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Sample records for accelerating pyrite oxidation

  1. Pyrite oxidation by microbial consortia

    NASA Astrophysics Data System (ADS)

    Bostick, B. C.; Revill, K. L.; Doyle, C.; Kendelewicz, T.; Brown, G. E.; Spormann, A. M.; Fendorf, S.

    2003-12-01

    Acid mine drainage (AMD) is formed through pyrite oxidation, which produces acidity and releases toxic metals associated with pyrite and other sulfide minerals. Microbes accelerate pyrite oxidation markedly, thereby playing a major role in the production of AMD. Here, we probe pyrite oxidation by consortia of Thiobacillus ferrooxidans and thiooxidans using surface-sensitive photoelectron spectroscopy and X-ray absorption spectroscopy and compare them with surfaces oxidized through chemical and single species cultures. Microbial oxidation resulted in the formation of distinct oxidized surface species distributed non-uniformly over the pyrite surface; consortia produced a surface both more heterogeneous and more oxidized. In contrast, chemical oxidation proceeds without the build-up of passivating oxidation products. Surface morphology was not correlated with sites of nucleation or oxidation in any obvious manner. These results demonstrate that microbial oxidation occurs through a similar mechanism to chemical oxidation, but that the presence of complex microbial communities may impact the manner by which pyrite oxidation proceeds.

  2. Bacterial Oxidation of Pyritic Materials in Coal.

    PubMed

    Silverman, M P; Rogoff, M H; Wender, I

    1961-11-01

    Applicability of the manometric method for studying the oxidation of pyritic material in the presence of bacteria has been demonstrated. Resting cells of Ferrobacillus ferrooxidans accelerated the oxidation of coal pyrites and coarsely crystalline marcasite, but were inactive on coarsely crystalline pyrite. Resting cells of Thiobacillus thiooxidans were inactive on all pyrites tested. Oxidation rates in the presence of Ferrobacillus were increased by reducing the particle size of pyritic samples, and, in one case, by removing the CaCO(3) from a calcite-containing sample. PMID:16349610

  3. Bacterial Oxidation of Pyritic Materials in Coal.

    PubMed

    Silverman, M P; Rogoff, M H; Wender, I

    1961-11-01

    Applicability of the manometric method for studying the oxidation of pyritic material in the presence of bacteria has been demonstrated. Resting cells of Ferrobacillus ferrooxidans accelerated the oxidation of coal pyrites and coarsely crystalline marcasite, but were inactive on coarsely crystalline pyrite. Resting cells of Thiobacillus thiooxidans were inactive on all pyrites tested. Oxidation rates in the presence of Ferrobacillus were increased by reducing the particle size of pyritic samples, and, in one case, by removing the CaCO(3) from a calcite-containing sample.

  4. The surface oxidation of pyrite

    NASA Astrophysics Data System (ADS)

    Buckley, A. N.; Woods, R.

    1987-02-01

    The surface oxidation in air and air-saturated aqueous solutions of the iron sulfide mineral, pyrite, has been studied by X-ray photoelectron spectroscopy. Iron sulfate was produced on fracture surfaces within the first few minutes of exposure to air under ambient conditions. Iron oxide was also included in the oxidation products after prolonged exposure which implies that a sulfur product in addition to sulfate must be formed. It is suggested that this product is an iron-deficient sulfide. Elemental sulfur was not evident at surfaces exposed to air. Iron oxide rather than sulfate was present at abraded surfaces exposed to air for a few minutes. Oxidation of pyrite in air-saturated acid solutions resulted in the formation of a surface sulfur layer the extent and nature of which depended on solution composition and exposure time. Sulfate was the only sulfur oxidation product identified in alkaline solutions not containing soluble sulfide, and iron oxide remained at the surface after such treatment. Thin layers of elemental sulfur were observed at fracture surfaces immersed in aerated, dilute sodium sulfide solutions.

  5. Pyrite oxidation at circumneutral pH

    NASA Astrophysics Data System (ADS)

    Moses, Carl O.; Herman, Janet S.

    1991-02-01

    Previous studies of pyrite oxidation kinetics have concentrated primarily on the reaction at low pH, where Fe(III) has been assumed to be the dominant oxidant. Studies at circumneutral pH, necessitated by effective pH buffering in some pyrite oxidation systems, have often implicitly assumed that the dominant oxidant must be dissolved oxygen (DO), owing to the diminished solubility of Fe(III). In fact, Fe(III)(aq) is an effective pyrite oxidant at circumneutral pH, but the reaction cannot be sustained in the absence of DO. The purpose of this experimental study was to ascertain the relative roles of Fe(III) and DO in pyrite oxidation at circumneutral pH. The rate of pyrite oxidation was first-order with respect to the ratio of surface area to solution volume. Direct determinations of both Fe(II) (aq)> and Fe(III) (aq) demonstrated a dramatic loss of Fe(II) from the solution phase in excess of the loss for which oxidation alone could account. Based on rate data, we have concluded that Fe(II) is adsorbed onto the pyrite surface. Furthermore, Fe(II) is preferred as an adsorbate to Fe(III), which we attribute to both electrostatic and acid-base selectivity. We also found that the rate of pyrite oxidation by either Fe(III) (aq) or DO is reduced in the presence of aqueous Fe(II), which leads us to conclude that, under most natural conditions, neither Fe(III) (aq) nor DO directly attacks the pyrite surface. The present evidence suggests a mechanism for pyrite oxidation that involves adsorbed Fe( II ) giving up electrons to DO and the resulting Fe(III) rapidly accepting electrons from the pyrite. The adsorbed Fe is, thus, cyclically oxidized and reduced, while it acts as a conduit for electrons traveling from pyrite to DO. Oxygen is transferred from the hydration sphere of the adsorbed Fe to pyrite S. The cycle of adsorbed Fe oxidation and reduction and the successive addition of oxygen to pyrite S continues until a stable sulfoxy species dissociates from the surface. Prior

  6. Oxidation of pyrite in an anoxic atmosphere

    USGS Publications Warehouse

    Thorpe, A.N.; Senftle, F.E.; Alexander, Corrine; Dulong, F.T.; LaCount, R.B.; Friedman, S.

    1987-01-01

    Pyrite (FeS2) inclusions in coal, when heated in an oxygen deficient atmosphere (approximately 1% oxygen), become coated with magnetic Fe3O4 due to oxidation. Most of the FeS2 can thus be removed from the coal by magnetic separation to reduce the sulphur concentration. The oxidation products have been studied in greater detail by measuring the SO2 and O2 in the effluent gas during the heating process and by performing further magnetic measurements. At 582 K, the pyrite surface was oxidized to FeSO4. Significant oxidation of FeSO4 and FeS2 to Fe3O4 was observed starting at 677 K. At about 681 K, the Fe3O4 is further oxidized to ??-Fe2O3. At 681 K, under isothermal conditions, the oxidation is impeded by the ??-Fe2O3 formed on the surfaces of the grains. If the temperature is rapidly increased, the oxygen penetrates the ??-Fe2O3 veneer to the FeS2 core of the pyrite grains and oxidizes essentially the whole pyrite mass to Fe3O4 before ??-Fe2O3 can be formed. ?? 1987.

  7. Leaching of pyrite by acidophilic heterotrophic iron-oxidizing bacteria in pure and mixed cultures

    SciTech Connect

    Bacelar-Nicolau, P.; Johnson, D.B.

    1999-02-01

    Seven strains of heterotrophic iron-oxidizing acidophilic bacteria were examined to determine their abilities to promote oxidative dissolution of pyrite (FeS{sub 2}) when they were grown in pure cultures and in mixed cultures with sulfur-oxidizing Thiobacillus spp. Only one of the isolates (strain T-24) oxidized pyrite when it was grown in pyrite-basal salts medium. However, when pyrite-containing cultures were supplemented with 0.02% (wt/vol) yeast extract, most of the isolates oxidized pyrite, and one (strain T-24) promoted rates of mineral dissolution similar to the rates observed with the iron-oxidizing autotroph Thiobacillus ferroxidans. Pyrite oxidation by another isolate (strain T-21) occurred in cultures containing between 0.005 and 0.05% (wt/vol) yeast extract but was completely inhibited in cultures containing 0.5% yeast extract. Ferrous iron was also needed for mineral dissolution by the iron-oxidizing heterotrophs, indicating that these organisms oxidize pyrite via the indirect mechanism. Mixed cultures of three isolates (strains T-21, T-232, and T-24) and the sulfur-oxidizing autotroph Thiobacillus thiooxidans promoted pyrite dissolution; since neither strains T-21 and T-23 nor T. thiooxidans could oxidize this mineral in yeast extract-free media, this was a novel example of bacterial synergism. Mixed cultures of strains T-21 and T-23 and the sulfur-oxidizing mixotroph Thiobacillus acidophilus also oxidized pyrite but to a lesser extent than did mixed cultures containing T. thiooxidans. Pyrite leaching by strain T -23 grown in an organic compound-rich medium and incubated either shaken or unshaken was also assessed. The potential environmental significance of iron-oxidizing heterotrophs in accelerating pyrite oxidation is discussed.

  8. Influence factors for the oxidation of pyrite by oxygen and birnessite in aqueous systems.

    PubMed

    Qiu, Guohong; Luo, Yao; Chen, Cheng; Lv, Qiang; Tan, Wenfeng; Liu, Fan; Liu, Chengshuai

    2016-07-01

    The oxidation of exposed pyrite causes acid mine drainage, soil acidification, and the release of toxic metal ions. As the important abiotic oxidants in supergene environments, oxygen and manganese oxides participate in the oxidation of pyrite. In this work, the oxidation processes of natural pyrite by oxygen and birnessite were studied in simulated systems, and the influence of pH, Fe(II) and Cr(III) on the intermediates and redox rate was investigated. SO4(2-) and elemental S were formed as the major and minor products, respectively, during the oxidation processes. Ferric (hydr) oxides including Fe(OH)3 and goethite were formed with low degree of crystallinity. Low pH and long-term reaction facilitated the formation of goethite and ferric hydroxide, respectively. The rate of pyrite oxidation by birnessite was enhanced in the presence of air (oxygen), and Fe(II) ions played a key role in the redox process. The addition of Fe(II) ions to the reaction system significantly enhanced the oxidation rate of pyrite; however, the presence of Cr(III) ions remarkably decreased the pyrite oxidation rate in aqueous systems. The introduction of Fe(II) ions to form a Fe(III)/Fe(II) redox couple facilitated the electron transfer and accelerated the oxidation rate of pyrite. The present work suggests that isolation from air and decreasing the concentration of Fe(II) ions in aqueous solutions might be effective strategies to reduce the oxidation rate of pyrite in mining soils.

  9. As(V) and As(III) reactions on pristine pyrite and on surface-oxidized pyrite.

    PubMed

    Sun, Fenglong; Dempsey, Brian A; Osseo-Asare, Kwadwo A

    2012-12-15

    Reactions of As(III) and As(V) with pyrite were investigated using pristine pyrite (produced and reacted in a rigorously anoxic environment with P(O2)<10(-8)atm) and using surface-oxidized pyrite (produced under anoxic conditions, exposed to air, then stored and reacted under rigorously anoxic conditions). Results with surface-oxidized pyrite were similar to previously reported arsenic-pyrite results. However As(III) adsorbed over a broader pH range on pristine pyrite than on surface-oxidized pyrite, As(V) adsorbed over a narrower pH range on pristine pyrite than on surface-oxidized pyrite, and adsorbed As(V) on pristine pyrite was reduced to As(III) but adsorbed As(V) was not reduced with surface-oxidized pyrite. Reduction of As(V) with pristine pyrite was first-order in total As(V), Fe(II) was released, and sulfur was oxidized. The proposed mechanism for pyrite oxidation by As(V) was similar to the published mechanism for oxidation by O(2) and rates were compared. The results can be used to predict the removals of As(V) and As(III) on pyrite in continuously anoxic environments or on pyrite in intermittently oxic/anoxic environments. Rigorous cleanup and continuous maintenance of strictly anoxic conditions are required if commercial or produced pyrites are to be used as surrogates for pristine pyrite. PMID:23000211

  10. As(V) and As(III) reactions on pristine pyrite and on surface-oxidized pyrite.

    PubMed

    Sun, Fenglong; Dempsey, Brian A; Osseo-Asare, Kwadwo A

    2012-12-15

    Reactions of As(III) and As(V) with pyrite were investigated using pristine pyrite (produced and reacted in a rigorously anoxic environment with P(O2)<10(-8)atm) and using surface-oxidized pyrite (produced under anoxic conditions, exposed to air, then stored and reacted under rigorously anoxic conditions). Results with surface-oxidized pyrite were similar to previously reported arsenic-pyrite results. However As(III) adsorbed over a broader pH range on pristine pyrite than on surface-oxidized pyrite, As(V) adsorbed over a narrower pH range on pristine pyrite than on surface-oxidized pyrite, and adsorbed As(V) on pristine pyrite was reduced to As(III) but adsorbed As(V) was not reduced with surface-oxidized pyrite. Reduction of As(V) with pristine pyrite was first-order in total As(V), Fe(II) was released, and sulfur was oxidized. The proposed mechanism for pyrite oxidation by As(V) was similar to the published mechanism for oxidation by O(2) and rates were compared. The results can be used to predict the removals of As(V) and As(III) on pyrite in continuously anoxic environments or on pyrite in intermittently oxic/anoxic environments. Rigorous cleanup and continuous maintenance of strictly anoxic conditions are required if commercial or produced pyrites are to be used as surrogates for pristine pyrite.

  11. Oxidation of coal and coal pyrite mechanisms and influence on surface characteristics. [Coal pyrite electrodes

    SciTech Connect

    Doyle, F.M.

    1992-01-01

    The objective of this research is to develop a mechanistic understanding of the oxidation of coal and coal pyrite, and to correlate the intrinsic physical and chemical properties of these minerals, along with changes resulting from oxidation, with those surface properties that influence the behavior in physical cleaning processes. The results will provide fundamental insight into oxidation, in terms of the bulk and surface chemistry, the microstructure, and the semiconductor properties of the pyrite. During the eighth quarter, wet chemical and dry oxidation tests were done on Upper Freeport coal from the Troutville [number sign]2 Mine, Clearfield County, Pennsylvania. In addition electrochemical experiments were done on electrodes prepared from Upper Freeport coal pyrite and Pittsburgh coal pyrite samples provided by the US Bureau of Mines, Pittsburgh Research Center, Pennsylvania.

  12. Controlling incipient oxidation of pyrite for improved rejection. Final report

    SciTech Connect

    Yoon, R.H.; Richardson, P.E.; Tao, D.P.

    1996-04-01

    It is well known that superficial oxidation of pyrite produces a hydrophobic sulfur-rich surface and creates problems in separating the mineral from coal using surface-based processes such as flotation and agglomeration. Numerous studies of pyrite oxidation have been conducted but most of them were concerned with the advanced stages of oxidation, and as a result it was not possible to establish a relationship between oxidation and flotation behavior. A better understanding of the mechanisms and kinetics of the incipient oxidation reactions, which may vary with the origin, morphology, texture, and solid state properties of pyrite, can lead to the development of new processes that can improve pyrite rejection from coal. This project is aimed at better understanding of the mechanisms involved during the initial stages of pyrite oxidation to foster the development of advanced coal cleaning technologies. Studies were conducted by fracturing pyrite electrodes in-situ in an electrochemical cell to create virgin surfaces. Electrochemical and photoelectrochemical techniques were employed to characterize the incipient oxidation of pyrite in aqueous solutions. Microflotation tests were conducted to obtain information on the hydrophobicity of pyrite under controlled E{sub h} and pH conditions, and the results were correlated with electrochemical studies.

  13. Influence factors for the oxidation of pyrite by oxygen and birnessite in aqueous systems.

    PubMed

    Qiu, Guohong; Luo, Yao; Chen, Cheng; Lv, Qiang; Tan, Wenfeng; Liu, Fan; Liu, Chengshuai

    2016-07-01

    The oxidation of exposed pyrite causes acid mine drainage, soil acidification, and the release of toxic metal ions. As the important abiotic oxidants in supergene environments, oxygen and manganese oxides participate in the oxidation of pyrite. In this work, the oxidation processes of natural pyrite by oxygen and birnessite were studied in simulated systems, and the influence of pH, Fe(II) and Cr(III) on the intermediates and redox rate was investigated. SO4(2-) and elemental S were formed as the major and minor products, respectively, during the oxidation processes. Ferric (hydr) oxides including Fe(OH)3 and goethite were formed with low degree of crystallinity. Low pH and long-term reaction facilitated the formation of goethite and ferric hydroxide, respectively. The rate of pyrite oxidation by birnessite was enhanced in the presence of air (oxygen), and Fe(II) ions played a key role in the redox process. The addition of Fe(II) ions to the reaction system significantly enhanced the oxidation rate of pyrite; however, the presence of Cr(III) ions remarkably decreased the pyrite oxidation rate in aqueous systems. The introduction of Fe(II) ions to form a Fe(III)/Fe(II) redox couple facilitated the electron transfer and accelerated the oxidation rate of pyrite. The present work suggests that isolation from air and decreasing the concentration of Fe(II) ions in aqueous solutions might be effective strategies to reduce the oxidation rate of pyrite in mining soils. PMID:27372130

  14. Corrosion and Electrochemical Oxidation of a Pyrite by Thiobacillus ferrooxidans

    PubMed Central

    Mustin, C.; Berthelin, J.; Marion, P.; de Donato, P.

    1992-01-01

    The oxidation of a pure pyrite by Thiobacillus ferrooxidans is not really a constant phenomenon; it must be considered to be more like a succession of different steps which need characterization. Electrochemical studies using a combination of a platinum electrode and a specific pyrite electrode (packed-ground-pyrite electrode) revealed four steps in the bioleaching process. Each step can be identified by the electrochemical behavior (redox potentials) of pyrite, which in turn can be related to chemical (leachate content), bacterial (growth), and physical (corrosion patterns) parameters of the leaching process. A comparison of the oxidation rates of iron and sulfur indicated the nonstoichiometric bacterial oxidation of a pure pyrite in which superficial phenomena, aqueous oxidation, and deep crystal dissolution are successively involved. Images PMID:16348688

  15. Role of organic matter in framboidal pyrite oxidation.

    PubMed

    Rigby, P A; Dobos, S K; Cook, F J; Goonetilleke, A

    2006-08-31

    An experimental system has been set up to investigate the reaction kinetics of framboidal pyrite oxidation in real, reactive acid sulfate soil assemblages. This study was undertaken to determine the degree to which pyrite oxidation rates are reduced by bacteriological reactions and organic matter, which both modify the net reaction mechanisms and compete for available oxygen. The results from these experimental runs not only confirm the role of organic matter in mitigating pyrite oxidation but indicate that at least initially, the acidity produced is consumed or otherwise ameliorated by parallel reactions. Tracking pH or [H+] in both a reactor and in soil does not accurately reflect reaction progress and may not correctly indicate the true level of risk. In comparison, the tracking of pyrite oxidation with the concentration of sulfate in solution is not affected by side reactions or precipitation and is therefore a better indicator for the rate of pyrite destruction. PMID:16839593

  16. Oxidation of pyrite in coal to magnetite

    USGS Publications Warehouse

    Thorpe, A.N.; Senftle, F.E.; Alexander, C.C.; Dulong, F.T.

    1984-01-01

    When bituminous coal is heated in an inert atmosphere (He) containing small amounts of oxygen at 393-455 ??C, pyrite (FeS2) in coal is partially converted to magnetite (Fe304). The maximum amount of Fe304 formed during the time of heating corresponds to 5-20% of the total pyrite present, depending on the coal sample. The magnetite forms as an outer crust on the pyrite grains. The fact that the magnetic properties of the pyrite grains are substantially increased by the magnetite crust suggests that pyrite can be separated from coal by use of a low magnetic field. In a laboratory test, 75% removal is obtained by means of a 500 Oe magnet on three samples, and 60% on a fourth sample. ?? 1984.

  17. MECHANISMS OF PYRITE OXIDATION TO NON-SLAGGING SPECIES

    SciTech Connect

    Professor Reginald E. Mitchell

    2002-09-01

    A project was undertaken to characterize the oxidation of iron pyrite to the non-slagging species magnetite during pulverized coal combustion. The work was aimed at defining the pyrite transformations responsible for the higher slagging propensity of staged, low-NO{sub x} pulverized coal combustor burners. With such burners, coal is injected into a reducing environment. Consequently, the products of pyrite combustion become shifted from non-depositing, oxidized species such as Fe{sub 3}O{sub 4} to highly-depositing, reduced species such as FeO and Fe{sub 1-x}S, where x ranges from 0 to 0.125. The propensity for slagging can be minimized by the judicious redistribution of furnace air to maximize the oxide formation rate. This must be accomplished with minimal degradation of other aspects of boiler performance. To effect this, an understanding of the rate-limiting mechanisms of pyrite oxidation is required. The overall objectives of this project were to characterize the various mechanisms that control overall pyrite combustion rates and to synthesize the mechanisms into a pyrite combustion model. These objectives were achieved. The model produced has the capability of being incorporated into numerical codes developed to predict phenomena occurring in coal-fired boilers and furnaces. Such comprehensive codes can be used to formulate and test strategies for enhancing pyrite transformation rates that involve the minor adjustment of firing conditions. Ultimately, the benefit of this research project is intended to be an increase in the range of coals compatible with staged, low-NO{sub x} combustor retrofits. Project activities were aimed at identifying the mechanisms of pyrite combustion and quantifying their effects on the overall oxidation rate in order to formulate a model for pyrite conversion during coal combustion. Chemical and physical processes requiring characterization included pyrite intraparticle kinetics and mass transfer, gas-phase kinetics and mass

  18. Studies of incipient oxidation of coal-pyrite for improved pyrite rejection

    SciTech Connect

    Yoon, R.H.; Richardson, P.E.

    1992-01-01

    In order to foster the development of advanced coal cleaning technologies fundamental studies.of the initial stages of pyrite oxidation have been.initiated. This work is being done on pyrite surfaces that are freshly fractured in an electrolyte solution. This procedure produces surfaces that are initially unoxidized, allowing the subsequent oxidation processes to be studied in detail. It is shown that freshly fractured pyrite electrodes instantaneously (at fracture) assume a rest potential several hundred millivolts more negative than the usual open-circuit potential. A finite, anodic photocurrent, is also observed on the fractured electrodes. Following cleavage, the rest potential increases, indicating an oxidation reaction occurring on the electrodes. The photocurrent is relatively insensitive to this oxidation process, and to moderate anodic and cathodic polarization. However, strong cathodic polarization to about -0.76 V (SHE) at pH 9.2 causes the photocurrent to decrease to zero. No reversal in the sign of the photocurrent is observed and it is believed that the flat band potential occurs near -0.76 V, i.e., where the photocurrent goes to zero. Voltammetry indicates that pyrite also undergoes cathodic decomposition at -0.76 V. This establishes that pyrite must be cathodically decomposed to reach the flat band potential.

  19. The effect of As, Co, and Ni impurities on pyrite oxidation kinetics: An electrochemical study of synthetic pyrite

    NASA Astrophysics Data System (ADS)

    Lehner, Stephen; Savage, Kaye; Ciobanu, Madalina; Cliffel, David E.

