial soil materials of the acidic site had experienced considerable losses of Cr, Cu, Mn and Ni compared to the underlying parent material due to oxidation and acidification, yet only minor losses of Fe and Zn. In general, the metals most depleted from the acidified surface soil materials exhibited the greatest sequestration in the surface soil materials of the tidally remediated site. An exception to this was iron, which accumulated to highly elevated concentrations in the surficial soil materials of the tidally remediated site. The "acid-soluble", "organic" and "pyritic" fractions displayed the greatest increase in metals following tidal remediation. This study demonstrates that prolonged tidal re-inundation of severely acidified acid sulfate soil landscapes leads to the immobilisation of trace metals through the surficial accumulation of iron oxides, organic material and pyrite. Copyright © 2011 Elsevier Ltd. All rights reserved.

  18. Microwave Synthesis of Zinc Hydroxy Sulfate Nanoplates and Zinc Oxide Nanorods in the Classroom

    Science.gov (United States)

    Dziedzic, Rafal M.; Gillian-Daniel, Anne Lynn; Peterson, Greta M.; Martínez-Herna´ndez, Kermin J.

    2014-01-01

    In this hands-on, inquiry-based lab, high school and undergraduate students learn about nanotechnology by synthesizing their own nanoparticles in a single class period. This simple synthesis of zinc oxide nanorods and zinc hydroxy sulfate nanoplates can be done in 15 min using a household microwave oven. Reagent concentration, reaction…

  19. Using Sulfate-Amended Sediment Slurry Batch Reactors to Evaluate Mercury Methylation

    International Nuclear Information System (INIS)

    Harmon, S.M.

    2003-01-01

    In the methylated form, mercury represents a concern to public health primarily through the consumption of contaminated fish tissue. Research conducted on the methylation of mercury strongly suggests the process is microbial in nature and facilitated principally by sulfate-reducing bacteria. This study addressed the potential for mercury methylation by varying sulfate treatments and wetland-based soil in microbial slurry reactors with available inorganic mercury. Under anoxic laboratory conditions conducive to growth of naturally occurring sulfate-reducing bacteria in the soil, it was possible to evaluate how various sulfate additions influenced the methylation of inorganic mercury added to overlying water. Treatments included sulfate amendments ranging FR-om 25 to 500 mg/L (0.26 to 5.2 mM) above the soil's natural sulfate level. This study also provided an assessment of mercury methylation relative to sulfate-reducing bacterial population growth and subsequent sulfide production. Mercury methylation in sulfate treatments did not exceed that of the non-amended control during a 35-day incubation. However, increases in methylmercury concentration were linked to bacterial growth and sulfate reduction. A time lag in methylation in the highest treatment correlated with an equivalent lag in bacterial growth

  20. Competitive, microbially-mediated reduction of nitrate with sulfide and aromatic oil components in a low-temperature, western Canadian oil reservoir.

    Science.gov (United States)

    Lambo, Adewale J; Noke, Kim; Larter, Steve R; Voordouw, Gerrit

    2008-12-01

    Fields from which oil is produced by injection of sulfate-bearing water often exhibit an increase in sulfide concentration with time (souring). Nitrate added to the injection water lowers the sulfide concentration by the action of sulfide-oxidizing, nitrate-reducing bacteria (SO-NRB). However, the injected nitrate can also be reduced with oil organics by heterotrophic NRB (hNRB). Aqueous volatile fatty acids (VFAs; a mixture of acetate, propionate, and butyrate) are considered important electron donors in this regard. Injection and produced waters from a western Canadian oil field with a low in situ reservoir temperature (30 degrees C) had only 0.1-0.2 mM VFAs. Amendment of these waters with nitrate gave therefore only partial reduction. More nitrate was reduced when 2% (v/v) oil was added, with light oil giving more reduction than heavy oil. GC-MS analysis of in vitro degraded oils and electron balance considerations indicated that toluene served as the primary electron donor for nitrate reduction. The differences in the extent of nitrate reduction were thus related to the toluene content of the light and heavy oil (30 and 5 mM, respectively). Reduction of nitrate with sulfide by SO-NRB always preceded that with oil organics by hNRB, even though microbially catalyzed kinetics with either electron donor were similar. Inhibition of hNRB by sulfide is responsible for this phenomenon. Injected nitrate will thus initially be reduced with sulfide through the action of SO-NRB. However, once sulfide has been eliminated from the near-injection wellbore region, oil organics will be targeted by the action of hNRB. Hence, despite the kinetic advantage of SO-NRB, the nitrate dose required to eliminate sulfide from a reservoir depends on the concentration of hNRB-degradable oil organics, with toluene being the most important in the field under study. Because the toluene concentration is lower in heavy oilthan in light oil, nitrate injection into a heavy-oil-producing field of

  1. Potential Impacts of two SO2 oxidation pathways on regional sulfate concentrations: acqueous-hase oxidation by NO2 and gas-phase oxidation by Stabilized Criegee Intermediates

    Science.gov (United States)

    We examine the potential impacts of two additional sulfate production pathways using the Community Multiscale Air Quality modeling system. First we evaluate the impact of the aqueous-phase oxidation of S(IV) by nitrogen dioxide using two published rate constants, differing by 1-2...

  2. Bacterial Disproportionation of Elemental Sulfur Coupled to Chemical Reduction of Iron or Manganese

    Science.gov (United States)

    Thamdrup, Bo; Finster, Kai; Hansen, Jens Würgler; Bak, Friedhelm

    1993-01-01

    A new chemolithotrophic bacterial metabolism was discovered in anaerobic marine enrichment cultures. Cultures in defined medium with elemental sulfur (S0) and amorphous ferric hydroxide (FeOOH) as sole substrates showed intense formation of sulfate. Furthermore, precipitation of ferrous sulfide and pyrite was observed. The transformations were accompanied by growth of slightly curved, rod-shaped bacteria. The quantification of the products revealed that S0 was microbially disproportionated to sulfate and sulfide, as follows: 4S0 + 4H2O → SO42- + 3H2S + 2H+. Subsequent chemical reactions between the formed sulfide and the added FeOOH led to the observed precipitation of iron sulfides. Sulfate and iron sulfides were also produced when FeOOH was replaced by FeCO3. Further enrichment with manganese oxide, MnO2, instead of FeOOH yielded stable cultures which formed sulfate during concomitant reduction of MnO2 to Mn2+. Growth of small rod-shaped bacteria was observed. When incubated without MnO2, the culture did not grow but produced small amounts of SO42- and H2S at a ratio of 1:3, indicating again a disproportionation of S0. The observed microbial disproportionation of S0 only proceeds significantly in the presence of sulfide-scavenging agents such as iron and manganese compounds. The population density of bacteria capable of S0 disproportionation in the presence of FeOOH or MnO2 was high, > 104 cm-3 in coastal sediments. The metabolism offers an explanation for recent observations of anaerobic sulfide oxidation to sulfate in anoxic sediments. PMID:16348835

  3. Impact of Sulfide on Nitrate Conversion in Eutrophic Nitrate-Rich Marine Sludge

    DEFF Research Database (Denmark)

    Schwermer, Carsten U.; Krieger, Bärbel; Lavik, Gaute

    2006-01-01

    IMPACT OF SULFIDE ON NITRATE CONVERSION IN EUTROPHIC NITRATE-RICH MARINE SLUDGE C.U. Schwermer 1, B.U. Krieger 2, G. Lavik 1, A. Schramm 3, J. van Rijn 4, D. de Beer 1, D. Minz 5, E. Cytryn 4, M. Kuypers 1, A. Gieseke 1 1 Max Planck Institute for Marine Microbiology, Bremen, Germany; 2 Dept...... nitrate conversion from denitrification to dissimilatory nitrate-reduction to ammonium (DNRA). In situ microsensor profiling in stagnant sludge revealed the typical stratification of nitrate reduction on top of sulfate reduction. Increasing the bulk nitrate concentration lead to a downward shift....... Our results show that the presence of sulfide generally decreased growth rates but increased N2O production. We conclude that sulfide plays a key role in causing incomplete denitrification, presumably by inhibiting the N2O reductase, and enhancing DNRA compared to denitrification.  ...

  4. Biodegradation of BTEX and Other Petroleum Hydrocarbons by Enhanced and Controlled Sulfate Reduction

    Energy Technology Data Exchange (ETDEWEB)

    Song Jin

    2007-07-01

    High concentrations of sulfide in the groundwater at a field site near South Lovedale, OK, were inhibiting sulfate reducing bacteria (SRB) that are known to degrade contaminants including benzene, toluene, ethylbenzene, and m+p-xylenes (BTEX). Microcosms were established in the laboratory using groundwater and sediment collected from the field site and amended with various nutrient, substrate, and inhibitor treatments. All microcosms were initially amended with FeCl{sub 2} to induce FeS precipitation and, thereby, reduce sulfide concentrations. Complete removal of BTEX was observed within 39 days in treatments with various combinations of nutrient and substrate amendments. Results indicate that elevated concentration of sulfide is a limiting factor to BTEX biodegradation at this site, and that treating the groundwater with FeCl{sub 2} is an effective remedy to facilitate and enhance BTEX degradation by the indigenous SRB population. On another site in Moore, OK, studies were conducted to investigate barium in the groundwater. BTEX biodegradation by SRB is suspected to mobilize barium from its precipitants in groundwater. Data from microcosms demonstrated instantaneous precipitation of barium when sulfate was added; however, barium was detected redissolving for a short period and precipitating eventually, when active sulfate reduction was occurring and BTEX was degraded through the process. SEM elemental spectra of the evolved show that sulfur was not present, which may exclude BaSO{sub 4} and BaS as a possible precipitates. The XRD analysis suggests that barium probably ended in BaS complexing with other amorphous species. Results from this study suggest that SRB may be able to use the sulfate from barite (BaSO{sub 4}) as an electron acceptor, resulting in the release of free barium ions (Ba{sup 2+}), and re-precipitate it in BaS, which exposes more toxicity to human and ecological health.

  5. A novel reverse osmosis membrane by ferrous sulfate assisted controlled oxidation of polyamide layer

    Science.gov (United States)

    Raval, Hiren D.; Raviya, Mayur R.; Gauswami, Maulik V.

    2017-11-01

    With growing desalination capacity, it is very important to evaluate the performance of thin film composite reverse osmosis (TFC RO) membrane in terms of energy consumption for desalination. There is a trade-off between salt rejection and water-flux of TFC RO membrane. This article presents a novel approach of analyzing the effect of mixture of an oxidizing agent sodium hypochlorite and a reducing agent ferrous sulfate on virgin TFC RO membrane. Experiments were carried out by varying the concentrations of both sodium hypochlorite and ferrous sulfate. The negative charge was induced on the membrane due to the treatment of combination of sodium hypochlorite and ferrous sulfate, thereby resulting in higher rejection of negative ions due to repulsive force. Membrane treated with 1000 mg l-1 sodium hypochlorite and 2000 mg l-1 ferrous sulfate showed the best salt rejection i.e. 96.23%. The characterization was carried out to understand the charge on the membrane surface by Zeta potential, morphology of membrane surface by scanning electron microscope (SEM), surface roughness features by atomic force microscope (AFM) and chemical structural changes by nuclear magnetic resonance (NMR) analysis.

  6. 21 CFR 184.1261 - Copper sulfate.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Copper sulfate. 184.1261 Section 184.1261 Food and... Substances Affirmed as GRAS § 184.1261 Copper sulfate. (a) Copper sulfate (cupric sulfate, CuSO4·5H2O, CAS... the reaction of sulfuric acid with cupric oxide or with copper metal. (b) The ingredient must be of a...

  7. Ferrous Iron Oxidation by Thiobacillus ferrooxidans: Inhibition with Benzoic Acid, Sorbic Acid, and Sodium Lauryl Sulfate

    Science.gov (United States)

    Onysko, Steven J.; Kleinmann, Robert L. P.; Erickson, Patricia M.

    1984-01-01

    Benzoic acid, sorbic acid, and sodium lauryl sulfate at low concentrations (5 to 10 mg/liter) each effectively inhibited bacterial oxidation of ferrous iron in batch cultures of Thiobacillus ferrooxidans. The rate of chemical oxidation of ferrous iron in low-pH, sterile batch reactors was not substantially affected at the tested concentrations (5 to 50 mg/liter) of any of the compounds. PMID:16346592

  8. Reaksi Pemasaman Senyawa Pirit pada Tanah Rawa Pasang Surut

    Directory of Open Access Journals (Sweden)

    Bambang Joko Priatmadi

    2009-01-01

    Full Text Available Acidity Reaction of Pyrite in Tidal Swampland (B.J. Priatmadi and A. Haris: Most of swamp soils in tidal landare Acid Sulfate Soils. Acid sulfate soils are the common name given to soils containing iron sulfides (pyrite. Thesoils are characterized by very low pH and high amount of soluble S and Fe, resulted from oxidation of pyrite whensoils are drained. This study was aimed to determine acidity pattern, iron and sulfate solubility as the impact of thelength time of oxidized, the effect of inhibitors application to acidity rate of sulfidic materials and top soils. Thematerials are: (1 soils at pyritic layer (sulfidic materials and (2 soils at 0 – 20 cm from soil surface. Soils issampled at Barambai reclaimed area, Barito Kuala Regency, South Kalimantan Province. In the laboratory soilstreated with some ameliorants, that are silica, phosphate and lime applied with dosage 2 t ha-1 with 3 replicationstimes. The soils incubated for 2 weeks under submerged condition. After soil incubation, soil exposed to the air for1 week, 2 weeks, 4 weeks, and 6 weeks. Parameters of soil analysis include pH, sulfate and iron soluble. Results ofthis study showed that (1 soil acidity rate of sulfidic materials more faster than upper soils when soils and sulfidicmaterials oxidized intensively, (2 at submerged soil condition or high soil water content, the application of ameliorantseffective increasing the soil pH of the upper soils, (3 at further oxidized soil condition or lower soil water content,the application of ameliorants inhibited acidity rate of soils and sulfidic materials, and (4 at further oxidized soilcondition or lower soil water content, the application of ameliorants increased iron solubility of soils and sulfidicmaterials.

  9. Isotopic data from proterozoic sediment-hosted sulfide deposits of Brazil: Implications for their metallogenic evolution and for mineral exploration

    International Nuclear Information System (INIS)

    Misi, Aroldo; Coelho, Carlos E.S.; Franca Rocha, Washington J.S.; Gomez, Adriana S.R.; Cunha, Iona A.; Iyer, Sundaram S.; Tassinari, Colombo C.G.; Kyle, J. Richard

    1998-01-01

    Geological, petrographic, fluid inclusions studies and isotopic data of seven Proterozoic sediment-hosted Pb-Zn-Ag sulfide deposits of Brazil, permit the estimation of the age of the hosting sequence and the mineralization, the nature of the sulfur and metal sources, the temperature range of sulfide formation and the environment of deposition of the mineral deposits. The studies suggest that they were formed during periods of extensional tectonics: Growth faults or reactivated basement faults were responsible for localized circulation of metal-bearing fluids within the sedimentary sequences. In most cases, sulfides were formed by the reduction of sedimentary sulfates. Linear structures are important controls for sulfide concentration in these Proterozoic basins. (author)

  10. Sulfide Species Optical Monitoring by a Miniaturized Silicon Photomultiplier

    Directory of Open Access Journals (Sweden)

    Salvatore Petralia

    2018-02-01

    Full Text Available The monitoring of water-soluble pollutants is receiving a growing interest from the scientific community. In this context, sulfide anion species S2− and HS− are particularly relevant since they can cause acute and chronic toxicity including neurological effects and at high concentrations, even death. In this study, a new strategy for fast and sensitive optical detection of sulfide species in water samples is described. The method uses an integrated silicon photomultiplier (SiPM device coupled with the appropriate analytical strategy applied in a plastic microchip with dried reagents on board. More specifically, all sulfide species (H2S, HS− and S2− in water samples are detected by the fluorescence signal emitted upon the reaction with N,N-dimethyl-phenylenediamine sulfate in the presence of Fe3+, leading to the formation of the fluorescent methylene blue (MB species. It has been proven that the system herein proposed is able to measure sulfide concentration in a linear range from 0–10 mg L−1 with a sensitivity value of about 6.7 µA mg−1 L and a detection limit of 0.5 mg L−1. A comparison with conventional UV-Vis detection method has been also carried out. Data show a very good linear correlation (R2 = 0.98093, proving the effectiveness of the method. Results pave the way toward the development of portable and low-cost device systems for water-soluble sulfide pollutants.

  11. Neonatal Maturation of Paracetamol (Acetaminophen) Glucuronidation, Sulfation, and Oxidation Based on a Parent-Metabolite Population Pharmacokinetic Model.

    Science.gov (United States)

    Cook, Sarah F; Stockmann, Chris; Samiee-Zafarghandy, Samira; King, Amber D; Deutsch, Nina; Williams, Elaine F; Wilkins, Diana G; Sherwin, Catherine M T; van den Anker, John N

    2016-11-01

    This study aimed to model the population pharmacokinetics of intravenous paracetamol and its major metabolites in neonates and to identify influential patient characteristics, especially those affecting the formation clearance (CL formation ) of oxidative pathway metabolites. Neonates with a clinical indication for intravenous analgesia received five 15-mg/kg doses of paracetamol at 12-h intervals (paracetamol, paracetamol-glucuronide, paracetamol-sulfate, and the combined oxidative pathway metabolites (paracetamol-cysteine and paracetamol-N-acetylcysteine) were simultaneously modeled in NONMEM 7.2. The model incorporated 259 plasma and 350 urine samples from 35 neonates with a mean gestational age of 33.6 weeks (standard deviation 6.6). CL formation for all metabolites increased with weight; CL formation for glucuronidation and oxidation also increased with postnatal age. At the mean weight (2.3 kg) and postnatal age (7.5 days), CL formation estimates (bootstrap 95% confidence interval; between-subject variability) were 0.049 L/h (0.038-0.062; 62 %) for glucuronidation, 0.21 L/h (0.17-0.24; 33 %) for sulfation, and 0.058 L/h (0.044-0.078; 72 %) for oxidation. Expression of individual oxidation CL formation as a fraction of total individual paracetamol clearance showed that, on average, fractional oxidation CL formation increased paracetamol and its metabolites in neonates. Maturational changes in the fraction of paracetamol undergoing oxidation were small relative to between-subject variability.

  12. Geochemical and stable isotopic constraints on the generation and passive treatment of acidic, Fe-SO{sub 4} rich waters

    Energy Technology Data Exchange (ETDEWEB)

    Matthies, Romy, E-mail: rmatthies@uwaterloo.ca [School of Civil Engineering and Geosciences, Newcastle University, Newcastle upon Tyne, NE1 7RU (United Kingdom); Aplin, Andrew C., E-mail: andrew.aplin@ncl.ac.uk [School of Civil Engineering and Geosciences, Newcastle University, Newcastle upon Tyne, NE1 7RU (United Kingdom); Boyce, Adrian J., E-mail: a.boyce@suerc.gla.ac.uk [Scottish Universities Environment Research Centre, East Kilbride, G75 0QF (United Kingdom); Jarvis, Adam P., E-mail: a.p.jarvis@ncl.ac.uk [School of Civil Engineering and Geosciences, Newcastle University, Newcastle upon Tyne, NE1 7RU (United Kingdom)

    2012-03-15

    Reducing and Alkalinity Producing Systems (RAPS) remediate net-acidic metalliferous mine drainage by creating anoxic conditions in which bacterial sulfate reduction (BSR) raises alkalinity and drives the precipitation of iron and other chalcophilic elements as sulfides. We report chemical and stable isotopic data from a study monitoring the biogeochemical processes involved in the generation of mine waters and their remediation by two RAPS. Sulfur isotopes show that sulfate in all mine waters has a common source (pyrite oxidation), whilst oxygen isotopes show that oxidation of pyritic sulfur is mediated by Fe(III){sub aq}. The isotopic composition of dissolved sulfide, combined with the sulfur and oxygen isotopic composition of sulfate in RAPS effluents, proves BSR and details its dual isotope systematics. The occurrence and isotopic composition of solid phase iron sulfides indicate the removal of reduced sulfur within the RAPS, with significant amounts of elemental sulfur indicating reoxidation steps. However, only 0 to 9% of solid phase iron occurs as Fe sulfides, with approximately 70% of the removed iron occurs as Fe(III) (hydr)oxides. Some of the (hydr)oxide is supplied to the wetland as solids and is simply filtered by the wetland substrate, playing no role in alkalinity generation or proton removal. However, the majority of iron is supplied as dissolved Fe(II), indicating that acid generating oxidation and hydrolysis reactions dominate iron removal. The overall contribution of BSR to the sulfur geochemistry in the RAPS is limited and sulfate retention is dominated by sulfate precipitation, comparable to aerobic treatment systems, and show that the proton acidity resulting from iron oxidation and hydrolysis must be subsequently neutralised by calcite dissolution and/or BSR deeper in the RAPS sediments. BSR is not as important as previously thought for metal removal in RAPS. The results have practical consequences for the design, treatment performance and long

  13. Productivity Contribution of Paleozoic Woodlands to the Formation of Shale-Hosted Massive Sulfide Deposits in the Iberian Pyrite Belt (Tharsis, Spain)

    Science.gov (United States)

    Fernández-Remolar, David C.; Harir, Mourad; Carrizo, Daniel; Schmitt-Kopplin, Philippe; Amils, Ricardo

    2018-03-01

    The geological materials produced during catastrophic and destructive events are an essential source of paleobiological knowledge. The paleobiological information recorded by such events can be rich in information on the size, diversity, and structure of paleocommunities. In this regard, the geobiological study of late Devonian organic matter sampled in Tharsis (Iberian Pyrite Belt) provided some new insights into a Paleozoic woodland community, which was recorded as massive sulfides and black shale deposits affected by a catastrophic event. Sample analysis using TOF-SIMS (Time of Flight Secondary Ion Mass Spectrometer), and complemented by GC/MS (Gas Chromatrograph/Mass Spectrometer) identified organic compounds showing a very distinct distribution in the rock. While phytochemical compounds occur homogeneously in the sample matrix that is composed of black shale, the microbial-derived organics are more abundant in the sulfide nodules. The cooccurrence of sulfur bacteria compounds and the overwhelming presence of phytochemicals provide support for the hypothesis that the formation of the massive sulfides resulted from a high rate of vegetal debris production and its oxidation through sulfate reduction under suboxic to anoxic conditions. A continuous supply of iron from hydrothermal activity coupled with microbial activity was strictly necessary to produce this massive orebody. A rough estimate of the woodland biomass was made possible by accounting for the microbial sulfur production activity recorded in the metallic sulfide. As a result, the biomass size of the late Devonian woodland community was comparable to modern woodlands like the Amazon or Congo rainforests.

  14. One-step hydrothermal synthesis of three-dimensional porous Ni-Co sulfide/reduced graphene oxide composite with optimal incorporation of carbon nanotubes for high performance supercapacitors

    Science.gov (United States)

    Chiu, Cheng-Ting; Chen, Dong-Hwang

    2018-04-01

    Three-dimensional (3D) porous Ni-Co sulfide/reduced graphene oxide composite with the appropriate incorporation of carbon nanotubes (NCS/rGO/CNT) was fabricated as a promising material for supercapacitor electrodes. It combined the high pseudo-capacitance of Ni-Co sulfide as well as the large specific surface area and electrical double layer capacitance of reduced graphene oxide (rGO). Carbon nanotubes (CNTs) were incorporated to act as the spacer for hindering the restacking of rGO and to construct a conductive network for enhancing the electron transport. The 3D porous NCS/rGO/CNT composite was fabricated by a facile one-step hydrothermal process in which Ni-Co sulfide nanosheets were synthesized and graphene oxide was reduced simultaneously. It was shown that the capacitance and cyclic performance indeed could be effectively improved via the appropriate addition of CNTs. In addition, a flexible all-solid-state asymmetric supercapacitor based on the NCS/rGO/CNT electrode was fabricated and exhibited the same capacitive electrochemical performance under bending. Also, it could successfully turn on a light-emitting diode light, revealing its feasibility in practical application. All results demonstrated that the developed NCS/rGO/CNT composite has potential application in supercapacitors.

  15. Estudo da oxidação dos sulfetos sintéticos molibdenita (MoS2 e covelita (CuS por Acidithiobacillus ferrooxidans via respirometria celular Oxidation study of the synthetic sulfides molybdenite (MoS2 and covellite (CuS by Acidithiobacillus ferrooxidans using respirometric experiments

    Directory of Open Access Journals (Sweden)

    Wilmo E. Francisco Junior

    2009-01-01

    Full Text Available This paper analyses the oxidation of covellite and molybdenite by Acidithiobacillus ferrooxidans strain LR using respirometric experiments. The results showed that both sulfides were oxidized by A. ferrooxidans, however, the covellite oxidation was much higher than molybdenite. Regarding the kinetic oxidation, the findings revealed that just molybdenite oxidation followed the classical Michaelis-Menten kinetic. It is probably associated with the pathway which these sulfides react to chemistry-bacterial attack, what is influenced by its electronic structures. Besides, experiments conducted in the presence of Fe3+ did not indicate alterations in molybdenite oxidation. Thus, ferric ions seem not to be essential to the sulfide oxidations.

  16. Separate zones of sulfate and sulfide release from subducted mafic oceanic crust

    Science.gov (United States)

    Tomkins, Andrew G.; Evans, Katy A.