    2007-05-01

    Synthetic pyrite crystals doped with As, Co, or Ni, undoped pyrite, and natural arsenian pyrite from Leadville, Colorado were investigated with electrochemical techniques and solid-state measurements of semiconducting properties to determine the effect of impurity content on pyrite's oxidation behavior. Potential step experiments, cyclic voltammetry, and AC voltammetry were performed in a standard three-electrode electrochemical cell setup. A pH 1.78 sulfuric acid solution containing 1 mM ferric iron, open to atmospheric oxygen, was chosen to approximate water affected by acid drainage. Van der Pauw/Hall effect measurements determined resistivity, carrier concentration and carrier mobility. The anodic dissolution of pyrite and the reduction of ferric iron half-reactions are taken as proxies for natural pyrite oxidation. Pyrite containing no impurities is least reactive. Pyrite with As is more reactive than pyrite with either Ni or Co despite lower dopant concentration. As, Co, and Ni impurities introduce bulk defect states at different energy levels within the band gap. Higher reactivity of impure pyrite suggests that introduced defect levels lead to higher density of occupied surface states at the solid-solution interface and increased metallic behavior. The current density generated from potential step experiments increased with increasing As concentration. The higher reactivity of As-doped pyrite may be related to p-type conductivity and corrosion by holes. The results of this study suggest that considering the impurity content of pyrite in mining waste may lead to more accurate risk assessment of acid producing potential.

  20. The mechanisms of pyrite oxidation and leaching: A fundamental perspective

    NASA Astrophysics Data System (ADS)

    Chandra, A. P.; Gerson, A. R.

    2010-09-01

    Pyrite is the earth's most abundant sulfide mineral. Its frequent undesirable association with minerals of economic value such as sphalerite, chalcopyrite and galena, and precious metals such as gold necessitates costly separation processes such as leaching and flotation. Additionally pyrite oxidation is a major contributor to the environmental problem of acid rock drainage. The surface oxidation reactions of pyrite are therefore important both economically and environmentally. Significant variations in electrical properties resulting from lattice substitution of minor and trace elements into the lattice structure exist between pyrite from different geographical locations. Furthermore the presence of low coordination surface sites as a result of conchoidal fracture causes a reduction in the band gap at the surface compared to the bulk thus adding further electrochemical variability. Given the now general acceptance after decades of research that electrochemistry dominates the oxidation process, the geographical location, elemental composition and semi-conductor type (n or p) of pyrite are important considerations. Aqueous pyrite oxidation results in the production of sulfate and ferrous iron. However other products such as elemental sulfur, polysulfides, hydrogen sulfide, ferric hydroxide, iron oxide and iron(III) oxyhydroxide may also form. Intermediate species such as thiosulfate, sulfite and polythionates are also proposed to occur. Oxidation and leach rates are generally influenced by solution Eh, pH, oxidant type and concentration, hydrodynamics, grain size and surface area in relation to solution volume, temperature and pressure. Of these, solution Eh is most critical as expected for an electrochemically controlled process, and directly correlates with surface area normalised rates. Studies using mixed mineral systems further indicate the importance of electrochemical processes during the oxidation process. Spatially resolved surface characterisation of fresh

  1. Oxidation of pyrite surfaces: a photoelectron spectroscopic study

    NASA Astrophysics Data System (ADS)

    Karthe, S.; Szargan, R.; Suoninen, E.

    1993-10-01

    Surfaces of pyrite (FeS 2) differently prepared in situ and ex situ have been studied before and after contact to air and air-saturated aqueous solutions of 4≤pH≤10 by means of photoelectron spectroscopy. Pyrite surfaces fractured or scraped in situ revealed FeS-like species concentrated in the surface region. Preparation (polishing, grinding, powdering) and prolonged oxidation in air mainly resulted in basic iron sulphate and iron oxide/hydroxide. A promoting effect of an increased surface roughness due to the preparation was observed for the formation of iron oxide/hydroxide compared with sulphate in contrast to the natural oxidation process. Oxidation in air also led to sulphur-rich species identified as iron-deficient regions below monolayer coverage. Similar regions were present at ground surfaces exposed to air-saturated solution of pH4 and pH5. In near-neutral to alkaline solution mainly iron hydroxy-oxide is formed the layer thickness of which was estimated in the range of 0.5 nm (pH5) to 1.7 nm (pH10).

  2. Oxidation of coal and coal pyrite mechanisms and influence on surface characteristics

    SciTech Connect

    Doyle, F.M.

    1992-01-01

    During the ninth quarter, electrochemical experiments were done on electrodes prepared from Upper Freeport coal pyrite and Pittsburgh coal pyrite samples provided by the US Bureau of Mines, Pittsburgh Research Center, Pennsylvania. Scanning electron microscopy and energy dispersive X-ray analysis were done to characterize the morphology and composition of the surface of as-received coal, oxidized coal and coal pyrite. In addition, electrokinetic tests were done on Upper Freeport coal pyrite.

  3. A Silica/Fly Ash-Based technology for Controlling Pyrite Oxidation.

    SciTech Connect

    1997-09-21

    The overall objective of this project is to develop methodologies by which sodium metasilicate or fly ash may produce an effective coating on pyrite surfaces for inhibiting pyrite oxidation. Milestones for the following periods include: First six-months - (1) Characterize pyrite surface reactions for understanding pyrite coating establishment. (2) Start a preliminary outdoor leaching - column experiment using 10 kg mine pyritic spoil treated with silicates to evaluate potential application of coatings on a large scale. Second six-months - (1) Characterize silicate - iron reactions in solution and on pyrite surface for understanding pyrite silica - coating formation. Third six-months - (1) Evaluate pyrite surface deposition of silicate having Na - silicate or fly ash as source. Fourth six- months - (1) Evaluate silicate coating durability in large outdoor columns.

  4. Pyrite Oxidation under initially neutral pH conditions and in the presence of Acidithiobacillus ferrooxidans and micromolar hydrogen peroxide

    NASA Astrophysics Data System (ADS)

    Ma, Y.; Lin, C.

    2012-01-01

    Hydrogen peroxide (H2O2) at a micromolar level played a role in the microbial surface oxidation of pyrite crystals under initially neutral pH. When the mineral-bacteria system was cyclically exposed to 50 μM H2O2, the colonization of Acidithiobacillus ferrooxidans onto the mineral surface was markedly enhanced, as compared to the control (no added H2O2). This can be attributed to the effects of H2O2 on increasing the roughness of the mineral surfaces, as well as the acidity and Fe2+ concentration at the mineral-solution interfaces. All of these effects tended to create more favourable nano- to micro-scale environments in the mineral surfaces for the cell adsorption. However, higher H2O2 levels inhibited the attachment of cells onto the mineral surfaces, possibly due to the oxidative stress in the bacteria when they approached the mineral surfaces where high levels of free radicals are present as a result of Fenton-like reactions. The more aggressive nature of H2O2 as an oxidant caused marked surface flaking of the mineral surface. The XPS results suggest that H2O2 accelerated the oxidation of pyrite-S and consequently facilitated the overall corrosion cycle of pyrite surfaces. This was accompanied by pH drop in the solution in contact with the pyrite cubes.

  5. A SILICA/FLY ASH-BASED TECHNOLOGY FOR CONTROLLING PYRITE OXIDATION

    SciTech Connect

    DR. V.P. EVANGELOU

    1998-02-10

    The results of pyrite oxidation in mining areas are very low pH and elevated concentrations of iron and sulfate in the groundwater. Pyrite oxidation is therefore the main cause for acid mine drainage production. One approach to prevent AMD production is microencapsulation of pyrite crystals with an iron-oxide/silica coating (Zhang and Evangelou, 1998). Coating prevents diffusion of oxygen and Fe{sup 3+} to the crystal's surface and they are no longer able to oxidize it. The objective of this portion of the study was to test the hypothesis that fly ash is able to provide the necessary silica for iron-oxide/silica coating formation on the pyrite surfaces thus, decreasing pyrite oxidation and diminishing acid mine drainage production.

  6. Oxidation of synthesized sub-micron pyrite (FeS2) in seawater

    NASA Astrophysics Data System (ADS)

    Gartman, Amy; Luther, George W.

    2014-11-01

    Synthesized sub-micron pyrite was oxidized in 0.2 μm-filtered Sargasso seawater in order to investigate the rate of oxidation and reaction end-products. Over the initial phase of the reaction, the sub-micron pyrite behaved as a soluble entity as the initial rate of oxidation was determined to be first order with respect to both pyrite and oxygen concentration, where the rate is described as -dFeS2/dt = k[FeS2][O2] and k, the rate constant, is 7.60 × 10-5 + 6.29 × 10-5 μM-1 day-1 at 25 °C. Oxidation proceeds inward from an initial surface oxidation of the pyrite and the formation of an amorphous mixed valence Fe(II)/(III) oxide surrounding the remaining pyrite core. The oxidation rates obtained through this study are up to two orders of magnitude slower than reported in previous pyrite oxidation studies using ground rather than synthesized pyrite at similar pH values. These results may be applied anywhere seawater and sub-micron pyrite are found, including hydrothermal vents, salt marshes and marine sediments.

  7. Controlling incipient oxidation of pyrite for improved rejection. Eighth quarterly technical progress report, July 1, 1994--September 30, 1994

    SciTech Connect

    Yoon, R.H.; Richardson, P.E.

    1994-12-31

    The major objectives of this work are (1) to determine the Eh-pH conditions under which pyrite is stable, (2) to determine the mechanism of the initial stages of pyrite oxidation and (3) to determine if the semi-conducting properties of pyrite effects its oxidation behavior. It is known that moderate oxidation of pyrite produces a hydrophobic surface product. This hydrophobic product makes it extremely difficult to depress pyrite in coal flotation circuits. The eventual objective of this work is to prevent pyrite oxidation in order to better depress pyrite in coal flotation circuits. In this work clean, unoxidized pyrite surfaces are being produced by fracturing pyrite electrodes in an electrochemical cell. It has been shown that pyrite assumes a unique potential referred to as the ``stable potential`` at the instance it is fractured and that this potential is several hundred millivolts more negative than the steady state mixed potential of pyrite. It has also been shown that by holding the potential of pyrite at its stable potential during fracture, pyrite undergoes neither oxidation nor reduction. It has also been found that fresh pyrite surfaces created by fracture in an electrochemical begin to oxidize at potentials that are about 200 mV more negative than the potentials reported in the literature for pyrite oxidation. This is attributed to the fact that most work on pyrite has employed polished electrodes that have pre-existing oxidation products on the surface. The existence of a pH dependent stable potential for freshly fractured pyrite electrodes was based on studies conducted mainly on pyrite from Peru.

  8. The role of carbonate ions in pyrite oxidation in aqueous systems

    NASA Astrophysics Data System (ADS)

    Caldeira, Claudia L.; Ciminelli, Virginia S. T.; Osseo-Asare, Kwadwo

    2010-03-01

    The mechanism of pyrite oxidation in carbonate-containing alkaline solutions at 80 °C was investigated with the help of rate experiments, thermodynamic modeling and diffuse reflectance infrared spectroscopy (DRIFTS). Pyrite oxidation rate increased with pH and was enhanced by addition of bicarbonate/carbonate ions. The carbonate effect was found to be limited to moderately alkaline conditions (pH 8-11). Metastable Eh-pH diagrams, at 25 °C, indicate that soluble iron-carbonate complexes (FeHCO 3-, FeCO 30, Fe(CO 3)(OH) - and FeCO 32-) may coexist with pyrite in the pH range of 6-12.5. Above pH 11 and 13, the Fe(II) and Fe(III) hydroxocomplexes, respectively, become stable, even in the presence of carbonate/bicarbonate ions. Surface-bound carbonate complexes on iron were also identified with DRIFTS as products of pyrite oxidation in addition to iron oxyhydroxides and soluble sulfate species. The conditions under which thermodynamic and DRIFTS analyses indicate the presence of carbonate compounds also correspond to those in which the fastest rate of pyrite oxidation in carbonate solutions was observed. Following the Singer-Stumm model for pyrite oxidation in acidic solutions, it is assumed that Fe(III) is the preferred pyrite oxidant under alkaline conditions. We propose that carbonate ions facilitate the electron transfer from soluble iron(II)-carbonate to O 2, increase the iron solubility, and provide buffered, favorable alkaline conditions at the reaction front, which in turn favors the overall kinetics of pyrite oxidation. Therefore, the electron transfer from sulfur atoms to O 2 is facilitated by the formation of the cycle of Fe(II)-pyrite/Fe(III)-carbonate redox couple at the pyrite surface.

  9. Anoxic pyrite oxidation by water radiolysis products — A potential source of biosustaining energy

    NASA Astrophysics Data System (ADS)

    Lefticariu, Liliana; Pratt, Lisa A.; LaVerne, Jay A.; Schimmelmann, Arndt

    2010-03-01

    Radiolysis on rocky planetary bodies provides chemical species across redox gradients that can supply energy for microbial life in subsurface environments. We investigated the oxidation of pyrite to aqueous sulfate (SO 42-) by water γ-radiolysis products with concomitant production of molecular hydrogen (H 2). The production of H 2, the only gaseous product recovered at the end of pyrite-water irradiation experiments, was found to be dependent on pyrite/water ratios. The yield of radiolytically-produced SO 42- correlated with the total irradiation dose. The effectiveness of γ-radiation in oxidative dissolution of pyrite is determined by (1) redox reactions between radiolytically-produced oxidants and pyrite, and (2) the interaction between γ-radiation and pyrite's crystalline structure. Radiolytic oxidation of reduced sulfur occurs with the oxidants HO ● (hydroxyl radical) and Fe 3+ (ferric iron) involving two different pathways. The radiolytic production of these two chemical oxidants is self-sustaining in the presence of water and Fe 2+ in the system. Radiolytic oxidation can produce significant sulfur isotope effects by preferentially bringing 34S into solution as sulfate and leaving a 32S-enriched elemental sulfur layer on the pyrite surface. Experimental abiotic fractionations of sulfur isotopes between original pyrite and its sulfur oxidation products are significant and indicate that isotopically distinct sulfate is being produced during oxidation. Based on measured radiolysis constants for pyrite and radiation dose estimates for continental crust, we show that radiolysis of water coupled to oxidation of metallic sulfides could be a significant source of sulfate in many geological environments. Implications of this work are broad, impacting our assessment of the potential for life to exist in subsurface environments on Earth as well as in extraterrestrial environments.

  10. Mechanisms of Sb(III) oxidation by pyrite-induced hydroxyl radicals and hydrogen peroxide.

    PubMed

    Kong, Linghao; Hu, Xingyun; He, Mengchang

    2015-03-17

    Antimony (Sb) is an element of growing interest, and its toxicity and mobility are strongly influenced by redox processes. Sb(III) oxidation mechanisms in pyrite suspensions were comprehensively investigated by kinetic measurements in oxic and anoxic conditions and simulated sunlight. Sb(III) was oxidized to Sb(V) in both solution and on pyrite surfaces in oxic conditions; the oxidation efficiency of Sb(III) was gradually enhanced with the increase of pH. The pyrite-induced hydroxyl radical (·OH) and hydrogen peroxide (H2O2) are the oxidants for Sb(III) oxidation. ·OH is the oxidant for Sb(III) oxidation in acidic solutions, and H2O2 becomes the main oxidant in neutral and alkaline solutions. ·OH and H2O2 can be generated by the reaction of previously existing FeIII(pyrite) and H2O on pyrite in anoxic conditions. The oxygen molecule is the crucial factor in continuously producing ·OH and H2O2 for Sb(III) oxidation. The efficiency of Sb(III) oxidation was enhanced in surface-oxidized pyrite (SOP) suspension, more ·OH formed through Fenton reaction in acidic solutions, but Fe(IV) and H2O2 were formed in neutral and alkaline solutions. Under the illumination of simulated sunlight, more ·OH and H2O2 were produced in the pyrite suspension, and the oxidation efficiency of Sb(III) was remarkably enhanced. In conclusion, Sb(III) can be oxidized to Sb(V) in the presence of pyrite, which will greatly influence the fate of Sb(III) in the environment.

  11. Role of hydrogen peroxide and hydroxyl radical in pyrite oxidation by molecular oxygen

    NASA Astrophysics Data System (ADS)

    Schoonen, Martin A. A.; Harrington, Andrea D.; Laffers, Richard; Strongin, Daniel R.

    2010-09-01

    Hydrogen peroxide and hydroxyl radical are readily formed during the oxidation of pyrite with molecular oxygen over a wide range of pH conditions. However, pretreatment of the pyrite surface influences how much of the intermediates are formed and their fate. Acid-washed pyrite produces significant amounts of hydrogen peroxide and hydroxyl radical when suspended in air-saturated water. However, the hydrogen peroxide concentration shows an exponential decrease with time. Suspensions made with partially oxidized pyrite yield significantly lower amounts of hydrogen peroxide product. The presence of Fe(III)-oxide or Fe(III)-hydroxide patches facilitates the conversion of hydrogen peroxide to oxygen and water. Hence, the degree to which a pyrite surface is covered with patches of Fe(III)-oxide or Fe(III)-hydroxide patches is an important control on the concentration of hydrogen peroxide in solution. Hydrogen peroxide appears to be an important intermediate in the four-electron transfer from pyrite to molecular oxygen. Addition of catalase, an enzyme that decomposes hydrogen peroxide to water and molecular oxygen, to a pyrite suspension reduces the oxidation rate by 40%. By contrast, hydroxyl radical does not appear to play a significant role in the oxidation mechanism. It is estimated on the basis of a molecular oxygen and sulfate mass balance that 5-6% of the molecular oxygen is consumed without forming sulfate.

  12. Controlling of incipient oxidation of pyrite for improved rejection. Sixth quarterly technical progress report, January 1, 1994--March 31, 1994

    SciTech Connect

    Yoon, R.H.; Richardson, P.E.

    1994-07-01

    The major objectives of this work are (1) to determine the Eh-pH conditions under which pyrite is stable, (2) to determine the mechanism of the initial stages of pyrite oxidation, and (3) to determine if the semiconducting properties of pyrite affect its oxidation behavior. It is known that moderate oxidation of pyrite produces a hydrophobic surface product. This hydrophobic product makes it extremely difficult to depress pyrite in coal flotation circuits. The eventual objective of this work is to prevent pyrite oxidation in order to better depress pyrite in coal flotation circuits. In this work clean, unoxidized pyrite surfaces are being produced by fracturing pyrite electrodes in an electrochemical cell. It has been shown that by holding the potential at different values during fracture and measuring the current passed at fracture, pyrite oxidation or reduction can be precisely controlled, or prevented. It has also been found that fresh pyrite surfaces, created by fracture in an electrochemical cell, begin to oxidize at potentials that are about 200 mV more negative than the potentials reported in the literature for pyrite oxidation. This is attributed to the fact that most work on pyrite has employed polished electrodes that have preexisting oxidation products on the surface. Electrochemical reduction and oxidation of these preexisting products essentially mask the oxidation of pyrite itselL In addition, photocurrent measurements show that freshly-fractured pyrite surfaces are charged negatively. This negative charge is believed to result from an intrinsic, acceptor-like surface state. This report period, voltammetric and photocurrent studies have been carried out as a function of pH and the photoresponse of pyrites from different sources have been determined.

  13. Mechanisms of pyrite oxidation to non-slagging species. Quartery report, October 1, 1995--December 31, 1995

    SciTech Connect

    Akan-Etuk, A.E.J.; Mitchell, R.E.

    1996-03-01

    This paper presents results of investigations on the transformation of iron pyrite to non-slagging species during staged combustion of pulverized coal. Work focuses on the oxidation of iron pyrite to magnetite.

  14. Mechanisms of hydroxyl radical production from abiotic oxidation of pyrite under acidic conditions

    NASA Astrophysics Data System (ADS)

    Zhang, Peng; Yuan, Songhu; Liao, Peng

    2016-01-01

    Hydroxyl radicals (radOH) produced from pyrite oxidation by O2 have been recognized, but mechanisms regarding the production under anoxic and oxic conditions are not well understood. In this study, the mechanisms of radOH production from pyrite oxidation under anoxic and oxic conditions were explored using benzoic acid (BA) as an radOH probe. Batch experiments were conducted at pH 2.6 to explore radOH production under anoxic and oxic conditions. The cumulative radOH concentrations produced under anoxic and oxic conditions increased linearly to 7.5 and 52.2 μM, respectively within 10 h at 10 g/L pyrite. Under anoxic conditions, radOH was produced from the oxidation of H2O on the sulfur-deficient sites on pyrite surface, showing an increased production with the increase of pyrite surface exposure due to oxidation. Under oxic conditions, the formation of radOH proceeds predominantly via the two-electron reduction of O2 on pyrite surface along with a minor contribution from the oxidation of H2O on surface sulfur-defects and the reactions of Fe2+/sulfur intermediates with O2. For both O2 reduction and H2O oxidation on the surface sulfur-defects, H2O2 was the predominant intermediate, which subsequently transformed to radOH through Fenton mechanism. The radOH produced had a significant impact on the transformation of contaminants in the environment. Anoxic pyrite suspensions oxidized 13.9% As(III) (C0 = 6.67 μM) and 17.6% sulfanilamide (C0 = 2.91 μM) within 10 h at pH 2.6 and 10 g/L pyrite, while oxic pyrite suspensions improved the oxidation percentages to 55.4% for As(III) and 51.9% for sulfanilamide. The ratios of anoxic to oxic oxidation are consistent with the relative contribution of surface sulfur-defects to radOH production. However, Fe2+ produced from pyrite oxidation competed with the contaminants for radOH, which is of particular significance with the increase of time in a static environment. We conclude that radOH can be produced from abiotic oxidation of

  15. Characterization of solid reaction products from wet oxidation of pyrite in coal using alkaline solutions

    SciTech Connect

    Greer, R.T.; Markuszewski, R.; Wheelock, T.D.

    1980-01-01

    Oxidation of pyrite alone and pyrite embedded in coal by leaching with hot solutions of sodium carbonate containing dissolved oxygen under pressure produces hematite, the major solid reaction product. The hematite is deposited as a concentric rim surrounding the core of unreacted pyrite. The thickness of the rim is greater for products obtained after longer leaching time or under conditions of higher oxygen partial pressure. The product is identified as hematite by X-ray diffraction analysis. Data from scanning electron microscopy, and energy-dispersive X-ray analysis show that under these conditions of desulfurization, phase transformations occur (from pyrite to hematite). In addition, great differences in porosity of the two zones (core and rim) are observed. The nature and extent of these transformations are discussed in terms of the desulfurization potential of pyrite in coal. (10 refs.)

  16. Oxidation of coal and coal pyrite mechanisms and influence on surface characteristics. Technical progress report, December 31, 1992

    SciTech Connect

    Doyle, F.M.

    1992-12-31

    During the ninth quarter, electrochemical experiments were done on electrodes prepared from Upper Freeport coal pyrite and Pittsburgh coal pyrite samples provided by the US Bureau of Mines, Pittsburgh Research Center, Pennsylvania. Scanning electron microscopy and energy dispersive X-ray analysis were done to characterize the morphology and composition of the surface of as-received coal, oxidized coal and coal pyrite. In addition, electrokinetic tests were done on Upper Freeport coal pyrite.

  17. Oxidation of coal and coal pyrite mechanisms and influence on surface characteristics

    SciTech Connect

    Doyle, F.M.

    1992-01-28

    The objective of this research is to develop a mechanistic understanding of the oxidation of coal and coal pyrite, and to correlate the intrinsic physical and chemical properties of these minerals, along with changes resulting from oxidation, with those surface properties that influence the behavior in physical coal cleaning processes. The results will provide fundamental insight into oxidation, in terms of the bulk and surface chemistry, the microstructure, and the semiconductor properties of the pyrite. During the fifth quarter, wet chemical and dry oxidation tests were done on Upper Freeport coal from the Troutville {number sign}2 Mine, Clearfield County, Pennsylvania.

  18. Oxidation of coal and coal pyrite mechanisms and influence on surface characteristics

    SciTech Connect

    Doyle, F.M.

    1991-09-24

    The objective of this research is to develop a mechanistic understanding of the oxidation of coal and coal pyrite, and to correlate the intrinsic physical and chemical properties of these minerals, along with changes resulting from oxidation, with those surface properties that influence the behavior in physical coal cleaning processes. The results will provide fundamental insight into oxidation, in terms of the bulk and surface chemistry, the microstructure, and the semiconductor properties of the pyrite. During the fourth quarter, characterization and oxidation tests were done on Upper Freeport coal from the Troutville {number sign}2 Mine, Clearfield County, Pennsylvania. In addition, standard test methods for characterizing pyrite-bearing materials were studied. 3 figs., 2 tabs.

  19. Leaching of Pyrites of Various Reactivities by Thiobacillus ferrooxidans.

    PubMed

    Baldi, F; Clark, T; Pollack, S S; Olson, G J

    1992-06-01

    Wide variations were found in the rate of chemical and microbiological leaching of iron from pyritic materials from various sources. Thiobacillus ferrooxidans accelerated leaching of iron from all of the pyritic materials tested in shake flask suspensions at loadings of 0.4% (wt/vol) pulp density. The most chemically reactive pyrites exhibited the fastest bioleaching rates. However, at 2.0% pulp density, a delay in onset of bioleaching occurred with two of the pyrites derived from coal sources. T. ferrooxidans was unable to oxidize the most chemically reactive pyrite at 2.0% pulp density. No inhibition of pyrite oxidation by T. ferrooxidans occurred with mineral pyrite at 2.0% pulp density. Experiments with the most chemically reactive pyrite indicated that the leachates from the material were not inhibitory to iron oxidation by T. ferrooxidans. PMID:16348718

  20. Leaching of Pyrites of Various Reactivities by Thiobacillus ferrooxidans.

    PubMed

    Baldi, F; Clark, T; Pollack, S S; Olson, G J

    1992-06-01

    Wide variations were found in the rate of chemical and microbiological leaching of iron from pyritic materials from various sources. Thiobacillus ferrooxidans accelerated leaching of iron from all of the pyritic materials tested in shake flask suspensions at loadings of 0.4% (wt/vol) pulp density. The most chemically reactive pyrites exhibited the fastest bioleaching rates. However, at 2.0% pulp density, a delay in onset of bioleaching occurred with two of the pyrites derived from coal sources. T. ferrooxidans was unable to oxidize the most chemically reactive pyrite at 2.0% pulp density. No inhibition of pyrite oxidation by T. ferrooxidans occurred with mineral pyrite at 2.0% pulp density. Experiments with the most chemically reactive pyrite indicated that the leachates from the material were not inhibitory to iron oxidation by T. ferrooxidans.

  1. Leaching of pyrites of various reactivities by Thiobacillus ferrooxidans

    SciTech Connect

    Baldi, F. ); Clark, T.; Pollack, S.S.; Olson, G.J. )

    1992-06-01

    Variations were found in the rate of chemical and microbiological leaching of iron from pyritic materials from various sources. Thiobacillus ferrooxidans accelerated leaching of iron from all of the pyritic materials tested in shake flask suspensions at loadings of 0.4% (wt/vol) pulp density. The most chemically reactive pyrites exhibited the fastest bioleaching rates. However, at 2.0% pulp density, a delay in onset of bioleaching occurred with two of the pyrites derived from coal sources. T. ferrooxidans was unable to oxidize the most chemically reactive pyrite at 2.0% pulp density. No inhibition of pyrite oxidation by T. ferrooxidans occurred with mineral pyrite at 2.0% pulp density. Experiments with the most chemically reactive pyrite indicated that the leachates from the material were not inhibitory to iron oxidation by T. ferrooxidans.

  2. Leaching of Pyrites of Various Reactivities by Thiobacillus ferrooxidans

    PubMed Central

    Baldi, Franco; Clark, Thomas; Pollack, S. S.; Olson, Gregory J.

    1992-01-01

    Wide variations were found in the rate of chemical and microbiological leaching of iron from pyritic materials from various sources. Thiobacillus ferrooxidans accelerated leaching of iron from all of the pyritic materials tested in shake flask suspensions at loadings of 0.4% (wt/vol) pulp density. The most chemically reactive pyrites exhibited the fastest bioleaching rates. However, at 2.0% pulp density, a delay in onset of bioleaching occurred with two of the pyrites derived from coal sources. T. ferrooxidans was unable to oxidize the most chemically reactive pyrite at 2.0% pulp density. No inhibition of pyrite oxidation by T. ferrooxidans occurred with mineral pyrite at 2.0% pulp density. Experiments with the most chemically reactive pyrite indicated that the leachates from the material were not inhibitory to iron oxidation by T. ferrooxidans. PMID:16348718

  3. Do dislocations and stacking faults increase the oxidation rate of pyrites?

    SciTech Connect

    Martello, D.V.; Diehl, J.R.; Tamilia, J.P.; Pollack, S.S.; Vecchio, K.S.; Graham, R.A.

    1994-11-01

    XPS, SEM, and TEM studies were made on coal, non-coal, and shock-loaded pyrites that had been experimentally weathered under high relative humidity. Reactivity (oxidation) of the different pyrite samples may be related to their stacking fault densities. A coal pyrite sample that had the highest stacking fault concentration was also the most reactive pyrite. No systematic relationship between reactivity and dislocation density was observed. Shock-loaded samples exposed to mean bulk shock temperatures between 175 and 475{degrees}C showed an increase in the number of reactive sites and shock-loaded samples exposed to mean bulk shock temperatures between 500 and 700{degrees}C showed decreases in the number of reactive sites.

  4. Progressive oxidation of pyrite in five bituminous coal samples: An As XANES and 57Fe Mössbauer spectroscopic study

    USGS Publications Warehouse

    Kolker, Allan; Huggins, Frank E.

    2007-01-01

    Naturally occurring pyrite commonly contains minor substituted metals and metalloids (As, Se, Hg, Cu, Ni, etc.) that can be released to the environment as a result of its weathering. Arsenic, often the most abundant minor constituent in pyrite, is a sensitive monitor of progressive pyrite oxidation in coal. To test the effect of pyrite composition and environmental parameters on the rate and extent of pyrite oxidation in coal, splits of five bituminous coal samples having differing amounts of pyrite and extents of As substitution in the pyrite, were exposed to a range of simulated weathering conditions over a period of 17 months. Samples investigated include a Springfield coal from Indiana (whole coal pyritic S = 2.13 wt.%; As in pyrite = detection limit (d.l.) to 0.06 wt.%), two Pittsburgh coal samples from West Virginia (pyritic S = 1.32–1.58 wt.%; As in pyrite = d.l. to 0.34 wt.%), and two samples from the Warrior Basin, Alabama (pyritic S = 0.26–0.27 wt.%; As in pyrite = d.l. to 2.72 wt.%). Samples were collected from active mine faces, and expected differences in the concentration of As in pyrite were confirmed by electron microprobe analysis. Experimental weathering conditions in test chambers were maintained as follows: (1) dry Ar atmosphere; (2) dry O2 atmosphere; (3) room atmosphere (relative humidity ∼20–60%); and (4) room atmosphere with samples wetted periodically with double-distilled water. Sample splits were removed after one month, nine months, and 17 months to monitor the extent of As and Fe oxidation using As X-ray absorption near-edge structure (XANES) spectroscopy and 57Fe Mössbauer spectroscopy, respectively. Arsenic XANES spectroscopy shows progressive oxidation of pyritic As to arsenate, with wetted samples showing the most rapid oxidation. 57Fe Mössbauer spectroscopy also shows a much greater proportion of Fe3+ forms (jarosite, Fe3+ sulfate, FeOOH) for samples stored under wet conditions, but much less

  5. On and S isotopic composition of dissolved and attached oxidation products of pyrite by Acidithiobacillus ferrooxidans: Comparison with abiotic oxidations

    NASA Astrophysics Data System (ADS)

    Pisapia, Céline; Chaussidon, M.; Mustin, C.; Humbert, B.

    2007-05-01

    The acidophilic iron-oxidizing bacterium, Acidithiobacillus ferrooxidans, plays a part in the pyrite oxidation process and has been widely studied in order to determine the kinetics of the reactions and the isotopic composition of dissolved product sulphates, but the details of the oxidation processes at the surface of pyrite are still poorly known. In this study, oxygen and sulphur isotopic compositions (δ 18O and δ 34S) were analyzed for dissolved sulphates and water from experimental aerobic acidic (pH < 2) pyrite oxidation by A. ferrooxidans. The oxidation products attached to the pyrite surfaces were studied for their morphology (SEM), their chemistry (Raman spectroscopy) and for their δ 18O (ion microprobe). They were compared to abiotically (Fe 3+, H 2O 2, O 2) oxidized pyrite surface compounds in order to constrain the oxidation pathways and to look for the existence of potential biosignatures for this system. The pyrite dissolution evolved from non-stoichiometric (during the first days) to stoichiometric (with increasing time) resulting in dissolved sulphates having distinct δ 18O (e.g. +11.0‰ and -2.0‰, respectively) and δ 34S (+4.5‰ and +2.8‰, respectively) values. The "oxidation layer" at the surface of pyrite is complex and made of iron oxides, sulphate, polysulphide, elemental sulphur and polythionates. Bio- and Fe 3+-oxidation favour the development of monophased micrometric bumps made of hematite or sulphate while other abiotic oxidation processes result in more variable oxidation products. The δ 18O of these oxidation products at the surface of oxidized pyrites are strongly variable (from ≈-40‰ to ≈+30‰) for all experiments. Isotopic fractionation between sulphates and pyrite, Δ34S-pyrite, is equal to -1.3‰ and +0.4‰ for sulphates formed by stoichiometric and non-stoichiometric processes, respectively. These two values likely reflect either a S-S or a Fe-S bond breaking process. The Δ18O-HO and Δ18O-O are estimated to

  6. Controlling incipient oxidation of pyrite for improved rejection. Technical progress report for the ninth quarter, October 1--December 31, 1994

    SciTech Connect

    Yoon, R.H.; Richardson, P.E.

    1995-07-01

    The major objectives of this work are (1) to determine the Eh-pH conditions under which pyrite is stable, (2) to determine the mechanism of the initial stages of pyrite oxidation, and (3) to determine if the semi-conducting properties of pyrite effects its oxidation behavior. It is known that moderate oxidation of pyrite produces a hydrophobic surface product. This hydrophobic product makes it extremely difficult to depress pyrite in coal flotation circuits. The eventual objective of this work is to prevent pyrite oxidation in order to better depress pyrite in coal flotation circuits. It has been shown that by holding the potential of pyrite at its stable potential during fracture, pyrite undergoes neither oxidation nor reduction. It has also been found that fresh pyrite surfaces created by fracture in an electrochemical begin to oxidize at potentials that are about 200 mV more negative than the potentials reported in the literature for pyrite oxidation. This report period, electrochemical impedance spectroscopy (EIS) studies were continued. As discussed in the seventh quarterly progress report, the impedance of pyrite does not show the characteristics expected for either semi-conducting or metallic electrodes. Additional studies were conducted to confirm the anomalous impedance behavior. For this purpose, freshly fractured surfaces were progressively polished on 600 and 1,200 grit silicon carbide paper, and with 0.3 {micro} {alpha}-alumina and 0.05 {micro} {gamma}-alumina micropolish. Polishing is known to introduce defects in the lattice structure of semi-conducting electrodes and it was anticipated that the defects would effect the interfacial capacitance.

  7. Bacterial and chemical oxidation of pyritic mine tailings at low temperatures

    NASA Astrophysics Data System (ADS)

    Elberling, Bo; Schippers, Axel; Sand, Wolfgang

    2000-02-01

    Microbial and chemical sulfide oxidation activity and oxygen consumption was investigated in the active layer of pyritic mine tailings at Nanisivik Mine, located in a permafrost area on Baffin Island in northern Canada. Samples of tailings were collected up to a depth of 60 cm in mid-August 1998 at 4 sites, for which the metabolic activity of sulfur- and iron-oxidizing leaching bacteria besides the chemical pyrite oxidation activity were measured on 39 tailings samples and 7 samples from a natural pyritic site by calorimetry. The tailings of varying age and water content were deposited under alkaline conditions. In situ oxygen uptake rates were measured at the tailings surface every third day, prior to sampling. In addition, cell counts of iron(II), sulfur, and thiosulfate oxidizing, lithotrophic bacteria and chemoorganotrophic microorganisms were determined quantitatively by the most-probable-number technique or by agar-plating. Results show consistent pyrite oxidation rates based on in situ oxygen uptake rates, and laboratory heat output measurements. Litho- and organotrophic bacteria were found in the tailings. Calorimetric measurements revealed that the present bacterial activity is responsible for approximately one third of the ongoing oxidation. Although leaching bacteria have previously been found in the Arctic, this study is the first to prove the significance of bacterial activity in the overall pollution resulting from tailings deposited in the Arctic.

  8. Studies of incipient oxidation of coal-pyrite for improved pyrite rejection. First quarterly technical progress report, October 1, 1992--December 31, 1992

    SciTech Connect

    Yoon, R.H.; Richardson, P.E.

    1992-12-31

    In order to foster the development of advanced coal cleaning technologies fundamental studies.of the initial stages of pyrite oxidation have been.initiated. This work is being done on pyrite surfaces that are freshly fractured in an electrolyte solution. This procedure produces surfaces that are initially unoxidized, allowing the subsequent oxidation processes to be studied in detail. It is shown that freshly fractured pyrite electrodes instantaneously (at fracture) assume a rest potential several hundred millivolts more negative than the usual open-circuit potential. A finite, anodic photocurrent, is also observed on the fractured electrodes. Following cleavage, the rest potential increases, indicating an oxidation reaction occurring on the electrodes. The photocurrent is relatively insensitive to this oxidation process, and to moderate anodic and cathodic polarization. However, strong cathodic polarization to about -0.76 V (SHE) at pH 9.2 causes the photocurrent to decrease to zero. No reversal in the sign of the photocurrent is observed and it is believed that the flat band potential occurs near -0.76 V, i.e., where the photocurrent goes to zero. Voltammetry indicates that pyrite also undergoes cathodic decomposition at -0.76 V. This establishes that pyrite must be cathodically decomposed to reach the flat band potential.

  9. Studies of incipient oxidation of pyrite for improved rejection. Fifth quarterly technical progress report, October 1, 1993--December 31, 1993

    SciTech Connect

    Yoon, R.H.; Richardson, P.E.

    1993-12-31

    Oxidation of fresh surfaces of coal- and mineral-pyrite has been studied using electrochemical and photoelectrochemical techniques. This work was undertaken to better understand the oxidation processes that cause self-induced flotation of pyrite. Fresh surfaces were created by fracturing pyrite in situ, i.e., in solution. Chronoamperometry was used to determine the potential at which a newly created surface does not show oxidation or reduction currents. The ``stable`` potentials for pyrite are {minus}0.28 V (SHE) at pH 9.2 and 0 V at pH 4.6. Subsequent cyclic voltammograms show the incipient oxidation mechanism that involves the formation of sulfur products, which are believed to be hydrophobic. It is shown that the lower flotation edge of pyrite coincides with its incipient oxidation potential. The photocurrent generated at fractured pyrite surfaces by chopped illumination was used to determine the semiconducting characteristics of the electrodes. The results indicate that a spontaneous depletion layer is formed on the fresh surfaces of n-type pyrite. The depletion layer is attributed to an intrinsic, acceptor-like surface state. Charge storage in this surface state pins the band edges over a wide potential range, accounting for the metallic-like electrochemical behavior that has been reported for pyrite. The existence of an intrinsic surface state is consistent with XPS studies on pyrite surfaces prepared in vacuum, which reveal an FeS-like species in the surface region. During this report period, all of the data previously obtained has been analyzed in an attempt to better understand the mechanism of pyrite flotation with respect to its oxidation. The results of this analysis are included in this quarterly report. In addition, samples of pyrite from seven different sources were obtained. In situ fracture, photoelectrochemical and cyclic voltammetry studies have been conducted on electrodes made from these pyrites.

  10. The formation, oxidation and distribution of pyrite nanoparticles emitted from hydrothermal vents: A laboratory and field based approach

    NASA Astrophysics Data System (ADS)

    Gartman, Amy

    Recent research identified the presence of nanoparticulate pyrite in hydrothermal vent black smoker emissions, and suggested that these nanoparticles may be a transport pathway for iron from hydrothermal vents to the larger ocean basin. Here, nanoparticulate pyrite was synthesized via a hydrothermal method and oxidized in air- saturated seawater, in order to explore how hydrothermally emitted pyrite forms, and may behave in oxic seawater. Additionally, hydrothermal emissions from the Mid- Atlantic Ridge were investigated for iron and sulfide speciation and reactions relating to pyrite formation. Pyrite was synthesized via both the Fe(II) + S(0) and the FeS + H 2S pathways of pyrite formation, and factors including surfactant and synthesis time were varied in order to modify morphology. The FeS + H 2S formation pathway, which is likely the pathway of pyrite formation occurring at hydrothermal sites, reproduces the pyrite nano and sub- micron particles found in black smoker emissions most closely. The oxidation of these pyrite particles results in an initial oxidation rate that is first order with respect to both the pyrite and oxygen concentration in seawater. This work is unique to previous studies on pyrite oxidation in that it uses synthesized, rather than ground and sieved pyrite, and uses seawater as the medium of oxidation. Along with the rate data, this study also demonstrates that the initial oxide formed from pyrite oxidation under these conditions is poorly crystalline and contains Fe(II) and Fe(III). Pyrite nanoparticles were identified at each of the three sites investigated at the Mid-Atlantic Ridge (Rainbow, TAG and Snakepit), and their presence at these sites, when combined with previous data from Lau Basin and EPR 9 °N demonstrates that they are likely to be a ubiquitous component of black- smoker hydrothermal emissions. The Rainbow site exhibited the highest concentration of nanoparticulate pyrite measured anywhere to date (1.15 mM). The potential

  11. Further studies of the effects of oxidation on the surface properties of coal and coal pyrite

    SciTech Connect

    Herrera, M.N.

    1994-12-31

    The objective of this research was to investigate the oxidation behavior of coal and coal pyrite and to correlate the changes in the surface properties induced by oxidation, along with the intrinsic physical and chemical properties of these organic and inorganic materials, with the behavior in physical coal cleaning processes. This provide more fundamental knowledge for understanding the way in which different factors interact in a medium as heterogeneous as coal. Fourteen coal samples of different ranks ranging from high to medium sulfur content were studied by dry oxidation tests at different temperatures and humidities, and by wet oxidation tests using different oxidizing agents. The concentration of surface oxygen functional groups was determined by ion-exchange methods. The changes in the coal composition with oxidation were analyzed by spectroscopic techniques. The wettability of as-received and oxidized coal and coal pyrite samples was assessed by film flotation tests. The electrokinetic behavior of different coals and coal pyrite samples was studied by electrokinetic tests using electrophoresis. Possible oxidation mechanisms have been proposed to explain the changes on the coal surface induced by different oxidation treatments.

  12. Mechanisms of pyrite oxidation to non-slagging species. Quarterly report, January 1--March 31, 1997

    SciTech Connect

    Akan-Etuk, A.E.J.; Mitchell, R.E.

    1997-12-31

    This document is the eleventh quarterly status report on a project that is concerned with enhancing the transformation of iron pyrite to non-slagging species during staged, low-NO{sub x} pulverized coal (P.C.) combustion. The research project is intended to advance PETC`s efforts to improve the technical understanding of the high-temperature chemical and physical processes involved in the utilization of coal. The work focuses on the mechanistic description and rate quantification of the effects of fuel properties and combustion environment on the oxidation of iron pyrite to form the non-slagging species magnetite. Activities during this report period were associated with the numerical encoding of the pyrite combustion model. The computer program resulting from the efforts put forth is intended to provide predictive capabilities with respect to pyrite composition during pulverized coal firing. The subroutines that have been written to track the fate of a pyrite particle of specified size and composition flowing in a gaseous environment of specified oxygen concentration, temperature, and velocity are being debugged and tested.

  13. Mechanisms of pyrite oxidation to non-slagging species. Quarterly report, October 1--December 31, 1996

    SciTech Connect

    Akan-Etuk, A.E.J.; Mitchell, R.E.

    1997-12-31

    This document is the tenth quarterly status report on a project that is concerned with enhancing the transformation of iron pyrite to non-slagging species during staged, low-NO{sub x} pulverized coal (P.C.) combustion. The research project is intended to advance PETC`s efforts to improve the technical understanding of the high-temperature chemical and physical processes involved in the utilization of coal. The work focuses on the mechanistic description and rate quantification of the effects of fuel properties and combustion environment on the oxidation of iron pyrite to form the non-slagging species magnetite. During this report period numerical encoding of a pyrite combustion model was embarked upon. The effort was intended to lead to predictive capabilities with respect to pyrite composition during pulverized coal firing. Many subroutines were written of a FORTRAN computer program to track the fate of a pyrite particle by integrating time-dependent differential equations for species, momentum, and energy conservation. Inputs to the program include fuel-related properties such as particle size and composition, as well as properties of the reactor environment such as oxygen level, temperature, gas velocity, and a set of initial and final positions.

  14. The kinetics of the oxidation of pyrite by ferric ions and dissolved oxygen: An electrochemical study

    SciTech Connect

    Holmes, P.R.; Crundwell, F.K.

    2000-01-01

    The dissolution of pyrite is important in the geochemical cycling of iron and sulphur, in the formation of acid mine drainage, and in the extraction of metals by bacterial leaching. Many researchers have studied the kinetics of dissolution, and the rate of dissolution has often been found to be half-order in ferric ions or oxygen. Previous work has not adequately explained the kinetics of dissolution of pyrite. The dissolution of pyrite is an oxidation-reduction reaction. The kinetics of the oxidation and reduction half-reactions was studied independently using electrochemical techniques of voltammetry. The kinetics of the overall reaction was studied by the electrochemical technique of potentiometry, which consisted of measuring the mixed potential of a sample of corroding pyrite in solutions of different compositions. The kinetics of the half reactions are related to the kinetics of the overall dissolution reaction by the condition that there is no accumulation of charge. This principle is used to derive expressions for the mixed potential and the rate of dissolution, which successfully describe the mixed potential measurements and the kinetics of dissolution reported in the literature. It is shown that the observations of half-order kinetics and that the oxygen in the sulphate product arises from water are both a direct consequence of the electrochemical mechanism. Thus it is concluded that the electrochemical reaction steps occurring at the mineral-solution interface control the rate of dissolution. Raman spectroscopy was used to analyze reaction products formed on the pyrite surface. The results indicated that small amounts of polysulphides form on the surface of the pyrite. However, it was also found that the mixed (corrosion) potential does not change over a 14-day leaching period. This indicates that even though polysulphide material is present on the surface, it does not influence the rate of the reactions occurring at the surface. Measurement of the

  15. Pyrite oxidation in saturated and Unsaturated Porous Media Flow: AComparison of alternative mathematical modeling approaches

    SciTech Connect

    Xu, Tianfu; White, Stephen P.; Pruess, Karsten

    1998-02-15

    Pyrite (FeS{sub 2}) is one of the most common naturally occurring minerals that is present in many subsurface environments. It plays an important role in the genesis of enriched ore deposits through weathering reactions, is the most abundant sulfide mineral in many mine tailings, and is the primary source of acid drainage from mines and waste rock piles. The pyrite oxidation reaction serves as a prototype for oxidative weathering processes with broad significance for geoscientific, engineering, and environmental applications. Mathematical modeling of these processes is extremely challenging because aqueous concentrations of key species vary over an enormous range, oxygen inventory and supply are typically small in comparison to pyrite inventory, and chemical reactions are complex, involving kinetic control and microbial catalysis. We present the mathematical formulation of a general multi-phase advective-diffusive reactive transport model for redox processes. Two alternative implementations were made in the TOUGHREACT and TOUGH2-CHEM simulation codes which use sequential iteration and simultaneous solution, respectively. The simulators are applied to reactive consumption of pyrite in (1) saturated flow of oxidizing water, and (2) saturated-unsaturated flow in which oxygen transport occurs in both aqueous and gas phases. Geochemical evolutions predicted from different process models are compared, and issues of numerical accuracy and efficiency are discussed.