    2015-10-01

    that this zoned sulfur liberation might be one of the factors that lead to the apparently redox-influenced zoned distribution of ore deposit types in the Andean arc. Furthermore, given the lack of sulfate-associated sea floor oxidation prior to the second great oxidation event, the pattern of sulfur transfer from the slab to the sub-arc mantle likely changed over time, becoming shallower and more oxidised from the Neoproterozoic onwards.

  17. ELECTROCHEMICAL DETERMINATION OF HYDROGEN SULFIDE AT CARBON NANOTUBE MODIFIED ELECTRODES. (R830900)

    Science.gov (United States)

    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...

  18. Controls on Weathering of Pyrrhotite in a Low-Sulfide, Granitic Mine-Waste Rock in the Canadian Arctic

    Science.gov (United States)

    Langman, J. B.; Holland, S.; Sinclair, S.; Blowes, D.

    2013-12-01

    -thaw cycle. Such rate factors are necessary to predict acid rock drainage and implement best management practices to minimize environmental impacts. To better understand the early geochemical evolution of the waste rock, sulfide minerals from different periods in the experiments were analyzed for discrete mineral characteristics indicative of a weathered state. Element transfer from the mineral to aqueous phase is transport limited because of the formation of Fe-(oxy)hydroxide weathered rims that can be an inhibitor of dissolution. Application of various x-ray spectroscopy techniques indicated that pyrrhotite transforms to marcasite [FeS2] prior to formation of Fe(II)-(oxy)hydroxides and further to Fe(III)-hydroxide/oxides. Iron appears to migrate through the weathered rims leaving the S-rich layer behind, and oxygen likely is retarded from migrating inward with formation of Fe(III) species. As these Fe-mineral transformations occur, they influence the retention of the secondary metals such as Co and Ni that preferentially remain in the +2 oxidation state and may leave the system as hydroxides, oxides, and sulfates. Understanding mineral evolution in this climate assists in adjusting appropriate rate factors for temporal changes in element release from the weathering of the pyrrhotite.

  19. Recycled Archean sulfur in the mantle wedge of the Mariana Forearc and microbial sulfate reduction within an extremely alkaline serpentine seamount

    Science.gov (United States)

    Aoyama, Shinnosuke; Nishizawa, Manabu; Miyazaki, Junichi; Shibuya, Takazo; Ueno, Yuichiro; Takai, Ken

    2018-06-01

    The identification of microbial activity under extreme conditions is important to define potential boundaries of the habitable and uninhabitable zones of terrestrial and extraterrestrial living forms. The subseafloor regimes of serpentinite seamounts in the Mariana Forearc are among the most extreme environments for life on earth owing to the widespread presence of highly alkaline fluids with pH values greater than 12. The potential activity of sulfate-reducing microorganisms has been suggested within the South Chamorro serpentinite seamounts on the basis of depletion of sulfate and enrichment of dissolved sulfide in pore water. However, the vertical distribution of sulfate-reducing microorganisms and the origin of sulfate are still uncertain. To address these issues, we analyzed quadruple sulfur isotopes of sulfide minerals and pore water sulfate in the upper 56 m of sedimentary sequences at the summit of the S. Chamorro Seamount and those of dissolved sulfate in upwelling fluids collected as deep as 202 mbsf (meters below the seafloor) in a cased hole near the summit of the same seamount. The depth profiles of the concentrations and the δ34S and Δ33S‧ values of sulfide minerals and pore water sulfate indicate microbial sulfate reduction as deep as 30 mbsf. Further, apparent isotopic fractionations (34ε) and exponents of mass dependent relationships (33λ) during sulfate reduction are estimated to be 62 ± 14‰ and 0.512 ± 0.002, respectively. The upwelling fluids show both the chlorine depletion relative to seawater and the negative δ15N values of ammonia (-4‰). Although these signatures point to dehydration of the subducting oceanic plate, the negative Δ33S‧ values of sulfate (-0.16‰ to -0.26‰ with analytical errors of ±0.01‰) are unlikely to originate from surrounding modern crusts. Instead, sulfate in the upwelling fluid likely possess non-mass-dependent (NMD) sulfur. Because NMD sulfur was produced primarily in the Archean atmosphere, our

  20. Modeling of ferric sulfate decomposition and sulfation of potassium chloride during grate‐firing of biomass

    DEFF Research Database (Denmark)

    Wu, Hao; Jespersen, Jacob Boll; Jappe Frandsen, Flemming

    2013-01-01

    Ferric sulfate is used as an additive in biomass combustion to convert the released potassium chloride to the less harmful potassium sulfate. The decomposition of ferric sulfate is studied in a fast heating rate thermogravimetric analyzer and a volumetric reaction model is proposed to describe...... the process. The yields of sulfur oxides from ferric sulfate decomposition under boiler conditions are investigated experimentally, revealing a distribution of approximately 40% SO3 and 60% SO2. The ferric sulfate decomposition model is combined with a detailed kinetic model of gas‐phase KCl sulfation...... and a model of K2SO4 condensation to simulate the sulfation of KCl by ferric sulfate addition. The simulation results show good agreements with experiments conducted in a biomass grate‐firing reactor. The results indicate that the SO3 released from ferric sulfate decomposition is the main contributor to KCl...

  1. Biochemistry, physiology and biotechnology of sulfate-reducing bacteria.

    Science.gov (United States)

    Barton, Larry L; Fauque, Guy D

    2009-01-01

    Chemolithotrophic bacteria that use sulfate as terminal electron acceptor (sulfate-reducing bacteria) constitute a unique physiological group of microorganisms that couple anaerobic electron transport to ATP synthesis. These bacteria (220 species of 60 genera) can use a large variety of compounds as electron donors and to mediate electron flow they have a vast array of proteins with redox active metal groups. This chapter deals with the distribution in the environment and the major physiological and metabolic characteristics of sulfate-reducing bacteria (SRB). This chapter presents our current knowledge of soluble electron transfer proteins and transmembrane redox complexes that are playing an essential role in the dissimilatory sulfate reduction pathway of SRB of the genus Desulfovibrio. Environmentally important activities displayed by SRB are a consequence of the unique electron transport components or the production of high levels of H(2)S. The capability of SRB to utilize hydrocarbons in pure cultures and consortia has resulted in using these bacteria for bioremediation of BTEX (benzene, toluene, ethylbenzene and xylene) compounds in contaminated soils. Specific strains of SRB are capable of reducing 3-chlorobenzoate, chloroethenes, or nitroaromatic compounds and this has resulted in proposals to use SRB for bioremediation of environments containing trinitrotoluene and polychloroethenes. Since SRB have displayed dissimilatory reduction of U(VI) and Cr(VI), several biotechnology procedures have been proposed for using SRB in bioremediation of toxic metals. Additional non-specific metal reductase activity has resulted in using SRB for recovery of precious metals (e.g. platinum, palladium and gold) from waste streams. Since bacterially produced sulfide contributes to the souring of oil fields, corrosion of concrete, and discoloration of stonework is a serious problem, there is considerable interest in controlling the sulfidogenic activity of the SRB. The

  2. Enhanced performance of denitrifying sulfide removal process under micro-aerobic condition

    International Nuclear Information System (INIS)

    Chen Chuan; Ren Nanqi; Wang Aijie; Liu Lihong; Lee, Duu-Jong

    2010-01-01

    The denitrifying sulfide removal (DSR) process with bio-granules comprising both heterotrophic and autotrophic denitrifiers can simultaneously convert nitrate, sulfide and acetate into di-nitrogen gas, elementary sulfur and carbon dioxide, respectively, at high loading rates. This study determines the reaction rate of sulfide oxidized into sulfur, as well as the reduction of nitrate to nitrite, would be enhanced under a micro-aerobic condition. The presence of limited oxygen mitigated the inhibition effects of sulfide on denitrifier activities, and enhanced the performance of DSR granules. The advantages and disadvantages of applying the micro-aerobic condition to the DSR process are discussed.

  3. 21 CFR 184.1443 - Magnesium sulfate.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Magnesium sulfate. 184.1443 Section 184.1443 Food... Specific Substances Affirmed as GRAS § 184.1443 Magnesium sulfate. (a) Magnesium sulfate (MgSO4·7H2O, CAS... magnesium oxide, hydroxide, or carbonate with sulfuric acid and evaporating the solution to crystallization...

  4. Evaluating the oxidation of shale during hydraulic fracturing using SEM-EDS and spectrocolorimetry

    Science.gov (United States)

    Tan, X. Y.; Nakashima, S.

    2017-12-01

    During hydraulic fracturing (fracking) for shale gas/oil extraction, oxygen is introduced into deep oxygen-poor environments, and Fe2+-bearing minerals in rocks can be oxidized thus leading to the degradation of rock quality. Akita diatomaceous shale is considered to be one of the source rocks for oil and gas fields in northwestern Japan. Outcrops of Akita shale often show presence of jarosite (Fe sulfate: yellow) and/or goethite (Fe hydroxide: brown to orange) as oxidation products of pyrite (FeS2). Several series of oxidation experiments of Akita shale under dry, humid, and wet conditions were conducted at temperatures of around 30 oC and 50oC for 30-40 days. Portable color spectro-colorimeters were used to monitor color changes of the rock surfaces every hour. SEM-EDS, UV-Vis, and Raman spectroscopic analyses were performed on the rock sample surface to examine the chemical and mineralogical compositions of Akita shale before and after the dry, humid, and wet experiments. In SEM-EDS analyses before the humid experiment, Fe and S containing phases show their atomic ratio close to 1:2 indicating that this is pyrite (FeS2). After the experiment, the ratio changed to around 1:1 suggesting a conversion from pyrite (FeS2) to mackinawite-like mineral (FeS). In addition, the formation of Ca sulfate (possibly gypsum: CaSO4.2H2O) and goethite-like Fe hydroxide were identified which were not present initially. Therefore, oxidation pathways of iron sulfide (pyrite: FeS2) via FeS to sulfate is confirmed by our humid experiments around 30oC on Akita shale. These oxidation processes might occur during the fracking of shale within relatively short time periods associated with precipitation of sulfates and hydroxides. Therefore, further studies are needed for their effects on rock properties and gas/oil production.

  5. Is climate influenced by biogenic atmospheric sulfur compounds. Beeinflussen biogene atmosphaerische Schwefelverbindungen das Klima

    Energy Technology Data Exchange (ETDEWEB)

    Georgii, H W

    1990-01-01

    About 10 years ago, traces of gaseous sulfur compounds were detected in the atmosphere which are of mainly biogenic origin and are formed in large areas in the oceans by phytoplankton. Continental sources, too, are important. These gases - dimethyl sulfide, carbon bisulfide and carbonyl sulfide - provide an important, if not the main, part to the natural sulfur budget of the atmosphere. While dimethyl sulfide and carbon bisulfide are quickly oxidized in the lower atmosphere forming sulfate particles in the process, carbonyl sulfide is an inert gas which is oxidized only after reaching the stratosphere. Lately, the relevance of these trace components to climate is being discussed. Conceivably, they might influence the radiation budget of the earth via the formation of aerosol particles: While, in the case of dimethyl sulfide, these would change the microphysical parameters of maritime clouds, an increase in the production of carbonyl sulfide would entail a strengthening of the stratospheric sulfate particle layer. Both processes might have a stabilizing effect on the climate as they act in opposite direction to the much discussed greenhouse effect. (orig.).

  6. Isotope geochemistry of waters affected by mining activities in Sierra Minera and Portman Bay (SE, Spain)

    International Nuclear Information System (INIS)

    García-Lorenzo, Mari Luz; Martínez-Sánchez, María José; Pérez-Sirvent, Carmen; Agudo, Inés; Recio, Clemente

    2014-01-01

    Highlights: • Waters have a meteoric origin even in samples located near the shore. • Marine infiltration only takes place in the deepest layers. • Sulfate enrichment was caused by oxidative dissolution of pyrite by ferric iron. - Abstract: The objective of this work was to evaluate processes affecting waters from Portman Bay by way of stable isotopic analysis, particularly H and O stable isotopes from water and S and O from dissolved sulfates. In addition, surface waters from Sierra Minera were examined for the purpose of determining if these waters are affected by similar processes. The results obtained indicate that Portman Bay waters are meteoric, and marine infiltration only takes place in the deepest layers near the shore or if water remains stagnated in sediments with low permeability. The main source of sulfate was the oxidation of sulfides, resulting in the liberation of acid, sulfate and metals. In order to assess the mechanism responsible for sulfide oxidation, the stoichiometric isotope balance model and the general isotope balance model were tested, suggesting that the oxidation via Fe 3+ was predominant in the surface, and controlled by Acidithiobacillus ferrooxidans, while at depth, sulfate reduction occurred

  7. Interactions among sulfide-oxidizing bacteria

    Science.gov (United States)

    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.

  8. Reaction of Hydrogen Sulfide with Oxygen in the Presence ofSulfite

    Energy Technology Data Exchange (ETDEWEB)

    Weres, Oleh; Tsao, Leon

    1983-01-01

    Commonly, abatement of hydrogen sulfide emissions from a geothermal powerplant requires that hydrogen sulfide dissolved in the cooling water be eliminated by chemical reaction. Oxidation by atmospheric oxygen is the preferred reaction, but requires a suitable catalyst. Nickel is the most potent and thereby cheapest catalyst for this purpose. One Mg/L nickel in the cooling water would allow 99% removal of hydrogen sulfide to be attained. A major drawback of catalytic air oxidation is that colloidal sulfur is a major reaction product; this causes rapid sludge accumulation and deposition of sulfur scale. The authors studied the kinetics and product distribution of the reaction of hydrogen sulfide with oxygen, catalyzed by nickel. Adding sodium sulfite to the solution completely suppresses formation of colloidal sulfur by converting it to thiosulfate. The oxidation reaction is an autocatalytic, free radical chain reaction. A rate expression for this reaction and a detailed reaction mechanism were developed. Nickel catalyzes the chain initiation step, and polysulfidoradical ions propagate the chains. Several complexes of iron and cobalt were also studied. Iron citrate and iron N-hydroxyEDT are the most effective iron based catalysts. Uncomplexed cobalt is as effective as nickel, but forms a precipitate of cobalt oxysulfide and is too expensive for practical use.

  9. Reaction of hydrogen sulfide with oxygen in the presence of sulfite

    Energy Technology Data Exchange (ETDEWEB)

    Weres, O.; Tsao, L.

    1983-01-14

    Commonly, abatement of hydrogen sulfide emission from a geothermal powerplant requires that hydrogen sulfide dissolved in the cooling water be eliminated by chemical reaction. Oxidation by atmospheric oxygen is the preferred reaction, but requires a suitable catalyst. Nickel is the most potent and thereby cheapest catalyst for this purpose. One mg/L nickel in the cooling water would allow 99% removal of hydrogen sulfide to be attained. A major drawback of catalytic air oxidation is that colloidal sulfur is a major reaction product; this causes rapid sludge accumulation and deposition of sulfur scale. We studied the kinetics and product distribution of the reaction of hydrogen sulfide with oxygen, catalyzed by nickel. Adding sodium sulfite to the solution completely suppresses formation of colloidal sulfur by converting it to thiosulfate. The oxidation reaction is an autocatalytic, free radical chain reaction. A rate expression for this reaction and a detailed reaction mechanism were developed. Nickel catalyzes the chain initiation step, and polysulfidoradical ions propagate the chains. Several complexes of iron and cobalt were also studied. Iron citrate and iron N-hydroxyEDTA are the most effective iron based catalysts. Uncomplexed cobalt is as effective as nickel, but forms a precipitate of cobalt oxysulfide and is too expensive for practical use. 33 figures, 9 tables.

  10. Corrosion Behavior of Cu40Zn in Sulfide-Polluted 3.5% NaCl Solution

    Science.gov (United States)

    Song, Q. N.; Xu, N.; Bao, Y. F.; Jiang, Y. F.; Gu, W.; Yang, Z.; Zheng, Y. G.; Qiao, Y. X.

    2017-10-01

    The corrosion behavior of a duplex-phase brass Cu40Zn in clean and sulfide-polluted 3.5% NaCl solutions was investigated by conducting electrochemical and gravimetric measurements. The corrosion product films were analyzed by scanning electron microscopy, energy-dispersive spectroscopy and x-ray diffraction. The presence of sulfide shifted the corrosion potential of Cu40Zn toward a more negative value by 100 mV and increased the mass loss rate by a factor of 1.257 compared with the result in the clean solution. The corrosion product film in the clean solution was thin and compact; it mainly consisted of oxides, such as ZnO and Cu2O. By contrast, the film in the sulfide-polluted solution was thick and porous. It mainly contained sulfides and zinc hydroxide chloride (i.e., Zn5(OH)8Cl2·H2O). The presence of sulfide ions accelerated the corrosion damage of Cu40Zn by hindering the formation of protective oxides and promoting the formation of a defective film which consisted of sulfides and hydroxide chlorides.

  11. Relative importance of nitrate and sulfate aerosol production mechanisms in urban atmospheres

    International Nuclear Information System (INIS)

    Middleton, P.; Kiang, C.S.

    1979-01-01

    The relative importance of the various sulfate and nitrate aerosol production mechanisms is calculated for different atmospheric conditions. The calculation scheme used to determine the rates of nitrate and sulfate production, based on the concept that vapor transfer to the aerosols and nitrate and sulfate formation within the aerosols are coupled kinetic processes, considers sulfate formation by ozone and hydrogen peroxide oxidation and catalytic oxidation in the presence of soot, iron and manganese of sulfite solutions and sulfuric acid condensation and nitrate formation by the liquid-phase oxidation of dissolved nitrogen oxides for different initial gas concentrations and particle compositions and sizes. It is found that sulfate production is higher under daytime conditions, primarily proceeding by mechanisms involving sulfuric acid and hydrogen peroxide, while at night oxidation processes on the surface of the aerosol film are more important. Nitrate tends to decrease nighttime sulfate production due to an increase in aerosol acidity and nitrate production is found to be higher under nighttime conditions and in the winter

  12. Reaction products and corrosion of molybdenum electrode in glass melt containing antimony oxides and sodium sulfate

    Czech Academy of Sciences Publication Activity Database

    Matěj, J.; Langrová, Anna

    2012-01-01

    Roč. 56, č. 3 (2012), s. 280-285 ISSN 0862-5468 Institutional support: RVO:67985831 Keywords : antimony oxides * corrosion * glass melt * Molybdenum electrode * sulfate Subject RIV: DD - Geochemistry Impact factor: 0.418, year: 2012 http://www.ceramics-silikaty.cz/2012/pdf/2012_03_280.pdf

  13. Mechanisms of Corrosion of Copper-Nickel Alloys in Sulfide-Polluted Seawater

    Science.gov (United States)

    1981-02-01

    anaerobic bacteria, which convert the natural sulfate content of the seawater into sulfides. Also, the putrefaction of organic compounds containing...corrosion rate bozause the Cu2 0 growth3 292 probably follows a parabolic rate law. The corrosion behavior at high oxygen concentrations (> 7.0 g/m ) is...determined using the rotating ring disk electrode method or SRI’s recently developed rotating cylinder- collector electrode.3 In these methods, the

  14. Biogeochemical cycling of arsenic in coastal salinized aquifers: Evidence from sulfur isotope study

    International Nuclear Information System (INIS)

    Kao, Yu-Hsuan; Wang, Sheng-Wei; Liu, Chen-Wuing; Wang, Pei-Ling; Wang, Chung-Ho; Maji, Sanjoy Kumar

    2011-01-01

    Arsenic (As) contamination of groundwater, accompanied by critical salinization, occurs in the southwestern coastal area of Taiwan. Statistical analyses and geochemical calculations indicate that a possible source of aqueous arsenic is the reductive dissolution of As-bearing iron oxyhydroxides. There are few reports of the influence of sulfate-sulfide redox cycling on arsenic mobility in brackish groundwater. We evaluated the contribution of sulfate reduction and sulfide re-oxidation on As enrichment using δ 34 S [SO 4 ] and δ 18 O [SO 4 ] sulfur isotopic analyses of groundwater. Fifty-three groundwater samples were divided into groups of high-As content and salinized (Type A), low-As and non-salinized (Type B), and high-As and non-salinized (Type C) groundwaters, based on hydro-geochemical analysis. The relatively high enrichment of 34 S [SO 4 ] and 18 O [SO 4 ] present in Type A, caused by microbial-mediated reduction of sulfate, and high 18 O enrichment factor (ε [SO 4 -H 2 O] ), suggests that sulfur disproportionation is an important process during the reductive dissolution of As-containing iron oxyhydroxides. Limited co-precipitation of ion-sulfide increased the rate of As liberation under anaerobic conditions. In contrast to this, Type B and Type C groundwater samples showed high δ 18 O [SO 4 ] and low δ 34 S [SO 4 ] values under mildly reducing conditions. Base on 18 O mass balance calculations, the oxide sources of sulfate are from infiltrated atmospheric O 2 , caused by additional recharge of dissolved oxygen and sulfide re-oxidation. The anthropogenic influence of extensive pumping also promotes atmospheric oxygen entry into aquifers, altering redox conditions, and increasing the rate of As release into groundwater. - Highlights: → Seawater intrusion and elevated As are the main issues of groundwater in Taiwan. → Sulfur and oxygen isotopes of sulfate were analyzed to evaluate the As mobility. → Reductive dissolution of Fe minerals and

  15. Control of Microbial Sulfide Production with Biocides and Nitrate in Oil Reservoir Simulating Bioreactors.

    Directory of Open Access Journals (Sweden)

    Yuan eXue

    2015-12-01

    Full Text Available Oil reservoir souring by the microbial reduction of sulfate to sulfide is unwanted, because it enhances corrosion of metal infrastructure used for oil production and processing. Reservoir souring can be prevented or remediated by the injection of nitrate or biocides, although injection of biocides into reservoirs is not commonly done. Whether combined application of these agents may give synergistic reservoir souring control is unknown. In order to address this we have used up-flow sand-packed bioreactors injected with 2 mM sulfate and volatile fatty acids (VFA, 3 mM each of acetate, propionate and butyrate at a flow rate of 3 or 6 pore volumes per day. Pulsed injection of the biocides glutaraldehyde (Glut, benzalkonium chloride (BAC and cocodiamine was used to control souring. Souring control was determined as the recovery time (RT needed to re-establish an aqueous sulfide concentration of 0.8-1 mM (of the 1.7-2 mM before the pulse. Pulses were either for a long time (120 h at low concentration (long-low or for a short time (1 h at high concentration (short-high. The short-high strategy gave better souring control with Glut, whereas the long-low strategy was better with cocodiamine. Continuous injection of 2 mM nitrate alone was not effective, because 3 mM VFA can fully reduce both 2 mM nitrate to nitrite and N2 and, subsequently, 2 mM sulfate to sulfide. No synergy was observed for short-high pulsed biocides and continuously injected nitrate. However, use of continuous nitrate and long-low pulsed biocide gave synergistic souring control with BAC and Glut, as indicated by increased RTs in the presence, as compared to the absence of nitrate. Increased production of nitrite, which increases the effectiveness of souring control by biocides, is the most likely cause for this synergy.

  16. Kinetics and Mechanistic Chemistry of Oxidation of Butacaine Sulfate by Chloramine-B in Acid Medium

    International Nuclear Information System (INIS)

    Shubha, Jayachamarajapura Pranesh; Kotabagi, Vinutha; Puttaswamy

    2012-01-01

    Butacaine sulfate is an ester of p-aminobenzoic acid which has been widely used as a local anaesthetic and it is a long standing agent particularly for spinal anaesthesia. For this reason, a kinetic study of oxidation of butacaine sulfate by sodium N-chlorobenzenesulfonamide (chloramine-B or CAB) has been carried out in HClO 4 medium at 303 K in order to explore this redox system mechanistic chemistry. The rate shows a first-order dependence on both [CAB] o , and [substrate] o , and a fractional-order dependence on acid concentration. Decrease of dielectric constant of the medium, by adding methanol, increases the rate of the reaction. Variation of ionic strength and addition of benzenesulfonamide or NaCl have no significant effect on the rate. The reaction was studied at different temperatures and the activation parameters have been evaluated. The stoichiometry of the reaction has been found to be 1:2 and the oxidation products have been identified by spectral analysis. The observed results have been explained by plausible mechanism and the related rate law has been deduced

  17. Characterization of the marine propionate-degrading, sulfate-reducing bacterium Desulfofaba fastidiosa sp. nov. and reclassification of Desulfomusa hansenii as Desulfofaba hansenii comb. nov.

    Science.gov (United States)

    Abildgaard, Lone; Ramsing, Niels Birger; Finster, Kai

    2004-03-01

    A rod-shaped, slightly curved sulfate reducer, designated strain P2(T), was isolated from the sulfate-methane transition zone of a marine sediment. Cells were motile by means of a single polar flagellum. The strain reduced sulfate, thiosulfate and sulfite to sulfide and used propionate, lactate and 1-propanol as electron donors. Strain P2(T) also grew by fermentation of lactate. Propionate was oxidized incompletely to acetate and CO(2). The DNA G+C content was 48.8 mol%. Sequence analysis of the small-subunit rDNA and the dissimilatory sulfite reductase gene revealed that strain P2(T) was related to the genera Desulfonema, Desulfococcus, Desulfosarcina, 'Desulfobotulus', Desulfofaba, Desulfomusa and Desulfofrigus. These genera include incomplete as well as complete oxidizers of substrates. Strain P2(T) shared important morphological and physiological traits with Desulfofaba gelida and Desulfomusa hansenii, including the ability to oxidize propionate incompletely to acetate. The 16S rRNA gene similarities of P2(T) to Desulfofaba gelida and Desulfomusa hansenii were respectively 92.9 and 91.5 %. Combining phenotypic and genotypic traits, we propose strain P2(T) to be a member of the genus Desulfofaba. The name Desulfofaba fastidiosa sp. nov. (type strain P2(T)=DSM 15249(T)=ATCC BAA-815(T)) is proposed, reflecting the limited number of substrates consumed by the strain. In addition, the reclassification of Desulfomusa hansenii as a member of the genus Desulfofaba, Desulfofaba hansenii comb. nov., is proposed. A common line of descent and a number of shared phenotypic traits support this reclassification.