  16. Denitrification coupled to pyrite oxidation and changes in groundwater quality in a shallow sandy aquifer

    NASA Astrophysics Data System (ADS)

    Zhang, Yan-Chun; Slomp, Caroline P.; Broers, Hans Peter; Passier, Hilde F.; Cappellen, Philippe Van

    2009-11-01

    This study focuses on denitrification in a sandy aquifer using geochemical analyses of both sediment and groundwater, combined with groundwater age dating ( 3H/ 3He). The study sites are located underneath cultivated fields and an adjacent forested area at Oostrum, The Netherlands. Shallow groundwater in the region has high nitrate concentrations (up to 8 mM) due to intense fertilizer application. Nitrate removal from the groundwater below cultivated fields correlates with sulfate production, and the release of dissolved Fe 2+ and pyrite-associated trace metals (e.g. As, Ni, Co and Zn). These results, and the presence of pyrite in the sediment matrix within the nitrate removal zone, indicate that denitrification coupled to pyrite oxidation is a major process in the aquifer. Significant nitrate loss coupled to sulfate production is further confirmed by comparing historical estimates of regional sulfate and nitrate loadings to age-dated groundwater sulfate and nitrate concentrations, for the period 1950-2000. However, the observed increases in sulfate concentration are about 50% lower than would be expected from complete oxidation of pyrite to sulfate, possibly due to the accumulation of intermediate oxidation state sulfur compounds, such as elemental sulfur. Pollutant concentrations (NO 3, Cl, As, Co and Ni) measured in the groundwater beneath the agricultural areas in 1996 and 2006 show systematic decreases most likely due to declining fertilizer use.

  17. Sulfur species leached from pyrite during oxidative desulfurization of coal in alkaline solutions

    SciTech Connect

    Stephenson, M.D.; Wheelock, T.D.; Markuszewski, R.

    1983-01-01

    The results indicate that thiosulfate, sulfite, and sulfate are the principal soluble sulfur species produced when coal-derived pyrite leached with a hot alkaline solution containing dissolved oxygen. The distribution of soluble sulfur species in the leachate was found to depend on leaching temperature, oxygen partial pressure, leachant composition, and time of contact. At lower temperatures and oxygen partial pressures and with a short time of contact between the leaching solution and pyrite, the leachate sulfur species were dominated by thiosulfate. However, the leachate also contained significant amounts of sulfite and sulfate. When the temperature, oxygen partial pressure, or time of contact were increased, the proportions of thiosulfate and sulfite decreased and the proportion of sulfate increased. It was observed also that reacted pyrite particles catalyzed the oxidation of thiosulfate to sulfite and sulfate. Consequently when pyrite was oxidized in a stirred reactor for 1 h at elevated temperature and oxygen partial pressure, most of the dissolved sulfur appeared as sulfate and very little as thiosulfate or sulfite. 10 references, 4 figures, 1 table.

  18. Kinetics of the transpassive oxidation of pyrite. Technical progress report, July 1, 1992--October 20, 1992

    SciTech Connect

    Hu, Weibai; Huang, Qinping; Zhu, Ximeng; Li, Jun; Bodily, D.M.; Wadsworth, M.E.

    1992-12-31

    In the transpassive region, about 0.4 to 0.8 V (SCE), aggressive oxidation of pyrite occurred. The reaction products in this region were Fe(III) oxide, sulfate ion and partially oxidized sulfur intermediates. The growth kinetics of the reaction of pyrite were studied using chronoamperometry measurement with both stationary and rotating disk electrodes. The effect of electrode rotation speed, solution pH and temperature were examined. Potentiostatic measurements were well correlated by a paralinear rate equation, suggesting the formation of an intermediate passive film, associated with the simultaneous dissolution of the outer layer of the film. Activation energies of 66.17 kJ/mole (15.83 kcal/mole) and 38.67 kJ/mole (9.25 kcal/mole) were obtained for associated parabolic and linear rate constants respectively, at an applied potential of 0.6 V.

  19. Superparamagnetic Fe3O4 particles formed by oxidation of pyrite heated in an anoxic atmosphere

    USGS Publications Warehouse

    Thorpe, A.N.; Senftle, F.E.; Talley, R.; Hetherington, S.; Dulong, F.

    1990-01-01

    As a follow-up to previous gas analysis experiments in which pyrite was heated to 681 K in an anoxic (oxygen starved) atmosphere, the first oxidation product, FeSO4, was studied as a bulk material. No decomposition of FeSO4 to Fe3O4 was observed in the temperature range studied. The lack of decomposition of bulk FeSO4 to Fe3O4 suggests that FeS2 oxidizes directly to Fe3O4, or that FeSO4, FeS2 and O2 react together to form Fe3O4. Magnetic susceptibility and magnetization measurements, along with magnetic hysteresis curves, show that small particles of Fe3O4 form on the pyrite surface, rather than a continuous layer of bulk Fe3O4. A working model describing the oxidation steps is presented. ?? 1990.

  20. Oxidation of coal and coal pyrite mechanisms and influence on surface characteristics

    SciTech Connect

    Doyle, F.M.

    1992-06-30

    during the seventh quarter, electrokinetic, humic acid extraction and film flotation tests were done on oxidized samples of Upper Freeport coal from the Troutville {number sign} 2 Mine, Clearfield County, Pennsylvania. Scanning electron microscopy and energy dispersive X-ray analysis was done to characterize the morphology and composition of the surface of as-received coal, oxidized coal, oxidized coal after extraction of humic acids and humic acid extracted from oxidized coal. In addition, electrochemical studies were done on electrodes prepared from coal pyrite samples.

  1. Framboidal and idiomorphic pyrite in the upper Maastrichtian sedimentary rocks at Gabal Oweina, Nile Valley, Egypt: Formation processes, oxidation products and genetic implications to the origin of framboidal pyrite

    NASA Astrophysics Data System (ADS)

    Soliman, Mamdouh F.; El Goresy, Ahmed

    2012-08-01

    their aggregation (to individual framboids), infilling (in the interstices by additional pyritic material), compaction and homogenization (of all these materials). Furthermore, we encounter for the first time in nature idiomorphic pyrite crystals that integrated numerous framboids, using them as their nucleation and growth sites without erasing or modifying their pristine morphology. Elemental sulfur contains minor concentration of Sb, Ni, Cd and Cu strongly suggesting their presence as submicron sulfide crystallite inclusions. SEM and microprobe investigations revealed that goethite is present as a weathering product in all morphological types of pyrite however; only an iron-sulfate (presumably melanterite) was encountered as oxidation product of the multi-framboids and the euhedral aggregate crystals. The upper Maastrichtian sediments not only contain a menagerie of pyrite morphologies but probably a complete record of the formation process and the geochemical conditions of the growth of framboids, single pyrite crystals, pyrite burrows, pyritized Mn-Fe-oxide framboids and finally their weathered products. The various pyrite forms strongly suggest a multistage process that led to their formation without any evidence for mackinawite, pyrrhotite or greigite, precursors. There is also no evidence in the Oweina sediments for post pyrite formation of mackinawite, pyrrhotite or greigite. The presence of elemental sulfur containing minor concentrations of Sb, Ni, Cd and Cu with pyrite framboids indicates that the pore solutions were geochemically supersaturated in sulfur thus inhibiting the crystallization of any iron sulfide other than pyrite. This cast considerable doubt on the assumed mackinawite or greigite precursors as prerequisite for formation of pyrite framboids.

  2. Dithiophosphinate-pyrite interaction: voltammetry and DRIFT spectroscopy investigations at oxidizing potentials.

    PubMed

    Güler, Taki

    2005-08-15

    The electrochemistry of dithiophosphinate (DTPI) adsorption on pyrite was investigated by cyclic voltammetry (CV) and diffuse reflectance infrared Fourier transformation (DRIFT) spectroscopy at oxidizing potentials under acid, neutral, and alkaline conditions. CV study showed that the mineral surface was covered by porous ferric oxyhydroxide species. Irreversible DTPI adsorption on the pyrite surface and inhibition of electron transfer to some extent were also observed from electrochemical work. Major collector species were determined from DRIFT spectroscopy study as adsorbed collector compound, DTPI degrees , and dimer of dithiophosphinate, (DTPI)2. Maximum adsorption density of DTPI was obtained in acid solution. It decreased sharply under neutral and alkaline conditions due to heavy surface oxidation at higher pH.

  3. Oxidation of coal and coal pyrite mechanisms and influence on surface characteristics. Technical progress report, September 30, 1992

    SciTech Connect

    Doyle, F.M.

    1992-12-31

    The objective of this research is to develop a mechanistic understanding of the oxidation of coal and coal pyrite, and to correlate the intrinsic physical and chemical properties of these minerals, along with changes resulting from oxidation, with those surface properties that influence the behavior in physical cleaning processes. The results will provide fundamental insight into oxidation, in terms of the bulk and surface chemistry, the microstructure, and the semiconductor properties of the pyrite. During the eighth quarter, wet chemical and dry oxidation tests were done on Upper Freeport coal from the Troutville {number_sign}2 Mine, Clearfield County, Pennsylvania. In addition electrochemical experiments were done on electrodes prepared from Upper Freeport coal pyrite and Pittsburgh coal pyrite samples provided by the US Bureau of Mines, Pittsburgh Research Center, Pennsylvania.

  4. Oxidation of coal and coal pyrite mechanisms and influence on surface characteristics. Technical progress report, June 1995--August 1995

    SciTech Connect

    Doyle, F.M.

    1996-03-01

    The objective of this research is to develop a mechanistic understanding of the oxidation of coal and coal pyrite, and to correlate the intrinsic physical and chemical properties of these minerals, along with changes resulting from oxidation, with those surface properties that influence the behavior in physical cleaning processes. The action of coal and pyrite as reducing agents and as waste processing sorptive material for wastes outside the industry are also discussed.

  5. Stable isotope geochemistry of acid mine drainage: Experimental oxidation of pyrite

    USGS Publications Warehouse

    Taylor, B.E.; Wheeler, M.C.; Nordstrom, D.K.

    1984-01-01

    Sulfate and water from experiments in which pyrite was oxidized at a pH of 2.0 were analyzed for sulfur and oxygen stable isotopes. Experiments were conducted under both aerobic and anaerobic sterile conditions, as well as under aerobic conditions in the presence of Thiobacillus ferrooxidans, to elucidate the pathways of oxidation. Oxygen isotope fractionation between SO2-4 and H2O varied from +4.0 %. (anaerobic, sterile) to + 18.0 %. (aerobic, with T. ferrooxidans.). The oxygen isotope composition of dissolved oxygen utilized in both chemical and microbially-mediated oxidation was also determined (+11.4 %., by T. ferrooxidans; +18.4 %., chemical). Contributions of water-derived oxygen and dissolved oxygen to the sulfate produced in the oxidation of pyrite could thus be estimated. Water-derived oxygen constituted from 23 to ~ 100 percent of the oxygen in the sulfate produced in the experiments, and this closely approximates the range of contribution in natural acid mine drainage. Oxidation of sulfides in anaerobic, water-saturated environments occurs primarily by chemical oxidation pathways, whereas oxidation of sulfides in well-aerated, unsaturated zone environments occurs dominantly by microbially mediated pathways. ?? 1984.

  6. Oxidation of coal and coal pyrite mechanisms and influence on surface characteristics. Progress report

    SciTech Connect

    Doyle, F.M.

    1995-02-28

    The objective of this research is to develop a mechanistic understanding of the oxidation of coal and coal pyrite, and to correlate the intrinsic physical and chemical properties of these minerals, along with changes resulting from oxidation, with those surface properties that influence the behavior in physical cleaning processes. Work during the eighteenth quarter has focused on severe oxidation of coal by thermal and chemical treatment, and on investigating the partition of metal ions between such strongly oxidized coal samples and aqueous solutions. This partitioning behavior is being followed to obtain further information on the chemistry of the coal surfaces after different oxidation treatments, for example, whether partition occurs by an ion-exchange mechanism, or whether the surface is capable of changing the oxidation state of metallic species, with concurrent surface or bulk precipitation.

  7. Nitrate reduction coupled with pyrite oxidation in the surface sediments of a sulfide-rich ecosystem

    NASA Astrophysics Data System (ADS)

    Hayakawa, Atsushi; Hatakeyama, Mizuho; Asano, Ryoki; Ishikawa, Yuichi; Hidaka, Shin

    2013-06-01

    studies of denitrification have focused on organic carbon as an electron donor, but reduced sulfur can also support denitrification. Few studies have reported nitrate (NO3-) reduction coupled with pyrite oxidation and its stoichiometry in surface sediments, especially without experimental pyrite addition. In this study, we evaluated NO3- reduction coupled with sulfur oxidation by long-term incubation of surface sediments from a sulfide-rich ecosystem in Akita Prefecture, Japan. The surface sediments were sampled from a mud pool and a riverbed. Fresh sediments and water were incubated under anoxic conditions (and one oxic condition) at 20°C. NO3- addition increased the SO42- concentration and decreased the NO3- concentration. SO42- production (∆SO42-) was strongly and linearly correlated with NO3- consumption (∆NO3-) during the incubation period (R2 = 0.983, P < 0.01, and n = 8), and the slope of the regression (∆NO3-/∆SO42-) and the stoichiometry indicated sulfur-driven NO3- reduction by indigenous autotrophic denitrifying bacteria. Framboidal pyrite and marcasite (both FeS2) were present in the sediments and functioned as the electron donors for autotrophic denitrification. Both ∆NO3- and ∆SO42- were higher in the riverbed sediment than in the mud pool sediment, likely because of the higher amount of easily oxidizable S (pyrite) in the riverbed sediment. Consistently low ammonium (NH4+) concentrations indicated that NO3- reduction by dissimilatory NO3- reduction to NH4+ was small but could not be disregarded. Our results demonstrate that sulfide-rich ecosystems with easily oxidizable metal-bound sulfides such as FeS2 near the ground surface may act as denitrification hot spots.

  8. A silica/fly ash-based technology for controlling pyrite oxidation. Semi-annual technical progress report, September 1, 1995--February 29, 1996

    SciTech Connect

    Evangelou, V.P.

    1996-03-28

    The overall objective is to develop methodologies by which sodium metasilicate or fly ash may produce an effective coating on pyrite surfaces for inhibiting pyrite oxidation. Accomplishments are described for the following tasks: Pyrite surface reactivity; Micro column leaching experiments; and Large column leaching experiments.

  9. A silica/fly ash-based technology for controlling pyrite oxidation. Semi-annual, March 1, 1996 - August 31, 1996

    SciTech Connect

    Evangelou, V.P.

    1996-12-31

    The overall objective is to develop methodologies by which metasilicate or fly ash may produce an effective coating on pyrite surfaces for inhibiting pyrite oxidation. During the past six months, the investigators produced wet chemistry evidence demonstrating that pyrite-HCO{sub 3} complexes promote pyrite oxidation. This is an important finding for their over all strategy in controlling pyrite oxidation because it suggests that pyrite microencapsulation is important in order to control oxidation in near cirumneutral pH environments produced by addition of alkaline material, e.g., fly ash. In their previous studies, the investigators reported that pyrite microencapsulation could be carried out by reacting pyrite with a pH buffered solution and in the presence of metasilicate. The coating formed on the surface of pyrite appeared to be an amorphous iron-oxide-silicate material which inhibited pyrite oxidation. During this past six months, the investigators evaluated: the molecular mechanisms of silicate adsorption by iron oxide; the effects of silicate on the bulk and surface properties of iron oxides; and the effect of silicate on metal-cation adsorption properties by iron oxides.

  10. Aerobic bacterial pyrite oxidation and acid rock drainage during the Great Oxidation Event.

    PubMed

    Konhauser, Kurt O; Lalonde, Stefan V; Planavsky, Noah J; Pecoits, Ernesto; Lyons, Timothy W; Mojzsis, Stephen J; Rouxel, Olivier J; Barley, Mark E; Rosìere, Carlos; Fralick, Phillip W; Kump, Lee R; Bekker, Andrey

    2011-10-20

    The enrichment of redox-sensitive trace metals in ancient marine sedimentary rocks has been used to determine the timing of the oxidation of the Earth's land surface. Chromium (Cr) is among the emerging proxies for tracking the effects of atmospheric oxygenation on continental weathering; this is because its supply to the oceans is dominated by terrestrial processes that can be recorded in the Cr isotope composition of Precambrian iron formations. However, the factors controlling past and present seawater Cr isotope composition are poorly understood. Here we provide an independent and complementary record of marine Cr supply, in the form of Cr concentrations and authigenic enrichment in iron-rich sedimentary rocks. Our data suggest that Cr was largely immobile on land until around 2.48 Gyr ago, but within the 160 Myr that followed--and synchronous with independent evidence for oxygenation associated with the Great Oxidation Event (see, for example, refs 4-6)--marked excursions in Cr content and Cr/Ti ratios indicate that Cr was solubilized at a scale unrivalled in history. As Cr isotope fractionations at that time were muted, Cr must have been mobilized predominantly in reduced, Cr(III), form. We demonstrate that only the oxidation of an abundant and previously stable crustal pyrite reservoir by aerobic-respiring, chemolithoautotrophic bacteria could have generated the degree of acidity required to solubilize Cr(III) from ultramafic source rocks and residual soils. This profound shift in weathering regimes beginning at 2.48 Gyr ago constitutes the earliest known geochemical evidence for acidophilic aerobes and the resulting acid rock drainage, and accounts for independent evidence of an increased supply of dissolved sulphate and sulphide-hosted trace elements to the oceans around that time. Our model adds to amassing evidence that the Archaean-Palaeoproterozoic boundary was marked by a substantial shift in terrestrial geochemistry and biology. PMID:22012395

  11. Aerobic bacterial pyrite oxidation and acid rock drainage during the Great Oxidation Event.

    PubMed

    Konhauser, Kurt O; Lalonde, Stefan V; Planavsky, Noah J; Pecoits, Ernesto; Lyons, Timothy W; Mojzsis, Stephen J; Rouxel, Olivier J; Barley, Mark E; Rosìere, Carlos; Fralick, Phillip W; Kump, Lee R; Bekker, Andrey

    2011-10-19

    The enrichment of redox-sensitive trace metals in ancient marine sedimentary rocks has been used to determine the timing of the oxidation of the Earth's land surface. Chromium (Cr) is among the emerging proxies for tracking the effects of atmospheric oxygenation on continental weathering; this is because its supply to the oceans is dominated by terrestrial processes that can be recorded in the Cr isotope composition of Precambrian iron formations. However, the factors controlling past and present seawater Cr isotope composition are poorly understood. Here we provide an independent and complementary record of marine Cr supply, in the form of Cr concentrations and authigenic enrichment in iron-rich sedimentary rocks. Our data suggest that Cr was largely immobile on land until around 2.48 Gyr ago, but within the 160 Myr that followed--and synchronous with independent evidence for oxygenation associated with the Great Oxidation Event (see, for example, refs 4-6)--marked excursions in Cr content and Cr/Ti ratios indicate that Cr was solubilized at a scale unrivalled in history. As Cr isotope fractionations at that time were muted, Cr must have been mobilized predominantly in reduced, Cr(III), form. We demonstrate that only the oxidation of an abundant and previously stable crustal pyrite reservoir by aerobic-respiring, chemolithoautotrophic bacteria could have generated the degree of acidity required to solubilize Cr(III) from ultramafic source rocks and residual soils. This profound shift in weathering regimes beginning at 2.48 Gyr ago constitutes the earliest known geochemical evidence for acidophilic aerobes and the resulting acid rock drainage, and accounts for independent evidence of an increased supply of dissolved sulphate and sulphide-hosted trace elements to the oceans around that time. Our model adds to amassing evidence that the Archaean-Palaeoproterozoic boundary was marked by a substantial shift in terrestrial geochemistry and biology.

  12. Inhibition of pyrite oxidation by surface coating: a long-term field study.

    PubMed

    Kang, Chan-Ung; Jeon, Byong-Hun; Park, Seong-Sook; Kang, Jin-Soo; Kim, Kang-Ho; Kim, Dong-Kwan; Choi, Ui-Kyu; Kim, Sun-Joon

    2016-10-01

    Pyrite and other iron sulfides are readily oxidized by dissolved oxygen in aqueous phase, producing acidity and Fe(2+), which causes significant environmental problems. Applications of surface coating agents (Na2SiO3 and KH2PO4) were conducted at Boeun (Chungbuk, South Korea) outcrop site, and their efficiencies to inhibit the oxidation of sulfide minerals were monitored for a long-term period (449 days). The rock sample showed positive Net Acid Production Potential (NAPP = 20.23) and low Net Acid Generation pH (NAGpH = 2.42) values, suggesting that the rock sample was categorized in the potential acid-forming group. For the monitored time period (449 days), field study results showed that the application of Na2SiO3 effectively inhibited the pyrite oxidation as compared to KH2PO4. Na2SiO3 as a surface coating agent maintained pH 5-6 and reduced oxidation of pyrite surface up to 99.95 and 97.70 % indicated by Fe(2+) and SO4 (2-) release, respectively. The scanning electron microscope and energy-dispersive X-ray spectrometer analysis indicated that the morphology of rock surface was completely changed attributable to formation of iron silicate coating. The experimental results suggested that the treatment with Na2SiO3 was highly effective and it might be applicable on field for inhibition of iron sulfide oxidation. PMID:26493832

  13. The effect of rehabilitation on the rate of oxidation of pyrite in a mine waste rock dump.

    PubMed

    Harries, J R; Ritchie, A I

    1987-06-01

    Temperature profiles within a mine waste rock dump undergoing pyritic oxidation have been used to estimate the rate of oxidation and the sites where oxidation was occurring. The waste rock dump is located at the abandoned Rum Jungle mine site in Northern Australia and was a major source of pollution to the local river system. The dump was rehabilitated in 1983-84 by reshaping to reduce erosion and covering with clay and soil to reduce infiltration of water.Heat source distributions were derived from temperature profiles measured in the dump. The oxidation of pyritic material is the main cause of heat in the dump, hence the rate and location of oxidation can be obtained from the distribution of heat sources. A comparison of the heat source distributions before and after rehabilitation showed that rehabilitation greatly reduced or stopped the oxidation of pyrite in the dump.

  14. Pyrite oxidation and reduction - Molecular orbital theory considerations. [for geochemical redox processes

    NASA Technical Reports Server (NTRS)

    Luther, George W., III

    1987-01-01

    In this paper, molecular orbital theory is used to explain a heterogeneous reaction mechanism for both pyrite oxidation and reduction. The mechanism demonstrates that the oxidation of FeS2 by Fe(3+) may occur as a result of three important criteria: (1) the presence of a suitable oxidant having a vacant orbital (in case of liquid phase) or site (solid phase) to bind to the FeS2 via sulfur; (2) the initial formation of a persulfido (disulfide) bridge between FeS2 and the oxidant, and (3) an electron transfer from a pi(asterisk) orbital in S2(2-) to a pi or pi(asterisk) orbital of the oxidant.

  15. Pyrite as a sustainable catalyst in electro-Fenton process for improving oxidation of sulfamethazine. Kinetics, mechanism and toxicity assessment.

    PubMed

    Barhoumi, Natija; Oturan, Nihal; Olvera-Vargas, Hugo; Brillas, Enric; Gadri, Abdellatif; Ammar, Salah; Oturan, Mehmet A

    2016-05-01

    The degradation of 0.20 mM sulfamethazine (SMT) solutions was investigated by heterogeneous electro-Fenton (EF) process using pyrite as source of Fe(2+) (catalyst) and pH regulator in an undivided electrochemical cell equipped either with a Pt or a BDD anode and carbon-felt as cathode. Effect of pyrite concentration and applied current on the oxidative degradation kinetics and mineralization efficiency has been studied. The higher oxidation power of the process, named "Pyrite-EF″ using BDD anode was demonstrated. Pyrite-EF showed a better performance for the oxidation/mineralization of the drug SMT in comparison to the classic EF process: 95% and 87% TOC removal by Pyrite-EF with BDD and Pt anodes, respectively, versus 90% and 83% by classical EF with BDD and Pt anodes, respectively. The rate constant of the oxidation of SMT by OH was determined by the competition kinetics method and found to be 1.87 × 10(9) mol(-1) L s(-1). Based on the identified reaction intermediates by HPLC and GS-MS, as well as released SO4(2-), NH4(+) and NO3(-) ions, a plausible reaction pathway was proposed for the mineralization of SMT during Pyrite-EF process. Toxicity assessment by means of Microtox method revealed the formation of some toxic intermediates during the treatment. However, toxicity of the solution was removed at the end of treatment.

  16. Oxidation of coal and coal pyrite mechanisms and influence on surface characteristics. Technical progress report, [September--December 1991

    SciTech Connect

    Doyle, F.M.

    1992-01-28

    The objective of this research is to develop a mechanistic understanding of the oxidation of coal and coal pyrite, and to correlate the intrinsic physical and chemical properties of these minerals, along with changes resulting from oxidation, with those surface properties that influence the behavior in physical coal cleaning processes. The results will provide fundamental insight into oxidation, in terms of the bulk and surface chemistry, the microstructure, and the semiconductor properties of the pyrite. During the fifth quarter, wet chemical and dry oxidation tests were done on Upper Freeport coal from the Troutville {number_sign}2 Mine, Clearfield County, Pennsylvania.

  17. The effect of limestone treatments on the rate of acid generation from pyritic mine gangue.

    PubMed

    Burt, R A; Caruccio, F T

    1986-09-01

    Surface water enters the Haile Gold Mine, Lancaster County, South Carolina by means of a small stream and is ponded behind a dam and in an abandoned pit. This water is affected by acidic drainage. In spite of the large exposures of potentially acid producing pyritic rock, the flux of acid to the water is relatively low. Nevertheless, the resulting pH values of the mine water are low (around 3.5) due to negligible buffering capacity. In view of the observed low release of acidity, the potential for acid drainage abatement by limestone ameliorants appears feasible.This study investigated the effects of limestone treatment on acid generation rates of the Haile mine pyritic rocks through a series of leaching experiments. Below a critical alkalinity threshold value, solutions of dissolved limestone were found consistently to accelerate the rate of pyrite oxidation by varying degrees. The oxidation rates were further accelerated by admixing solid limestone with the pyritic rock. However, after a period of about a month, the pyrite oxidation rate of the admixed samples declined to a level lower than that of untreated pyrite. Leachates produced by the pyrite and limestone mixtures contained little if any iron. Further, in the mixtures, an alteration of the pyrite surface was apparent.The observed behaviour of the treated pyrite appears to be related to the immersion of the pyrite grains within a high alkalinity/high pH environment. The high pH increases the rate of oxidation of ferrous iron which results in a higher concentration of ferric iron at the pyrite surface. This, in turn, increases the rate of pyrite oxidation. Above a threshold alkalinity value, the precipitation of hydrous iron oxides at the pyrite surface eventually outpaces acid generation and coats the pyrite surface, retarding the rate of pyrite oxidation. PMID:24214013

  18. Effect of Phospholipid on Pyrite Oxidation and Microbial Communities under Simulated Acid Mine Drainage (AMD) Conditions.

    PubMed

    Pierre Louis, Andro-Marc; Yu, Hui; Shumlas, Samantha L; Van Aken, Benoit; Schoonen, Martin A A; Strongin, Daniel R

    2015-07-01

    The effect of phospholipid on the biogeochemistry of pyrite oxidation, which leads to acid mine drainage (AMD) chemistry in the environment, was investigated. Metagenomic analyses were carried out to understand how the microbial community structure, which developed during the oxidation of pyrite-containing coal mining overburden/waste rock (OWR), was affected by the presence of adsorbed phospholipid. Using columns packed with OWR (with and without lipid adsorption), the release of sulfate (SO4(2-)) and soluble iron (FeTot) was investigated. Exposure of lipid-free OWR to flowing pH-neutral water resulted in an acidic effluent with a pH range of 2-4.5 over a 3-year period. The average concentration of FeTot and SO4(2-) in the effluent was ≥20 and ≥30 mg/L, respectively. In contrast, in packed-column experiments where OWR was first treated with phospholipid, the effluent pH remained at ∼6.5 and the average concentrations of FeTot and SO4(2-) were ≤2 and l.6 mg/L, respectively. 16S rDNA metagenomic pyrosequencing analysis of the microbial communities associated with OWR samples revealed the development of AMD-like communities dominated by acidophilic sulfide-oxidizing bacteria on untreated OWR samples, but not on refuse pretreated with phospholipid. PMID:26018867

  19. Sulfite exchange dominates oxygen isotope compositions of sulfate produced from abiotic pyrite oxidation

    NASA Astrophysics Data System (ADS)

    Kohl, I. E.; Bao, H.

    2009-12-01

    The oxidation of reduced sulfur compounds (solid, liquid and gas phase) is of primary importance when attempting to understand the global sulfur and oxygen cycles as preserved in sulfate minerals. It has long been known that O2, H2O, and Fe3+ all play an important role during this oxidation process, especially during the oxidation of sulfide minerals. The exact role of each oxidant and/or oxygen source has yet to be experimentally determined for oxidation in aqueous solutions over a range of pH values. In addition, the reported air O2 signal being incorporated in product sulfate appears to be highly variable (9-60%), which could be due to the presence of multiple oxidation pathways or the inability of the traditional δ18O label to differentiate kinetic effects on the degree of oxygen exchange. Here we test the affect of pH dependent sulfite-water oxygen exchange rate and precipitation of ferric hydroxides on the produced sulfate’s O2/H2O ratio. Our experiments utilize a Δ17O isotope label in the solutions, enabling a quantitative determination of oxygen source ratios (O2 vs. H2O) in the produced sulfate. We oxidized crushed pyrite grains aerobically in sterile, buffered solutions at pH=2,7,9,10, and 11. A duplicate set was spiked with Fe3+. The results from the reactors indicate that despite the pH dependency of sulfite-water exchange rate, fast at low pH and slow at high pH, the stability of intermediates, thiosulfate and especially sulfite, in alkaline solutions allows the exchange to proceed to equilibrium. This resulted in sulfate produced above pH=9 to contain 21-24% air O2 signal, indicating the last oxidation step, producing sulfate from sulfite, proceeded with direct incorporation of dissolved air O2 as represented by equation (1). The role of Fe3+ under alkaline conditions was observed to be negligible. SO32- + 1/2O2 → SO42- (1) In the pH=2 reactor, the O2% in the produced sulfate was 21% with the addition of Fe3+, but was 28-29% without the Fe3

  20. Potential climate change effects on water tables and pyrite oxidation in headwater catchments in Colorado

    USGS Publications Warehouse

    Webb, Richard M.; Mast, M. Alisa; Manning, Andrew H.; Clow, David W.; Campbell, Donald H.; Medley, C. Nicholas; Patterson, Glenn; Parker, Melanie J.

    2011-01-01

    A water, energy, and biogeochemical model (WEBMOD) was constructed to simulate hydrology and pyrite oxidation for the period October 1992 through September 1997. The hydrologic model simulates processes in Loch Vale, a 6.6-km² granitic watershed that drains the east side of the Continental Divide. Parameters describing pyrite oxidation were derived sulfate concentrations measured in pore water and stream water in Handcart Gulch, a naturally acidic watershed in the Colorado Mineral Belt. Average monthly differences in precipitation and temperature between current and future climates, as predicted by using six global circulation models and three carbondioxide emission scenarios, were input into WEBMOD to identify possible shifts in the quantity and quality of the water flowing from the watershed for the period 2005 through 2100. Initial results suggest that increased air temperatures will result in earlier snowmelt compared to current conditions. Average sulfate concentrations and acidity in streams draining hydrothermally altered terrain may decrease as water tables rise in response to greater overall precipitation and earlier snowmelt, although a net increase of sulfate load was simulated as a result of greater overall discharge. Evapotranspiration is expected to increase but not enough to offset the increase in precipitation.

  1. Oxygen and sulfur isotope systematics of sulfate produced by bacterial and abiotic oxidation of pyrite

    USGS Publications Warehouse

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

    2007-01-01

    To better understand reaction pathways of pyrite oxidation and biogeochemical controls on ??18O and ??34S values of the generated sulfate in acid mine drainage (AMD) and other natural environments, we conducted a series of pyrite oxidation experiments in the laboratory. Our biological and abiotic experiments were conducted under aerobic conditions by using O2 as an oxidizing agent and under anaerobic conditions by using dissolved Fe(III)aq as an oxidant with varying ??18OH2O values in the presence and absence of Acidithiobacillus ferrooxidans. In addition, aerobic biological experiments were designed as short- and long-term experiments where the final pH was controlled at ???2.7 and 2.2, respectively. Due to the slower kinetics of abiotic sulfide oxidation, the aerobic abiotic experiments were only conducted as long term with a final pH of ???2.7. The ??34SSO4 values from both the biological and abiotic anaerobic experiments indicated a small but significant sulfur isotope fractionation (???-0.7???) in contrast to no significant fractionation observed from any of the aerobic experiments. Relative percentages of the incorporation of water-derived oxygen and dissolved oxygen (O2) to sulfate were estimated, in addition to the oxygen isotope fractionation between sulfate and water, and dissolved oxygen. As expected, during the biological and abiotic anaerobic experiments all of the sulfate oxygen was derived from water. The percentage incorporation of water-derived oxygen into sulfate during the oxidation experiments by O2 varied with longer incubation and lower pH, but not due to the presence or absence of bacteria. These percentages were estimated as 85%, 92% and 87% from the short-term biological, long-term biological and abiotic control experiments, respectively. An oxygen isotope fractionation effect between sulfate and water (??18 OSO4 s(-) H2 O) of ???3.5??? was determined for the anaerobic (biological and abiotic) experiments. This measured ??18 OSO42 - s(-) H2

  2. The interaction of iron pyrite with oxygen, nitrogen and nitrogen oxides: a first-principles study.

    PubMed

    Sacchi, Marco; Galbraith, Martin C E; Jenkins, Stephen J

    2012-03-14

    Sulphide materials, in particular MoS(2), have recently received great attention from the surface science community due to their extraordinary catalytic properties. Interestingly, the chemical activity of iron pyrite (FeS(2)) (the most common sulphide mineral on Earth), and in particular its potential for catalytic applications, has not been investigated so thoroughly. In this study, we use density functional theory (DFT) to investigate the surface interactions of fundamental atmospheric components such as oxygen and nitrogen, and we have explored the adsorption and dissociation of nitrogen monoxide (NO) and nitrogen dioxide (NO(2)) on the FeS(2)(100) surface. Our results show that both those environmentally important NO(x) species chemisorb on the surface Fe sites, while the S sites are basically unreactive for all the molecular species considered in this study and even prevent NO(2) adsorption onto one of the non-equivalent Fe-Fe bridge sites of the (1 × 1)-FeS(2)(100) surface. From the calculated high barrier for NO and NO(2) direct dissociation on this surface, we can deduce that both nitrogen oxides species are adsorbed molecularly on pyrite surfaces.

  3. Near-neutral oxidation of pyrite in coal slurry solids. [Quarterly] technical report, September 1--November 30, 1994

    SciTech Connect

    Frost, J.K.; Dreher, G.B.

    1994-12-31

    In this research project we plan to determine the rate of oxidation of pyrite associated with coaly particles (coal slurry solid) when the pH of the surrounding environment is held at approximately 7.8. Coaly particles that contain pyrite are generated during the preparation of Illinois Basin coal for market. These particles are discharged to an impoundment, which eventually must be reclaimed. The purpose for reclamation is either to prevent the generation of acidic solution as the pyrite in the coal slurry solid reacts with air, or to prevent the migration of the acidic solution to a groundwater aquifer. The reclamation is usually accomplished by covering the impoundment with a four-foot-thick layer of topsoil. One possible alternative method for reclamation of a coal slurry impoundment is to mix in alkaline residue from the fluidized-bed combustion of coal. This codisposal would slow the production of acid and would also neutralize any acid produced. If the codisposal method is found to be environmentally acceptable, it will save the coal mining companies part of their cost of reclamation, and also provide a safe and useful disposal outlet for a portion of the residue that is generated by the fluidized-bed combustion of coal. During this quarter we purchased and set up two automatic titrators, which will be used in determining the rate of pyrite oxidation at nearly neutral pH. The titrators will provide a means for maintaining the pH at the desired level. The rate at which sulfate ion is produced as a result of pyrite oxidation will be used to measure the amount of pyrite oxidized over time.

  4. Cretaceous Cu-Au, pyrite, and Fe-oxide-apatite deposits in the Ningwu basin, Lower Yangtze Area, Eastern China

    NASA Astrophysics Data System (ADS)

    Yu, Jin-Jie; Lu, Bang-Cheng; Wang, Tie-Zhu; Che, Lin-Rui

    2015-05-01

    The Cretaceous Ningwu volcanic basin of the Middle and Lower Yangtze River Valley metallogenic belt of eastern China hosts numerous Fe-oxide-apatite, Cu-Au, and pyrite deposits. The mineralization in the Ningwu basin is associated with subvolcanic rocks, consisting of gabbro-diorite porphyry and/or pyroxene diorite. However, the mineralization is associated with subvolcanic and volcanic rock suite belonging to the Niangniangshan Formation in the Tongjing Cu-Au deposit, including nosean-bearing aegirine-augite syenites, quartz syenites, and quartz monzonites. The zoning displayed by the alteration and mineralization comprises: (1) an upper light-colored zone of argillic, carbonate, and pyrite alteration and silicification that is locally associated with pyrite and gold mineralization, (2) a central dark-colored zone of diopside, fluorapatite-magnetite, phlogopite, and garnet alteration associated with fluorapatite-magnetite mineralization, and (3) a lowermost light-colored zone of extensive albite alteration. The Cu-Au and pyrite orebodies are peripheral to the Fe-oxide-apatite deposits in this area and overlie the iron orebodies, including the Meishan Cu-Au deposit in the northern Ningwu basin and the pyrite deposits in the central Ningwu basin. The δ34S values of sulfides from the Fe-oxide-apatite, Cu-Au, and pyrite deposits in the Ningwu basin show large variation, with a mixed sulfur source, including magmatic sulfur and/or a mixture of sulfur derived from a magmatic component, country rock, and thermochemical reduction of sulfate at 200-300 °C. The ore-forming fluids associated with iron mineralization were derived mainly from magmatic fluids, and the late-stage ore-forming fluids related to Cu-Au and pyrite mineralization may have formed by the introduction of cooler meteoric water to the system. The Fe-oxide-apatite, Cu-Au, and pyrite deposits of the Ningwu basin formed in an extensional environment and are associated with a large-scale magmatic

  5. A proposed origin for fossilized Pennsylvanian plant cuticles by pyrite oxidation (Sydney Coalfield, Nova Scotia, Canada)

    USGS Publications Warehouse

    Zodrow, E.L.; Mastalerz, Maria

    2009-01-01

    Fossilized cuticles, though rare in the roof rocks of coal seam in the younger part of the Pennsylvanian Sydney Coalfield, Nova Scotia, represent nearly all of the major plant groups. Selected for investigation, by methods of Fourier transform infrared spectroscopy (FTIR) and elemental analysis, are fossilized cuticles (FCs) and cuticles extracted from compressions by Schulze's process (CCs) of Alethopteris ambigua. These investigations are supplemented by FTIR analysis of FCs and CCs of Cordaites principalis, and a cuticle-fossilized medullosalean(?) axis. The purpose of this study is threefold: (1) to try to determine biochemical discriminators between FCs and CCs of the same species using semi-quantitative FTIR techniques; (2) to assess the effects chemical treatments have, particularly Schulze's process, on functional groups; and most importantly (3) to study the primary origin of FCs. Results are equivocal in respect to (1); (2) after Schulze's treatment aliphatic moieties tend to be reduced relative to oxygenated groups, and some aliphatic chains may be shortened; and (3) a primary chemical model is proposed. The model is based on a variety of geological observations, including stratal distribution, clay and pyrite mineralogies associated with FCs and compressions, and regional geological structure. The model presupposes compression-cuticle fossilization under anoxic conditions for late authigenic deposition of sub-micron-sized pyrite on the compressions. Rock joints subsequently provided conduits for oxygen-enriched ground-water circulation to initiate in situ pyritic oxidation that produced sulfuric acid for macerating compressions, with resultant loss of vitrinite, but with preservation of cuticles as FCs. The timing of the process remains undetermined, though it is assumed to be late to post-diagenetic. Although FCs represent a pathway of organic matter transformation (pomd) distinct from other plant-fossilization processes, global applicability of the

  6. Evidence of CFC degradation in groundwater under pyrite-oxidizing conditions

    USGS Publications Warehouse

    Sebol, L.A.; Robertson, W.D.; Busenberg, E.; Plummer, L.N.; Ryan, M.C.; Schiff, S.L.

    2007-01-01

    A detailed local-scale monitoring network was used to assess CFC distribution in an unconfined sand aquifer in southwestern Ontario where the zone of 1-5-year-old groundwater was known with certainty because of prior use of a bromide tracer. Groundwater ???5 years old was confined to an aerobic zone at ???5 m depth and had CFC concentrations consistent with modern atmospheric mixing ratios at recharge temperatures of 7-11 ??C, as was observed in the 3-m thick vadose zone at the site. At depths below 6 m, the groundwater became progressively more reducing, however, with a denitrifying horizon at 6-7 m depth, and a Mn and Fe reducing zone below 7 m depth. In the anaerobic zone, 3H/3He ratios indicated that groundwater-age continued to increase uniformly with depth, to a maximum value of 27 years at 13 m depth. CFC concentrations, however, decreased abruptly within the denitrifying zone, leading to substantial age overestimation compared to the 3H/3He ages. Noble gas data indicated that the apparent CFC mass loss was not likely the result of gas stripping from possible bubble formation; thus, CFC degradation was indicated in the anoxic zone. The field data are consistent with first-order degradation rates of 0.3 yr-1 for CFC-12, 0.7 yr-1 for CFC-11, and 1.6 yr-1 for CFC-113. CFC attenuation at this site coincides with a zone where reduced S (pyrite) is actively oxidized by NO3 and dissolved oxygen (DO). Similar behavior has been observed at other sites [Tesoriero, A.J., Liebscher, H., Cox, S.E., 2000. Mechanism and rate of denitrification in an agricultural watershed: electron and mass balance along groundwater flow path. Water Resour. Res. 36 (6), 1545-1559; Hinsby, K., Hojberg, A.L., Engesgaard, P., Jensen, K.H., Larsen, F., Plummer, L.N., Busenberg, E., Accepted for publication. Transport and degradation of chlorofluorocarbons (CFCs) in a pyritic aquifer, Rabis Creek, Denmark. Water Resour. Res.], further demonstrating that the use of CFCs for age-dating anaerobic

  7. Mechanisms of pyrite oxidation to non-slagging species. Quarterly report, July 1, 1996--September 30, 1996

    SciTech Connect

    Akan-Etuk, A.E.J.; Mitchell, R.E.

    1997-03-01

    The information presented constitutes the report for the period July 1 to September 30, 1996. Characterization of intraparticle mass transport limitations during pyrite oxidation was embarked upon. The effort was intended to confirm that intraparticle transport limitations are negligible. Samples of 20 micron pyrite particles extracted from the flow reactor after oxidation at 1550 K in 1% oxygen level were analyzed. The samples has been extracted after reaction times of 42 ms, 52 ms, 77 ms, and 146 ms. For these samples, the bulk product compositions previously determined by X-ray diffraction analysis consisted of varying proportions of FeS{sub 2}, Fe{sub 1-X}S, FeO, and Fe{sub 3}O{sub 4}. The particles were analyzed to determine if the iron compounds previously identified by bulk X- ray diffraction analysis (XRD) were well mixed within individual particles. The extracted pyrite particles, epoxied and sectioned, were subjected to a variety of analytical techniques using the microprobe (JEOL 733 Superprobe). Secondary electron and backscatter electron imaging was performed. Iron, sulfur, and oxygen elemental X-ray maps were generated. Energy dispersive spectrometry was used for qualitative elemental analysis of selected particles. These particles were subsequently subjected to qualitative elemental analysis by wavelength dispersive spectrometry (WDS) using Fe{sub 2}O{sub 3} and FeS{sub 2} as standards. During WDS analysis, micron-radius hemispherical volumes bisected by sectioning plane were sampled. The microprobe analyses of oxidized pyrite showed that, generally, particles could be modeled as well-stirred, having negligible compositional gradients of the scale of the particle radius. In all four samples of pyrite analyzed, there were particle edge effects. Furthermore, there were finger-like projections of different phases in mixed-phase particles. Nevertheless, compositional gradients were of concern only in the 77 ms samples.

  8. Surface electrochemical control for fine coal and pyrite separation

    SciTech Connect

    Hu, Weibai; Huang, Qinping; Li, Jun; Zhu, Ximeng; Bodily, D.M.; Liang, Jun; Zhong, Tingke; Wadsworth, M.E.

    1991-01-01

    The ongoing work includes the characterization of coal pyrites, the floatability evaluation of three typical US coal samples, the flotation behavior of coal pyrites, the electrochemical measurement of the surface properties of coal pyrites, and the characterization of species produced at pyrite surfaces. This report contains three sections, Transpassive Oxidation of Pyrite,'' Flotation and Electrochemical Pretreatment,'' and Flotation Kinetics of Coal and Coal Pyrite.''

  9. Oxidation of coal and coal pyrite mechanisms and influence on surface characteristics. Technical progress report, [March--May 1992

    SciTech Connect

    Doyle, F.M.

    1992-06-30

    during the seventh quarter, electrokinetic, humic acid extraction and film flotation tests were done on oxidized samples of Upper Freeport coal from the Troutville {number_sign} 2 Mine, Clearfield County, Pennsylvania. Scanning electron microscopy and energy dispersive X-ray analysis was done to characterize the morphology and composition of the surface of as-received coal, oxidized coal, oxidized coal after extraction of humic acids and humic acid extracted from oxidized coal. In addition, electrochemical studies were done on electrodes prepared from coal pyrite samples.

  10. Near-neutral oxidation of pyrite in coal slurry solids. Technical report, March 1--May 31, 1995

    SciTech Connect

    Frost, J.K.

    1995-12-31

    In this research project are determining the rate of oxidation of pyrite associated with coaly particles (coal slurry solid) when the pH of the surrounding environment is held at approximately 7.8. Coaly particles that contain pyrite are generated during the preparation of Illinois Basin coal for market. These particles are discharged to an impoundment, which eventually must be reclaimed. The purpose for reclamation is either to prevent the generation of acidic solution as the pyrite in the coal slurry solid reacts with air, or to prevent the migration of the acidic solution to a groundwater aquifer. The reclamation is usually accomplished by covering the impoundment with a four-foot-thick layer of topsoil. One possible alternative method for reclamation of a coal slurry impoundment is to mix in alkaline residue from the fluidized-bed combustion of coal. This codisposal would slow the production of acid and would also neutralize any acid produced. If the codisposal method is found to be environmentally acceptable, it will save the coal mining companies part of their cost of reclamation, and also provide a safe and useful disposal outlet for a portion of the residue that is generated by the fluidized-bed combustion of coal. Pyrite oxidation experiments were conducted during the quarter in the following manner. Air, free of carbon dioxide, is bubbled through water in a covered beaker. The pH is adjusted to 7.8 and the solution is circulated by a peristaltic pump through the coal slurry sample contained in a cellulose thimble in a Soxhlet tube mounted above the beaker. The pH of the solution is continuously statted to 7.8 by addition of NaOH solution. Samples are pipetted from the reaction solution for sulfate determination. The rate of oxidation of pyrite in coal slurry solids sample CSS-2a was calculated from the rate of production of sulfate ion to be 1.71 {times} 10{sup {minus}6} {micro}mole pyrite per minute per {micro}mole of pyrite present.