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

    Science.gov (United States)

    Meyer, Birte; Kuever, Jan

    2007-12-01

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

  19. Copper oxide--copper sulfate water-splitting cycle

    Energy Technology Data Exchange (ETDEWEB)

    Foh, S. E.; Schreiber, J. D.; Dafler, J. R.

    1978-08-01

    A hybrid copper oxide--copper sulfate thermochemical water-splitting cycle, IGT's H-5, has been demonstrated in the laboratory with recycled materials. The optimum configuration and operating conditions for the electrolytic hydrogen-producing step have not yet been defined. With cooperative funding (A.G.A./G.R.I./DOE) a conceptual flowsheet was developed for this cycle and a load-line efficiency of about 37% calculated. This figure is the result of a single iteration on the original base case flow sheet and compares well with the values calculated for other processes at this stage of development. An iterative optimization of process conditions would improve efficiency. The data required to perform an economic analysis are not yet available and the electrolysis step must be more fully defined. An attractive process efficiency, relatively few corrosive materials, and few gas-phase separations are attributes of Cycle H-5 that lead us to believe hydrogen costs (to be developed during future analyses) would be improved significantly over similar processes analyzed to date.

  20. Enhanced performance of denitrifying sulfide removal process under micro-aerobic condition.

    Science.gov (United States)

    Chen, Chuan; Ren, Nanqi; Wang, Aijie; Liu, Lihong; Lee, Duu-Jong

    2010-07-15

    The denitrifying sulfide removal (DSR) process with bio-granules comprising both heterotrophic and autotrophic denitrifiers can simultaneously convert nitrate, sulfide and acetate into di-nitrogen gas, elementary sulfur and carbon dioxide, respectively, at high loading rates. This study determines the reaction rate of sulfide oxidized into sulfur, as well as the reduction of nitrate to nitrite, would be enhanced under a micro-aerobic condition. The presence of limited oxygen mitigated the inhibition effects of sulfide on denitrifier activities, and enhanced the performance of DSR granules. The advantages and disadvantages of applying the micro-aerobic condition to the DSR process are discussed. 2010 Elsevier B.V. All rights reserved.

  1. Pyrite formation and mineral transformation pathways upon sulfidation of ferric hydroxides depend on mineral type and sulfide concentration

    NARCIS (Netherlands)

    Peiffer, Stefan; Behrends, Thilo; Hellige, Katrin; Larese-Casanova, Philip; Wan, Moli; Pollok, Kilian

    2015-01-01

    The reaction of ferric (hydr)oxides with dissolved sulfide does not lead to the instantaneous production of thermodynamically stable products but can induce a variety of mineral transformations including the formation of metastable intermediates. The importance of the various transformation pathways

  2. Substantial Seasonal Contribution of Observed Biogenic Sulfate Particles to Cloud Condensation Nuclei.

    Science.gov (United States)

    Sanchez, Kevin J; Chen, Chia-Li; Russell, Lynn M; Betha, Raghu; Liu, Jun; Price, Derek J; Massoli, Paola; Ziemba, Luke D; Crosbie, Ewan C; Moore, Richard H; Müller, Markus; Schiller, Sven A; Wisthaler, Armin; Lee, Alex K Y; Quinn, Patricia K; Bates, Timothy S; Porter, Jack; Bell, Thomas G; Saltzman, Eric S; Vaillancourt, Robert D; Behrenfeld, Mike J

    2018-02-19

    Biogenic sources contribute to cloud condensation nuclei (CCN) in the clean marine atmosphere, but few measurements exist to constrain climate model simulations of their importance. The chemical composition of individual atmospheric aerosol particles showed two types of sulfate-containing particles in clean marine air masses in addition to mass-based Estimated Salt particles. Both types of sulfate particles lack combustion tracers and correlate, for some conditions, to atmospheric or seawater dimethyl sulfide (DMS) concentrations, which means their source was largely biogenic. The first type is identified as New Sulfate because their large sulfate mass fraction (63% sulfate) and association with entrainment conditions means they could have formed by nucleation in the free troposphere. The second type is Added Sulfate particles (38% sulfate), because they are preexisting particles onto which additional sulfate condensed. New Sulfate particles accounted for 31% (7 cm -3 ) and 33% (36 cm -3 ) CCN at 0.1% supersaturation in late-autumn and late-spring, respectively, whereas sea spray provided 55% (13 cm -3 ) in late-autumn but only 4% (4 cm -3 ) in late-spring. Our results show a clear seasonal difference in the marine CCN budget, which illustrates how important phytoplankton-produced DMS emissions are for CCN in the North Atlantic.

  3. Study on the sulfidation behavior of smithsonite

    International Nuclear Information System (INIS)

    Wu, Dandan; Wen, Shuming; Deng, Jiushuai; Liu, Jian; Mao, Yingbo

    2015-01-01

    Highlights: • Zeta potential showed that the pH IEP of smithsonite decreased from 7.7 to 6. • ICP test showed the gradual reduction of C S in the solution. • SEM showed that the mineral surface was partially changed to ZnS film. • XPS indicated that the presence of a characteristic signal peak of sulfur ions. - Abstract: Zinc extraction from low-grade mineral resources of oxidized zinc has recently become a focus of study. Sulfidation is an important process in oxidized ore flotation. In this study, the influence of sulfur ion adsorption on smithsonite surface was investigated with the use of zeta potential, inductively coupled plasma (ICP), scanning electron microscope (SEM), and X-ray photoelectron spectroscopic studies. Zeta potential measurements of sodium sulfide showed that sulfur ions were adsorbed onto the surface of pure smithsonite, as evidenced by the increased negative charge and the decrease in the pH IEP of smithsonite from 7.7 to 6 after sodium sulfide treatment. The ICP test revealed the gradual reduction in sulfur ion adsorption onto the surface of smithsonite in pulp sulfur. After 30 min of absorption, C S in the solution declined from 1000 × 10 −6 mol/L to 1.4 × 10 −6 mol/L. SEM results showed that the mineral surface was partially changed to ZnS film after sodium sulfide treatment, whereas EDS analysis results showed that 2% S is contained on the smithsonite surface. X-ray photoelectron spectroscopy results indicated the presence of a characteristic signal peak of sulfur ions after sulfidation. Sulfur concentration increased to 11.89%, whereas oxygen concentration decreased from 42.31% to 13.74%. Sulfur ions were not only present during chemical adsorption, but were also incorporated into the crystal lattices of minerals by the exchange reaction between S 2− and CO 3 2− ions

  4. Modeling the mutualistic interactions between tubeworms and microbial consortia.

    Directory of Open Access Journals (Sweden)

    Erik E Cordes

    2005-03-01

    Full Text Available The deep-sea vestimentiferan tubeworm Lamellibrachia luymesi forms large aggregations at hydrocarbon seeps in the Gulf of Mexico that may persist for over 250 y. Here, we present the results of a diagenetic model in which tubeworm aggregation persistence is achieved through augmentation of the supply of sulfate to hydrocarbon seep sediments. In the model, L. luymesi releases the sulfate generated by its internal, chemoautotrophic, sulfide-oxidizing symbionts through posterior root-like extensions of its body. The sulfate fuels sulfate reduction, commonly coupled to anaerobic methane oxidation and hydrocarbon degradation by bacterial-archaeal consortia. If sulfate is released by the tubeworms, sulfide generation mainly by hydrocarbon degradation is sufficient to support moderate-sized aggregations of L. luymesi for hundreds of years. The results of this model expand our concept of the potential benefits derived from complex interspecific relationships, in this case involving members of all three domains of life.

  5. Recycling of ferrous sulfate by the synthesis of a new super oxidant material 'Referox'

    Energy Technology Data Exchange (ETDEWEB)

    Evrard, O. [Universite Henri Poincare, Vandoeuvre (France); Dupre, B.; Jeannot, C.; Kanari, N.; Gaballah, I.; Ninane, L.; Verstraete, W.; Denomme, S.; Belsue, M.

    2001-07-01

    This European Union-sponsored project was initiated to develop a process to recycle industrial ferrous sulfate by the synthesis of a superoxidant containing hexavalent (FeVI) iron. Hexavalent iron, also called ferrates, can be used in decontamination of industrial effluents, decolorisation and purification of effluents from the textile and tanning industries, oxidation of cyanide to cyanates, soil remediation, water treatment and in a variety of other processes. Dry synthesis of potassium ferrate, using calcium hypochlorite as the oxidizing agent, was successful. By using chlorine instead of calcium hypochlorite and by partially substituting sodium hydroxide for potassium hydroxide the cost of the synthesis was significantly reduced. Recycling of ferrous sulfate at room temperature by the synthesis of potassium ferrate (FeVI) using gaseous chlorine instead of solid calcium hypochlorite was also successful. The yield of the synthesis was about 65 per cent for the used industrial ferrous sulfate samples. Large scale experimentation of the potassium ferrate synthesis was also carried out, obtaining potassium ferrate that remained stable for several months. The ferrates were used in the treatment of drinking water, wastewater, soil remediation, and effluent decontamination. Encouraging results were obtained. An additional benefit found was that use of the ferrates as bactericide for water treatment instead of chlorine gas eliminates the generation of halo-organic compounds which are suspected to be carcinogenic. 2 figs.

  6. Bacterial formation of phosphatic laminites off Peru.

    Science.gov (United States)

    Arning, E T; Birgel, D; Brunner, B; Peckmann, J

    2009-06-01

    Authigenic phosphatic laminites enclosed in phosphorite crusts from the shelf off Peru (10 degrees 01' S and 10 degrees 24' S) consist of carbonate fluorapatite layers, which contain abundant sulfide minerals including pyrite (FeS(2)) and sphalerite (ZnS). Low delta(34)S(pyrite) values (average -28.8 per thousand) agree with bacterial sulfate reduction and subsequent pyrite formation. Stable sulfur isotopic compositions of sulfate bound in carbonate fluorapatite are lower than that of sulfate from ambient sea water, suggesting bacterial reoxidation of sulfide by sulfide-oxidizing bacteria. The release of phosphorus and subsequent formation of the autochthonous phosphatic laminites are apparently caused by the activity of sulfate-reducing bacteria and associated sulfide-oxidizing bacteria. Following an extraction-phosphorite dissolution-extraction procedure, molecular fossils of sulfate-reducing bacteria (mono-O-alkyl glycerol ethers, di-O-alkyl glycerol ethers, as well as the short-chain branched fatty acids i/ai-C(15:0), i/ai-C(17:0) and 10MeC(16:0)) are found to be among the most abundant compounds. The fact that these molecular fossils of sulfate-reducing bacteria are distinctly more abundant after dissolution of the phosphatic laminite reveals that the lipids are tightly bound to the mineral lattice of carbonate fluorapatite. Moreover, compared with the autochthonous laminite, molecular fossils of sulfate-reducing bacteria are: (1) significantly less abundant and (2) not as tightly bound to the mineral lattice in the other, allochthonous facies of the Peruvian crusts consisting of phosphatic coated grains. These observations confirm the importance of sulfate-reducing bacteria in the formation of the phosphatic laminite. Model calculations highlight that organic matter degradation by sulfate-reducing bacteria has the potential to liberate sufficient phosphorus for phosphogenesis.

  7. Anglesite and silver recovery from jarosite residues through roasting and sulfidization-flotation in zinc hydrometallurgy.

    Science.gov (United States)

    Han, Haisheng; Sun, Wei; Hu, Yuehua; Jia, Baoliang; Tang, Honghu

    2014-08-15

    Hazardous jarosite residues contain abundant valuable minerals that are difficult to be recovered by traditional flotation process. This study presents a new route, roasting combined with sulfidization-flotation, for the recovery of anglesite and silver from jarosite residues of zinc hydrometallurgy. Surface appearance and elemental distribution of jarosite residues was examined by scanning electron microscopy and energy dispersive X-ray spectrometry analysis, respectively. Decomposition and transformation mechanisms of jarosite residues were illustrated by differential thermal analysis. Results showed that after roasting combined with flotation, the grade and recovery of lead were 43.89% and 66.86%, respectively, and those of silver were 1.3 kg/t and 81.60%, respectively. At 600-700 °C, jarosite was decomposed to release encapsulated valuable minerals such as anglesite (PbSO4) and silver mineral; silver jarosite decomposed into silver sulfate (Ag2SO4); and zinc ferrite (ZnO · Fe2O3) decomposed into zinc sulfate (ZnSO4) and hematite (Fe2O3). Bared anglesite and silver minerals were modified by sodium sulfide and easily collected by flotation collectors. This study demonstrates that the combination of roasting and sulfidization-flotation provides a promising process for the recovery of zinc, lead, and silver from jarosite residues of zinc hydrometallurgy. Copyright © 2014 Elsevier B.V. All rights reserved.

  8. Design and scale-up of an oxidative scrubbing process for the selective removal of hydrogen sulfide from biogas

    Energy Technology Data Exchange (ETDEWEB)

    Krischan, J., E-mail: jutta_krischan@hotmail.com [Vienna University of Technology, Institute of Chemical Engineering, Getreidemarkt 9/166, 1060 Vienna (Austria); Makaruk, A., E-mail: aleksander.makaruk@tuwien.ac.at [Vienna University of Technology, Institute of Chemical Engineering, Getreidemarkt 9/166, 1060 Vienna (Austria); Harasek, M., E-mail: michael.harasek@tuwien.ac.at [Vienna University of Technology, Institute of Chemical Engineering, Getreidemarkt 9/166, 1060 Vienna (Austria)

    2012-05-15

    Highlights: Black-Right-Pointing-Pointer Alkaline oxidative scrubbing proved for biogas desulfurization Black-Right-Pointing-Pointer Effect of operating conditions on hydrogen sulfide removal efficiency. Black-Right-Pointing-Pointer Minimization of caustic and oxidant consumption. Black-Right-Pointing-Pointer Process control via pH, redox potential and conductivity measurement. Black-Right-Pointing-Pointer Investigation of long-term behavior of pilot plant operation. - Abstract: Reliable and selective removal of hydrogen sulfide (H{sub 2}S) is an essential part of the biogas upgrading procedure in order to obtain a marketable and competitive natural gas substitute for flexible utilization. A promising biogas desulfurization technology has to ensure high separation efficiency regardless of process conditions or H{sub 2}S load without the use or production of toxic or ecologically harmful substances. Alkaline oxidative scrubbing is an interesting alternative to existing desulfurization technologies and is investigated in this work. In experiments on a stirred tank reactor and a continuous scrubbing column in laboratory-scale, H{sub 2}S was absorbed from a gas stream containing large amounts of carbon dioxide (CO{sub 2}) into an aqueous solution prepared from sodium hydroxide (NaOH), sodium bicarbonate (NaHCO{sub 3}) and hydrogen peroxide (H{sub 2}O{sub 2}). The influence of pH, redox potential and solution aging on the absorption efficiency and the consumption of chemicals was investigated. Because of the irreversible oxidation reactions of dissolved H{sub 2}S with H{sub 2}O{sub 2}, high H{sub 2}S removal efficiencies were achieved while the CO{sub 2} absorption was kept low. At an existing biogas upgrading plant an industrial-scale pilot scrubber was constructed, which efficiently desulfurizes 180 m{sup 3}/h of raw biogas with an average removal efficiency of 97%, even at relatively high and strongly fluctuating H{sub 2}S contents in the crude gas.

  9. Design and scale-up of an oxidative scrubbing process for the selective removal of hydrogen sulfide from biogas

    International Nuclear Information System (INIS)

    Krischan, J.; Makaruk, A.; Harasek, M.

    2012-01-01

    Highlights: ► Alkaline oxidative scrubbing proved for biogas desulfurization ► Effect of operating conditions on hydrogen sulfide removal efficiency. ► Minimization of caustic and oxidant consumption. ► Process control via pH, redox potential and conductivity measurement. ► Investigation of long-term behavior of pilot plant operation. - Abstract: Reliable and selective removal of hydrogen sulfide (H 2 S) is an essential part of the biogas upgrading procedure in order to obtain a marketable and competitive natural gas substitute for flexible utilization. A promising biogas desulfurization technology has to ensure high separation efficiency regardless of process conditions or H 2 S load without the use or production of toxic or ecologically harmful substances. Alkaline oxidative scrubbing is an interesting alternative to existing desulfurization technologies and is investigated in this work. In experiments on a stirred tank reactor and a continuous scrubbing column in laboratory-scale, H 2 S was absorbed from a gas stream containing large amounts of carbon dioxide (CO 2 ) into an aqueous solution prepared from sodium hydroxide (NaOH), sodium bicarbonate (NaHCO 3 ) and hydrogen peroxide (H 2 O 2 ). The influence of pH, redox potential and solution aging on the absorption efficiency and the consumption of chemicals was investigated. Because of the irreversible oxidation reactions of dissolved H 2 S with H 2 O 2 , high H 2 S removal efficiencies were achieved while the CO 2 absorption was kept low. At an existing biogas upgrading plant an industrial-scale pilot scrubber was constructed, which efficiently desulfurizes 180 m 3 /h of raw biogas with an average removal efficiency of 97%, even at relatively high and strongly fluctuating H 2 S contents in the crude gas.

  10. Reduction of Net Sulfide Production Rate by Nitrate in Wastewater Bioreactors. Kinetics and Changes in the Microbial Community

    DEFF Research Database (Denmark)

    Villahermosa, Desiree; Corzo, Alfonso; Gonzalez, J M

    2013-01-01

    Nitrate addition stimulated sulfide oxidation by increasing the activity of nitrate-reducing sulfide-oxidizing bacteria (NR-SOB), decreasing the concentration of dissolved H2S in the water phase and, consequently, its release to the atmosphere of a pilot-scale anaerobic bioreactor. The effect of ...

  11. Effect of active zinc oxide dispersion on reduced graphite oxide for hydrogen sulfide adsorption at mid-temperature

    Science.gov (United States)

    Song, Hoon Sub; Park, Moon Gyu; Croiset, Eric; Chen, Zhongwei; Nam, Sung Chan; Ryu, Ho-Jung; Yi, Kwang Bok

    2013-09-01

    Composites of Zinc oxide (ZnO) with reduced graphite oxide (rGO) were synthesized and used as adsorbents for hydrogen sulfide (H2S) at 300 °C. Various characterization methods (TGA, XRD, FT-IR, TEM and XPS) were performed in order to link their H2S adsorption performance to the properties of the adsorbent's surface. Microwave-assisted reduction process of graphite oxide (GO) provided mild reduction environment, allowing oxygen-containing functional groups to remain on the rGO surface. It was confirmed that for the ZnO/rGO synthesize using the microwave-assisted reduction method, the ZnO particle size and the degree of ZnO dispersion remained stable over time at 300 °C, which was not the case for only the ZnO particles themselves. This stable highly dispersed feature allows for sustained high surface area over time. This was confirmed through breakthrough experiments for H2S adsorption where it was found that the ZnO/rGO composite showed almost four times higher ZnO utilization efficiency than ZnO itself. The effect of the H2 and CO2 on H2S adsorption was also investigated. The presence of hydrogen in the H2S stream had a positive effect on the removal of H2S since it allows a reducing environment for Znsbnd O and Znsbnd S bonds, leading to more active sites (Zn2+) to sulfur molecules. On the other hand, the presence of carbon dioxide (CO2) showed the opposite trend, likely due to the oxidation environment and also due to possible competitive adsorption between H2S and CO2.

  12. Effect of active zinc oxide dispersion on reduced graphite oxide for hydrogen sulfide adsorption at mid-temperature

    International Nuclear Information System (INIS)

    Song, Hoon Sub; Park, Moon Gyu; Croiset, Eric; Chen, Zhongwei; Nam, Sung Chan; Ryu, Ho-Jung; Yi, Kwang Bok

    2013-01-01

    Composites of Zinc oxide (ZnO) with reduced graphite oxide (rGO) were synthesized and used as adsorbents for hydrogen sulfide (H 2 S) at 300 °C. Various characterization methods (TGA, XRD, FT-IR, TEM and XPS) were performed in order to link their H 2 S adsorption performance to the properties of the adsorbent's surface. Microwave-assisted reduction process of graphite oxide (GO) provided mild reduction environment, allowing oxygen-containing functional groups to remain on the rGO surface. It was confirmed that for the ZnO/rGO synthesize using the microwave-assisted reduction method, the ZnO particle size and the degree of ZnO dispersion remained stable over time at 300 °C, which was not the case for only the ZnO particles themselves. This stable highly dispersed feature allows for sustained high surface area over time. This was confirmed through breakthrough experiments for H 2 S adsorption where it was found that the ZnO/rGO composite showed almost four times higher ZnO utilization efficiency than ZnO itself. The effect of the H 2 and CO 2 on H 2 S adsorption was also investigated. The presence of hydrogen in the H 2 S stream had a positive effect on the removal of H 2 S since it allows a reducing environment for Zn-O and Zn-S bonds, leading to more active sites (Zn 2+ ) to sulfur molecules. On the other hand, the presence of carbon dioxide (CO 2 ) showed the opposite trend, likely due to the oxidation environment and also due to possible competitive adsorption between H 2 S and CO 2 .

  13. Sulfidation treatment of copper-containing plating sludge towards copper resource recovery.

    Science.gov (United States)

    Kuchar, D; Fukuta, T; Onyango, M S; Matsuda, H

    2006-11-02

    The present study is concerned with the sulfidation treatment of copper-containing plating sludge towards copper resource recovery by flotation of copper sulfide from treated sludge. The sulfidation treatment was carried out by contacting simulated or real copper plating sludge with Na(2)S solution for a period of 5 min to 24 h. The initial molar ratio of S(2-) to Cu(2+) (S(2-) to Me(2+) in the case of real sludge) was adjusted to 1.00, 1.25 or 1.50, while the solid to liquid ratio was set at 1:50. As a result, it was found that copper compounds were converted to various copper sulfides within the first 5 min. In the case of simulated copper sludge, CuS was identified as the main sulfidation product at the molar ratio of S(2-) to Cu(2+) of 1.00, while Cu(7)S(4) (Roxbyite) was mainly found at the molar ratios of S(2-) to Cu(2+) of 1.50 and 1.25. Based on the measurements of oxidation-reduction potential, the formation of either CuS or Cu(7)S(4) at different S(2-) to Cu(2+) molar ratios was attributed to the changes in the oxidation-reduction potential. By contrast, in the case of sulfidation treatment of real copper sludge, CuS was predominantly formed, irrespective of S(2-) to Me(2+) molar ratio.

  14. Chemical dissolution of sulfide minerals

    Science.gov (United States)

    Chao, T.T.; Sanzolone, R.F.

    1977-01-01

    Chemical dissolution treatments involving the use of aqua regia, 4 N HNO3, H2O2-ascorbic acid, oxalic acid, KClO3+HCl, and KClO3+HCl followed by 4 N HNO3 were applied to specimens of nine common sulfide minerals (galena, chalcopyrite, cinnabar, molybdenite, orpiment, pyrite, stibnite, sphalerite, and tetrahedrite) mixed individually with a clay loam soil. The resultant decrease in the total sulfur content of the mixture, as determined by using the Leco induction furnace, was used to evaluate the effectiveness of each chemical treatment. A combination of KClO3+HCl followed by 4 N HNO3 boiling gently for 20 min has been shown to be very effective in dissolving all the sulfide minerals. This treatment is recommended to dissolve metals residing in sulfide minerals admixed with secondary weathering products, as one step in a fractionation scheme whereby metals in soluble and adsorbed forms, and those associated with organic materials and secondary oxides, are first removed by other chemical extractants.

  15. Sulfated tin oxide (STO – Structural properties and application in catalysis: A review

    Directory of Open Access Journals (Sweden)

    Ravi Varala

    2016-07-01

    Full Text Available Catalysis is an important area of chemistry, with an extensive amount of work going on in this area of sciences, toward synthesis and evaluation of newer catalysts. There are many reports for different conversion reactions such as oxidation, reduction, coupling, alkylation, and acylation for which various catalysts have been used such as mixed metal oxides, metal nanoparticles, metal organic complexes and many others. Among the many catalysts reported, the one catalyst that caught our attention due to its exploitation for a plethora of organic conversions is the sulfated tin oxide (STO, which is due to the low cost, greater stability and high efficiency of the catalyst. In this review, we have attempted to compile data about the structural properties of STO, and its applications as catalysts in various organic synthesis are presented. The literature data up to 2014 were collected and considered for the review.

  16. Metal-free carbon materials-catalyzed sulfate radical-based advanced oxidation processes: A review on heterogeneous catalysts and applications.