  11. Mechanisms of pyrite oxidation to non-slagging species. Quarterly report, April 1, 1995--June 30, 1995

    SciTech Connect

    Akan-Etuk, A.E.J.; Mitchell, R.E.

    1995-12-01

    This document is the fourth quarterly status report on a project that is conducted at the High Temperature Gasdynamics Laboratory at Stanford University, Stanford, California and is concerned with enhancing the transformation of iron pyrite to non-slagging species during staged, low-NO{sub x} pulverized coal (P.C.) combustion. The research project is intended to advance PETC`s efforts to improve our technical understanding of the high-temperature chemical and physical processes involved in the utilization of coal. The work focuses on the mechanistic description and rate quantification of the effects of fuel properties and combustion environment on the oxidation of iron pyrite to form the non-slagging species magnetite. The knowledge gained from this work is intended to be incorporated into numerical codes that can be used to formulate anti-slagging strategies involving minimal disturbance of coal combustor performance. This project is to be performed over the three-year period from September 1994 to August 1997. The project aims to identify the mechanisms of pyrite combustion and to quantify their effects, in order to formulate a general rate expression for the combustion of pyrite that accounts for coal properties as well as furnace conditions.

  12. Pyrite problems in the coal mining industry. Information circular/1994

    SciTech Connect

    Miron, Y.

    1993-09-01

    The presence of pyrite (FeS2) in coal can cause or contribute to several problems for the coal mining industry. These problems, which include spontaneous combustion, roof falls, floor heave, and accidental explosions in coal surface mining when ammonium nitrate-fuel oil (ANFO) explosives are used, result from pyrite oxidation. Pyrite oxidizes exothermically in the presence of air and moisture to form a large variety of products, including hydrated ferrous and ferric sulfates, and sulfuric acid. Some of the products are reactive chemicals and strong oxidants. The volume of many of these oxidation products exceeds the original volume of the pyrite; as a result, the adjacent coal disintegrates and its surface increases, rendering it more susceptible to oxidation. The heat from pyrite oxidation raises the temperature of the adjacent coal, accelerating the oxidation and self-heating rates of the coal. Additional hazards are fires or explosions caused by the frictional ignition of methane when the pyrite in the coal is struck by a cutting bit during mining.

  13. Mechanisms of pyrite oxidation to non-slagging species. Quarterly report, January 1, 1995--March 31, 1995

    SciTech Connect

    Akan-Etuk, A.E.J.; Mitchell, R.E.

    1995-08-01

    This document is the third quarterly status report on a project conducted at the High Temperature Gasdynamics Laboratory at Stanford University, Stanford, California and concerned with enhancing the transformation of iron pyrite to non-slagging species during staged, low-NO{sub x} pulverized coal (P.C.) combustion. The research project is intended to advance PETC`s efforts to improve our technical understanding of the high-temperature chemical and physical processes involved in the utilization of coal. The work focuses on the mechanistic description and rate quantification of the effects of fuel properties and combustion environment on the oxidation of iron pyrite to form the non-slagging species magnetite. The knowledge gained from this work is intended to be incorporated into numerical codes that can be used to formulate anti-slagging strategies involving minimal disturbance of coal combustor performance.

  14. Microbial Oxidation of Fe2+ and Pyrite Exposed to Flux of Micromolar H2O2 in Acidic Media

    PubMed Central

    Ma, Yingqun; Lin, Chuxia

    2013-01-01

    At an initial pH of 2, while abiotic oxidation of aqueous Fe2+ was enhanced by a flux of H2O2 at micromolar concentrations, bio-oxidation of aqueous Fe2+ could be impeded due to oxidative stress/damage in Acidithiobacillus ferrooxidans caused by Fenton reaction-derived hydroxyl radical, particularly when the molar ratio of Fe2+ to H2O2 was low. When pyrite cubes were intermittently exposed to fluxes of micromolar H2O2, the reduced Fe2+-Fe3+ conversion rate in the solution (due to reduced microbial activity) weakened the Fe3+-catalyzed oxidation of cubic pyrite and added to relative importance of H2O2-driven oxidation in the corrosion of mineral surfaces for the treatments with high H2O2 doses. This had effects on reducing the build-up of a passivating coating layer on the mineral surfaces. Cell attachment to the mineral surfaces was only observed at the later stage of the experiment after the solutions became less favorable for the growth of planktonic bacteria. PMID:23760258

  15. Comparison of Different Methods for Determination of Pyrite Oxidation Rate in Wate Rock Pile at Mine Doyon, Quebec, Canada

    NASA Astrophysics Data System (ADS)

    Sracek, O.; Nicholson, R.; Gélinas, P.; Lefebvre, R.

    2004-05-01

    Mine Doyon is a gold mine located close to Noranda, Québec, Canada. The South waste rock pile contains mostly highly friable sericite schists with pyrite content up to 7 wt percent. Oxidation of pyrite resulted in the production of acid mine drainage with pH values of about 2.0, and sulfate concentrations in pore water above 200 g/L. The waste rock material is characterized by high permeability allowing thermally driven convective supply of oxygen at temperatures reaching up to 67oC close to the slopes of the pile. Several methods for the determination of pyrite oxidation rate (POR) in waste rock have been compared and evaluated. Methods based on data collected in situ such as the interpretation of oxygen concentration profiles in waste rock pile and pyrite concentrations in solid phase were compared with the oxygen consumption method (OCM) in the laboratory. Analytical 1-D solution based on oxygen and temperature profiles in the pile was used for preliminary determination of POR. Analytical modeling results were used as an input for 2-D numerical model using TOUGH AMD. POR values based on pyrite mass balance (PMB) in solid phase were also calculated, assuming that average pyrite content in the deep, almost non-oxidized zone of the pile represents pre-oxidation conditions. Calculations were performed for prismatic columns with 1 m2 base. An approach based on dissolved sulfate mass balance was not used because of the lack of data from early stage of the pile and the non-conservative behavior of sulfate (precipitation of gypsum and jarosite in the pile). Finally, the oxygen consumption method (OCM) in the laboratory was based on oxygen concentration decline in headspace of closed chamber, where samples of waste rock sprinkled by water were located. Both fresh samples from mining operation and partially weathered samples collected in the pile were used. A range of POR values (mol(O2).kg-1.s-1) were obtained from the various methods. At Site 6 on the slope of the pile

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

  17. Near-neutral oxidation of pyrite in coal slurry solids. Quarterly report, 1 December 1994--28 February 1995

    SciTech Connect

    Frost, J.K.; Dreher, G.B.

    1995-12-31

    In this research project we plan to determine the rate of oxidation of pyrite associated with coaly particles when the pH of the surrounding environment is held at approximately 7.8. Coaly particles that contain pyrite are generated during the preparation of Illinois Basin coal for market. These particles are discharged to an impoundment, which eventually must be reclaimed. The purpose for reclamation is either to prevent the Generation of acidic solution as the pyrite in the coal slurry solid reacts with air, or to prevent the migration of the acidic solution to a groundwater aquifer. The reclamation is usually accomplished by covering the impoundment with a four-foot-thick layer of topsoil. One possible alternative method for reclamation of a coal slurry impoundment is to mix in alkaline residue from the fluidized-bed combustion of coal. This codisposal would slow the production of acid and would also neutralize any acid produced. If the codisposal method is found to be environmentally acceptable, it will save the coal mining companies part of their cost of reclamation, and also provide a safe and useful disposal outlet for a portion of the residue that is Generated by the fluidized-bed combustion of coal.

  18. Effect of Surface Oxidation on Interfacial Water Structure at a Pyrite (100) Surface as Studied by Molecular Dynamics Simulation

    SciTech Connect

    Jin, Jiaqi; Miller, Jan D.; Dang, Liem X.; Wick, Collin D.

    2015-06-01

    In the first part of this paper, a Scanning Electron Microscopy and contact angle study of a pyrite surface (100) is reported describing the relationship between surface oxidation and the hydrophilic surface state. In addition to these experimental results, the following simulated surface states were examined using Molecular Dynamics Simulation (MDS): fresh unoxidized (100) surface; polysulfide at the (100) surface; elemental sulfur at the (100) surface. Crystal structures for the polysulfide and elemental sulfur at the (100) surface were simulated using Density Functional Theory (DFT) quantum chemical calculations. The well known oxidation mechanism which involves formation of a metal deficient layer was also described with DFT. Our MDS results of the behavior of interfacial water at the fresh and oxidized pyrite (100) surfaces without/with the presence of ferric hydroxide include simulated contact angles, number density distribution for water, water dipole orientation, water residence time, and hydrogen-bonding considerations. The significance of the formation of ferric hydroxide islands in accounting for the corresponding hydrophilic surface state is revealed not only from experimental contact angle measurements but also from simulated contact angle measurements using MDS. The hydrophilic surface state developed at oxidized pyrite surfaces has been described by MDS, on which basis the surface state is explained based on interfacial water structure. The Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences (BES), of the DOE funded work performed by Liem X. Dang. Battelle operates the Pacific Northwest National Laboratory for DOE. The calculations were carried out using computer resources provided by BES.

  19. Experimental study of metastable sulfur oxyanion formation during pyrite oxidation at pH 6-9 and 30oC.

    USGS Publications Warehouse

    Goldhaber, M.B.

    1983-01-01

    Metastable sulphur oxyanions accumulate as intermediates in the pathway of pyrite oxidation over the pH range 6-9. The rate of oxidation is chemically controlled and is not limited to adsorption. The oxidation mechanism incorporates initial adsorption of oxygen to the pyrite surface followed by a rate-determining step that is reaction-controlled. The postulated sequence of S reactions is that thiosulphate is a precursor to tetrathionate and that sulphite is the precursor to sulphate. Experimental results indicate that production of metastable S oxyanions during nonbiogenic oxidation of iron disulphide minerals is possible. -M.S.

  20. Radium-226 and low pH in groundwater due to oxidation of authigenic pyrite; Savannah River Site, South Carolina

    SciTech Connect

    KUBILIUS, WALTER

    2005-12-21

    The origin of elevated radium-226 in groundwater beneath a sanitary landfill at the Savannah River Site (SRS) was investigated. Nearly one hundred monitoring wells are developed in the Steed Pond Aquifer (SPA), which consists of 100-150 ft of Coastal Plain sand, iron oxides, and minor clay. Wells screened in the upper and middle portions of the aquifer have average Ra-226 between 0.5 and 2.5 pCi/L, and average pHs above 4.7. However, wells screened near the base of the aquifer exhibit higher average Ra-226 concentrations of 2.5 to 4.6 pCi/L, with some measurements exceeding the MCL of 5 pCi/L, and show average pHs of 4.1 to 4.7. These wells are not downgradient of the landfill, and are not impacted by landfill leachate. The Crouch Branch Confining Unit (CBCU) underlies the aquifer, and is composed partly of reduced gray/brown clay with lignite and authigenic pyrite. Gamma ray logs show that the SPA has low gamma counts, but the CBCU is consistently elevated. Groundwater with high radium/low pH also contains elevated sulfate concentrations. pH calculations indicate that sulfate is in the form of sulfuric acid. A model for the origin of elevated Ra-226 levels in deeper SPA wells envisions infiltration of oxygenated SPA groundwater into reduced pyritic CBCU sediments, with consequent oxidative pyrite dissolution, and acidification of groundwater. Then, naturally occurring CBCU radium dissolves, and mixes into the Steed Pond Aquifer.

  1. Surface oxidation of pyrite under ambient atmospheric and aqueous (pH = 2 to 10) conditions: electronic structure and mineralogy from X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Todd, E. C.; Sherman, D. M.; Purton, J. A.

    2003-03-01

    The nature of the surface oxidation phase on pyrite, FeS 2, reacted in aqueous electrolytes at pH = 2 to 10 and with air under ambient atmospheric conditions was studied using synchrotron-based oxygen K edge, sulfur L III edge, and iron L II,III edge X-ray absorption spectroscopy. We demonstrate that O K edge X-ray absorption spectra provide a sensitive probe of sulfide surface oxidation that is complementary to X-ray photoelectron spectroscopy. Using total electron yield detection, the top 20 to 50 Å of the pyrite surface is characterized. In air, pyrite oxidizes to form predominantly ferric sulfate. In aqueous air-saturated solutions, the surface oxidation products of pyrite vary with pH, with a marked transition occurring around pH 4. Below pH = 4, a ferric (hydroxy)sulfate is the main oxidation product on the pyrite surface. At higher pH, we find iron(III) oxyhydroxide in addition to ferric (hydroxy)sulfate on the surface. Under the most alkaline conditions, the O K edge spectrum closely resembles that of goethite, FeOOH, and the surface is oxidized to the extent that no FeS 2 can be detected in the X-ray absorption spectra. In a 1.667 × 10 -3 mol/L Fe 3+ solution with ferric iron present as FeCl 3 in NaCl, the oxidation of pyrite is autocatalyzed, and formation of the surface iron(III) oxyhydroxide phase is promoted at low pH.

  2. Solid oxide materials research accelerated electrochemical testing

    SciTech Connect

    Windisch, C.; Arey, B.

    1995-08-01

    The objectives of this work were to develop methods for accelerated testing of cathode materials for solid oxide fuel cells under selected operating conditions. The methods would be used to evaluate the performance of LSM cathode material.

  3. Semiconductor electrochemistry of coal pyrite

    SciTech Connect

    Osseo-Asare, K.

    1992-05-01

    This project seeks to advance the fundamental understanding of the physicochemical processes occurring at the pyrite/aqueous interface, in the context of coal cleaning, coal desulfurization, and acid mine drainage. A novel approach to the study of pyrite aqueous electrochemistry is proposed, based on the use of both synthetic and natural (i.e. coal-derived) pyrite specimens, the utilization of pyrite both in the form of micro (i.e. colloidal and subcolloidal) and macro (i.e. rotating ring disk)-electrodes, and the application of in-situ direct electroanalytical and spectroelectrochemical characterization techniques. Central to this research is the recognition that pyrite is a semiconductor material. (Photo)electrochemical experiments will be conducted to unravel the mechanisms of anodic and cathodic processes such as those associated with pyrite decomposition and the reduction of oxidants such as molecular oxygen and the ferric ion.

  4. Complete removal of AHPS synthetic dye from water using new electro-fenton oxidation catalyzed by natural pyrite as heterogeneous catalyst.

    PubMed

    Labiadh, Lazhar; Oturan, Mehmet A; Panizza, Marco; Hamadi, Nawfel Ben; Ammar, Salah

    2015-10-30

    The mineralization of a new azo dye - the (4-amino-3-hydroxy-2-p-tolylazo-naphthalene-1-sulfonic acid) (AHPS) - has been studied by a novel electrochemical advanced oxidation process (EAOP), consisting in electro-Fenton (EF) oxidation, catalyzed by pyrite as the heterogeneous catalyst - the so-called 'pyrite-EF'. This solid pyrite used as heterogeneous catalyst instead of a soluble iron salt, is the catalyst the system needs for production of hydroxyl radicals. Experiments were performed in an undivided cell equipped with a BDD anode and a commercial carbon felt cathode to electrogenerate in situ H2O2 and regenerate ferrous ions as catalyst. The effects on operating parameters, such as applied current, pyrite concentration and initial dye content, were investigated. AHPS decay and mineralization efficiencies were monitored by HPLC analyses and TOC measurements, respectively. Experimental results showed that AHPS was quickly oxidized by hydroxyl radicals (OH) produced simultaneously both on BDD surface by water discharge and in solution bulk from electrochemically assisted Fenton's reaction with a pseudo-first-order reaction. AHPS solutions with 175 mg L(-1) (100 mg L(-1) initial TOC) content were then almost completely mineralized in 8h. Moreover, the results demonstrated that, under the same conditions, AHPS degradation by pyrite electro-Fenton process was more powerful than the conventional electro-Fenton process. PMID:25935408

  5. Accelerated oxidation processes is biodiesel

    SciTech Connect

    Canakci, M.; Monyem, A.; Van Gerpen, J.

    1999-12-01

    Biodiesel is an alternative fuel for diesel engines that can be produced from renewable feedstocks such as vegetable oil and animal fats. These feedstocks are reacted with an alcohol to produce alkyl monoesters that can be used in conventional diesel engines with little or no modification. Biodiesel, especially if produced from highly unsaturated oils, oxidizes more rapidly than diesel fuel. This article reports the results of experiments to track the chemical and physical changes that occur in biodiesel as it oxidizes. These results show the impact of time, oxygen flow rate, temperature, metals, and feedstock type on the rate of oxidation. Blending with diesel fuel and the addition of antioxidants are explored also. The data indicate that without antioxidants, biodiesel will oxidize very quickly at temperatures typical of diesel engines. This oxidation results in increases in peroxide value, acid value, and viscosity. While the peroxide value generally reaches a plateau of about 350 meq/kg ester, the acid value and viscosity increase monotonically as oxidation proceeds.

  6. A Silica/Fly Ash-Based Technology for Controlling Pyrite Oxidation

    SciTech Connect

    V. P. Evangelou

    1997-04-14

    The purpose of our studies during this past six-month period was to evaluate the surface properties of iron-oxide-silicate coatings. The specific objectives were (a) to evaluate the mechanisms and ability of hydrous ferric oxide (HFO) to adsorb silica (Si); (b) to evaluate the effects of Si on the bulk and surface properties of HFO; and (c) to evaluate the effect of Si on heavy-metal adsorption properties by iron-oxides.

  7. Antioxidative system and oxidative stress markers in wild populations of Erica australis L. differentially exposed to pyrite mining activities.

    PubMed

    Márquez-García, Belén; Córdoba, Francisco

    2009-11-01

    Erica australis L. is a widely distributed shrub able to grow in a variety of environments. In the Iberian Pyritic Belt (SW Spain and Portugal), E. australis can be observed growing successfully in very acidic and highly metal-enriched soils. However, no data about the metal tolerance of this plant in wild populations have been reported so far. In this study, we have analysed metal contents in the leaves of E. australis from three wild populations growing in soils affected by metals in different ways (mine wastes, the terrace of a river affected by acid mine drainage and soils not affected by mining activities but enriched in metals due the geology of the area) and, taking into account that metals may generate reactive oxygen species, we also assayed the oxidative damages and the antioxidative defences. All plants contained high levels of Fe and Mn in the leaves, but plants exposed to mining activities also accumulate different levels of As, Ni, Mo, Pb, and Zn depending on the population considered. Our data show that E. australis responds to metal-catalysed production of reactive radicals by oxidising ascorbic acid, which is present at concentrations much higher than described in other plant species, but it is highly oxidised, close to 40%. Ascorbic acid may counteract reactive oxygen species, and no cell damage was produced, as shown by the low levels of H(2)O(2) and lipid peroxidation found compared with other plant species and no damage reflected in pigment levels. PMID:19726038

  8. Surface electrochemical control for fine coal and pyrite separation. Technical progress report, October 1, 1991--December 31, 1991

    SciTech Connect

    Hu, Weibai; Huang, Qinping; Li, Jun; Zhu, Ximeng; Bodily, D.M.; Liang, Jun; Zhong, Tingke; Wadsworth, M.E.

    1991-12-31

    The ongoing work includes the characterization of coal pyrites, the floatability evaluation of three typical US coal samples, the flotation behavior of coal pyrites, the electrochemical measurement of the surface properties of coal pyrites, and the characterization of species produced at pyrite surfaces. This report contains three sections, ``Transpassive Oxidation of Pyrite,`` ``Flotation and Electrochemical Pretreatment,`` and ``Flotation Kinetics of Coal and Coal Pyrite.``

  9. Mechanisms of pyrite oxidation to non-slagging species. Quarterly report, January 1, 1996--March 31, 1996

    SciTech Connect

    Akan-Etuk, A.E.J.; Mitchell, R.E.

    1996-05-01

    This document is the seventh quarterly status report on a project that is conducted at the High Temperature Gasdynamics Laboratory at Stanford University, Stanford, California and is concerned with enhancing the transformation of iron pyrite to non-slagging species during staged, low-NO{sub X} pulverized coal (P. C.) combustion. The project aims to identify the mechanisms of pyrite combustion and to quantify their effects, in order to formulate a general rate expression for the combustion of pyrite that accounts for coal properties as well as furnace conditions. In general, the project has the following objectives: 1) the characterization of the various mechanisms of intraparticle mass transfer and chemical reaction that control overall pyrite combustion rates and 2) the synthesis of the reaction rate resistances of the various mechanisms into a general rate expression for pyrite combustion. The knowledge gained from this project will be incorporated into numerical codes and utilized to formulate slagging abatement strategies involving the minor adjustment of firing conditions. Ultimately, the benefit of this research program is intended to be an increase in the range of coals compatible with staged, low-NO{sub X} combustor retrofits. 9 refs., 12 figs.

  10. NaCl-induced accelerated oxidation of chromium

    SciTech Connect

    Shinata, Y.; Nishi, Y.

    1986-10-01

    This paper describes new phenomena about chloride-induced ;accelerated oxidation of chromium. Thermal analysis was adopted to examine the oxidation, which was studied particularly in the case of NaCl. The presence of NaCl remarkably accelerates the oxidation of chromium. The process occurs below the melting point of NaCl, and the main reaction product is Cr/sub 2/O/sub 3/. In the accelerated oxidation NaCl plays a catalytic role because it is not consumed significantly in the process. DTA analysis reveals that the heat of reaction also accelerates the rate of oxidation, especially at an early stage of the reaction. The accelerated oxidation takes place similarly under the presence of chlorides other than NaCl, but the oxidation rate depends on the kind of salt. Therefore the Cl/sup -/ anion plays an important role in the process, while the nature of the cation affects the rate of acceleration.

  11. Acceleration of Biochar Surface Oxidation during Composting?

    PubMed

    Wiedner, Katja; Fischer, Daniel; Walther, Sabine; Criscuoli, Irene; Favilli, Filippo; Nelle, Oliver; Glaser, Bruno

    2015-04-22

    Biochar composting experiments were performed to determine whether composting is a suitable method to accelerate biochar surface oxidation for increasing its reactivity. To assess the results, surface properties of Terra Preta (Brazil) and ancient charcoal pit (Northern Italy) biochars were additionally investigated. Calculation of O/C ratios by energy-dispersive X-ray spectroscopy demonstrated the anticipated increasing values from fresh biochars (0.13) to composted biochars (0.40), and finally charcoal pit biochars (0.54) and ancient Terra Preta biochars (0.64). By means of Fourier transformation infrared microscopy, formation of carboxylic and phenolic groups on biochars surface could be detected. Carboxylic acids of three composted biochars increased up to 14%, whereas one composted biochar showed a 21% lower proportion of carboxylic acids compared to the corresponding fresh biochar. Phenolic groups increased by 23% for the last mentioned biochar, and on all other biochars phenolic groups decreased up to 22%. Results showed that biochar surface oxidation can be accelerated through composting but still far away from ancient biochars. PMID:25802948

  12. Mechanisms of pyrite oxidation to non-slagging species. Quarterly report, April 1, 1996 - June 30, 1996

    SciTech Connect

    Das, K.; Akan-Etuk, A.E.J.; Mitchell, R.E.

    1996-12-01

    This document is the eighth quarterly status report on a project that is conducted at the High Temperature Gasdynamics Laboratory at Stanford University, Stanford, California and is concerned with enhancing the transformation of iron pyrite to non-slagging species during staged, low-NO{sub x} pulverized coal (P. C.) combustion. In general, the project has the following objectives: (1) the characterization of the various mechanisms of intraparticle mass transfer and chemical reaction that control overall pyrite combustion rates and (2) the synthesis of the reaction rate resistances of the various mechanisms into a general rate expression for pyrite combustion. The knowledge gained from this project will be incorporated into numerical codes and utilized to formulate slagging abatement strategies involving the minor adjustment of firing conditions. Ultimately, the benefit of this research program is intended to be an increase in the range of coals compatible with staged, low-NO{sub X} combustor retrofits.