    Science.gov (United States)

    Zhao, Qingxia; Mao, Qiming; Zhou, Yaoyu; Wei, Jianhong; Liu, Xiaocheng; Yang, Junying; Luo, Lin; Zhang, Jiachao; Chen, Hong; Chen, Hongbo; Tang, Lin

    2017-12-01

    In recent years, advanced oxidation processes (AOPs), especially sulfate radical based AOPs have been widely used in various fields of wastewater treatment due to their capability and adaptability in decontamination. Recently, metal-free carbon materials catalysts in sulfate radical production has been more and more concerned because these materials have been demonstrated to be promising alternatives to conventional metal-based catalysts, but the review of metal-free catalysts is rare. The present review outlines the current state of knowledge on the generation of sulfate radical using metal-free catalysts including carbon nanotubes, graphene, mesoporous carbon, activated carbon, activated carbon fiber, nanodiamond. The mechanism such as the radical pathway and non-radical pathway, and factors influencing of the activation of sulfate radical was also be revealed. Knowledge gaps and research needs have been identified, which include the perspectives on challenges related to metal-free catalyst, heterogeneous metal-free catalyst/persulfate systems and their potential in practical environmental remediation. Copyright © 2017 Elsevier Ltd. All rights reserved.

  17. Hydrogen sulfide production and volatilization in a polymictic eutrophic saline lake, Salton Sea, California.

    Science.gov (United States)

    Reese, Brandi Kiel; Anderson, Michael A; Amrhein, Christopher

    2008-11-15

    The Salton Sea is a large shallow saline lake located in southern California that is noted for high sulfate concentrations, substantial algal productivity, and very warm water column temperatures. These conditions are well-suited for sulfide production, and sulfide has been implicated in summer fish kills, although no studies have been conducted to specifically understand hydrogen sulfide production and volatilization there. Despite polymictic mixing patterns and relatively short accumulation periods, the amount of sulfide produced is comparable to meromictic lakes. Sulfide levels in the Salton Sea reached concentrations of 1.2 mmol L(-1) of total free sulfide in the hypolimnion and 5.6 mmol L(-1) in the sediment pore water. Strong winds in late July mixed H2S into the surface water, where it depleted the entire water column of dissolved oxygen and reached a concentration of 0.1 mmol L(-1). Sulfide concentrations exceeded the toxicity threshold of tilapia (Oreochromis mossambicus) and combined with strong anoxia throughout the water column, resulted in a massive fish kill. The mixing of sulfide into the surface waters also increased atmospheric H2S concentrations, reaching 1.0 micromol m(-3). The flux of sulfide from the sediment into the water column was estimated to range from 2-3 mmol m(-2) day(-1) during the winter and up to 8 mmol m(-2) day(-1) during the summer. Application of the two-layer model for volatilization indicates that up to 19 mmol m(-2) day(-1) volatilized from the surface during the mixing event. We estimate that as much as 3400 Mg year(-1) or approximately 26% of sulfide that diffused into the water column from the deepest sediments may have been volatilized to the atmosphere.

  18. An experimental study of Fe-Ni exchange between sulfide melt and olivine at upper mantle conditions: implications for mantle sulfide compositions and phase equilibria

    Science.gov (United States)

    Zhang, Zhou; von der Handt, Anette; Hirschmann, Marc M.

    2018-03-01

    The behavior of nickel in the Earth's mantle is controlled by sulfide melt-olivine reaction. Prior to this study, experiments were carried out at low pressures with narrow range of Ni/Fe in sulfide melt. As the mantle becomes more reduced with depth, experiments at comparable conditions provide an assessment of the effect of pressure at low-oxygen fugacity conditions. In this study, we constrain the Fe-Ni composition of molten sulfide in the Earth's upper mantle via sulfide melt-olivine reaction experiments at 2 GPa, 1200 and 1400 °C, with sulfide melt X_{{{Ni}}}^{{{Sulfide}}}={{Ni}}/{{Ni+{Fe}}} (atomic ratio) ranging from 0 to 0.94. To verify the approach to equilibrium and to explore the effect of {f_{{{O}2}}} on Fe-Ni exchange between phases, four different suites of experiments were conducted, varying in their experimental geometry and initial composition. Effects of Ni secondary fluorescence on olivine analyses were corrected using the PENELOPE algorithm (Baró et al., Nucl Instrum Methods Phys Res B 100:31-46, 1995), "zero time" experiments, and measurements before and after dissolution of surrounding sulfides. Oxygen fugacities in the experiments, estimated from the measured O contents of sulfide melts and from the compositions of coexisting olivines, were 3.0 ± 1.0 log units more reduced than the fayalite-magnetite-quartz (FMQ) buffer (suite 1, 2 and 3), and FMQ - 1 or more oxidized (suite 4). For the reduced (suites 1-3) experiments, Fe-Ni distribution coefficients K_{{D}}{}={(X_{{{Ni}}}^{{{sulfide}}}/X_{{{Fe}}}^{{{sulfide}}})}/{(X_{{{Ni}}^{{{olivine}}}/X_{{{Fe}}}^{{{olivine}}})}} are small, averaging 10.0 ± 5.7, with little variation as a function of total Ni content. More oxidized experiments (suite 4) give larger values of K D (21.1-25.2). Compared to previous determinations at 100 kPa, values of K D from this study are chiefly lower, in large part owing to the more reduced conditions of the experiments. The observed difference does not seem

  19. High temperature oxidation-sulfidation behavior of Cr-Al2O3 and Nb-Al2O3 composites densified by spark plasma sintering

    International Nuclear Information System (INIS)

    Saucedo-Acuna, R.A.; Monreal-Romero, H.; Martinez-Villafane, A.; Chacon-Nava, J.G.; Arce-Colunga, U.; Gaona-Tiburcio, C.; De la Torre, S.D.

    2007-01-01

    The high temperature oxidation-sulfidation behavior of Cr-Al 2 O 3 and Nb-Al 2 O 3 composites prepared by mechanical alloying (MA) and spark plasma sintering (SPS) has been studied. These composite powders have a particular metal-ceramic interpenetrating network and excellent mechanical properties. Oxidation-sulfidation tests were carried out at 900 deg. C, in a 2.5%SO 2 + 3.6%O 2 + N 2 (balance) atmosphere for 48 h. The results revealed the influence of the sintering conditions on the specimens corrosion resistance, i.e. the Cr-Al 2 O 3 and Nb-Al 2 O 3 composite sintered at 1310 deg. C/4 min showed better corrosion resistance (lower weight gains) compared with those found for the 1440 deg. C/5 min conditions. For the former composite, a protective Cr 2 O 3 layer immediately forms upon heating, whereas for the later pest disintegration was noted. Thus, under the same sintering conditions the Nb-Al 2 O 3 composites showed the highest weight gains. The oxidation products were investigated by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy

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

    Science.gov (United States)

    Meyer, Birte; Kuever, Jan

    2007-01-01

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

  1. Quantitative microbial community analysis of three different sulfidic mine tailing dumps generating acid mine drainage.

    Science.gov (United States)

    Kock, Dagmar; Schippers, Axel

    2008-08-01

    The microbial communities of three different sulfidic and acidic mine waste tailing dumps located in Botswana, Germany, and Sweden were quantitatively analyzed using quantitative real-time PCR (Q-PCR), fluorescence in situ hybridization (FISH), catalyzed reporter deposition-FISH (CARD-FISH), Sybr green II direct counting, and the most probable number (MPN) cultivation technique. Depth profiles of cell numbers showed that the compositions of the microbial communities are greatly different at the three sites and also strongly varied between zones of oxidized and unoxidized tailings. Maximum cell numbers of up to 10(9) cells g(-1) dry weight were determined in the pyrite or pyrrhotite oxidation zones, whereas cell numbers in unoxidized tailings were significantly lower. Bacteria dominated over Archaea and Eukarya at all tailing sites. The acidophilic Fe(II)- and/or sulfur-oxidizing Acidithiobacillus spp. dominated over the acidophilic Fe(II)-oxidizing Leptospirillum spp. among the Bacteria at two sites. The two genera were equally abundant at the third site. The acidophilic Fe(II)- and sulfur-oxidizing Sulfobacillus spp. were generally less abundant. The acidophilic Fe(III)-reducing Acidiphilium spp. could be found at only one site. The neutrophilic Fe(III)-reducing Geobacteraceae as well as the dsrA gene of sulfate reducers were quantifiable at all three sites. FISH analysis provided reliable data only for tailing zones with high microbial activity, whereas CARD-FISH, Q-PCR, Sybr green II staining, and MPN were suitable methods for a quantitative microbial community analysis of tailings in general.

  2. Oxidation of Gas-Phase SO2 on the Surfaces of Acidic Microdroplets: Implications for Sulfate and Sulfate Radical Anion Formation in the Atmospheric Liquid Phase.

    Science.gov (United States)

    Hung, Hui-Ming; Hoffmann, Michael R

    2015-12-01

    The oxidation of SO2(g) on the interfacial layers of microdroplet surfaces was investigated using a spray-chamber reactor coupled to an electrospray ionization mass spectrometer. Four major ions, HSO3(-), SO3(•-), SO4(•-) and HSO4(-), were observed as the SO2(g)/N2(g) gas-mixture was passed through a suspended microdroplet flow, where the residence time in the dynamic reaction zone was limited to a few hundred microseconds. The relatively high signal intensities of SO3(•-), SO4(•-), and HSO4(-) compared to those of HSO3(-) as observed at pH SO2·H2O, which is also affected by the pH dependent uptake coefficient. When H2O2(g) was introduced into the spray chamber simultaneously with SO2(g), HSO3(-) is rapidly oxidized to form bisulfate in the pH range of 3 to 5. Conversion to sulfate was less at pH SO2(g) on the acidic microdroplets was estimated as 1.5 × 10(6) [S(IV)] (M s(-1)) at pH ≤ 3. In the presence of acidic aerosols, this oxidation rate is approximately 2 orders of magnitude higher than the rate of oxidation with H2O2(g) at a typical atmospheric H2O2(g) concentration of 1 ppb. This finding highlights the relative importance of the acidic surfaces for SO2 oxidation in the atmosphere. Surface chemical reactions on aquated aerosol surfaces, as observed in this study, are overlooked in most atmospheric chemistry models. These reaction pathways may contribute to the rapid production of sulfate aerosols that is often observed in regions impacted by acidic haze aerosol such as Beijing and other megacities around the world.

  3. Atmospherically Relevant Radicals Derived from the Oxidation of Dimethyl Sulfide.

    Science.gov (United States)

    Mardyukov, Artur; Schreiner, Peter R

    2018-02-20

    The large number and amounts of volatile organosulfur compounds emitted to the atmosphere and the enormous variety of their reactions in various oxidation states make experimental measurements of even a small fraction of them a daunting task. Dimethyl sulfide (DMS) is a product of biological processes involving marine phytoplankton, and it is estimated to account for approximately 60% of the total natural sulfur gases released to the atmosphere. Ocean-emitted DMS has been suggested to play a role in atmospheric aerosol formation and thereby cloud formation. The reaction of ·OH with DMS is known to proceed by two independent channels: abstraction and addition. The oxidation of DMS is believed to be initiated by the reaction with ·OH and NO 3 · radicals, which eventually leads to the formation of sulfuric acid (H 2 SO 4 ) and methanesulfonic acid (CH 3 SO 3 H). The reaction of DMS with NO 3 · appears to proceed exclusively by hydrogen abstraction. The oxidation of DMS consists of a complex sequence of reactions. Depending on the time of the day or altitude, it may take a variety of pathways. In general, however, the oxidation proceeds via chains of radical reactions. Dimethyl sulfoxide (DMSO) has been reported to be a major product of the addition channel. Dimethyl sulfone (DMSO 2 ), SO 2 , CH 3 SO 3 H, and methanesulfinic acid (CH 3 S(O)OH) have been observed as products of further oxidation of DMSO. Understanding the details of DMS oxidation requires in-depth knowledge of the elementary steps of this seemingly simple transformation, which in turn requires a combination of experimental and theoretical methods. The methylthiyl (CH 3 S·), methylsulfinyl (CH 3 SO·), methylsulfonyl (CH 3 SO 2 ·), and methylsulfonyloxyl (CH 3 SO 3 ·) radicals have been postulated as intermediates in the oxidation of DMS. Therefore, studying the chemistry of sulfur-containing free radicals in the laboratory also is the basis for understanding the mechanism of DMS oxidation in the

  4. Nitrite accumulation in continuous-flow partial autotrophic denitrification reactor using sulfide as electron donor.

    Science.gov (United States)

    Liu, Chunshuang; Li, Wenfei; Li, Xuechen; Zhao, Dongfeng; Ma, Bin; Wang, Yongqiang; Liu, Fang; Lee, Duu-Jong

    2017-11-01

    The nitrite accumulation in handling nitrate and sulfide-laden wastewater in a continuous-flow upflow anaerobic sludge blanket reactor was studied. At sulfide/nitrate-nitrogen ratio of 1:0.76 and loading rates of 1.2kg-Sm -3 d -1 and 0.4kg-Nm -3 d -1 , the elemental sulfur and nitrite accumulation rates peaked at 90% and 70%, respectively, with Acrobacter, Azoarcus and Thauera presenting the functional strains in the studied reactor. The accumulated nitrite was proposed a promising feedstock for anaerobic ammonia oxidation process. An integrated partial autotrophic denitrification-anaerobic ammonia oxidation-aeration process for handling the ammonia and sulfide-laden wastewaters is proposed for further studies. Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. Integrating nitric oxide, nitrite and hydrogen sulfide signaling in the physiological adaptions to hypoxia: A comparative approach

    DEFF Research Database (Denmark)

    Fago, Angela; B. Jensen, Frank; Tota, Bruno

    2012-01-01

    Hydrogen sulfide (H2S), nitric oxide (NO) and nitrite (NO2-) are formed in vivo and are of crucial importance in the tissue response to hypoxia, particularly in the cardiovascular system, where these signaling molecules are involved in a multitude of processes including the regulation of vascular...... tone, cellular metabolic function and cytoprotection. This report summarizes current advances on the mechanisms by which these signaling pathways act and may have evolved in animals with different tolerance to hypoxia, as presented and discussed during the scientific sessions of the annual meeting...

  6. Effects of Sodium Citrate on the Ammonium Sulfate Recycled Leaching of Low-Grade Zinc Oxide Ores

    Science.gov (United States)

    Yang, Kun; Li, Shi-wei; Zhang, Li-bo; Peng, Jin-hui; Ma, Ai-yuan; Wang, Bao-bao

    2016-03-01

    The effects of sodium citrate on ammonium sulfate recycled leaching of low-grade zinc oxide ores were studied. By applying various kinds of detection and analysis techniques such as chemical composition analysis, chemical phase method, scanning electron microscopy and energy dispersive spectrum (SEM/EDS), X-ray diffraction (XRD) and Fourier-transforming infrared spectrum (FT-IR), zinc raw ore, its leaching slag and the functional mechanism of sodium citrate were investigated. Based on a comprehensive analysis, it can be concluded that in contrast to hemimorphite (Zn4Si2O7(OH)2 · H2O), amorphous smithsonite (ZnCO3) and zinc silicate (Zn2SiO4) prove to be refractory phases under ammonium sulfate leaching, while sodium citrate has a better chelating action with the refractory phases, resulting in a higher zinc leaching rate. Under conditions of [NH3]/[NH3]T molar ratio being 0.5, [NH3]T being 7.5 mol/L, [Na3C6H5O7] being 0.2 mol/L, S/L ratio being 1:5, temperature being 303 K, holding time being 1 h in each of the two stages, and stirring rate being 300 rpm, the leaching rate of zinc reached 93.4%. In this article, sulfate ammonium recycled technology also reveals its unique advantage in processing low-grade zinc oxide ores accompanied by high silicon and high alkaline gangue.

  7. Reduced graphene oxide wrapped Fe3O4-Co3O4 yolk-shell nanostructures for advanced catalytic oxidation based on sulfate radicals

    Science.gov (United States)

    Zhang, Lishu; Yang, Xijia; Han, Erfen; Zhao, Lijun; Lian, Jianshe

    2017-02-01

    In this work, we designed and synthesized a high performance catalyst of reduced graphene oxide (RGO) wrapped Fe3O4-Co3O4 (RGO/Fe3O4-Co3O4) yolk-shell nanostructures for advanced catalytic oxidation based on sulfate radicals. The synergistic catalytic action of the RGO/Fe3O4-Co3O4 yolk-shell nanostructures activate the peroxymonosulfate (PMS) to produce sulfate radicals (SO4rad -) for organic dyes degradation, and the Orange II can be almost completely degradated in 5 min. Meanwhile the RGO wrapping prevents the loss of cobalt in the catalytic process, and the RGO/Fe3O4-Co3O4 can be recycled after catalyzed reaction due to the presence of magnetic iron core. What's more, it can maintain almost the same high catalytic activity even after 10 cycles through repeated NaBH4 reduction treatment. Hence, RGO/Fe3O4-Co3O4 yolk-shell nanostructures possess a great opportunity to become a promising candidate for waste water treatment in industry.

  8. Isotopic constraints on heterogeneous sulfate production in Beijing haze

    Science.gov (United States)

    He, Pengzhen; Alexander, Becky; Geng, Lei; Chi, Xiyuan; Fan, Shidong; Zhan, Haicong; Kang, Hui; Zheng, Guangjie; Cheng, Yafang; Su, Hang; Liu, Cheng; Xie, Zhouqing

    2018-04-01

    Discerning mechanisms of sulfate formation during fine-particle pollution (referred to as haze hereafter) in Beijing is important for understanding the rapid evolution of haze and for developing cost-effective air pollution mitigation strategies. Here we present observations of the oxygen-17 excess of PM2.5 sulfate (Δ17O(SO42-)) collected in Beijing haze from October 2014 to January 2015 to constrain possible sulfate formation pathways. Throughout the sampling campaign, the 12-hourly averaged PM2.5 concentrations ranged from 16 to 323 µg m-3 with a mean of (141 ± 88 (1σ)) µg m-3, with SO42- representing 8-25 % of PM2.5 mass. The observed Δ17O(SO42-) varied from 0.1 to 1.6 ‰ with a mean of (0.9 ± 0.3) ‰. Δ17O(SO42-) increased with PM2.5 levels in October 2014 while the opposite trend was observed from November 2014 to January 2015. Our estimate suggested that in-cloud reactions dominated sulfate production on polluted days (PDs, PM2.5 ≥ 75 µg m-3) of Case II in October 2014 due to the relatively high cloud liquid water content, with a fractional contribution of up to 68 %. During PDs of Cases I and III-V, heterogeneous sulfate production (Phet) was estimated to contribute 41-54 % to total sulfate formation with a mean of (48 ± 5) %. For the specific mechanisms of heterogeneous oxidation of SO2, chemical reaction kinetics calculations suggested S(IV) ( = SO2 ⚫ H2O + HSO3- + SO32-) oxidation by H2O2 in aerosol water accounted for 5-13 % of Phet. The relative importance of heterogeneous sulfate production by other mechanisms was constrained by our observed Δ17O(SO42-). Heterogeneous sulfate production via S(IV) oxidation by O3 was estimated to contribute 21-22 % of Phet on average. Heterogeneous sulfate production pathways that result in zero-Δ17O(SO42-), such as S(IV) oxidation by NO2 in aerosol water and/or by O2 via a radical chain mechanism, contributed the remaining 66-73 % of Phet. The assumption about the thermodynamic state of aerosols

  9. An experimental and theoretical method for determination of standard electrode potential for the redox couple diphenyl sulfone/diphenyl sulfide

    Science.gov (United States)

    Song, Y. Z.; Wei, K. X.; Lv, J. S.

    2013-12-01

    DFT calculations were performed for diphenyl sulfide and diphenyl sulfone. The electrochemistry of diphenyl sulfide on the gold electrode was investigated by cyclic voltammety and the results show that standard electrode potential for redox couple diphenyl sulfone/diphenyl sulfide is 1.058 V, which is consistent with that of 1.057 calculated at B3LYP/6-31++G( d, p)-IEFPCM level. The front orbit theory and Mulliken charges of molecular explain well on the oxidation of diphenyl sulfide in oxidative desulfurization. According to equilibrium theory the experimental equilibrium constant in the oxidative desulfurization of H2O2, is 1.17 × 1048, which is consistent with the theoretical equilibrium constant is 2.18 × 1048 at B3LYP/6-31++G( d, p)-IEFPCM level.

  10. Paleomagnetic dating of non-sulfide Zn-Pb ores in SW Sardinia (Italy: a first attempt

    Directory of Open Access Journals (Sweden)

    L. Sagnotti

    2005-06-01

    Full Text Available A first paleomagnetic investigation aimed at constraining the age of the non-sulfide Zn-Pb ore deposits in the Iglesiente district (SW Sardinia, Italy was carried out. In these ores, the oxidation of primary sulfides, hosted in Cambrian carbonate rocks, was related to several paleoweathering episodes spanning from the Mesozoic onward. Paleomagnetic analyses were performed on 43 cores from 4 different localities, containing: a non-oxidized primary sulfides and host rock, b oxidized Fe-rich hydrothermal dolomites and (c supergene oxidation ore («Calamine». Reliable data were obtained from 18 samples; the others show uninterpretable results due to low magnetic intensity or to scattered demagnetization trajectories. Three of them show a scattered Characteristic Remanent Magnetization (ChRM, likely carried by the original (i.e. Paleozoic magnetic iron sulfides. The remaining 15 samples show a well defined and coherent ChRM, carried by high-coercivity minerals, acquired after the last phase of counterclockwise rotation of Sardinia (that is after 16 Myr, in a time interval long enough to span at least one reversal of the geomagnetic field. Hematite is the main magnetic carrier in the limestone, whereas weathered hydrothermal dolomite contains goethite or a mixture of both. The results suggest that paleomagnetism can be used to constrain the timing of oxidation in supergene-enriched ores.

  11. Red soil as a regenerable sorbent for high temperature removal of hydrogen sulfide from coal gas

    International Nuclear Information System (INIS)

    Ko, T.-H.; Chu Hsin; Lin, H.-P.; Peng, C.-Y.

    2006-01-01

    In this study, hydrogen sulfide (H 2 S) was removed from coal gas by red soil under high temperature in a fixed-bed reactor. Red soil powders were collected from the northern, center and southern of Taiwan. They were characterized by XRPD, porosity analysis and DCB chemical analysis. Results show that the greater sulfur content of LP red soils is attributed to the higher free iron oxides and suitable sulfidation temperature is around 773 K. High temperature has a negative effect for use red soil as a desulfurization sorbent due to thermodynamic limitation in a reduction atmosphere. During 10 cycles of regeneration, after the first cycle the red soil remained stable with a breakthrough time between 31 and 36 min. Hydrogen adversely affects sulfidation reaction, whereas CO exhibits a positive effect due to a water-shift reaction. COS was formed during the sulfidation stage and this was attributed to the reaction of H 2 S and CO. Results of XRPD indicated that, hematite is the dominant active species in fresh red soil and iron sulfide (FeS) is a product of the reaction between hematite and hydrogen sulfide in red soils. The spinel phase FeAl 2 O 4 was found during regeneration, moreover, the amount of free iron oxides decreased after regeneration indicating the some of the free iron oxide formed a spinel phase, further reducting the overall desulfurization efficiency

  12. A peroxotungstate-ionic liquid brush assembly: an efficient and reusable catalyst for selectively oxidizing sulfides with aqueous H{sub 2}O{sub 2} solution in neat water

    Energy Technology Data Exchange (ETDEWEB)

    Shi, Xianying; Ma, Wenjuan; Ou, Hui; Han, Xiaoyan; Lu, Congmin; Chen, Yan; Wei, Junfa, E-mail: shixy@snnu.edu.cn, E-mail: weijf@snnu.edu.cn [School of Chemistry and Chemical Engineering, Shaanxi Normal University and Key Laboratory for Macromolecular Science of Shaanxi Province, Xian (China)

    2012-08-15

    An efficient and reusable heterogeneous catalytic assembly of peroxotungstate held in a ionic liquid (IL) brush was synthesized and an environmentally-friendly procedure was developed for selective oxidation of sulfides at room temperature using 30 wt.% hydrogen peroxide as the terminal oxidant and water as a sole solvent. No organic co-solvent or other additive was needed. A 1.5-2.0 mol% (based on W atom) loading catalyst was found to be sufficient for a smooth and clean reaction. Both aliphatic and aromatic sulfides were efficiently and selectively transformed into their respective sulfoxides or sulfones by simply controlling of equivalents of hydrogen peroxide. In addition to the high catalytic activity, the catalyst exhibits excellent chemoselectivity. Sensitive functional groups, such as double bond and hydroxyl, remained under the oxidation conditions the reaction even with an excess hydrogen peroxide. The catalyst was easily recovered (via simple filtration) and reused at least eight times without a noticeable loss of activity. (author)

  13. Selective detection of acetone and hydrogen sulfide for the diagnosis of diabetes and halitosis using SnO(2) nanofibers functionalized with reduced graphene oxide nanosheets.