  13. Annual sulfate budgets for Dutch lowland peat polders: The soil is a major sulfate source through peat and pyrite oxidation

    NASA Astrophysics Data System (ADS)

    Vermaat, Jan E.; Harmsen, Joop; Hellmann, Fritz A.; van der Geest, Harm G.; de Klein, Jeroen J. M.; Kosten, Sarian; Smolders, Alfons J. P.; Verhoeven, Jos T. A.; Mes, Ron G.; Ouboter, Maarten

    2016-02-01

    Annual sulfate mass balances have been constructed for four low-lying peat polders in the Netherlands, to resolve the origin of high sulfate concentrations in surface water, which is considered a water quality problem, as indicated amongst others by the absence of sensitive water plant species. Potential limitation of these plants to areas with low sulfate was analyzed with a spatial match-up of two large databases. The peat polders are generally used for dairy farming or nature conservation, and have considerable areas of shallow surface water (mean 16%, range 6-43%). As a consequence of continuous drainage, the peat in these polders mineralizes causing subsidence rates generally ranging between 2 and 10 mm y-1. Together with pyrite oxidation, this peat mineralization the most important internal source of sulfate, providing an estimated 96 kg SO4 ha-1 mm-1 subsidence y-1. External sources are precipitation and water supplied during summer to compensate for water shortage, but these were found to be minor compared to internal release. The most important output flux is discharge of excess surface water during autumn and winter. If only external fluxes in and out of a polder are evaluated, inputs average 37 ± 9 and exports 169 ± 17 kg S ha-1 y-1. During summer, when evapotranspiration exceeds rainfall, sulfate accumulates in the unsaturated zone, to be flushed away and drained off during the wet autumn and winter. In some polders, upward seepage from early Holocene, brackish sediments can be a source of sulfate. Peat polders export sulfate to the regional water system and the sea during winter drainage. The available sulfate probably only plays a minor role in the oxidation of peat: we estimate that this is less than 10% whereas aerobic mineralization is the most important. Most surface waters in these polders have high sulfate concentrations, which generally decline during the growing season when aquatic sediments are a sink. In the sediment, this sulfur is

  14. The effect of pulse venting on anaerobic oxidation of methane and pyrite formation in the cold seep environment, offshore SW Taiwan

    NASA Astrophysics Data System (ADS)

    Cheng, Wan-Yen; Lin, Saulwood; Tseng, Yi-Ting; Chen, NeiChen; Hsieh, I.-Chih

    2016-04-01

    AOM (Anaerobic oxidation of methane) is a key process in seep environment. Sulfate was consumed during oxidation of methane or organic matter with pyrite as a major end product in the anoxic marine environment. Typical changes observed in the pore water include an increase of methane with depth beneath the SMTZ (sulfate methane transition zone), as a result of diffusion and/or advection, and appearances of a dissolved sulfide maximum underneath a dissolved iron peak with depth. A number of other related biogeochemical processes and end products may register their respective changes in sediments as a result of AOM and related reactions. However, flux, time and duration of gas migration may have changed by either long term processes, e.g., tectonic activities and/or climatic induced sea level changes, or short term, e.g., tidal variations. There is relatively little study addressing termination of gas migrations and subsequent changes in the seep environments. In this study, we will present our study on a seep environment where pulses of gas migration may have occurred with a number of chemical anomalies in sediments. We have collected pore water and sediments for their chemical compositions of sulfate, dissolved sulfide, chloride, organic carbon, carbonate carbon and pyrite as well as echo sounding for flares, and towcam for sea surface topography and benthic community. Our results show that methane gas may have migrated in sediments in carrying out AOM reaction and pyrite formation, however, gas migration may have been relatively short and in pulses. Pulses of gas migration resulted in little or even no sulfate reduction in pore water, but with appearance of dissolved sulfide as well as very high concentrations of pyrite in sediments. Flares were observed but not constantly at the site where chemical anomalies were observed. Pulses of gas migration may come from solid gas hydrate formation and dissociation as evidence from pore water chloride enrichment and

  15. Geochemical characterisation of pyrite oxidation and environmental problems related to release and transport of metals from a coal washing low-grade waste dump, Shahrood, northeast Iran.

    PubMed

    Doulati Ardejani, Faramarz; Jodieri Shokri, Behshad; Moradzadeh, Ali; Shafaei, Seyed Ziadin; Kakaei, Reza

    2011-12-01

    Pyrite oxidation and release of the oxidation products from a low-grade coal waste dump to stream, groundwater and soil was investigated by geochemical and hydrogeochemical techniques at Alborz Sharghi coal washing plant, Shahrood, northeast Iran. Hydrogeochemical analysis of water samples indicates that the metal concentrations in the stream waters were low. Moreover, the pH of the water showed no considerable change. The analysis of the stream water samples shows that except the physical changes, pyrite oxidation process within the coal washing waste dump has not affected the quality of the stream water. Water type was determined to be calcium sulphate. The results of the analysis of groundwater samples indicate that the pH varies from 7.41 to 7.51. The concentrations of the toxic metals were low. The concentration of SO4 is slightly above than its standard concentration in potable water. It seems that the groundwater less affected by the coal washing operation in the study area. Geochemical analysis of the sediment samples shows that Fe concentration decreases gradually downstream the waste dump with pH rising. SO(4) decreases rapidly downstream direction. Copper, Zn and Co concentrations decrease with distance from the waste dump due to a dilution effect by the mixing of uncontaminated sediments. These elements, in particular, Zn are considerably elevated in sediment sample collected at the nearest distance to the waste dump. There is no doubt that such investigations can help to develop an appropriate water remediation plan.

  16. Use of O 2 consumption and CO 2 production in kinetic cells to delineate pyrite oxidation-carbonate buffering and microbial respiration in unsaturated media

    NASA Astrophysics Data System (ADS)

    Lee, Eung Seok; Hendry, M. Jim; Hollings, P.

    2003-09-01

    Identifying zones of sulphide oxidation and carbonate buffering is important in the development of a management plan for mine waste-rock piles. In this study, we used a kinetic cell technique to measure rates of O 2 consumption and CO 2 production in low sulphide (<0.12 wt.% S), low inorganic carbon (<0.20 wt.% C inorganic), gneissic waste rock and associated organic-rich lake sediment (0.7 wt.% C organic), and forest soil (1.4 wt.% C organic) collected from the Key Lake uranium mine in Saskatchewan, Canada. Solid chemistry, stable carbon isotope, pore water sulphate concentration data, and stoichiometric considerations indicated that O 2 consumption and CO 2 production were constrained by microbial respiration in the lake sediment and forest soil and by pyrite oxidation-carbonate buffering in the gneissic waste rock. Mean ratios of molar CO 2 production to O 2 consumption rates were 0.5 for lake sediment, 0.7 for forest soil, and 0.2 for gneissic waste rock. The different O 2/CO 2 ratios suggested that O 2-CO 2 monitoring may provide a practical tool for identifying the zones of microbial respiration and pyrite oxidation-carbonate buffering in mine waste-rock piles. Rates of O 2 consumption and CO 2 production were about one order of magnitude greater in lake sediment than in gneissic waste rock, indicating that microbial respiration would exert a control on the distribution of O 2 and CO 2 gas in waste-rock piles constructed upon the dewatered lake sediments.

  17. Sulfur chemistry in bacterial leaching of pyrite.

    PubMed

    Schippers, A; Jozsa, P; Sand, W

    1996-09-01

    In the case of pyrite bioleaching by Leptospirillum ferrooxidans, an organism without sulfur-oxidizing capacity, besides the production of tetra- and pentathionate, a considerable accumulation of elemental sulfur occurred. A similar result was obtained for chemical oxidation assays with acidic, sterile iron(III) ion-containing solutions. In the case of Thiobacillus ferrooxidans, only slight amounts of elemental sulfur were detectable because of the organism's capacity to oxidize sulfur compounds. In the course of oxidative, chemical pyrite degradation under alkaline conditions, the accumulation of tetrathionate, trithionate, and thiosulfate occurred. The data indicate that thiosulfate, trithionate, tetrathionate, and disulfane-monosulfonic acid are key intermediate sulfur compounds in oxidative pyrite degradation. A novel (cyclic) leaching mechanism is proposed which basically is indirect.

  18. Sulfur Chemistry in Bacterial Leaching of Pyrite

    PubMed Central

    Schippers, A.; Jozsa, P.; Sand, W.

    1996-01-01

    In the case of pyrite bioleaching by Leptospirillum ferrooxidans, an organism without sulfur-oxidizing capacity, besides the production of tetra- and pentathionate, a considerable accumulation of elemental sulfur occurred. A similar result was obtained for chemical oxidation assays with acidic, sterile iron(III) ion-containing solutions. In the case of Thiobacillus ferrooxidans, only slight amounts of elemental sulfur were detectable because of the organism's capacity to oxidize sulfur compounds. In the course of oxidative, chemical pyrite degradation under alkaline conditions, the accumulation of tetrathionate, trithionate, and thiosulfate occurred. The data indicate that thiosulfate, trithionate, tetrathionate, and disulfane-monosulfonic acid are key intermediate sulfur compounds in oxidative pyrite degradation. A novel (cyclic) leaching mechanism is proposed which basically is indirect. PMID:16535406

  19. Pyrite surface characterization and control for advanced fine coal desulfurization technologies

    SciTech Connect

    Wang, Xiang-Huai; Leonard, J.W.; Parekh, B.K.; Raichur, A.M.; Munirathinam, M.

    1991-01-01

    The objective of this project is to conduct extensive studies on the surface reactivity of pyrite by using electrochemical, surface analysis, potentiometric and calorimetric titration, and surface hydrophobicity characterization techniques and to correlate the alteration of the coal-pyrite surface with the efficiency of pyrite rejection in coal flotation. The products as well as their structure, the mechanisms and the kinetics of the oxidation of coal-pyrite surfaces and their interaction with various chemical reagents will be systematically studied and compared with that of mineral-pyrite and synthetic pyrite to determine the correlation between the surface reactivity of pyrite and the bulk chemical properties of pyrite and impurities. Four high quality coal pyrite samples from the Illinois No. 6, Kentucky No. 9, Pittsburgh No. 8 and Upper Freeport coal seams, and several high purity mineral pyrite samples were acquired. Synthetic single pyrite crystals (5 mm in size) and microcrystalline pyrite particles (averaging 6 {mu}m in size) were carefully obtained. Surface hydrophobicities of coal- and ore-pyrites have been studied by contact angle titration and film flotation methods. The oxidation and reduction behavior of coal-pyrites, ore-pyrites and synthetic pyrite single crystals have been studied suing electrochemical methods, including cyclic voltammetry, rotating-disc electrode technique, open-circuit potential measurements and steady-polarization measurements. 7 refs., 14 figs.

  20. Pyrite Stability Under Venus Surface Conditions

    NASA Astrophysics Data System (ADS)

    Kohler, E.; Craig, P.; Port, S.; Chevrier, V.; Johnson, N.

    2015-12-01

    Radar mapping of the surface of Venus shows areas of high reflectivity in the Venusian highlands, increasing to 0.35 ± 0.04 to 0.43 ± 0.05 in the highlands from the planetary average of 0.14 ± 0.03. Iron sulfides, specifically pyrite (FeS2), can explain the observed high reflectivity. However, several studies suggest that pyrite is not stable under Venusian conditions and is destroyed on geologic timescales. To test the stability of pyrite on the Venusian surface, pyrite was heated in the Venus simulation chamber at NASA Goddard Space Flight Center to average Venusian surface conditions, and separately to highland conditions under an atmosphere of pure CO2 and separately under an atmosphere of 96.5% CO2, 3.5% N2 and 150 ppm SO2. After each run, the samples were weighed and analyzed using X-Ray Diffraction (XRD) to identify possible phase changes and determine the stability of pyrite under Venusian surface conditions. Under a pure CO2 atmosphere, the Fe in pyrite oxidizes to form hematite which is more stable at higher temperatures corresponding to the Venusian lowlands. Magnetite is the primary iron oxide that forms at lower temperatures corresponding to the radar-bright highlands. Our experiments also showed that the presence of atmospheric SO2 inhibits the oxidation of pyrite, increasing its stability under Venusian conditions, especially those corresponding to the highlands. This indicates that the relatively high level of SO2 in the Venusian atmosphere is key to the stability of pyrite, making it a possible candidate for the bright radar signal in the Venusian highlands.

  1. Control of pyrite surface chemistry in physical coal cleaning

    SciTech Connect

    Yoon, R.H.; Richardson, P.R.

    1992-06-24

    One of the most difficult separations in minerals processing involves the differential flotation of pyrite and coal. Under practical flotation conditions, they are both hydrophobic and no cost-effective method has been developed to efficiently reject the pyrite. The problem arises from inherent floatability of coal and pyrite. Coal is naturally hydrophobic and remains so under practical flotation. Although pyrite is believed to be naturally hydrophilic under practical flotation conditions it undergoes a relatively rapid incipient oxidation reaction that causes self-induced'' flotation. The oxidation product responsible for self-induced'' flotation is believed to be a metal polysulfide, excess sulfur in the lattice, or in some cases elemental sulfur. It is believed that if incipient oxidation of pyrite could be prevented, good pyrite rejection could be obtained. In order to gain a better understanding of how pyrite oxidizes, a new method of preparing fresh, unoxidized pyrite surfaces and a new method of studying pyrite oxidation have been developed this reporting period.

  2. Control of pyrite surface chemistry in physical coal cleaning

    SciTech Connect

    Yoon, R.H.; Luttrell, G.H.; Zachwieja, J.B.; Mielczarski, J.A.

    1992-03-18

    The separation of pyrite from coal by flotation is based on exploiting the wettability difference between coal and pyrite. There is evidence that the wettability of coal pyrite changes upon superficial oxidation. Therefore, the oxidation of coal pyrite has been studied under carefully controlled electrochemical conditions. In order to identify the species responsible for the changes in wettability, the surface products formed during oxidation have been identified by means of various surface analysis techniques, including X-ray photoelectron spectroscopy (XPS) and ion scattering spectroscopy (ISS). It has been found that pyrite oxidation creates a sulfur-rich surface along with iron oxides/hydroxides. The ratio between these hydrophobic and hydrophilic species correlates well with the results of the wettability measurements.

  3. Pyrite surface characterization and control for advanced fine coal desulfurization technologies

    SciTech Connect

    Wang, Xiang-Huai.

    1991-01-01

    The objective of this project is to conduct extensive studies on the surface reactivity of pyrite by using electrochemical, surface analysis, potentiometric and calorimetric titration, and surface hydrophobicity characterization techniques and to correlate the alteration of the coal-pyrite surface with the efficiency of pyrite rejection in coal flotation. The products as well as their structure, the mechanisms and the kinetics of the oxidation of coal-pyrite surfaces and their interaction with various chemical reagents will be systematically studied and compared with that of mineral-pyrite and synthetic pyrite to determine the correlation between the surface reactivity of pyrite and the bulk chemical properties of pyrite and impurities. The surface chemical studies and the studies of floatability of coal-pyrite and the effect of various parameters such as grinding media and environment, aging under different atmospheres, etc. on thereof, are directed at identifying the causes and possible solutions of the pyrite rejection problems in coal cleaning.

  4. Pyrite surface characterization and control for advanced fine coal desulfurization technologies

    SciTech Connect

    Wang, Xiang-Huai; Leonard, J.W.; Parekh, B.K.; Raichur, A.M.; Jiang, Chengliang.

    1991-01-01

    The objective of this project is to conduct extensive studies on the surface reactivity of pyrite by using electrochemical, surface analysis, potentiometric and calorimetric titration, and surface hydrophobicity characterization techniques and to correlate the alteration of the coal-pyrite surface with the efficiency of pyrite rejection in coal flotation. The products as well as their structure, the mechanisms and the kinetics of the oxidation of coal-pyrite surfaces and their interaction with various chemical reagents will be systematically studied and compared with that of mineral-pyrite and synthetic pyrite to determine the correlation between the surface reactivity of pyrite and the bulk chemical properties of pyrite and impurities. The surface chemical studies and the studies of floatability of coal-pyrite and the effect of various parameters such as grinding media and environment, aging under different atmospheres, etc. on thereof will lead to identifying the causes and possible solutions of the pyrite rejection problems in coal cleaning.

  5. Pyrite surface characterization and control for advanced fine coal desulfurization technologies

    SciTech Connect

    Wang, Xiang-Huai.

    1991-01-01

    The objective of this project is to conduct extensive studies on the surfaces reactivity of pyrite by using electrochemical, surface analysis, potentiometric and calorimetric titration, and surface hydrophobicity characterization techniques and to correlate the alteration of the coal-pyrite surface with the efficiency of the pyrite rejection in coal flotation. The product as well as their structure, the mechanism and the kinetics of the oxidation of coal-pyrite surfaces and their interaction with various chemical reagents will be systematically studied and compared with that of mineral-pyrite and synthetic pyrite to determine the correlation between the surface reactivity of pyrite and the bulk chemical properties of pyrite and impurities. The surface chemical studies and the studies of floatability of coal-pyrite and the effect of various parameters such as grinding media and environment, aging under different atmospheres, etc., are directed at identifying the cause and possible solutions of the pyrite rejection problems in coal cleaning.

  6. Pyrite-uranium polycrystal

    USGS Publications Warehouse

    King, A.G.

    1956-01-01

    A texture was observed in a sample of ore in 'Which pyrite and uraninite occurred as thin alternate layers paralleling crystal faces of a pyrite nucleus. This texture could be formed either by replacement or by syntaxis. Although syntactic growth forming polyerystals of two chemically dissimilar minerals has not been previously described, this explanation fits the observed data better than the explanation offered by replacement. It is proposed, therefore, that this occurrence is an example of a polycrystal of uraninite and pyrite and that the mechanism of formation is syntaxis.

  7. Control of pyrite surface chemistry in physical coal cleaning

    SciTech Connect

    Luttrell, G.H.; Yoon, R.H.; Zachwieja, J.; Lagno, M.

    1990-01-17

    To better understand the flotation behavior of coal pyrite, studies have been initiated to characterize the floatability of coal pyrite and mineral pyrite. The hydrophobicity of coal material pyrite was examined over a range of pH and oxidation times. The results indicate that surface oxidation plays an important role in coal and mineral pyrite hydrophobicity. The hydrophobicity of mineral pyrite decreases with increasing oxidation time (20 min. to 5 hr.) and increasing pH (pH 4.6 to 9.2), with maximum depression occurring at pH 9.2. However, coal pyrite exhibited low floatability, even at the lowest oxidation time, over the entire pH range. X-ray photoelectron spectroscopy (XPS) results suggest the growth of an oxidized iron layer as being responsible for the deterioration in floatability, while a sulfur-containing species present on the sample surfaces may promote floatability. Preliminary studies of the effect of frother indicate an enhancement in the floatability of both coal and mineral pyrite over the entire pH range.

  8. Control of pyrite surface chemistry in physical coal cleaning

    SciTech Connect

    Luttrell, G.H.; Yoon, R.H.; Zachwieja, J.B.; Lagno, M.L.

    1992-06-24

    Correlation of the hydrophobicity measurements of coal and mineral pyrite with changes in the surface composition of the samples as determined by x-ray photoelectron spectroscopy (XPS) reveals that similar surface oxidation products are found on both mineral and coal pyrite samples. The surface oxidation layer of these samples is comprised of different amounts of hydrophilic species (iron hydroxy-oxides and/or iron oxides) and hydrophobic species (polysulfide or elemental sulfur). The resulting hydrophobicity of these samples may be attributed to the ratio of hydrophilic (surface oxides) to hydrophobic (sulfur-containing) species in the surface oxidation layer. Also, coal pyrite samples were found to exhibit a greater degree of superficial oxidation and a less hydrophobic character as compared to the mineral pyrite samples.

  9. SEM and AFM images of pyrite surfaces after bioleaching by the indigenous Thiobacillus thiooxidans.

    PubMed

    Liu, H-L; Chen, B-Y; Lan, Y-W; Cheng, Y-C

    2003-09-01

    The bioleaching mechanism of pyrite by the indigenous Thiobacillus thiooxidans was examined with the aid of scanning electron microscopy (SEM) and atomic force microscopy (AFM) images of the pyrite surface. The presence of pyrite eliminated the lag phase during growth of this microorganism. This was due to the stimulatory effect on cell growth of the slight amount of Cu2+ that had leached from the pyrite. Zn2+ was found to be much more readily solubilized than Cu2+. The efficiency of bioleaching was four times higher than that of chemical leaching. SEM images provided evidence of direct cell attachment onto the pyrite surface, thereby enhancing the bioleaching rate. Furthermore, extracellular polymeric substances (EPSs) were found on the pyrite surface after 4 days of oxidation. AFM images showed that the pyrite surface area positively correlated with the oxidation rate. A combination of direct and indirect mechanism is probably responsible for the oxidation of pyrite by T. thiooxidans.

  10. Metal-accelerated oxidation in plant cell death

    SciTech Connect

    Czuba, M. )

    1993-05-01

    Cadmium and mercury toxicity is further enhanced by external oxidizing conditions O[sub 3] or inherent plant processes. Lepidium sativum L, Lycopersicon esculentum Mill., or Phaseolus vulgaris L, were grown inpeat-lite to maturity under continuous cadmium exposure followed by one oxidant (O[sub 3]-6 hr. 30 pphm) exposure, with or without foliar calcium pretreatments. In comparison, Daucus carota, L and other species grown in a 71-V suspension, with or without 2,4-D were exposed continuously to low levels of methylmercury during exponential growth and analyzed in aggregates of distinct populations. Proteins were extracted and analyzed. Mechanisms of toxicity and eventual cell death are Ca-mediated and involve chloroplast, stomatal-water relations and changes in oxidant-anti-oxidant components in cells. Whether the metal-accelerated oxidative damage proceeds to cell death, depends on the species and its differential biotransformation system and cell association component.

  11. A study of the interfacial chemistry of pyrite and coal in fine coal cleaning using flotation

    SciTech Connect

    Jiang, C.

    1993-12-31

    Surface oxidation, surface charge, and flotation properties have been systematically studied for coal, coal-pyrite and ore-pyrite. Electrochemical studies show that coal-pyrite exhibits much higher and more complex surface oxidation than ore-pyrite and its oxidation rate depends strongly on the carbon/coal content. Flotation studies indicate that pyrites have no self-induced floatability. Fuel oil significantly improves the floatability of coal and induces considerable flotation for coal-pyrite due to the hydrophobic interaction of fuel oil with the carbon/coal inclusions on the pyrite surface. Xanthate is a good collector for ore-pyrite but a poor collector for coal and coal-pyrite. The results from thermodynamic calculations, flotation and zeta potential measurements show that iron ions greatly affect the flotation of pyrite with xanthate and fuel oil. Various organic and inorganic chemicals have been examined for depressing coal-pyrite. It was found, for the first time, that sodium pyrophosphate is an effective depressant for coal-pyrite. Solution chemistry shows that pyrophosphate reacts with iron ions to form stable iron pyrophosphate complexes. Using pyrophosphate, the complete separation of pyrite from coal can be realized over a wide pH range at relatively low dosage.