    Science.gov (United States)

    Choi, Seon-Jin; Jang, Bong-Hoon; Lee, Seo-Jin; Min, Byoung Koun; Rothschild, Avner; Kim, Il-Doo

    2014-02-26

    Sensitive detection of acetone and hydrogen sulfide levels in exhaled human breath, serving as breath markers for some diseases such as diabetes and halitosis, may offer useful information for early diagnosis of these diseases. Exhaled breath analyzers using semiconductor metal oxide (SMO) gas sensors have attracted much attention because they offer low cost fabrication, miniaturization, and integration into portable devices for noninvasive medical diagnosis. However, SMO gas sensors often display cross sensitivity to interfering species. Therefore, selective real-time detection of specific disease markers is a major challenge that must be overcome to ensure reliable breath analysis. In this work, we report on highly sensitive and selective acetone and hydrogen sulfide detection achieved by sensitizing electrospun SnO2 nanofibers with reduced graphene oxide (RGO) nanosheets. SnO2 nanofibers mixed with a small amount (0.01 wt %) of RGO nanosheets exhibited sensitive response to hydrogen sulfide (Rair/Rgas = 34 at 5 ppm) at 200 °C, whereas sensitive acetone detection (Rair/Rgas = 10 at 5 ppm) was achieved by increasing the RGO loading to 5 wt % and raising the operation temperature to 350 °C. The detection limit of these sensors is predicted to be as low as 1 ppm for hydrogen sulfide and 100 ppb for acetone, respectively. These concentrations are much lower than in the exhaled breath of healthy people. This demonstrates that optimization of the RGO loading and the operation temperature of RGO-SnO2 nanocomposite gas sensors enables highly sensitive and selective detection of breath markers for the diagnosis of diabetes and halitosis.

  14. Combining in situ chemical oxidation, stabilization, and anaerobic bioremediation in a single application to reduce contaminant mass and leachability in soil.

    Science.gov (United States)

    Cassidy, Daniel P; Srivastava, Vipul J; Dombrowski, Frank J; Lingle, James W

    2015-10-30

    Laboratory batch reactors were maintained for 32 weeks to test the potential for an in situ remedy that combines chemical oxidation, stabilization, and anaerobic bioremediation in a single application to treat soil from a manufactured gas plant, contaminated with polycyclic aromatic hydrocarbons (PAH) and benzene, toluene, ethylbenzene, and xylenes (BTEX). Portland cement and slaked lime were used to activate the persulfate and to stabilize/encapsulate the contaminants that were not chemically oxidized. Native sulfate-reducing bacteria degraded residual contaminants using the sulfate left after persulfate activation. The ability of the combined remedy to reduce contaminant mass and leachability was compared with NaOH-activated persulfate, stabilization, and sulfate-reducing bioremediation as stand-alone technologies. The stabilization amendments increased pH and temperature sufficiently to activate the persulfate within 1 week. Activation with both stabilization amendments and NaOH removed between 55% and 70% of PAH and BTEX. However, combined persulfate and stabilization significantly reduced the leachability of residual BTEX and PAH compared with NaOH activation. Sulfide, 2-naphthoic acid, and the abundance of subunit A of the dissimilatory sulfite reductase gene (dsrA) were used to monitor native sulfate-reducing bacteria, which were negatively impacted by activated persulfate, but recovered completely within weeks. Copyright © 2015 Elsevier B.V. All rights reserved.

  15. Effects of precursor and sulfation on OMS-2 catalyst for oxidation of ethanol and acetaldehyde at low temperatures.

    Science.gov (United States)

    Wang, Renhu; Li, Junhua

    2010-06-01

    Volatile organic compounds (VOCs) emitted from many industrial processes and transportation activities are major organic pollutants in the atmosphere and toxic to human health. Octahedral molecular sieve (OMS-2) catalysts with different precursors and sulfate-acidified OMS-2 catalysts were synthesized using refluxing methods. The catalysts were investigated on complete oxidation of ethanol and acetaldehyde, and both demonstrated good reactivity. However, acidification resulted in a decrease in activity. OMS-2 catalyst using MnSO(4) as precursor exhibited the best catalytic performance and, thus, was selected for catalyst deactivation by sulfur dioxide. The results of this study suggested that the Mn-O bond of OMS-2 catalysts was the main determinant of the catalytic activity toward oxygenated VOC oxidation and weaker acid sites benefited higher acetaldehyde selectivity. Catalyst deactivation resulted from a strong but slow chemical interaction between the Mn-O bond and sulfur dioxide, probably forming manganese sulfate.

  16. Solubility Measurements and Modeling of Zinc, Lead and Iron Sulfides at High Temperatures and High Pressures

    DEFF Research Database (Denmark)

    Carolina Figueroa Murcia, Diana; Fosbøl, Philip Loldrup; Thomsen, Kaj

    Solubility measurements of sulfides in aqueous solutions are necessary to understand the behaviour of these scaling minerals in geothermal and oil reservoirs. The low solubility levels of Zinc Sulfide (ZnS), Lead Sulfide (PbS) and Iron Sulfide (FeS) make the solubility measurements a challenging...... oxygen atmosphere to avoid the risk of oxidation of sulfide minerals. The solution is kept in an equilibrium cell at constant temperature and pressure with continuous stirring. The concentration of Zn2+, Pb2+, Fe2+ and S2- are measured using Inductively Coupled Plasma Optical Emission spectrometry (ICP...

  17. Microbial conversion of sulfur dioxide in flue gas to sulfide using bulk drug industry wastewater as an organic source by mixed cultures of sulfate reducing bacteria

    International Nuclear Information System (INIS)

    Rao, A. Gangagni; Ravichandra, P.; Joseph, Johny; Jetty, Annapurna; Sarma, P.N.

    2007-01-01

    Mixed cultures of sulfate reducing bacteria (SRB) were isolated from anaerobic cultures and enriched with SRB media. Studies on batch and continuous reactors for the removal of SO 2 with bulk drug industry wastewater as an organic source using isolated mixed cultures of SRB revealed that isolation and enrichment methodology adopted in the present study were apt to suppress the undesirable growth of anaerobic bacteria other than SRB. Studies on anaerobic reactors showed that process was sustainable at COD/S ratio of 2.2 and above with optimum sulfur loading rate (SLR) of 5.46 kg S/(m 3 day), organic loading rate (OLR) of 12.63 kg COD/(m 3 day) and at hydraulic residence time (HRT) of 8 h. Free sulfide (FS) concentration in the range of 300-390 mg FS/l was found to be inhibitory to mixed cultures of SRB used in the present studies

  18. Effect of active zinc oxide dispersion on reduced graphite oxide for hydrogen sulfide adsorption at mid-temperature

    Energy Technology Data Exchange (ETDEWEB)

    Song, Hoon Sub [Department of Chemical Engineering, University of Waterloo, 200 University Avenue West, Waterloo, Ontario, N2L3G1 (Canada); Greenhouse Gas Department, Korea Institute of Energy Research, 152 Gajeong-ro, Yuseong-gu, Daejeon, 305-343 (Korea, Republic of); Park, Moon Gyu [Department of Chemical Engineering Education, Chungnam National University, 99 Daehak-ro, Yuseong-gu, Daejeon, 305-764 (Korea, Republic of); Croiset, Eric, E-mail: ecroiset@uwaterloo.ca [Department of Chemical Engineering, University of Waterloo, 200 University Avenue West, Waterloo, Ontario, N2L3G1 (Canada); Chen, Zhongwei [Department of Chemical Engineering, University of Waterloo, 200 University Avenue West, Waterloo, Ontario, N2L3G1 (Canada); Nam, Sung Chan; Ryu, Ho-Jung [Greenhouse Gas Department, Korea Institute of Energy Research, 152 Gajeong-ro, Yuseong-gu, Daejeon, 305-343 (Korea, Republic of); Yi, Kwang Bok, E-mail: cosy32@cnu.ac.kr [Department of Chemical Engineering Education, Chungnam National University, 99 Daehak-ro, Yuseong-gu, Daejeon, 305-764 (Korea, Republic of)

    2013-09-01

    Composites of Zinc oxide (ZnO) with reduced graphite oxide (rGO) were synthesized and used as adsorbents for hydrogen sulfide (H{sub 2}S) at 300 °C. Various characterization methods (TGA, XRD, FT-IR, TEM and XPS) were performed in order to link their H{sub 2}S adsorption performance to the properties of the adsorbent's surface. Microwave-assisted reduction process of graphite oxide (GO) provided mild reduction environment, allowing oxygen-containing functional groups to remain on the rGO surface. It was confirmed that for the ZnO/rGO synthesize using the microwave-assisted reduction method, the ZnO particle size and the degree of ZnO dispersion remained stable over time at 300 °C, which was not the case for only the ZnO particles themselves. This stable highly dispersed feature allows for sustained high surface area over time. This was confirmed through breakthrough experiments for H{sub 2}S adsorption where it was found that the ZnO/rGO composite showed almost four times higher ZnO utilization efficiency than ZnO itself. The effect of the H{sub 2} and CO{sub 2} on H{sub 2}S adsorption was also investigated. The presence of hydrogen in the H{sub 2}S stream had a positive effect on the removal of H{sub 2}S since it allows a reducing environment for Zn-O and Zn-S bonds, leading to more active sites (Zn{sup 2+}) to sulfur molecules. On the other hand, the presence of carbon dioxide (CO{sub 2}) showed the opposite trend, likely due to the oxidation environment and also due to possible competitive adsorption between H{sub 2}S and CO{sub 2}.

  19. Functional consortium for denitrifying sulfide removal process.

    Science.gov (United States)

    Chen, Chuan; Ren, Nanqi; Wang, Aijie; Liu, Lihong; Lee, Duu-Jong

    2010-03-01

    Denitrifying sulfide removal (DSR) process simultaneously converts sulfide, nitrate, and chemical oxygen demand from industrial wastewaters to elemental sulfur, nitrogen gas, and carbon dioxide, respectively. This investigation utilizes a dilution-to-extinction approach at 10(-2) to 10(-6) dilutions to elucidate the correlation between the composition of the microbial community and the DSR performance. In the original suspension and in 10(-2) dilution, the strains Stenotrophomonas sp., Thauera sp., and Azoarcus sp. are the heterotrophic denitrifiers and the strains Paracoccus sp. and Pseudomonas sp. are the sulfide-oxidizing denitrifers. The 10(-4) dilution is identified as the functional consortium for the present DSR system, which comprises two functional strains, Stenotrophomonas sp. strain Paracoccus sp. At 10(-6) dilution, all DSR performance was lost. The functions of the constituent cells in the DSR granules were discussed based on data obtained using the dilution-to-extinction approach.

  20. A model-based insight into the coupling of nitrogen and sulfur cycles in a coastal upwelling system

    DEFF Research Database (Denmark)

    Muchamad, Al Azhar; Canfield, Donald Eugene; Fennel, Katja

    2014-01-01

    is masked, however, by rapid sulfide oxidation, most likely through nitrate reduction. Thus, the cryptic sulfur cycle links with the nitrogen cycle in OMZ settings. Here, we model the physical-chemical water column structure and the observed process rates as driven by formation and sinking of organic...... heterotrophic nitrate reduction and sulfate reduction are responsible for 47% and 36%, respectively, of organic remineralization in a 150 m deep zone below mixed layer. Anammox contributes to 61% of the fixed nitrogen lost to N2 gas, while the rest of the loss is through canonical denitrification...... as a combination of organic matter oxidation by nitrite reduction and sulfide-driven denitrification. Mineralization coupled to heterotrophic nitrate reduction supplies ~48% of the ammonium required by anammox. Due to active sulfate reduction, model results suggest that sulfide-driven denitrification contributes...

  1. Comparative Study of Antidiabetic Activity and Oxidative Stress Induced by Zinc Oxide Nanoparticles and Zinc Sulfate in Diabetic Rats.

    Science.gov (United States)

    Nazarizadeh, Ali; Asri-Rezaie, Siamak

    2016-08-01

    In the current study, antidiabetic activity and toxic effects of zinc oxide nanoparticles (ZnO) were investigated in diabetic rats compared to zinc sulfate (ZnSO4) with particular emphasis on oxidative stress parameters. One hundred and twenty male Wistar rats were divided into two healthy and diabetic groups, randomly. Each major group was further subdivided into five subgroups and then orally supplemented with various doses of ZnO (1, 3, and 10 mg/kg) and ZnSO4 (30 mg/kg) for 56 consecutive days. ZnO showed greater antidiabetic activity compared to ZnSO4 evidenced by improved glucose disposal, insulin levels, and zinc status. The altered activities of erythrocyte antioxidant enzymes as well as raised levels of lipid peroxidation and a marked reduction of total antioxidant capacity were observed in rats receiving ZnO. ZnO nanoparticles acted as a potent antidiabetic agent, however, severely elicited oxidative stress particularly at higher doses.

  2. Influence of commercial (Fluka) naphthenic acids on acid volatile sulfide (AVS) production and divalent metal precipitation.

    Science.gov (United States)

    McQueen, Andrew D; Kinley, Ciera M; Rodgers, John H; Friesen, Vanessa; Bergsveinson, Jordyn; Haakensen, Monique C

    2016-12-01

    Energy-derived waters containing naphthenic acids (NAs) are complex mixtures often comprising a suite of potentially problematic constituents (e.g. organics, metals, and metalloids) that need treatment prior to beneficial use, including release to receiving aquatic systems. It has previously been suggested that NAs can have biostatic or biocidal properties that could inhibit microbially driven processes (e.g. dissimilatory sulfate reduction) used to transfer or transform metals in passive treatment systems (i.e. constructed wetlands). The overall objective of this study was to measure the effects of a commercially available (Fluka) NA on sulfate-reducing bacteria (SRB), production of sulfides (as acid-volatile sulfides [AVS]), and precipitation of divalent metals (i.e. Cu, Ni, Zn). These endpoints were assessed following 21-d aqueous exposures of NAs using bench-scale reactors. After 21-days, AVS molar concentrations were not statistically different (pAVS production was sufficient in all NA treatments to achieve ∑SEM:AVS AVS) could be used to treat metals occurring in NAs affected waters. Copyright © 2016 Elsevier Inc. All rights reserved.

  3. Biodiversity and Biological Degradation of Soil -2A ...

    Indian Academy of Sciences (India)

    biodiversity, conservation .... excavation of ores containing iron sulfides leads to oxidative production of sulfates. ... oxide, a significant greenhouse gas, may also occur. In addition to the ... ganisms rely on organic matter for food. Thus, a rich ...

  4. Biological and chemical sulfide oxidation in a Beggiatoa inhabited marine sediment

    DEFF Research Database (Denmark)

    Preisler, André; de Beer, Dirk; Lichtschlag, Anna

    2007-01-01

    The ecological niche of nitrate-storing Beggiatoa, and their contribution to the removal of sulfide were investigated in coastal sediment. With microsensors a clear suboxic zone of 2-10 cm thick was identified, where neither oxygen nor free sulfide was detectable. In this zone most of the Beggiat...

  5. Laser cleaning of sulfide scale on compressor impeller blade

    International Nuclear Information System (INIS)

    Tang, Q.H.; Zhou, D.; Wang, Y.L.; Liu, G.F.

    2015-01-01

    Highlights: • The effects of sulfide layers and fluence values on the mechanism of laser cleaning were experimentally established. • The specimen surface with sulfide scale becomes slightly smoother than that before laser cleaning. • The mechanism of laser cleaning the sulfide scale of stainless steel is spallation without oxidization. • It would avoid chemical waste and dust pollution using a fiber laser instead of using nitric acids or sandblasting. - Abstract: Sulfide scale on the surface of a compressor impeller blade can considerably reduce the impeller performance and its service life. To prepare for subsequent remanufacturing, such as plasma spraying, it needs to be removed completely. In the corrosion process on an FV(520)B stainless steel, sulfide scale is divided into two layers because of different outward diffusion rates of Cr, Ni and Fe. In this paper, the cleaning threshold values of the upper and inner layers and the damage threshold value of the substrate were investigated using a pulsed fiber laser. To obtain experimental evidence, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS) and 3D surface profilometry were employed to investigate the two kinds of sulfide layers on specimens before, during, and after laser cleaning.

  6. Sulfur isotopic analysis of carbonyl sulfide and its application for biogeochemical cycles

    Science.gov (United States)

    Hattori, Shohei; Kamezaki, Kazuki; Ogawa, Takahiro; Toyoda, Sakae; Katayama, Yoko; Yoshida, Naohiro

    2016-04-01

    Carbonyl sulfide (OCS or COS) is the most abundant gas containing sulfur in the atmosphere, with an average mixing ratio of 500 p.p.t.v. in the troposphere. OCS is suggested as a sulfur source of the stratospheric sulfate aerosols (SSA) which plays an important role in Earth's radiation budget and ozone depletion. Therefore, OCS budget should be validated for prediction of climate change, but the global OCS budget is imbalance. Recently we developed a promising new analytical method for measuring the stable sulfur isotopic compositions of OCS using nanomole level samples: the direct isotopic analytical technique of on-line gas chromatography-isotope ratio mass spectrometry (GC-IRMS) using fragmentation ions S+ (Hattori et al., 2015). The first measurement of the δ34S value for atmospheric OCS coupled with isotopic fractionation for OCS sink reactions in the stratosphere (Hattori et al., 2011; Schmidt et al., 2012; Hattori et al., 2012) explains the reported δ34S value for background stratospheric sulfate, suggesting that OCS is a potentially important source for background (nonepisodic or nonvolcanic) stratospheric sulfate aerosols. This new method measuring δ34S values of OCS can be used to investigate OCS sources and sinks in the troposphere to better understand its cycle. It is known that some microorganisms in soil can degrade OCS, but the mechanism and the contribution to the OCS in the air are still uncertain. In order to determine sulfur isotopic enrichment factor of OCS during degradation via microorganisms, incubation experiments were conducted using strains belonging to the genera Mycobacterium, Williamsia and Cupriavidus, isolated from natural soil environments (Kato et al., 2008). As a result, sulfur isotope ratios of OCS were increased during degradation of OCS, indicating that reaction for OC32S is faster than that for OC33S and OC34S. OCS degradation via microorganisms is not mass-independent fractionation (MIF) process, suggesting that this

  7. Study on the sulfidation behavior of smithsonite

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Dandan; Wen, Shuming, E-mail: shmwen@126.com; Deng, Jiushuai, E-mail: dengshuai689@163.com; Liu, Jian; Mao, Yingbo

    2015-02-28

    Highlights: • Zeta potential showed that the pH{sub IEP} of smithsonite decreased from 7.7 to 6. • ICP test showed the gradual reduction of C{sub S} in the solution. • SEM showed that the mineral surface was partially changed to ZnS film. • XPS indicated that the presence of a characteristic signal peak of sulfur ions. - Abstract: Zinc extraction from low-grade mineral resources of oxidized zinc has recently become a focus of study. Sulfidation is an important process in oxidized ore flotation. In this study, the influence of sulfur ion adsorption on smithsonite surface was investigated with the use of zeta potential, inductively coupled plasma (ICP), scanning electron microscope (SEM), and X-ray photoelectron spectroscopic studies. Zeta potential measurements of sodium sulfide showed that sulfur ions were adsorbed onto the surface of pure smithsonite, as evidenced by the increased negative charge and the decrease in the pH{sub IEP} of smithsonite from 7.7 to 6 after sodium sulfide treatment. The ICP test revealed the gradual reduction in sulfur ion adsorption onto the surface of smithsonite in pulp sulfur. After 30 min of absorption, C{sub S} in the solution declined from 1000 × 10{sup −6} mol/L to 1.4 × 10{sup −6} mol/L. SEM results showed that the mineral surface was partially changed to ZnS film after sodium sulfide treatment, whereas EDS analysis results showed that 2% S is contained on the smithsonite surface. X-ray photoelectron spectroscopy results indicated the presence of a characteristic signal peak of sulfur ions after sulfidation. Sulfur concentration increased to 11.89%, whereas oxygen concentration decreased from 42.31% to 13.74%. Sulfur ions were not only present during chemical adsorption, but were also incorporated into the crystal lattices of minerals by the exchange reaction between S{sup 2−} and CO{sub 3}{sup 2−} ions.

  8. Early diagenesis in the sediments of the Congo deep-sea fan dominated by massive terrigenous deposits: Part II - Iron-sulfur coupling

    Science.gov (United States)

    Taillefert, Martial; Beckler, Jordon S.; Cathalot, Cécile; Michalopoulos, Panagiotis; Corvaisier, Rudolph; Kiriazis, Nicole; Caprais, Jean-Claude; Pastor, Lucie; Rabouille, Christophe

    2017-08-01

    Deep-sea fans are well known depot centers for organic carbon that should promote sulfate reduction. At the same time, the high rates of deposition of unconsolidated metal oxides from terrigenous origin may also promote metal-reducing microbial activity. To investigate the eventual coupling between the iron and sulfur cycles in these environments, shallow sediment cores (Congo River deep-sea fan ( 5000 m) were profiled using a combination of geochemical methods. Interestingly, metal reduction dominated suboxic carbon remineralization processes in most of these sediments, while dissolved sulfide was absent. In some 'hotspot' patches, however, sulfate reduction produced large sulfide concentrations which supported chemosynthetic-based benthic megafauna. These environments were characterized by sharp geochemical boundaries compared to the iron-rich background environment, suggesting that FeS precipitation efficiently titrated iron and sulfide from the pore waters. A companion study demonstrated that methanogenesis was active in the deep sediment layers of these patchy ecosystems, suggesting that sulfate reduction was promoted by alternative anaerobic processes. These highly reduced habitats could be fueled by discrete, excess inputs of highly labile natural organic matter from Congo River turbidites or by exhumation of buried sulfide during channel flank erosion and slumping. Sulfidic conditions may be maintained by the mineralization of decomposition products from local benthic macrofauna or bacterial symbionts or by the production of more crystalline Fe(III) oxide phases that are less thermodynamically favorable than sulfate reduction in these bioturbated sediments. Overall, the iron and sulfur biogeochemical cycling in this environment is unique and much more similar to a coastal ecosystem than a deep-sea environment.

  9. The Determination of Hydrogen Sulfide in Stack Gases, Iodometric Titration After Sulfite Removal.

    Science.gov (United States)

    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…

  10. Effects of copper sulfate-oxidized or myeloperoxidase- modified LDL on lipid loading and programmed cell death in macrophages under hypoxia

    Directory of Open Access Journals (Sweden)

    Vlaminck B

    2014-09-01

    Full Text Available Benoit Vlaminck,1 Damien Calay,1 Marie Genin,1 Aude Sauvage,1 Noelle Ninane,1 Karim Zouaoui Boudjeltia,2 Martine Raes,1 Carine Michiels1 1Laboratory of Biochemistry and Cellular Biology (URBC, Namur Research Institute for Life Sciences (NARILIS, University of Namur, Namur, Belgium; 2Laboratory of Experimental Medicine (ULB 222 Unit, Universite Libre de Bruxelles, CHU de Charleroi, Charleroi, Belgium Abstract: Atheromatous plaques contain heavily lipid-loaded macrophages that die, hence generating the necrotic core of these plaques. Since plaque instability and rupture is often correlated with a large necrotic core, it is important to understand the mechanisms underlying foam cell death. Furthermore, macrophages within the plaque are associated with hypoxic areas but little is known about the effect of low oxygen partial pressure on macrophage death. The aim of this work was to unravel macrophage death mechanisms induced by oxidized low-density lipoproteins (LDL both under normoxia and hypoxia. Differentiated macrophages were incubated in the presence of native, copper sulfate-oxidized, or myeloperoxidase-modified LDL. The unfolded protein response, apoptosis, and autophagy were then investigated. The unfolded protein response and autophagy were triggered by myeloperoxidase-modified LDL and, to a larger extent, by copper sulfate-oxidized LDL. Electron microscopy observations showed that oxidized LDL induced excessive autophagy and apoptosis under normoxia, which were less marked under hypoxia. Myeloperoxidase-modified LDL were more toxic and induced a higher level of apoptosis. Hypoxia markedly decreased apoptosis and cell death, as marked by caspase activation. In conclusion, the cell death pathways induced by copper sulfate-oxidized and myeloperoxidase-modified LDL are different and are differentially modulated by hypoxia. Keywords: Ox-LDL, myeloperoxidase, hypoxia, UPR, apoptosis, autophagy, macrophages

  11. Biogeochemical cycling of arsenic in coastal salinized aquifers: Evidence from sulfur isotope study

    Energy Technology Data Exchange (ETDEWEB)

    Kao, Yu-Hsuan [Department of Bioenvironmental Systems Engineering, National Taiwan University, Taipei 106, Taiwan, ROC (China); Wang, Sheng-Wei [Agricultural Engineering Research Center, Chungli 320, Taiwan, ROC (China); Liu, Chen-Wuing, E-mail: lcw@gwater.agec.ntu.edu.tw [Department of Bioenvironmental Systems Engineering, National Taiwan University, Taipei 106, Taiwan, ROC (China); Wang, Pei-Ling [Institute of Oceanography, National Taiwan University, Taipei 106, Taiwan, ROC (China); Wang, Chung-Ho [Institute of Earth Sciences, Academia Sinica, Taipei 115, Taiwan, ROC (China); Maji, Sanjoy Kumar [Department of Bioenvironmental Systems Engineering, National Taiwan University, Taipei 106, Taiwan, ROC (China)

    2011-10-15

    Arsenic (As) contamination of groundwater, accompanied by critical salinization, occurs in the southwestern coastal area of Taiwan. Statistical analyses and geochemical calculations indicate that a possible source of aqueous arsenic is the reductive dissolution of As-bearing iron oxyhydroxides. There are few reports of the influence of sulfate-sulfide redox cycling on arsenic mobility in brackish groundwater. We evaluated the contribution of sulfate reduction and sulfide re-oxidation on As enrichment using {delta}{sup 34}S{sub [SO{sub 4]}} and {delta}{sup 18}O{sub [SO{sub 4]}} sulfur isotopic analyses of groundwater. Fifty-three groundwater samples were divided into groups of high-As content and salinized (Type A), low-As and non-salinized (Type B), and high-As and non-salinized (Type C) groundwaters, based on hydro-geochemical analysis. The relatively high enrichment of {sup 34}S{sub [SO{sub 4]}} and {sup 18}O{sub [SO{sub 4]}} present in Type A, caused by microbial-mediated reduction of sulfate, and high {sup 18}O enrichment factor ({epsilon}{sub [SO{sub 4-H{sub 2O]}}}), suggests that sulfur disproportionation is an important process during the reductive dissolution of As-containing iron oxyhydroxides. Limited co-precipitation of ion-sulfide increased the rate of As liberation under anaerobic conditions. In contrast to this, Type B and Type C groundwater samples showed high {delta}{sup 18}O{sub [SO{sub 4]}} and low {delta}{sup 34}S{sub [SO{sub 4]}} values under mildly reducing conditions. Base on {sup 18}O mass balance calculations, the oxide sources of sulfate are from infiltrated atmospheric O{sub 2}, caused by additional recharge of dissolved oxygen and sulfide re-oxidation. The anthropogenic influence of extensive pumping also promotes atmospheric oxygen entry into aquifers, altering redox conditions, and increasing the rate of As release into groundwater. - Highlights: {yields} Seawater intrusion and elevated As are the main issues of groundwater in Taiwan

  12. Synthesis of sulfates and sulfate derivates of selected metals under harsh conditions; Synthese von Sulfaten und Sulfatderivaten ausgewaehlter Metalle unter drastischen Bedingungen

    Energy Technology Data Exchange (ETDEWEB)

    Neuschulz, Kai

    2015-03-24

    In the course of this work sulfates und sulfate derivates of selected metals were synthesized under harsh conditions. The obtained compounds, in which the metal ions often reveal unusual oxidation states, have been characterized. Two mixed valent vanadium(IV/V) oxide sulfates (VO){sub 4}(SO{sub 4}){sub 5}, and (VO){sub 3}(SO{sub 4}){sub 4} and a vanadium(V) oxide sulfate (VO){sub 2}(SO{sub 4}){sub 3} as well as a complex anionic vanadium(V) oxide sulfate (NO)[VO(SO{sub 4}){sub 2}] have been obtained starting from vanadium or vanadium(V) oxide and oleum. All vanadium oxide sulfates reveal a similar thermal behavior. The decomposition residues are either pure vanadium(V) oxide or vanadium(IV) oxide or a mixture of both residues in different ratios. It was possible to synthesize binary tantalum(V) sulfate Ta{sub 2}(SO{sub 4}){sub 5} for the first time by reaction of pure sulfur(VI) oxide and tantalum(V) oxide at 150 C and to characterize. The complete absence of any oxide ligands at the metal center is of special interest in this compound. The reaction of tin(II) sulfate with oleum lead to the formation of tin(IV) sulfate Sn(SO{sub 4}){sub 2}. Using IR spectroscopy, the oxidation state +IV was confirmed for tin, due to the absence of OH-band in the IR-spectra, which would have meant the oxidation state +II. Using methanesulfonic acid as solvent and reactant on different synthetic routes the anhydrous methanesulfonates Mn(CH{sub 3}SO{sub 3}){sub 2}, and Fe(CH{sub 3}SO{sub 3}){sub 2}, Ga(CH{sub 3}SO{sub 3}){sub 3}, In(CH{sub 3}SO{sub 3}){sub 3}, and Tl(CH{sub 3}SO{sub 3}){sub 3}, as well as VO(CH{sub 3}SO{sub 3}){sub 2} and SnCl{sub 2}(CH{sub 3}SO{sub 3}){sub 2} were obtained. For the element thallium it was possible to obtain two mixed anionic compounds with the composition TlX{sub 2}(CH{sub 3}SO{sub 3}) (X = Cl or Br). All methanesulfonates show a similar thermal decomposition behavior forming the metal oxide as decomposition product. The thallium compounds represent

  13. Simultaneous Voltammetric/Amperometric Determination of Sulfide and Nitrite in Water at BDD Electrode

    Directory of Open Access Journals (Sweden)

    Anamaria Baciu

    2015-06-01

    Full Text Available This work reported new voltammetric/amperometric-based protocols using a commercial boron-doped diamond (BDD electrode for simple and fast simultaneous detection of sulfide and nitrite from water. Square-wave voltammetry operated under the optimized working conditions of 0.01 V step potential, 0.5 V modulation amplitude and 10 Hz frequency allowed achieving the best electroanalytical parameters for the simultaneous detection of nitrite and sulfide. For practical in-field detection applications, the multiple-pulsed amperometry technique was operated under optimized conditions, i.e., −0.5 V/SCE for a duration of 0.3 s as conditioning step, +0.85 V/SCE for a duration of 3 s that assure the sulfide oxidation and +1.25 V/SCE for a duration of 0.3 s, where the nitrite oxidation occurred, which allowed the simultaneously detection of sulfide and nitrite without interference between them. Good accuracy was found for this protocol in comparison with standardized methods for each anion. Also, no interference effect was found for the cation and anion species, which are common in the water matrix.

  14. Understanding hydrodenitrogenation on novel unsupported sulfide Mo-W-Ni catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Hein, J.; Hrabar, A.; Gutierrez, O.Y.; Lercher, J.A. [Technische Univ. Muenchen (Germany). Catalysis Research Center

    2011-07-01

    WNi, NiMo and Mo-W-Ni unsupported catalysts were synthesized, characterized and tested with respect to their hydrodenitrogenation properties using o-propylaniline as test reactant. The bimetallic oxide precursors are crystalline metallates, whereas the trimetallic materials are amorphous. In the sulfide form, the catalysts are mixtures of agglomerated Mo(W)S{sub 2} and Ni sulfides. The performance of all catalysts is similar, suggesting the same nature of active sites regardless the composition. Due to the lack of correlation between activity and density of coordinatively unsaturated sites of the catalysts, two kinds of active sites are proposed, i.e. coordinatively unsaturated sites and electron rich sites at the edges of the sulfides. (orig.)

  15. Study on the surface sulfidization behavior of smithsonite at high temperature

    Science.gov (United States)

    Lv, Jin-fang; Tong, Xiong; Zheng, Yong-xing; Xie, Xian; Wang, Cong-bing

    2018-04-01

    Surface sulfidization behavior of smithsonite at high temperature was investigated by X-ray powder diffractometer (XRD) along with thermodynamic calculation, X-ray photoelectron spectroscopy (XPS) and electron probe microanalysis (EPMA). The XRD and thermodynamic analyses indicated that the smithsonite was decomposed into zincite at high temperatures. After introducing a small amount of pyrite, artificial sulfides were formed at surface of the obtained zincite. The XPS analyses revealed that the sulfide species including zinc sulfide and zinc disulfide were generated at the zincite surface. The EPMA analyses demonstrated that the film of sulfides was unevenly distributed at the zincite surface. The average concentration of elemental sulfur at the sample surface increased with increasing of pyrite dosage. A suitable mole ratio of FeS2 to ZnCO3 for the surface thermal modification was determined to be about 0.3. These findings can provide theoretical support for improving the process during which the zinc recovery from refractory zinc oxide ores is achieved by xanthate flotation.

  16. Sulfide oxidation and the natural attenuation of arsenic and trace metals in the waste rocks of the abandoned Seobo tungsten mine, Korea

    International Nuclear Information System (INIS)

    Lee, Pyeong-koo; Kang, Min-Ju; Choi, Sang-Hoon; Touray, Jean-Claude

    2005-01-01

    Mineralogical examinations were performed to characterize the formation of secondary minerals and natural removal process of dissolved As and trace metals (Pb, Zn and Cu) from sulfide oxidation. Laboratory-based leaching tests were also conducted to determine whether the concentrations of As and trace metals in the leachates from waste-rock materials and contaminated soil could be affected by the presence acids such as acid rainwater or acid mine drainage. Waste-rock materials and contaminated soil were compared by 4-day leaching tests using HNO 3 solutions of increasing acidity (0.00001-0.1mole/L). Mineralogical studies of the waste rocks confirmed the presence of Fe-(oxy)hydroxides (e.g. goethite), jarosite, elemental S, Fe-sulfates, amorphous Fe-As phases, anglesite and covellite as secondary minerals. These secondary minerals act as mineralogical scavengers of dissolved trace metals, SO 4 2- and acidity released by sulfide oxidation. Arsenic was attenuated by the adsorption on Fe-(oxy)hydroxides and/or the formation of an amorphous Fe-As phase, with a Fe/As ratio=1 (maybe scorodite: FeAsO 4 .2H 2 O). Electron probe microanalyses data showed that the Fe-(oxy)hydroxides had high concentrations of Pb (up to 21wt%), with appreciable amounts of As (up to 7.7wt%), Zn (up to 4.6wt%) and Cu (up to 2.5wt%) indicating that dissolved metals were co-precipitated and adsorbed onto Fe-(oxy)hydroxides, Fe(Mn)-hydroxides and Fe-sulfates. The results of the leaching experiments within the pH-range 3.5-5.0 indicated that acidic rainstorms may leach minor amounts of Pb (ca. 1.7-4.0% of total), Zn (ca. 0.8-2.2% of total), Cu (ca. 0.0-0.2% of total) and As (ca. 0.02-0.1% of total) from waste rocks, including the dissolution of soluble secondary minerals previously formed during prolonged dry periods, while dissolution of these elements was negligible from the contaminated soil. In the pH-range 1.0-3.0, the leaching of Pb (ca. 2.4-31% of total) and As (ca. 0.1-5.8% of total) from

  17. Performance of a haloalkaliphilic bioreactor and bacterial community shifts under different COD/SO{sub 4}{sup 2−} ratios and hydraulic retention times

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Jie-Min [National Key Laboratory of Biochemical Engineering, Institute of Process Engineering, Chinese Academy of Sciences, PO Box 353, Beijing 100190 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Song, Zi-Yu [National Key Laboratory of Biochemical Engineering, Institute of Process Engineering, Chinese Academy of Sciences, PO Box 353, Beijing 100190 (China); Yan, Dao-Jiang; Liu, Yi-Lan [National Key Laboratory of Biochemical Engineering, Institute of Process Engineering, Chinese Academy of Sciences, PO Box 353, Beijing 100190 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Yang, Mao-Hua [National Key Laboratory of Biochemical Engineering, Institute of Process Engineering, Chinese Academy of Sciences, PO Box 353, Beijing 100190 (China); Cao, Hong-Bin [National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Institute of Process Engineering, Chinese Academy of Sciences, PO Box 353, Beijing 100190 (China); Xing, Jian-Min, E-mail: jmxing@home.ipe.ac.cn [National Key Laboratory of Biochemical Engineering, Institute of Process Engineering, Chinese Academy of Sciences, PO Box 353, Beijing 100190 (China)

    2014-06-01

    Highlights: • Haloalkaliphilic microorganisms were used to reduce sulfate. • Sulfide concentration reached up to 1603 mg/L. • There was no sulfide inhibition to haloalkaliphilic microorganisms. • Bacterial community of haloalkaliphilic bioreactor was studied. - Abstract: Sulfur dioxide from flue gas was converted into sulfate after the absorption of alkaline solutions. Haloalkaliphilic microorganisms have been used in reducing sulfate to decrease expenses and avoid sulfide inhibition. The effects of different COD/SO{sub 4}{sup 2−} ratios and hydraulic retention times (HRTs) on the sulfate removal efficiency and bacterial community were investigated in model experiments. Ethanol showed better performance as an electron donor than lactate. The optimum COD/SO{sub 4}{sup 2−} ratio and HRT were 4.0 and 18 h, respectively, with respective sulfate removal efficiency and rate of 97.8 ± 1.11% and 6.26 ± 0.0710 g/L d. Sulfide concentrations reached 1603 ± 3.38 mg/L. Based on denaturing gradient gel electrophoresis analysis of 16S rDNA, the major sulfate-reducing bacterium (SRB) was Desulfonatronovibrio sp., which was only detected at a COD/SO{sub 4}{sup 2−} ratio of 4.0 using ethanol as an electron donor. Different HRTs had no significant effect on the band corresponding to this species. PCR results show that methane-producing archaea (MPA) were from the acetoclastic methanogenic family Methanosarcinaceae. Quantitative real-time PCR did not demonstrate any significant competition between SRB and MPA. The findings of this study indicate that sulfate reduction, nitrate reduction, and sulfide oxidization may occur in the same bioreactor.

  18. Redistribution of elements between wastes and organic-bearing material in the dispersion train of gold-bearing sulfide tailings: Part I. Geochemistry and mineralogy.

    Science.gov (United States)

    Saryg-Ool, B Yu; Myagkaya, I N; Kirichenko, I S; Gustaytis, M A; Shuvaeva, O V; Zhmodik, S M; Lazareva, E V

    2017-03-01

    Migration and redistribution of elements during prolonged interaction of cyanide wastes with the underlying natural organic-bearing material have been studied in two ~40cm deep cores that sample primary ores and their weathering profile (wastes I and II, respectively) in the dispersion train of gold-bearing sulfide tailings in Siberia. Analytical results of SR-XRF, whole-rock XRF, AAS, CHNS, and SEM measurements of core samples show high K, Sr, Ti, and Fe enrichments and correlation of P 2 O 5 and Mn with LOI and C org . Organic material interlayered or mixed with the wastes accumulates Cu, Zn, Se, Cd, Ag, Au, and Hg. The peat that contacts wastes II bears up to 3wt.% Zn, 1000g/t Se, 100g/t Cd, and 8000g/t Hg. New phases of Zn and Hg sulfides and Hg selenides occur as abundant sheaths over bacterial cells suggesting microbial mediation in sorption of elements. Organic-bearing material in the cores contains 10-30g/t Au in 2-5cm thick intervals, both within and outside the intervals rich in sulfides and selenides. Most of gold is invisible but reaches 345g/t and forms 50nm to 1.5μm Au 0 particles in a thin 2-3cm interval of organic remnants mixed with wastes I. Vertical and lateral infiltration of AMD waters in peat and oxidative dissolution of wastes within the dispersion train of the Ursk tailings lead to redistribution of elements and their accumulation by combined physical (material's permeability, direction AMD), chemical (complexing, sorption by organic matter and Fe(III) hydroxides) and biochemical (metabolism of sulfate-reducing bacteria) processes. The accumulated elements form secondary sulfates, and Hg and Zn selenides. The results provide insights into accumulation of elements in the early history of coal and black shale deposits and have implications for remediation of polluted areas and for secondary enrichment technologies. Copyright © 2017 Elsevier B.V. All rights reserved.

  19. Anaerobic Methane-Oxidizing Microbial Community in a Coastal Marine Sediment: Anaerobic Methanotrophy Dominated by ANME-3.

    Science.gov (United States)

    Bhattarai, Susma; Cassarini, Chiara; Gonzalez-Gil, Graciela; Egger, Matthias; Slomp, Caroline P; Zhang, Yu; Esposito, Giovanni; Lens, Piet N L

    2017-10-01

    The microbial community inhabiting the shallow sulfate-methane transition zone in coastal sediments from marine Lake Grevelingen (The Netherlands) was characterized, and the ability of the microorganisms to carry out anaerobic oxidation of methane coupled to sulfate reduction was assessed in activity tests. In vitro activity tests of the sediment with methane and sulfate demonstrated sulfide production coupled to the simultaneous consumption of sulfate and methane at approximately equimolar ratios over a period of 150 days. The maximum sulfate reduction rate was 5 μmol sulfate per gram dry weight per day during the incubation period. Diverse archaeal and bacterial clades were retrieved from the sediment with the majority of them clustered with Euryarchaeota, Thaumarcheota, Bacteroidetes, and Proteobacteria. The 16S rRNA gene sequence analysis showed that the sediment from marine Lake Grevelingen contained anaerobic methanotrophic Archaea (ANME) and methanogens as archaeal clades with a role in the methane cycling. ANME at the studied site mainly belong to the ANME-3 clade. This study provides one of the few reports for the presence of ANME-3 in a shallow coastal sediment. Sulfate-reducing bacteria from Desulfobulbus clades were found among the sulfate reducers, however, with very low relative abundance. Desulfobulbus has previously been commonly found associated with ANME, whereas in our study, ANME-3 and Desulfobulbus were not observed simultaneously in clusters, suggesting the possibility of independent AOM by ANME-3.

  20. Studying inhibition of calcium oxalate stone formation: an in vitro approach for screening hydrogen sulfide and its metabolites

    Directory of Open Access Journals (Sweden)

    S. Vaitheeswari

    2015-06-01

    Full Text Available ABSTRACTPurpose:Calcium oxalate urolithiasis is one of the most common urinary tract diseases and is of high prevalence. The present study proposes to evaluate the antilithiatic property of hydrogen sulfide and its metabolites like thiosulfate & sulfate in an in vitro model.Materials and Methods:The antilithiatic activity of sodium hydrogen sulfide (NaSH, sodium thiosulfate (Na2S2O3 and sodium sulfate (Na2SO4 on the kinetics of calcium oxalate crystal formation was investigated both in physiological buffer and in urine from normal and recurrent stone forming volunteers. The stones were characterized by optical and spectroscopic techniques.Results:The stones were characterized to be monoclinic, prismatic and bipyramidal habit which is of calcium monohydrate and dihydrate nature. The FTIR displayed fingerprint corresponding to calcium oxalate in the control while in NaSH treated, S=O vibrations were visible in the spectrum. The order of percentage inhibition was NaSH>Na2S2O3>Na2SO4.Conclusion:Our study indicates that sodium hydrogen sulfide and its metabolite thiosulfate are inhibitors of calcium oxalate stone agglomeration which makes them unstable both in physiological buffer and in urine. This effect is attributed to pH changes and complexing of calcium by S2O32-and SO42- moiety produced by the test compounds.

  1. Garlic extracts prevent oxidative stress, hypertrophy and apoptosis in cardiomyocytes: a role for nitric oxide and hydrogen sulfide

    Science.gov (United States)

    2012-01-01

    Background In ancient times, plants were recognized for their medicinal properties. Later, the arrival of synthetic drugs pushed it to the backstage. However, from being merely used for food, plants are now been widely explored for their therapeutic value. The current study explores the potential of skin and flesh extracts from a hard-necked Rocambole variety of purple garlic in preventing cardiomyocyte hypertrophy and cell death. Methods Norepinephrine (NE) was used to induce hypertrophy in adult rat cardiomyocytes pretreated with garlic skin and flesh extracts. Cell death was measured as ratio of rod to round shaped cardiomyocytes. Fluorescent probes were used to measure apoptosis and oxidative stress in cardiomyocytes treated with and without extracts and NE. Pharmacological blockade of nitric oxide (NO) and hydrogen sulfide (H2S) were used to elucidate the mechanism of action of garlic extracts. Garlic extract samples were also tested for alliin and allicin concentrations. Results Exposure of cardiomyocytes to NE induced an increase in cell size and cell death; this increase was significantly prevented upon treatment with garlic skin and flesh extracts. Norepinephrine increased apoptosis and oxidative stress in cardiomyocytes which was prevented upon pretreatment with skin and flesh extracts; NO, and H2S blockers significantly inhibited this beneficial effect. Allicin and alliin concentration were significantly higher in garlic flesh extract when compared to the skin extract. Conclusion These results suggest that both skin and flesh garlic extracts are effective in preventing NE induced cardiomyocyte hypertrophy and cell death. Reduction in oxidative stress may also play an important role in the anti-hypertrophic and anti-apoptotic properties of garlic extracts. These beneficial effects may in part be mediated by NO and H2S. PMID:22931510

  2. Investigations on the role of hemoglobin in sulfide metabolism by intact human red blood cells.

    Science.gov (United States)

    Bianco, Christopher L; Savitsky, Anton; Feelisch, Martin; Cortese-Krott, Miriam M

    2018-03-01

    In addition to their role as oxygen transporters, red blood cells (RBCs) contribute to cardiovascular homeostasis by regulating nitric oxide (NO) metabolism via interaction of hemoglobin (Hb) with nitrite and NO itself. RBCs were proposed to also participate in sulfide metabolism. Although Hb is known to react with sulfide, sulfide metabolism by intact RBCs has not been characterized so far. Therefore we explored the role of Hb in sulfide metabolism in intact human RBCs. We find that upon exposure of washed RBCs to sulfide, no changes in oxy/deoxyhemoglobin (oxy/deoxyHb) are observed by UV-vis and EPR spectroscopy. However, sulfide reacts with methemoglobin (metHb), forming a methemoglobin-sulfide (metHb-SH) complex. Moreover, while metHb-SH is stable in cell-free systems even in the presence of biologically relevant thiols, it gradually decomposes to produce oxyHb, inorganic polysulfides and thiosulfate in intact cells, as detected by EPR and mass spectrometry. Taken together, our results demonstrate that under physiological conditions RBCs are able to metabolize sulfide via intermediate formation of a metHb-SH complex, which subsequently decomposes to oxyHb. We speculate that decomposition of metHb-SH is preceded by an inner-sphere electron transfer, forming reduced Hb (which binds oxygen to form oxyHb) and thiyl radical (a process we here define as "reductive sulfhydration"), which upon release, gives rise to the oxidized products, thiosulfate and polysulfides. Thus, not only is metHb an efficient scavenger and regulator of sulfide in blood, intracellular sulfide itself may play a role in keeping Hb in the reduced oxygen-binding form and, therefore, be involved in RBC physiology and function. Copyright © 2018 The Authors. Published by Elsevier Inc. All rights reserved.

  3. Global source attribution of sulfate concentration and direct and indirect radiative forcing

    Science.gov (United States)

    Yang, Yang; Wang, Hailong; Smith, Steven J.; Easter, Richard; Ma, Po-Lun; Qian, Yun; Yu, Hongbin; Li, Can; Rasch, Philip J.

    2017-07-01

    The global source-receptor relationships of sulfate concentrations, and direct and indirect radiative forcing (DRF and IRF) from 16 regions/sectors for years 2010-2014 are examined in this study through utilizing a sulfur source-tagging capability implemented in the Community Earth System Model (CESM) with winds nudged to reanalysis data. Sulfate concentrations are mostly contributed by local emissions in regions with high emissions, while over regions with relatively low SO2 emissions, the near-surface sulfate concentrations are primarily attributed to non-local sources from long-range transport. Regional source efficiencies of sulfate concentrations are higher over regions with dry atmospheric conditions and less export, suggesting that lifetime of aerosols, together with regional export, is important in determining regional air quality. The simulated global total sulfate DRF is -0.42 W m-2, with -0.31 W m-2 contributed by anthropogenic sulfate and -0.11 W m-2 contributed by natural sulfate, relative to a state with no sulfur emissions. In the Southern Hemisphere tropics, dimethyl sulfide (DMS) contributes 17-84 % to the total DRF. East Asia has the largest contribution of 20-30 % over the Northern Hemisphere mid- and high latitudes. A 20 % perturbation of sulfate and its precursor emissions gives a sulfate incremental IRF of -0.44 W m-2. DMS has the largest contribution, explaining -0.23 W m-2 of the global sulfate incremental IRF. Incremental IRF over regions in the Southern Hemisphere with low background aerosols is more sensitive to emission perturbation than that over the polluted Northern Hemisphere.

  4. Genesis of copper-lead mineralization in the regionally zoned Agnigundala Sulfide Belt, Cuddapah Basin, Andhra Pradesh, India

    Science.gov (United States)

    Bhattacharya, H. N.; Bandyopadhyay, Sandip

    2018-03-01

    Shallow marine sandstone-shale-carbonate sedimentary rocks of the Paleoproterozoic northern Cuddapah basin host copper (Nallakonda deposit), copper-lead (Dhukonda deposit), and lead mineralization (Bandalamottu deposit) which together constitute the Agnigundala Sulfide Belt. The Cu sulfide mineralization in sandstone is both stratabound and disseminated, and Pb sulfide mineralization occurs as stratabound fracture filling veins and/or replacement veins within dolomite. Systematic mineralogical and sulfur, carbon, and oxygen isotope studies of the three deposits indicate a common ore-fluid that deposited copper at Nallakonda, copper-lead at Dhukonda, and lead at Bandalamottu under progressive cooling during migration through sediments. The ore-fluid was of low temperature (water sulfate produced sulfide for ore deposition. It is envisaged that basal red-bed and evaporite-bearing rift-related continental to shallow marine sediments might have acted as the source for the metals. Rift-related faults developed during sedimentation in the basin might have punctured the ore-fluid pool in the lower sedimentary succession and also acted as conduits for their upward migration. The ore-bearing horizons have participated in deformations during basin inversion without any recognizable remobilization.

  5. Transport-Induced Spatial Patterns of Sulfur Isotopes (δ34S) as Biosignatures

    Science.gov (United States)

    Mansor, Muammar; Harouaka, Khadouja; Gonzales, Matthew S.; Macalady, Jennifer L.; Fantle, Matthew S.

    2018-01-01

    Cave minerals deposited in the presence of microbes may host geochemical biosignatures that can be utilized to detect subsurface life on Earth, Mars, or other habitable worlds. The sulfur isotopic composition of gypsum (CaSO4·2H2O) formed in the presence of sulfur-oxidizing microbes in the Frasassi cave system, Italy, was evaluated as a biosignature. Sulfur isotopic compositions (δ34SV-CDT) of gypsum sampled from cave rooms with sulfidic air varied from -11 to -24‰, with minor deposits of elemental sulfur having δ34S values between -17 and -19‰. Over centimeter-length scales, the δ34S values of gypsum varied by up to 8.5‰. Complementary laboratory experiments showed negligible fractionation during the oxidation of elemental sulfur to sulfate by Acidithiobacillus thiooxidans isolated from the caves. Additionally, gypsum precipitated in the presence and absence of microbes at acidic pH characteristic of the sulfidic cave walls has δ34S values that are on average 1‰ higher than sulfate. We therefore interpret the 8.5‰ variation in cave gypsum δ34S (toward more negative values) to reflect the isotopic effect of microbial sulfide oxidation directly to sulfate or via elemental sulfur intermediate. This range is similar to that expected by abiotic sulfide oxidation with oxygen, thus complicating the use of sulfur isotopes as a biosignature at centimeter-length scales. However, at the cave room (meter-length) scale, reactive transport modeling suggests that the overall ˜13‰ variability in gypsum δ34S reflects isotopic distillation of circulating H2S gas due to microbial sulfide oxidation occurring along the cave wall-atmosphere interface. Systematic variations of gypsum δ34S along gas flow paths can thus be interpreted as biogenic given that slow, abiotic oxidation cannot produce the same spatial patterns over similar length scales. The expression and preservation potential of this biosignature is dependent on gas flow parameters and diagenetic

  6. Fast Breaking Detergents: Their Role in the Generation of Hydrogen Sulfide in Oily-Water Wastes

    Science.gov (United States)

    1993-09-01

    acid (Dwyer & Tiedje, 1983) and Desulfowibrio desulfitricans to produce ethanol and acetic acid (Dwyer & Tiedje, 1986). Under anaerobic conditions, the...glycol, glycolic acid, hydrogen, carbon dioxide and a number of intermediates. The acetic acid and ethylene glycol are utilised by some species of SRB...are consequently being introduced. Hydrogen sulfide generation by anaerobic sulfate-reducing bacteria (SRB) is a concern for the RAN because it can

  7. Global source attribution of sulfate aerosol and its radiative forcing

    Science.gov (United States)

    Yang, Y.; Wang, H.; Smith, S.; Easter, R. C.; Ma, P. L.; Qian, Y.; Li, C.; Yu, H.; Rasch, P. J.

    2017-12-01

    Sulfate is an important aerosol that poses health risks and influences climate. Due to long-range atmospheric transport, local sulfate pollution could result from intercontinental influences, making domestic efforts of improving air quality inefficient. Accurate understanding of source attribution of sulfate and its radiative forcing is important for both regional air quality improvement and global climate mitigation. In this study, for the first time, a sulfur source-tagging capability is implemented in the Community Atmosphere Model (CAM5) to quantify the global source-receptor relationships of sulfate and its direct and indirect radiative forcing (DRF and IRF). Near-surface sulfate concentrations are mostly contributed by local emissions in regions with high emissions, while over regions with relatively low SO2 emissions, the near-surface sulfate is primarily attributed to non-local sources from long-range transport. The export of SO2 and sulfate from Europe contributes 20% of sulfate concentrations over North Africa, Russia and Central Asia. Sources from the Middle East account for 20% of sulfate over North Africa, Southern Africa and Central Asia in winter and autumn, and 20% over South Asia in spring. East Asia accounts for about 50% of sulfate over Southeast Asia in winter and autumn, 15% over Russia in summer, and 10% over North America in spring. South Asia contributes to 25% of sulfate over Southeast Asia in spring. Lifetime of aerosols, together with regional export, is found to determine regional air quality. The simulated global total sulfate DRF is -0.42 W m-2, with 75% contributed by anthropogenic sulfate and 25% contributed by natural sulfate. In the Southern Hemisphere tropics, dimethyl sulfide (DMS) contributes the most to the total DRF. East Asia has the largest contribution of 20-30% over the Northern Hemisphere mid- and high-latitudes. A 20% perturbation of sulfate and its precursor emissions gives a sulfate IRF of -0.44 W m-2. DMS has the

  8. Isotopic constraints on heterogeneous sulfate production in Beijing haze

    Directory of Open Access Journals (Sweden)

    P. He

    2018-04-01

    Full Text Available Discerning mechanisms of sulfate formation during fine-particle pollution (referred to as haze hereafter in Beijing is important for understanding the rapid evolution of haze and for developing cost-effective air pollution mitigation strategies. Here we present observations of the oxygen-17 excess of PM2.5 sulfate (Δ17O(SO42− collected in Beijing haze from October 2014 to January 2015 to constrain possible sulfate formation pathways. Throughout the sampling campaign, the 12-hourly averaged PM2.5 concentrations ranged from 16 to 323 µg m−3 with a mean of (141  ±  88 (1σ µg m−3, with SO42− representing 8–25 % of PM2.5 mass. The observed Δ17O(SO42− varied from 0.1 to 1.6 ‰ with a mean of (0.9  ±  0.3 ‰. Δ17O(SO42− increased with PM2.5 levels in October 2014 while the opposite trend was observed from November 2014 to January 2015. Our estimate suggested that in-cloud reactions dominated sulfate production on polluted days (PDs, PM2.5  ≥  75 µg m−3 of Case II in October 2014 due to the relatively high cloud liquid water content, with a fractional contribution of up to 68 %. During PDs of Cases I and III–V, heterogeneous sulfate production (Phet was estimated to contribute 41–54 % to total sulfate formation with a mean of (48  ±  5 %. For the specific mechanisms of heterogeneous oxidation of SO2, chemical reaction kinetics calculations suggested S(IV ( =  SO2 ⚫ H2O + HSO3−  +  SO32− oxidation by H2O2 in aerosol water accounted for 5–13 % of Phet. The relative importance of heterogeneous sulfate production by other mechanisms was constrained by our observed Δ17O(SO42−. Heterogeneous sulfate production via S(IV oxidation by O3 was estimated to contribute 21–22 % of Phet on average. Heterogeneous sulfate production pathways that result in zero-Δ17O(SO42−, such as S(IV oxidation by NO2 in aerosol water and/or by O2 via a

  9. Physiology and genetics of sulfur-oxidizing bacteria.

    Science.gov (United States)

    Friedrich, C G

    1998-01-01

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

  10. Association between catastrophic paleovegetation changes during Devonian-Carboniferous boundary and the formation of giant massive sulfide deposits

    Science.gov (United States)

    Menor-Salván, Cesar; Tornos, Fernando; Fernández-Remolar, David; Amils, Ricardo

    2010-11-01

    The Iberian Pyrite Belt (SW Iberia) is one of the largest sulfur anomalies in the Earth's crust. In the southern Iberian Pyrite Belt, more than 820 Mt of exhalative massive sulfides were deposited in less than one million years at the Devonian-Carboniferous boundary. The shale of the ore-bearing horizon contains biomarkers indicating major biogenic activity in a methanogenic setting, including a five-fold increase in typical vascular plant biomarkers and a significant anomaly in those probably indicating the presence of thermophilic Archaea. This contrasts with signatures in the average sedimentary rocks of the basin that indicate the sediments settled in oxic to sub-oxic environments, and that they have only minor biomarkers derived from continental paleoflora. These data show that the formation of the mineralization was not only related to major hydrothermal activity synchronous with volcanism but may also have been controlled by the input of large amounts of organic matter, mostly derived from the degradation of woodland detritus sourced in the nearby continent. This massive influx of organic matter could have accelerated extremophilic microbial activity that used short-chain hydrocarbons as electron donors for seawater sulfate reduction, resulting in concomitant massive sulfide precipitation. We propose that the giant massive sulfide deposits resulted from overlapping of geological and biological processes that occurred at the Devonian to Carboniferous transition, including: (1) continent collision during the onset of the Variscan orogeny leading to major paleogeographic changes and volcanism; (2) dramatic stress of continental ecosystems due to the combination of climatic change, volcanism, variations in the sea level and erosion on a regional scale; (3) major biomass destruction and increase of organic supply to marine environments; and, (4) generation of anoxic conditions and the thriving of sulfate reducing microorganisms. Under these conditions, massive

  11. Anglesite and silver recovery from jarosite residues through roasting and sulfidization-flotation in zinc hydrometallurgy

    International Nuclear Information System (INIS)

    Han, Haisheng; Sun, Wei; Hu, Yuehua; Jia, Baoliang; Tang, Honghu

    2014-01-01

    Highlights: • Jarosite precipitate hindered the recovery of valuable minerals. • Under 600–700 °C, jarosite decomposed and released the encapsulated valuable minerals. • The bared valuable minerals were easily collected by flotation process. • The new process was promising for dealing with jarosite residues. - Abstract: Hazardous jarosite residues contain abundant valuable minerals that are difficult to be recovered by traditional flotation process. This study presents a new route, roasting combined with sulfidization-flotation, for the recovery of anglesite and silver from jarosite residues of zinc hydrometallurgy. Surface appearance and elemental distribution of jarosite residues was examined by scanning electron microscopy and energy dispersive X-ray spectrometry analysis, respectively. Decomposition and transformation mechanisms of jarosite residues were illustrated by differential thermal analysis. Results showed that after roasting combined with flotation, the grade and recovery of lead were 43.89% and 66.86%, respectively, and those of silver were 1.3 kg/t and 81.60%, respectively. At 600–700 °C, jarosite was decomposed to release encapsulated valuable minerals such as anglesite (PbSO 4 ) and silver mineral; silver jarosite decomposed into silver sulfate (Ag 2 SO 4 ); and zinc ferrite (ZnO·Fe 2 O 3 ) decomposed into zinc sulfate (ZnSO 4 ) and hematite (Fe 2 O 3 ). Bared anglesite and silver minerals were modified by sodium sulfide and easily collected by flotation collectors. This study demonstrates that the combination of roasting and sulfidization-flotation provides a promising process for the recovery of zinc, lead, and silver from jarosite residues of zinc hydrometallurgy

  12. Combining in situ chemical oxidation, stabilization, and anaerobic bioremediation in a single application to reduce contaminant mass and leachability in soil

    Energy Technology Data Exchange (ETDEWEB)

    Cassidy, Daniel P., E-mail: daniel.cassidy@wmich.edu [Department of Geosciences, Western Michigan University, Kalamazoo, MI 49008 (United States); Srivastava, Vipul J., E-mail: vipul.srivastava@ch2m.com [CH2M HILL, 125S Wacker, Ste 3000, Chicago, IL 60606 (United States); Dombrowski, Frank J., E-mail: frank.dombrowski@we-energies.com [We Energies, 333W Everett St., A231, Milwaukee, WI 53203 (United States); Lingle, James W., E-mail: jlingle@epri.com [Electric Power Research Institute (EPRI), 4927W Willow Road, Brown Deer, WI 53223 (United States)

    2015-10-30

    Highlights: • Portland cement and lime activated persulfate by increasing pH and temperature. • Chemical oxidation achieved BTEX and PAH removal ranging from 55% to 75%. • Activating persulfate with ISS amendments reduced leachability more than NaOH. • Native sulfate-reducing bacteria degraded PAHs within weeks after ISCO finished. • ISCO, ISS, and anaerobic bioremediation were combined in a single application. - Abstract: Laboratory batch reactors were maintained for 32 weeks to test the potential for an in situ remedy that combines chemical oxidation, stabilization, and anaerobic bioremediation in a single application to treat soil from a manufactured gas plant, contaminated with polycyclic aromatic hydrocarbons (PAH) and benzene, toluene, ethylbenzene, and xylenes (BTEX). Portland cement and slaked lime were used to activate the persulfate and to stabilize/encapsulate the contaminants that were not chemically oxidized. Native sulfate-reducing bacteria degraded residual contaminants using the sulfate left after persulfate activation. The ability of the combined remedy to reduce contaminant mass and leachability was compared with NaOH-activated persulfate, stabilization, and sulfate-reducing bioremediation as stand-alone technologies. The stabilization amendments increased pH and temperature sufficiently to activate the persulfate within 1 week. Activation with both stabilization amendments and NaOH removed between 55% and 70% of PAH and BTEX. However, combined persulfate and stabilization significantly reduced the leachability of residual BTEX and PAH compared with NaOH activation. Sulfide, 2-naphthoic acid, and the abundance of subunit A of the dissimilatory sulfite reductase gene (dsrA) were used to monitor native sulfate-reducing bacteria, which were negatively impacted by activated persulfate, but recovered completely within weeks.

  13. Combining in situ chemical oxidation, stabilization, and anaerobic bioremediation in a single application to reduce contaminant mass and leachability in soil

    International Nuclear Information System (INIS)

    Cassidy, Daniel P.; Srivastava, Vipul J.; Dombrowski, Frank J.; Lingle, James W.

    2015-01-01

    Highlights: • Portland cement and lime activated persulfate by increasing pH and temperature. • Chemical oxidation achieved BTEX and PAH removal ranging from 55% to 75%. • Activating persulfate with ISS amendments reduced leachability more than NaOH. • Native sulfate-reducing bacteria degraded PAHs within weeks after ISCO finished. • ISCO, ISS, and anaerobic bioremediation were combined in a single application. - Abstract: Laboratory batch reactors were maintained for 32 weeks to test the potential for an in situ remedy that combines chemical oxidation, stabilization, and anaerobic bioremediation in a single application to treat soil from a manufactured gas plant, contaminated with polycyclic aromatic hydrocarbons (PAH) and benzene, toluene, ethylbenzene, and xylenes (BTEX). Portland cement and slaked lime were used to activate the persulfate and to stabilize/encapsulate the contaminants that were not chemically oxidized. Native sulfate-reducing bacteria degraded residual contaminants using the sulfate left after persulfate activation. The ability of the combined remedy to reduce contaminant mass and leachability was compared with NaOH-activated persulfate, stabilization, and sulfate-reducing bioremediation as stand-alone technologies. The stabilization amendments increased pH and temperature sufficiently to activate the persulfate within 1 week. Activation with both stabilization amendments and NaOH removed between 55% and 70% of PAH and BTEX. However, combined persulfate and stabilization significantly reduced the leachability of residual BTEX and PAH compared with NaOH activation. Sulfide, 2-naphthoic acid, and the abundance of subunit A of the dissimilatory sulfite reductase gene (dsrA) were used to monitor native sulfate-reducing bacteria, which were negatively impacted by activated persulfate, but recovered completely within weeks

  14. Trace Level Determination of Mesityl Oxide and Diacetone Alcohol in Atazanavir Sulfate Drug Substance by a Gas Chromatography Method.

    Science.gov (United States)

    Raju, K V S N; Pavan Kumar, K S R; Siva Krishna, N; Madhava Reddy, P; Sreenivas, N; Kumar Sharma, Hemant; Himabindu, G; Annapurna, N

    2016-01-01

    A capillary gas chromatography method with a short run time, using a flame ionization detector, has been developed for the quantitative determination of trace level analysis of mesityl oxide and diacetone alcohol in the atazanavir sulfate drug substance. The chromatographic method was achieved on a fused silica capillary column coated with 5% diphenyl and 95% dimethyl polysiloxane stationary phase (Rtx-5, 30 m x 0.53 mm x 5.0 µm). The run time was 20 min employing programmed temperature with a split mode (1:5) and was validated for specificity, sensitivity, precision, linearity, and accuracy. The detection and quantitation limits obtained for mesityl oxide and diacetone alcohol were 5 µg/g and 10 µg/g, respectively, for both of the analytes. The method was found to be linear in the range between 10 µg/g and 150 µg/g with a correlation coefficient greater than 0.999, and the average recoveries obtained in atazanavir sulfate were between 102.0% and 103.7%, respectively, for mesityl oxide and diacetone alcohol. The developed method was found to be robust and rugged. The detailed experimental results are discussed in this research paper.

  15. Biologically produced sulfur

    NARCIS (Netherlands)

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

    2003-01-01

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

  16. Gastrointestinal and microbial responses to sulfate-supplemented drinking water in mice.

    Science.gov (United States)

    Deplancke, Bart; Finster, Kai; Graham, W Vallen; Collier, Chad T; Thurmond, Joel E; Gaskins, H Rex

    2003-04-01

    There is increasing evidence that hydrogen sulfide (H2S), produced by intestinal sulfate-reducing bacteria (SRB), may be involved in the etiopathogenesis of chronic diseases such as ulcerative colitis and colorectal cancer. The activity of SRB, and thus H2S production, is likely determined by the availability of sulfur-containing compounds in the intestine. However, little is known about the impact of dietary or inorganic sulfate on intestinal sulfate and SRB-derived H2S concentrations. In this study, the effects of short-term (7 day) and long-term (1 year) inorganic sulfate supplementation of the drinking water on gastrointestinal (GI) sulfate and H2S concentrations (and thus activity of resident SRBs), and the density of large intestinal sulfomucin-containing goblet cells, were examined in C3H/HeJBir mice. Additionally, a PCR-denaturing gradient gel electrophoresis (DGGE)-based molecular ecology technique was used to examine the impact of sulfate-amended drinking water on microbial community structure throughout the GI tract. Average H2S concentrations ranged from 0.1 mM (stomach) to 1 mM (cecum). A sulfate reduction assay demonstrated in situ production of H2S throughout the GI tract, confirming the presence of SRB. However, H2S generation and concentrations were greatest in the cecum and colon. Sulfate supplementation of drinking water did not significantly increase intestinal sulfate or H2S concentrations, suggesting that inorganic sulfate is not an important modulator of intestinal H2S concentrations, although it altered the bacterial profiles of the stomach and distal colon of 1-year-old mice. This change in colonic bacterial profiles may reflect a corresponding increase in the density of sulfomucin-containing goblet cells in sulfate-supplemented compared with control mice.

  17. Acidic Microenvironments in Waste Rock Characterized by Neutral Drainage: Bacteria–Mineral Interactions at Sulfide Surfaces

    Directory of Open Access Journals (Sweden)

    John W. Dockrey

    2014-03-01

    Full Text Available Microbial populations and microbe-mineral interactions were examined in waste rock characterized by neutral rock drainage (NRD. Samples of three primary sulfide-bearing waste rock types (i.e., marble-hornfels, intrusive, exoskarn were collected from field-scale experiments at the Antamina Cu–Zn–Mo mine, Peru. Microbial communities within all samples were dominated by neutrophilic thiosulfate oxidizing bacteria. However, acidophilic iron and sulfur oxidizers were present within intrusive waste rock characterized by bulk circumneutral pH drainage. The extensive development of microbially colonized porous Fe(III (oxyhydroxide and Fe(III (oxyhydroxysulfate precipitates was observed at sulfide-mineral surfaces during examination by field emission-scanning electron microscopy-energy dispersive X-ray spectroscopy (FE-SEM-EDS. Linear combination fitting of bulk extended X-ray absorption fine structure (EXAFS spectra for these precipitates indicated they were composed of schwertmannite [Fe8O8(OH6–4.5(SO41–1.75], lepidocrocite [γ-FeO(OH] and K-jarosite [KFe3(OH6(SO42]. The presence of schwertmannite and K-jarosite is indicative of the development of localized acidic microenvironments at sulfide-mineral surfaces. Extensive bacterial colonization of this porous layer and pitting of underlying sulfide-mineral surfaces suggests that acidic microenvironments can play an important role in sulfide-mineral oxidation under bulk circumneutral pH conditions. These findings have important implications for water quality management in NRD settings.

  18. Hydrogen sulfide ameliorated L-NAME-induced hypertensive heart disease by the Akt/eNOS/NO pathway.

    Science.gov (United States)

    Jin, Sheng; Teng, Xu; Xiao, Lin; Xue, Hongmei; Guo, Qi; Duan, Xiaocui; Chen, Yuhong; Wu, Yuming

    2017-12-01

    Reductions in hydrogen sulfide (H 2 S) production have been implicated in the pathogenesis of hypertension; however, no studies have examined the functional role of hydrogen sulfide in hypertensive heart disease. We hypothesized that the endogenous production of hydrogen sulfide would be reduced and exogenous hydrogen sulfide would ameliorate cardiac dysfunction in N ω -nitro- L-arginine methyl ester ( L-NAME)-induced hypertensive rats. Therefore, this study investigated the cardioprotective effects of hydrogen sulfide on L-NAME-induced hypertensive heart disease and explored potential mechanisms. The rats were randomly divided into five groups: Control, Control + sodium hydrosulfide (NaHS), L-NAME, L-NAME + NaHS, and L-NAME + NaHS + glibenclamide (Gli) groups. Systolic blood pressure was monitored each week. In Langendorff-isolated rat heart, cardiac function represented by ±LV dP/dt max and left ventricular developing pressure was recorded after five weeks of treatment. Hematoxylin and Eosin and Masson's trichrome staining and myocardium ultrastructure under transmission electron microscopy were used to evaluate cardiac remodeling. The plasma nitric oxide and hydrogen sulfide concentrations, as well as nitric oxide synthases and cystathionine-γ-lyase activity in left ventricle tissue were determined. The protein expression of p-Akt, Akt, p-eNOS, and eNOS in left ventricle tissue was analyzed using Western blot. After five weeks of L-NAME treatment, there was a time-dependent hypertension, cardiac remodeling, and dysfunction accompanied by a decrease in eNOS phosphorylation, nitric oxide synthase activity, and nitric oxide concentration. Meanwhile, cystathionine-γ-lyase activity and hydrogen sulfide concentration were also decreased. NaHS treatment significantly increased plasma hydrogen sulfide concentration and subsequently promoted the Akt/eNOS/NO pathway which inhibited the development of hypertension and attenuated cardiac remodeling and

  19. Modeling of sulfation of potassium chloride by ferric sulfate addition during grate-firing of biomass

    DEFF Research Database (Denmark)

    Wu, Hao; Jespersen, Jacob Boll; Aho, Martti

    2013-01-01

    Potassium chloride, KCl, formed from critical ash-forming elements released during combustion may lead to severe ash deposition and corrosion problems in biomass-fired boilers. Ferric sulfate, Fe2(SO4)3 is an effective additive, which produces sulfur oxides (SO2 and SO3) to convert KCl to the less...... harmful K2SO4. In the present study the decomposition of ferric sulfate is studied in a fast-heating rate thermogravimetric analyzer (TGA), and a kinetic model is proposed to describe the decomposition process. The yields of SO2 and SO3 from ferric sulfate decomposition are investigated in a laboratory......-scale tube reactor. It is revealed that approximately 40% of the sulfur is released as SO3, the remaining fraction being released as SO2. The proposed decomposition model of ferric sulfate is combined with a detailed gas phase kinetic model of KCl sulfation, and a simplified model of K2SO4 condensation...

  20. Protective Effects of Hydrogen Sulfide in the Ageing Kidney.

    Science.gov (United States)

    Hou, Cui-Lan; Wang, Ming-Jie; Sun, Chen; Huang, Yong; Jin, Sheng; Mu, Xue-Pan; Chen, Ying; Zhu, Yi-Chun

    2016-01-01

    Aims . The study aimed to examine whether hydrogen sulfide (H 2 S) generation changed in the kidney of the ageing mouse and its relationship with impaired kidney function. Results . H 2 S levels in the plasma, urine, and kidney decreased significantly in ageing mice. The expression of two known H 2 S-producing enzymes in kidney, cystathionine γ -lyase (CSE) and cystathionine- β -synthase (CBS), decreased significantly during ageing. Chronic H 2 S donor (NaHS, 50  μ mol/kg/day, 10 weeks) treatment could alleviate oxidative stress levels and renal tubular interstitial collagen deposition. These protective effects may relate to transcription factor Nrf2 activation and antioxidant proteins such as HO-1, SIRT1, SOD1, and SOD2 expression upregulation in the ageing kidney after NaHS treatment. Furthermore, the expression of H 2 S-producing enzymes changed with exogenous H 2 S administration and contributed to elevated H 2 S levels in the ageing kidney. Conclusions . Endogenous hydrogen sulfide production in the ageing kidney is insufficient. Exogenous H 2 S can partially rescue ageing-related kidney dysfunction by reducing oxidative stress, decreasing collagen deposition, and enhancing Nrf2 nuclear translocation. Recovery of endogenous hydrogen sulfide production may also contribute to the beneficial effects of NaHS treatment.

  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

    Science.gov (United States)

    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. Textural, compositional, and sulfur isotope variations of sulfide minerals in the Red Dog Zn-Pb-Ag deposits, Brooks Range, Alaska: Implications for Ore Formation

    Science.gov (United States)

    Kelley, K.D.; Leach, D.L.; Johnson, C.A.; Clark, J.L.; Fayek, M.; Slack, J.F.; Anderson, V.M.; Ayuso, R.A.; Ridley, W.I.

    2004-01-01

    -column sulfate to form barite, and metals combined with H2S derived from bacterial sulfate reduction to form sulfides. Higher temperatures and salinities and relatively oxidized ore-stage fluids (stages 2 and 3) compared with stage 1 were probably important controls on the abundances and relative amounts of metals in the fluids and the resulting sulfide chemistry. Textural observations and isotopic data show that preexisting barite was reductively dissolved, providing a source of H2S for sulfide mineral formation. In stage 3, the continued flow of hydrothermal fluids caused thermal alteration of organic-rich mudstones and a build-up of methane that led to fluid overpressuring, hydrofracturing, and vein formation. Barite, red-brown sphalerite, and other sulfides were deposited in the veins, and preexisting barite was pervasively replaced by red-brown sphalerite. Hydrothermal activity ceased until Jurassic time when thrusting and large-scale fluid flow related to the Brookian orogeny remobilized and formed late tan sphalerite in tectonic breccias. ?? 2004 by Economic Geology.

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

    Directory of Open Access Journals (Sweden)

    Nurgul Balci

    2017-08-01

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

  4. Global source attribution of sulfate concentration and direct and indirect radiative forcing

    Directory of Open Access Journals (Sweden)

    Y. Yang

    2017-07-01

    Full Text Available The global source–receptor relationships of sulfate concentrations, and direct and indirect radiative forcing (DRF and IRF from 16 regions/sectors for years 2010–2014 are examined in this study through utilizing a sulfur source-tagging capability implemented in the Community Earth System Model (CESM with winds nudged to reanalysis data. Sulfate concentrations are mostly contributed by local emissions in regions with high emissions, while over regions with relatively low SO2 emissions, the near-surface sulfate concentrations are primarily attributed to non-local sources from long-range transport. Regional source efficiencies of sulfate concentrations are higher over regions with dry atmospheric conditions and less export, suggesting that lifetime of aerosols, together with regional export, is important in determining regional air quality. The simulated global total sulfate DRF is −0.42 W m−2, with −0.31 W m−2 contributed by anthropogenic sulfate and −0.11 W m−2 contributed by natural sulfate, relative to a state with no sulfur emissions. In the Southern Hemisphere tropics, dimethyl sulfide (DMS contributes 17–84 % to the total DRF. East Asia has the largest contribution of 20–30 % over the Northern Hemisphere mid- and high latitudes. A 20 % perturbation of sulfate and its precursor emissions gives a sulfate incremental IRF of −0.44 W m−2. DMS has the largest contribution, explaining −0.23 W m−2 of the global sulfate incremental IRF. Incremental IRF over regions in the Southern Hemisphere with low background aerosols is more sensitive to emission perturbation than that over the polluted Northern Hemisphere.

  5. Zirconium doped nano-dispersed oxides of Fe, Al and Zn for destruction of warfare agents

    International Nuclear Information System (INIS)

    Stengl, Vaclav; Houskova, Vendula; Bakardjieva, Snejana; Murafa, Nataliya; Marikova, Monika; Oplustil, Frantisek; Nemec, Tomas

    2010-01-01

    Zirconium doped nano dispersive oxides of Fe, Al and Zn were prepared by a homogeneous hydrolysis of the respective sulfate salts with urea in aqueous solutions. Synthesized metal oxide hydroxides were characterized using Brunauer-Emmett-Teller (BET) surface area and Barrett-Joiner-Halenda porosity (BJH), X-ray diffraction (XRD), infrared spectroscopy (IR), scanning electron microscopy (SEM) and energy-dispersive X-ray microanalysis (EDX). These oxides were taken for an experimental evaluation of their reactivity with sulfur mustard (HD or bis(2-chloroethyl)sulfide), soman (GD or (3,3'-Dimethylbutan-2-yl)-methylphosphonofluoridate) and VX agent (S-[2-(diisopropylamino)ethyl]-O-ethyl-methylphosphonothionate). The presence of Zr 4+ dopant can increase both the surface area and the surface hydroxylation of the resulting doped oxides, decreases their crystallites' sizes thereby it may contribute in enabling the substrate adsorption at the oxide surface thus it can accelerate the rate of degradation of warfare agents. Addition of Zr 4+ converts the product of the reaction of ferric sulphate with urea from ferrihydrite to goethite. We found out that doped oxo-hydroxides Zr-FeO(OH) - being prepared by a homogeneous hydrolysis of ferric and zirconium oxo-sulfates mixture in aqueous solutions - exhibit a comparatively higher degradation activity towards chemical warfare agents (CWAs). Degradation of soman or VX agent on Zr-doped FeO(OH) containing ca. 8.3 wt.% of zirconium proceeded to completion within 30 min.

  6. Zirconium doped nano-dispersed oxides of Fe, Al and Zn for destruction of warfare agents

    Energy Technology Data Exchange (ETDEWEB)

    Stengl, Vaclav, E-mail: stengl@uach.cz [Institute of Inorganic Chemistry AS CR v.v.i., 250 68 Rez (Czech Republic); Houskova, Vendula; Bakardjieva, Snejana; Murafa, Nataliya; Marikova, Monika [Institute of Inorganic Chemistry AS CR v.v.i., 250 68 Rez (Czech Republic); Oplustil, Frantisek; Nemec, Tomas [Military Technical Institute of Protection Brno, Veslarska 230, 628 00 Brno (Czech Republic)

    2010-11-15

    Zirconium doped nano dispersive oxides of Fe, Al and Zn were prepared by a homogeneous hydrolysis of the respective sulfate salts with urea in aqueous solutions. Synthesized metal oxide hydroxides were characterized using Brunauer-Emmett-Teller (BET) surface area and Barrett-Joiner-Halenda porosity (BJH), X-ray diffraction (XRD), infrared spectroscopy (IR), scanning electron microscopy (SEM) and energy-dispersive X-ray microanalysis (EDX). These oxides were taken for an experimental evaluation of their reactivity with sulfur mustard (HD or bis(2-chloroethyl)sulfide), soman (GD or (3,3'-Dimethylbutan-2-yl)-methylphosphonofluoridate) and VX agent (S-[2-(diisopropylamino)ethyl]-O-ethyl-methylphosphonothionate). The presence of Zr{sup 4+} dopant can increase both the surface area and the surface hydroxylation of the resulting doped oxides, decreases their crystallites' sizes thereby it may contribute in enabling the substrate adsorption at the oxide surface thus it can accelerate the rate of degradation of warfare agents. Addition of Zr{sup 4+} converts the product of the reaction of ferric sulphate with urea from ferrihydrite to goethite. We found out that doped oxo-hydroxides Zr-FeO(OH) - being prepared by a homogeneous hydrolysis of ferric and zirconium oxo-sulfates mixture in aqueous solutions - exhibit a comparatively higher degradation activity towards chemical warfare agents (CWAs). Degradation of soman or VX agent on Zr-doped FeO(OH) containing ca. 8.3 wt.% of zirconium proceeded to completion within 30 min.

  7. Sulfate, nitrate and blood pressure - An EPIC interaction between sulfur and nitrogen.

    Science.gov (United States)

    Kuhnle, Gunter G; Luben, Robert; Khaw, Kay-Tee; Feelisch, Martin

    2017-08-01

    Nitrate (NO 3 - )-rich foods such as green leafy vegetables are not only part of a healthy diet, but increasingly marketed for primary prevention of cardiovascular disease (CVD) and used as ergogenic aids by competitive athletes. While there is abundant evidence for mild hypotensive effects of nitrate on acute application there is limited data on chronic intake in humans, and results from animal studies suggest no long-term benefit. This is important as nitrate can also promote the formation of nitrosamines. It is therefore classified as 'probably carcinogenic to humans', although a beneficial effect on CVD risk might compensate for an increased cancer risk. Dietary nitrate requires reduction to nitrite (NO 2 - ) by oral commensal bacteria to contribute to the formation of nitric oxide (NO). The extensive crosstalk between NO and hydrogen sulfide (H 2 S) related metabolites may further affect nitrate's bioactivity. Using nitrate and nitrite concentrations of drinking water - the only dietary source continuously monitored for which detailed data exist - in conjunction with data of >14,000 participants of the EPIC-Norfolk study, we found no inverse associations with blood pressure or CVD risk. Instead, we found a strong interaction with sulfate (SO 4 2- ). At low sulfate concentrations, nitrate was inversely associated with BP (-4mmHg in top quintile) whereas this was reversed at higher concentrations (+3mmHg in top quintile). Our findings have a potentially significant impact for pharmacology, physiology and public health, redirecting our attention from the oral microbiome and mouthwash use to interaction with sulfur-containing dietary constituents. These results also indicate that nitrate bioactivation is more complex than hitherto assumed. The modulation of nitrate bioactivity by sulfate may render dietary lifestyle interventions aimed at increasing nitrate intake ineffective and even reverse potential antihypertensive effects, warranting further investigation

  8. Sulfation of ceria-zirconia model automotive emissions control catalysts

    Science.gov (United States)

    Nelson, Alan Edwin

    Cerium-zirconium mixed metal oxides are used in automotive emissions control catalysts to regulate the partial pressure of oxygen near the catalyst surface. The near surface oxygen partial pressure is regulated through transfer of atomic oxygen from the ceria-zirconia solid matrix to the platinum group metals to form metal oxides capable of oxidizing carbon monoxide and unburned hydrocarbons. Although the addition of zirconium in the cubic lattice of ceria increases the oxygen storage capacity and thermal stability of the ceria matrix, the cerium-zirconium oxide system remains particularly susceptible to deactivation from sulfur compounds. While the overall effect of sulfur on these systems is understood (partially irreversible deactivation), the fundamental and molecular interaction of sulfur with ceria-zirconia remains a challenging problem. Ceria-zirconia metal oxide solid solutions have been prepared through co-precipitation with nitrate precursors. The prepared powders were calcined and subsequently formed into planer wafers and characterized for chemical and physical attributes. The prepared samples were subsequently exposed to a sulfur dioxide based environment and characterized with spectroscopic techniques to characterize the extent of sulfation and the nature of surface sulfur species. The extent of sulfation of the model ceria-zirconia systems was characterized with Auger electron spectroscopy (AES) prior to and after treatment in a microreactor. Strong dependencies were observed between the atomic ratio of ceria to zirconia and the extent of sulfation. In addition, the partial pressure of sulfur dioxide during treatments also correlated to the extent of sulfation, while temperature only slightly effected the extent of sulfation. The AES data suggests the gas phase sulfur dioxide preferentially chemisorbs on surface ceria atoms and the extent of sulfation is heavily dependent on sulfur dioxide concentrations and only slightly dependent on catalyst

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

    Science.gov (United States)

    Frederiksen, Trine-Maria; Finster, Kai

    2003-06-01

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

  10. Successive changes in community structure of an ethylbenzene-degrading sulfate-reducing consortium.

    Science.gov (United States)

    Nakagawa, Tatsunori; Sato, Shinya; Yamamoto, Yoko; Fukui, Manabu

    2002-06-01

    The microbial community structure and successive changes in a mesophilic ethylbenzene-degrading sulfate-reducing consortium were for the first time clarified by the denaturing gradient gel electrophoresis (DGGE) analysis of the PCR amplified 16S rRNA gene fragments. At least ten bands on the DGGE gel were detected in the stationary phase. Phylogenetic analysis of the DGGE bands revealed that the consortium consisted of different eubacterial phyla including the delta subgroup of Proteobacteria, the order Sphingobacteriales, the order Spirochaetales, and the unknown bacterium. The most abundant band C was closely related to strain mXyS1, an m-xylene-degrading sulfate-reducing bacterium (SRB), and occurred as a sole band on DGGE gels in the logarithmic growth phase that 40% ethylbenzene was consumed accompanied by sulfide production. During further prolonged incubation, the dominancy of band C did not change. These results suggest that SRB corresponds to the most abundant band C and contributes mainly to the degradation of ethylbenzene coupled with sulfate reduction.

  11. Effect of Sodium Sulfide on Ni-Containing Carbon Monoxide Dehydrogenases

    Energy Technology Data Exchange (ETDEWEB)

    Jian Feng; Paul A. Lindahl

    2004-07-28

    OAK-B135 The structure of the active-site C-cluster in CO dehydrogenase from Carboxythermus hydrogenoformans includes a {mu}{sup 2}-sulfide ion bridged to the Ni and unique Fe, while the same cluster in enzymes from Rhodospirillum rubrum (CODH{sub Rr}) and Moorella thermoacetica (CODH{sub Mt}) lack this ion. This difference was investigated by exploring the effects of sodium sulfide on activity and spectral properties. Sulfide partially inhibited the CO oxidation activity of CODH{sub Rr} and generated a lag prior to steady-state. CODH{sub Mt} was inhibited similarly but without a lag. Adding sulfide to CODH{sub Mt} in the C{sub red1} state caused the g{sub av} = 1.82 EPR signal to decline and new features to appear, including one with g = 1.95, 1.85 and (1.70 or 1.62). Removing sulfide caused the g{sub av} = 1.82 signal to reappear and activity to recover. Sulfide did not affect the g{sub av} = 1.86 signal from the C{sub red2} state. A model was developed in which sulfide binds reversibly to C{sub red1}, inhibiting catalysis. Reducing this adduct causes sulfide to dissociate, C{sub red2} to develop, and activity to recover. Using this model, apparent K{sub I} values are 40 {+-} 10 nM for CODH{sub Rr} and 60 {+-} 30 {micro}M for CODH{sub Mt}. Effects of sulfide are analogous to those of other anions, including the substrate hydroxyl group, suggesting that these ions also bridge the Ni and unique Fe. This proposed arrangement raises the possibility that CO binding labilizes the bridging hydroxyl and increases its nucleophilic tendency towards attacking Ni-bound carbonyl.

  12. Tracking the transformation and transport of arsenic sulfide pigments in paints: synchrotron-based X-ray micro-analyses

    NARCIS (Netherlands)

    Keune, K.; Mass, J.; Meirer, F.; Pottasch, C.; van Loon, A.; Hull, A.; Church, J.; Pouyet, E.; Cotte, M.; Mehta, A.

    2015-01-01

    Realgar and orpiment, arsenic sulfide pigments used in historic paints, degrade under the influence of light, resulting in transparent, whitish, friable and/or crumbling paints. So far, para-realgar and arsenic trioxide have been identified as the main oxidation products of arsenic sulfide pigments.

  13. Tracking the transformation and transport of arsenic sulfide pigments in paints : synchrotron-based X-ray micro-analyses

    NARCIS (Netherlands)

    Keune, Katrien; Mass, Jennifer; Meirer, Florian; Pottasch, Carol; van Loon, Annelies; Hull, Alyssa; Church, Jonathan; Pouyet, Emeline; Cotte, Marine; Mehta, Apurva

    2015-01-01

    Realgar and orpiment, arsenic sulfide pigments used in historic paints, degrade under the influence of light, resulting in transparent, whitish, friable and/or crumbling paints. So far, para-realgar and arsenic trioxide have been identified as the main oxidation products of arsenic sulfide pigments.

  14. Mathematical modeling of simultaneous carbon-nitrogen-sulfur removal from industrial wastewater.

    Science.gov (United States)

    Xu, Xi-Jun; Chen, Chuan; Wang, Ai-Jie; Ni, Bing-Jie; Guo, Wan-Qian; Yuan, Ye; Huang, Cong; Zhou, Xu; Wu, Dong-Hai; Lee, Duu-Jong; Ren, Nan-Qi

    2017-01-05

    A mathematical model of carbon, nitrogen and sulfur removal (C-N-S) from industrial wastewater was constructed considering the interactions of sulfate-reducing bacteria (SRB), sulfide-oxidizing bacteria (SOB), nitrate-reducing bacteria (NRB), facultative bacteria (FB), and methane producing archaea (MPA). For the kinetic network, the bioconversion of C-N by heterotrophic denitrifiers (NO 3 - →NO 2 - →N 2 ), and that of C-S by SRB (SO 4 2- →S 2- ) and SOB (S 2- →S 0 ) was proposed and calibrated based on batch experimental data. The model closely predicted the profiles of nitrate, nitrite, sulfate, sulfide, lactate, acetate, methane and oxygen under both anaerobic and micro-aerobic conditions. The best-fit kinetic parameters had small 95% confidence regions with mean values approximately at the center. The model was further validated using independent data sets generated under different operating conditions. This work was the first successful mathematical modeling of simultaneous C-N-S removal from industrial wastewater and more importantly, the proposed model was proven feasible to simulate other relevant processes, such as sulfate-reducing, sulfide-oxidizing process (SR-SO) and denitrifying sulfide removal (DSR) process. The model developed is expected to enhance our ability to predict the treatment of carbon-nitrogen-sulfur contaminated industrial wastewater. Copyright © 2016 Elsevier B.V. All rights reserved.

  15. Assessment of sulfide production risk in soil during the infiltration of domestic wastewater treated by a sulfur-utilizing denitrification process.

    Science.gov (United States)

    Ghorbel, L; Coudert, L; Gilbert, Y; Mercier, G; Blais, J F

    2016-10-01

    This study aimed to determine the potential of sulfide generation during infiltration through soil of domestic wastewater treated by a sulfur-utilizing denitrification process. Three types of soil with different permeability rates (K s = 0.028, 0.0013, and 0.00015 cm/s) were investigated to evaluate the potential risk of sulfur generation during the infiltration of domestic wastewater treated by a sulfur-utilizing denitrification system. These soils were thoroughly characterized and tested to assess their capacity to be used as drainages for wastewaters. Experiments were conducted under two operating modes (saturated and unsaturated). Sulfate, sulfide, and chemical oxygen demand (COD) levels were determined over a period of 100 days. Despite the high concentration of sulfates (200 mg/L) under anaerobic conditions (ORP = -297 mV), no significant amount of sulfide was generated in the aqueous (soil permeability did not have a noticeable effect on the infiltration of domestic wastewater treated by a sulfur-utilizing denitrification system due to low contents of organic matter (i.e., dissolved organic carbon, DOC). The autotrophic denitrification process used to treat the domestic wastewater allowed the reduction of the concentration of biochemical oxygen demand (BOD5) below 5 mg/L, of DOC below 7 mg/L, and of COD below 100 mg/L.

  16. Luminescent hybrid lanthanide sulfates and lanthanide sulfonate-carboxylates with 1,10-phenanthroline involving in-situ oxidation of 2-mercaptonbenzoic acid

    Science.gov (United States)

    Zhong, Jie-Cen; Wan, Fang; Sun, Yan-Qiong; Chen, Yi-Ping

    2015-01-01

    A series of lanthanide sulfates and lanthanide sulfonate-carboxylates, [Ln2(phen)2(SO4)3(H2O)2]n (I:Ln=Nd(1a), Sm(1b), Eu(1c), phen=1,10-phenanthroline) and [Ln(phen)(2-SBA)(BZA)]n (II: Ln=Sm(2a), Eu(2b), Dy(2c), 2-SBA=2-sulfobenzoate, BZA=benzoate) have been hydrothermally synthesized from lanthanide oxide, 2-mercaptonbenzoic acid with phen as auxiliary ligand and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectra, TG analyses and luminescence spectroscopy. Interestingly, SO4 2 - anions in I came from the in situ deep oxidation of thiol groups of 2-mercaptonbenzoic acid while 2-sulfobenzoate and benzoate ligands in II from the middle oxidation and desulfuration reactions of 2-mercaptonbenzoic acid. Compounds I are organic-inorganic hybrid lanthanide sulfates, which have rare one-dimensional column-like structures. Complexes II are binuclear lanthanide sulfonate-carboxylates with 2-sulfobenzoate and benzoate as bridges and 1,10-phenanthroline as terminal. Photoluminescence studies reveal that complexes I and II exhibit strong lanthanide characteristic emission bands in the solid state at room temperature.

  17. Effect of Ammonium Chloride on the Efficiency with Which Copper Sulfate Activates Marmatite: Change in Solution Composition and Regulation of Surface Composition

    Directory of Open Access Journals (Sweden)

    Shengdong Zhang

    2018-06-01

    Full Text Available Zinc sulfide minerals are the primary choice for zinc extraction and marmatite is one of the two most common zinc sulphide minerals (sphalerite and marmatite, therefore it is of great significance to study and optimize the flotation of marmatite. To improve the activation of copper sulfate on marmatite, a method involving the addition of ammonium chloride is devised. The method has been proven to be an effective way of improving the activation efficiency of copper sulfate towards marmatite under alkaline conditions. The strengthening mechanism was studied using micro-flotation, adsorption test, X-ray photoelectron spectroscopy, and by analyzing changes in solution composition. Flotation test results show that the activation effect of the copper sulfate towards marmatite is enhanced with the addition of ammonium chloride. According to the results of the adsorption measurements and X-ray photoelectron spectroscopy analysis, when the marmatite surface is activated using copper sulfate with added ammonia chloride, it adsorbs more copper sulfide and less copper hydroxide and zinc hydroxide. These changes in surface composition are believed to occur via the following process: NH3(aq promotes the dissolution of zinc hydroxide and then facilitates the conversion of surface copper hydroxide to copper sulfide. In addition, the occurrence of Cu(NH3n2+ can promote the adsorption of copper ions (Cu2+ can be stored as Cu(NH3n2+ via complexation, and then, when the concentration of copper ions decreases, Cu2+ can be released through the decompositionof Cu(NH3n2+. Hence, the copper ion concentration can be maintained and this can facilitate the adsorption of Cu2+ on marmatite. Based on a comprehensive analysis of all our results, we propose that adding ammonium chloride to the copper sulfate changes the solution components (i.e., the presence of NH3(aq and Cu(NH3n2+ and then regulates the surface composition of marmatite. The change in surface composition

  18. Hydrogen sulfide increases nitric oxide production from endothelial cells by an Akt-dependent mechanism

    Directory of Open Access Journals (Sweden)

    Arturo J Cardounel

    2011-12-01

    Full Text Available Hydrogen sulfide (H2S and nitric oxide (NO are both gasotransmitters that can elicit synergistic vasodilatory responses in the in the cardiovascular system, but the mechanisms behind this synergy are unclear. In the current study we investigated the molecular mechanisms through which H2S regulates endothelial NO production. Initial studies were performed to establish the temporal and dose-dependent effects of H2S on NO generation using EPR spin trapping techniques. H2S stimulated a two-fold increase in NO production from endothelial nitric oxide synthase (eNOS, which was maximal 30 min after exposure to 25-150 µM H2S. Following 30 min H2S exposure, eNOS phosphorylation at Ser 1177 was significantly increased compared to control, consistent with eNOS activation. Pharmacological inhibition of Akt, the kinase responsible for Ser 1177 phosphorylation, attenuated the stimulatory effect of H2S on NO production. Taken together, these data demonstrate that H2S up-regulates NO production from eNOS through an Akt-dependent mechanism. These results implicate H2S in the regulation of NO in endothelial cells, and suggest that deficiencies in H2S signaling can directly impact processes regulated by NO.

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

    Science.gov (United States)

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

    2006-01-01

    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 (PFlurbiprofen (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. PMID:16491094

  20. Highly active sulfided CoMo catalysts supported on (ZrO{sub 2}–TiO{sub 2})/Al{sub 2}O{sub 3} ternary oxides

    Energy Technology Data Exchange (ETDEWEB)

    Escobar, José, E-mail: jeaguila@imp.mx [Instituto Mexicano del Petróleo, Eje Central Lázaro Cárdenas 152, Col. San Bartolo Atepehuacan, Gustavo A. Madero, México, D.F. 07730 (Mexico); De Los Reyes, José A., E-mail: jarh@xanum.uam.mx [Area de Ing. Química, UAM – Iztapalapa, San Rafael Atlixco 186, Col. Vicentina, Iztapalapa, México, D.F. 09340 (Mexico); Ulín, Carlos A. [Area de Ing. Química, UAM – Iztapalapa, San Rafael Atlixco 186, Col. Vicentina, Iztapalapa, México, D.F. 09340 (Mexico); Barrera, María C., E-mail: mcbdgavilan@gmail.com [Facultad de Ciencias Químicas, Universidad Veracruzana, Av. Universidad km. 7.5, Col. Santa Isabel, Coatzacoalcos, Veracruz, México, D.F. 96538 (Mexico)

    2013-12-16

    (ZrO{sub 2}–TiO{sub 2})/Al{sub 2}O{sub 3} ternary oxide at 20 mol% Al{sub 2}O{sub 3} (80% ZrO{sub 2}–TiO{sub 2}, in turn at 40–60 mol ratio) prepared by controlled co-precipitation (by urea thermal decomposition) of zirconium (ZrOCl{sub 2}·8H{sub 2}O) and titanium (TiCl{sub 4}) chlorides over a ground alumina substrate constitutes a promising material to be used as carrier of sulfided hydrodesulfurization (HDS) catalysts. After calcining (at 500 °C), the ternary oxide presented textural properties (S{sub g} = 387 m{sup 2} g{sup −1}, V{sub p} = 0.74 ml g{sup −1}, mean pore diameter = 7.6 nm) suitable to its utilization as carrier of catalysts applied in the oil-derived middle distillates HDS. As determined by temperature programmed-reduction and Raman and UV–vis spectroscopies ZrO{sub 2}–TiO{sub 2} deposition over alumina substrate resulted in decreased proportion of Mo{sup 6+} species in tetrahedral coordination on the oxidic impregnated material. As those species constitute hardly reducible precursors, their diminished concentration could be reflected in enhanced amount of Mo species susceptible of activation by sulfiding (H{sub 2}S/H{sub 2} at 400 °C) over our ternary carrier. Limiting the concentration of zirconia-titania (at 40–60 mol ratio) to 20 mol% in the mixed oxides support allowed the preparation of highly active promoted (by cobalt, at Co/(Co + Mo) = 0.3) MoS{sub 2} phase (at 2.8 atoms/nm{sup 2}), that formulation showing excellent properties in hydrodesulfurization (HDS) of both dibenzothiophene and highly-refractory 4,6-dimethyl-dibenzothiophene. Due to alike yields to various HDS products over CoMo/(ZrO{sub 2}–TiO{sub 2})/Al{sub 2}O{sub 3} and the corresponding Al{sub 2}O{sub 3}-supported formulation, presence of similar actives sites over those catalysts was strongly suggested. It seemed that enhanced concentration of octahedral Mo{sup 6+} over the oxidic impregnated precursor with (ZrO{sub 2}–TiO{sub 2})/Al{sub 2}O{sub 3