  12. The Historical Use Of Mine-Drainage And Pyrite-Oxidation Waters In Central And Eastern England, United Kingdom

    NASA Astrophysics Data System (ADS)

    Banks, David; Younger, Paul L.; Dumpleton, Steve

    1996-04-01

    Waters draining from abandoned coal or metals mines are often regarded as an environmental threat. Historical examples from the lead and coal mining industries of central and northeastern England illustrate that mine waters can also be regarded as an important resource in terms of 1) baseflow for effluent dilution; 2) drinking or industrial waters; 3) flocculating agents for sewage or water treatment; 4) spa waters; 5) sources of industrial minerals, including alkali metals and barium; and 6) a source of iron oxides or sulphates for tanning or pigmentation purposes. An appreciation of the potential economic value of mine waters and their contents is essential for the design of cost-effective treatment options.

  13. Electrochemistry of Thiobacillus ferrooxidans reactions with pyrite

    SciTech Connect

    Pesic, B.; Oliver, D.J.; Kim, Inbeum; De, G.C.

    1993-01-20

    A cyclic voltammetry technique was used to study the interactions of pyrite during bioleaching with the bacterium Thiobacillus ferrooxidans. Potential effects of heavy metals (silver and mercury) and varying the pH on the iron oxidizing ability of the bacterium are reported. Redox potential techniques were used to study effect of ferrous sulfate concentration and pH on bacterial growth.

  14. Effect of lattice defects on the electronic structures and floatability of pyrites

    NASA Astrophysics Data System (ADS)

    Xian, Yong-jun; Wen, Shu-ming; Chen, Xiu-ming; Deng, Jiu-shuai; Liu, Jian

    2012-12-01

    The electronic structures of three types of lattice defects in pyrites (i.e., As-substituted, Co-substituted, and intercrystalline Au pyrites) were calculated using the density functional theory (DFT). In addition, their band structures, density of states, and difference charge density were studied. The effect of the three types of lattice defects on the pyrite floatability was explored. The calculated results showed that the band-gaps of pyrites with Co-substitution and intercrystalline Au decreased significantly, which favors the oxidation of xanthate to dixanthogen and the adsorption of dixanthogen during pyrite flotation. The stability of the pyrites increased in the following order: As-substituted < perfect < Co-substituted < intercrystalline Au. Therefore, As-substituted pyrite is easier to be depressed by intensive oxidization compared to perfect pyrite in a strongly alkaline medium. However, Co-substituted and intercrystalline Au pyrites are more difficult to be depressed compared to perfect pyrite. The analysis of the Mulliken bond population and the electron density difference indicates that the covalence characteristic of the S-Fe bond is larger compared to the S-S bond in perfect pyrite. In addition, the presence of the three types of lattice defects in the pyrite bulk results in an increase in the covalence level of the S-Fe bond and a decrease in the covalence level of the S-S bond, which affect the natural floatability of the pyrites.

  15. Pyrite surface characterization and control for advanced fine coal desulfurization technologies. First annual report, September 1, 1990--August 30, 1991

    SciTech Connect

    Wang, Xiang-Huai

    1991-12-31

    The objective of this project is to conduct extensive studies on the surface reactivity of pyrite by using electrochemical, surface analysis, potentiometric and calorimetric titration, and surface hydrophobicity characterization techniques and to correlate the alteration of the coal-pyrite surface with the efficiency of pyrite rejection in coal flotation. The products as well as their structure, the mechanisms and the kinetics of the oxidation of coal-pyrite surfaces and their interaction with various chemical reagents will be systematically studied and compared with that of mineral-pyrite and synthetic pyrite to determine the correlation between the surface reactivity of pyrite and the bulk chemical properties of pyrite and impurities. The surface chemical studies and the studies of floatability of coal-pyrite and the effect of various parameters such as grinding media and environment, aging under different atmospheres, etc. on thereof, are directed at identifying the causes and possible solutions of the pyrite rejection problems in coal cleaning.

  16. Pyrite footprinting of RNA

    SciTech Connect

    Schlatterer, Joerg C.; Wieder, Matthew S.; Jones, Christopher D.; Pollack, Lois; Brenowitz, Michael

    2012-08-24

    Highlights: Black-Right-Pointing-Pointer RNA structure is mapped by pyrite mediated {sup {center_dot}}OH footprinting. Black-Right-Pointing-Pointer Repetitive experiments can be done in a powdered pyrite filled cartridge. Black-Right-Pointing-Pointer High {sup {center_dot}}OH reactivity of nucleotides imply dynamic role in Diels-Alderase catalysis. -- Abstract: In RNA, function follows form. Mapping the surface of RNA molecules with chemical and enzymatic probes has revealed invaluable information about structure and folding. Hydroxyl radicals ({sup {center_dot}}OH) map the surface of nucleic acids by cutting the backbone where it is accessible to solvent. Recent studies showed that a microfluidic chip containing pyrite (FeS{sub 2}) can produce sufficient {sup {center_dot}}OH to footprint DNA. The 49-nt Diels-Alder RNA enzyme catalyzes the C-C bond formation between a diene and a dienophile. A crystal structure, molecular dynamics simulation and atomic mutagenesis studies suggest that nucleotides of an asymmetric bulge participate in the dynamic architecture of the ribozyme's active center. Of note is that residue U42 directly interacts with the product in the crystallized RNA/product complex. Here, we use powdered pyrite held in a commercially available cartridge to footprint the Diels-Alderase ribozyme with single nucleotide resolution. Residues C39 to U42 are more reactive to {sup {center_dot}}OH than predicted by the solvent accessibility calculated from the crystal structure suggesting that this loop is dynamic in solution. The loop's flexibility may contribute to substrate recruitment and product release. Our implementation of pyrite-mediated {sup {center_dot}}OH footprinting is a readily accessible approach to gleaning information about the architecture of small RNA molecules.

  17. Authigenic pyrite formation and re-oxidation as an indicator of an unsteady-state redox sedimentary environment: Evidence from the intertidal mangrove sediments of Hainan Island, China

    NASA Astrophysics Data System (ADS)

    Ding, Hai; Yao, Suping; Chen, Jun

    2014-04-01

    Two cores of intertidal mangrove sediments from the Tanmen and Qinglan Harbors on Hainan Island, China, were investigated for their geochemical characteristics of carbon, nitrogen, iron and sulfur and the pyrite morphology and framboidal pyrite size distribution. A modified sequential iron extraction procedure revealed extremely high FeHR/FeT ratios (0.81±0.07, n=28). The pyrite results determined by the nitric acid digestion and chromium reduction method show a strong correlation (r=0.91, n=28), indicating that most of the chromium-reducible sulfur is pyrite, whereas the proportion of elemental sulfur is minor. The organic carbon concentrations and the atomic C/N ratios demonstrate that the organic carbon in the mangrove sediments is derived predominantly from higher plants. The chromium-reducible sulfur (CRS) values show a good linear logarithmic correlation with the total organic carbon (TOC), indicating that the process of sulfate reduction increases rapidly with the concentration of TOC at Qinglan Harbor (QL), which has low TOC contents (<5 wt%). In contrast, sulfate reduction increases slowly with high TOC (>5 wt%) at Tanmen Harbor (TM). These data suggest that pyrite formation at the QL site is controlled by the TOC contents, whereas at the TM site, the primary factor controlling the pyritization process is the supply rate of sulfate. Both sites have significantly high sulfate contents (average 1.67±0.45 wt% and 0.80±0.32 wt% at Tanmen and Qinglan, respectively), which are isotopically depleted in 34S (average -6.15±7.17‰ and -6.72±7.33‰ at Tanmen and Qinglan, respectively) suggesting that the sulfate is mainly from the reoxidation of reduced sulfides (mainly pyrite) instead of seawater sulfate during burial. The distributions of pyrite textures suggest that the pyrite in the mangrove swamps is formed mainly as framboids and only a few pyrite crystals are formed directly as euhedral crystals. The high mean diameters and standard deviations (7.0±4

  18. An improved pyrite pretreatment protocol for kinetic and isotopic studies

    NASA Astrophysics Data System (ADS)

    Mirzoyan, Natella; Kamyshny, Alexey; Halevy, Itay

    2014-05-01

    An improved pyrite pretreatment protocol for kinetic and isotopic studies Natella Mirzoyan1, Alexey Kamyshny Jr.2, Itay Halevy1 1Earth and Planetary Sciences, Weizmann Institute of Science, Rehovot 76100, Israel 2Geological and Environmental Sciences, Ben-Gurion University of the Negev, Beer Sheva 84105, Israel Pyrite is one of the most abundant and widespread of the sulfide minerals with a central role in biogeochemical cycles of iron and sulfur. Due to its diverse roles in the natural and anthropogenic sulfur cycle, pyrite has been extensively studied in various experimental investigations of the kinetics of its dissolution and oxidation, the isotopic fractionations associated with these reactions, and the microbiological processes involved. Pretreatment of pyrite for removal of oxidation impurities to prevent experimental artifacts and inaccuracies is often practiced. While numerous pyrite-cleaning methods have been used in experiments, a common pyrite pretreatment method, often used to investigate pyrite chemistry by the isotopic fractionations associated with it, includes several rinses by HCl, acetone and deionized water. Elemental sulfur (S0) is a common product of incomplete pyrite oxidation. Removal of S0 is desirable to avoid experimental biases associated with its participation in pyrite transformations, but is more complicated than the removal of sulfate. Although rinsing with an organic solvent is in part aimed at removing S0, to the best of our knowledge, the extraction efficiency of S0 in existing protocols has not been assessed. We have developed and tested a new protocol for elemental sulfur removal from the surface of pyrite by ultrasonication with warm acetone. Our data demonstrate the presence of large fractions of S0 on untreated pyrite particle surfaces, of which only approximately 60% was removed by the commonly used pretreatment method. The new protocol described here was found to be more efficient at S0 removal than the commonly used method

  19. [Dependence of the genotypic characteristics of Acidithiobacillus ferrooxidans on the physical, chemical, and electrophysical properties of pyrites].

    PubMed

    Tupikina, O V; Kondrat'eva, T F; Samorukova, V D; Rassulov, V A; Karavaĭko, G I

    2005-01-01

    Comparison of Acidithiobacillus ferrooxidans strains TFV-1 and TFBk with respect to their capacity to oxidize pyrite 1, with hole-type (p-type) conductivity, or pyrite 2, with an electron-type (n-type) conductivity, showed that, at a pulp density of 1%, both before and after its adaptation to the pyrites, strain TFBk, isolated from a substrate with a more complex mineral composition, grew faster and oxidized the pyrites of both conductivity types more efficiently than strain TFV-1, which was isolated from a mineralogically simple ore. At a pulp density of 3-5%, the oxidation of pyrite 1 by strain TFV-1 and both of the pyrites by strain TFBk began only after an artificial increase in Eh to 600 mV. If the pulp density was increased gradually, strain TFBk could oxidize the pyrites at its higher values than strain TFV-1, with the rate of pyrite 2 oxidation being higher than that of pyrite 1. During chemical oxidation of both of the pyrites, an increase was observed in the absolute values of the coefficients of thermoelectromotive force (KTEMF); during bacterial-chemical oxidation, the KTEMF of pyrite 1 changed insignificantly, whereas the KTEMF of pyrite 2 decreased. PMID:16315977

  20. [Dependence of the genotypic characteristics of Acidithiobacillus ferrooxidans on the physical, chemical, and electrophysical properties of pyrites].

    PubMed

    Tupikina, O V; Kondrat'eva, T F; Samorukova, V D; Rassulov, V A; Karavaĭko, G I

    2005-01-01

    Comparison of Acidithiobacillus ferrooxidans strains TFV-1 and TFBk with respect to their capacity to oxidize pyrite 1, with hole-type (p-type) conductivity, or pyrite 2, with an electron-type (n-type) conductivity, showed that, at a pulp density of 1%, both before and after its adaptation to the pyrites, strain TFBk, isolated from a substrate with a more complex mineral composition, grew faster and oxidized the pyrites of both conductivity types more efficiently than strain TFV-1, which was isolated from a mineralogically simple ore. At a pulp density of 3-5%, the oxidation of pyrite 1 by strain TFV-1 and both of the pyrites by strain TFBk began only after an artificial increase in Eh to 600 mV. If the pulp density was increased gradually, strain TFBk could oxidize the pyrites at its higher values than strain TFV-1, with the rate of pyrite 2 oxidation being higher than that of pyrite 1. During chemical oxidation of both of the pyrites, an increase was observed in the absolute values of the coefficients of thermoelectromotive force (KTEMF); during bacterial-chemical oxidation, the KTEMF of pyrite 1 changed insignificantly, whereas the KTEMF of pyrite 2 decreased.

  1. Control of pyrite surface chemistry in physical coal cleaning

    SciTech Connect

    Yoon, R.H.; Richardson, P.R.

    1992-01-01

    Over the past 10 years, much research has provided convincing evidence that one major difficulty in using froth flotation to separate pyrite from coal is the self-induced'' flotation of pyrite. Numerous studies have attempted to identify reactions that occur under moderate oxidizing conditions, which lead to self-induced flotation, and to identify the oxidization products. During the past two report periods, it was established that: (1) freshly fractured pyrite surfaces immediately assume, at fracture, an electrode potential several hundred millivolts more negative than the usual steady state mixed potentials. Within minutes after fracture, the electrodes oxidize and reach higher steady state potentials. It was also shown, by photocurrent measurements, that a negative surface charge (upward band bending) already exists on freshly fractured pyrite, and (2) particle bed electrodes can be used to control the oxidation of pyrite and to precisely determine the electrochemical conditions where flotation occurs, or is depressed. By circulating the solution phase to an ultraviolet spectrometer, soluble products produced on pyrite by oxidation and reduction can be determined, e.g., HS[sup [minus

  2. Interplay of voltage and temperature acceleration of oxide breakdown for ultra-thin gate oxides

    NASA Astrophysics Data System (ADS)

    Wu, E.; Suñé, J.; Lai, W.; Nowak, E.; McKenna, J.; Vayshenker, A.; Harmon, D.

    2002-11-01

    In this work, we resolved several seemingly conflicting experimental observations regarding temperature dependence of oxide breakdown in the context of change of voltage acceleration factors with reducing voltages. It is found that voltage acceleration factor is temperature dependent at a fixed voltage while voltage acceleration factors are temperature independent at a fixed TBD. We unequivocally demonstrated that strong temperature dependence of time(charge)-to-breakdown, TBD( QBD), observed on ultra-thin gate oxides (<5 nm) is not a thickness effect as previously suggested. It is a consequence of two experimental facts: (1) voltage-dependent voltage acceleration and (2) temperature-independent voltage acceleration at a fixed TBD window. For the first time, time-to-breakdown at low temperature of -50 °C is reported. It is found that Weibull slopes are insensitive to temperature variations using accurate area-scaling method. The stress-induced leakage current (SILC) was used as a measure of defect-generation rate and critical defect density to investigate its correlation with the directly measured breakdown data, QBD( TBD). The comprehensive and statistical measurements of SILC at breakdown as a function of temperature are presented in detail for the first time. Based on these results, we conclude that SILC-based measurements cannot adequately explain the temperature dependence of oxide breakdown. Finally, we provide a global picture for time-to-breakdown in voltage and temperature domains constructed from two important empirical relations based on comprehensive experimental database.

  3. Semiconductor electrochemistry coal pyrite. Quarterly technical progress report, October--December 1994

    SciTech Connect

    Osseo-Asare, K.; Wei, D.

    1995-01-01

    Pyrite dissolution in acidic solution was found to involve both electrochemical oxidation and chemical decomposition. The mechanism of chemical decomposition of pyrite in acidic solution may involve surface complexation of hydrogen ions. The anodic current of pyrite was relatively small in non-aqueous solution (acetonitrile) compared with that in aqueous solution. The implication is that the direct reaction of holes with S{sub 2}{sup 2{minus}} in the pyrite lattice was not significant and that the dissolution of pyrite required the presence of water. The anodic dissolution product was elemental sulfur which was detected by X-ray diffraction.

  4. Control of pyrite surface chemistry in physical coal cleaning

    SciTech Connect

    Luttrell, G.H.; Yoon, R.H.; Zachwieja, J.; Lagno, M.

    1992-06-24

    To better understand the surface chemical properties of coal and mineral pyrite, studies on the effect of flotation surfactants (frother and kerosene) on the degree of hydrophobicity have been conducted. The presence of either frother or kerosene enhanced the flotability of coal and mineral pyrite with a corresponding decrease in induction time over the pH range examined. Scanning electron microscopy (SEM) results indicate a correlation exists between the sample surface morphology and crystal structure and the observed hydrophobicity. As a result of the data obtained from the surface characterization studies, controlled surface oxidation was investigated as a possible pyrite rejection scheme in microbubble column flotation.

  5. Pyrite surface characterization and control for advanced fine coal desulfurization technologies

    SciTech Connect

    Wang, X.H.; Leonard, J.W.; Parekh, B.K.; Jiang, C.L.

    1992-01-01

    This is the 9th quarterly technical progress report for the project entitled Pyrite surface characterization and control for advanced fine coal desulfurization technologies'', DE-FG22-90PC90295. The work presented in this report was performed from September 1, 1992 to November 31, 1992. The objective of the project is to conduct extensive fundamental studies on the surface chemistry of pyrite oxidation and flotation and to understand how the alteration of the coal-pyrite surface affects the efficiency of pyrite rejection in coal flotation. During this reporting period, the surface oxidation of pyrite in various electrolytes was investigated. It has been demonstrated, for the first time, that borate, a pH buffer and electrolyte used by many previous investigators in studying sulfide mineral oxidation, actively participates in the surface oxidation of pyrite. In borate solutions, the surface oxidation of pyrite is tronly enhanced. The anodic oxidation potential of pyrite is lowered by more than 0.4 volts. The initial reaction of the borate enhanced pyrite oxidation can be described by:FeS[sub 2] + B(OH)[sub 4][sup =] ------> [S[sub 2]Fe-B(OH)[sub 4

  6. Pyrite Passivation by Triethylenetetramine: An Electrochemical Study

    PubMed Central

    Liu, Yun; Dang, Zhi; Xu, Yin; Xu, Tianyuan

    2013-01-01

    The potential of triethylenetetramine (TETA) to inhibit the oxidation of pyrite in H2SO4 solution had been investigated by using the open-circuit potential (OCP), cyclic voltammetry (CV), potentiodynamic polarization, and electrochemical impedance (EIS), respectively. Experimental results indicate that TETA is an efficient coating agent in preventing the oxidation of pyrite and that the inhibition efficiency is more pronounced with the increase of TETA. The data from potentiodynamic polarization show that the inhibition efficiency (η%) increases from 42.08% to 80.98% with the concentration of TETA increasing from 1% to 5%. These results are consistent with the measurement of EIS (43.09% to 82.55%). The information obtained from potentiodynamic polarization also displays that the TETA is a kind of mixed type inhibitor. PMID:23431501

  7. Pyrite microencapsulation: Potential for abatement of acid mine drainage

    SciTech Connect

    Seta, A.K.; Evangelou, V.P.

    1996-12-31

    Oxidation of pyrite in mining waste or overburden is the main source of acid mine drainage (AMD) production which causes major environmental pollution. Presently, the most common method of controlling AMD problems is through the mixing alkaline substances, such as limestone, with the AMD producing materials. However, the effectiveness of this method is still questionable. The main reason for this is that the surface of pyrite particles in mining waste are still exposed to the atmospheric O{sub 2} after treatment. Experimental evidence on novel pyrite microencapsulation technologies currently under development in our laboratory are presented. It was demonstrated that these technologies, which include ferric hydroxide-phosphate-coatings and ferric-hydroxide-silica coatings, could effectively protect pyrite from oxidation.

  8. Pyrite surface characterization and control for advanced fine coal desulfurization technologies

    SciTech Connect

    Wang, X.H.; Leonard, J.W.; Parekh, B.K.; Raichur, A.M.; Jiang, C.L.

    1992-01-01

    The objective of the project is to conduct extensive fundamental studies on the surface reactivity and surface hydrophobicity of coal-pyrites using various surface characterization techniques and to understand how the alteration of the coal-pyrite surface affects the efficiency of pyrite rejection in coal flotation. During this reporting period, the influence of the impurity content, particularly coal/carbon content, on the electrochemical oxidation of pyrite surfaces was investigated. The studies demonstrate that the coal/carbon content in coal-pyrite has a determining effect on the surface reactivity of pyrite. The oxidation behavior of high carbon-content coal-pyrite is completely different from that of purer coal-pyrite and ore-pyrite. The effects of flotation gases on the flotation behavior of coal and the surface hydrophobicity of various coal-pyrite were investigated. It was found from the lab-scale column flotation studies that among the various gases studied (air, oxygen, argon, nitrogen and carbon dioxide), carbon dioxide produced the best results with a combustible recovery of 90% and ash-content of less than 9 percent. Finally, the surface energetic studies revealed that the surfaces of pyrites and coals produced by wet grinding is more heterogenous than that prepared by dry grinding.

  9. Bacterial communities involved in soil formation and plant establishment triggered by pyrite bioweathering on arctic moraines.

    PubMed

    Mapelli, Francesca; Marasco, Ramona; Rizzi, Agostino; Baldi, Franco; Ventura, Stefano; Daffonchio, Daniele; Borin, Sara

    2011-02-01

    In arctic glacier moraines, bioweathering primed by microbial iron oxidizers creates fertility gradients that accelerate soil development and plant establishment. With the aim of investigating the change of bacterial diversity in a pyrite-weathered gradient, we analyzed the composition of the bacterial communities involved in the process by sequencing 16S rRNA gene libraries from different biological soil crusts (BSC). Bacterial communities in three BSC of different morphology, located within 1 m distance downstream a pyritic conglomerate rock, were significantly diverse. The glacier moraine surrounding the weathered site showed wide phylogenetic diversity and high evenness with 15 represented bacterial classes, dominated by Alphaproteobacteria and pioneer Cyanobacteria colonizers. The bioweathered area showed the lowest diversity indexes and only nine bacterial families, largely dominated by Acidobacteriaceae and Acetobacteraceae typical of acidic environments, in accordance with the low pH of the BSC. In the weathered BSC, iron-oxidizing bacteria were cultivated, with counts decreasing along with the increase of distance from the rock, and nutrient release from the rock was revealed by environmental scanning electron microscopy-energy dispersive X-ray analyses. The vegetated area showed the presence of Actinomycetales, Verrucomicrobiales, Gemmatimonadales, Burkholderiales, and Rhizobiales, denoting a bacterial community typical of developed soils and indicating that the lithoid substrate of the bare moraine was here subjected to an accelerated colonization, driven by iron-oxidizing activity.

  10. Bacterial communities involved in soil formation and plant establishment triggered by pyrite bioweathering on arctic moraines.

    PubMed

    Mapelli, Francesca; Marasco, Ramona; Rizzi, Agostino; Baldi, Franco; Ventura, Stefano; Daffonchio, Daniele; Borin, Sara

    2011-02-01

    In arctic glacier moraines, bioweathering primed by microbial iron oxidizers creates fertility gradients that accelerate soil development and plant establishment. With the aim of investigating the change of bacterial diversity in a pyrite-weathered gradient, we analyzed the composition of the bacterial communities involved in the process by sequencing 16S rRNA gene libraries from different biological soil crusts (BSC). Bacterial communities in three BSC of different morphology, located within 1 m distance downstream a pyritic conglomerate rock, were significantly diverse. The glacier moraine surrounding the weathered site showed wide phylogenetic diversity and high evenness with 15 represented bacterial classes, dominated by Alphaproteobacteria and pioneer Cyanobacteria colonizers. The bioweathered area showed the lowest diversity indexes and only nine bacterial families, largely dominated by Acidobacteriaceae and Acetobacteraceae typical of acidic environments, in accordance with the low pH of the BSC. In the weathered BSC, iron-oxidizing bacteria were cultivated, with counts decreasing along with the increase of distance from the rock, and nutrient release from the rock was revealed by environmental scanning electron microscopy-energy dispersive X-ray analyses. The vegetated area showed the presence of Actinomycetales, Verrucomicrobiales, Gemmatimonadales, Burkholderiales, and Rhizobiales, denoting a bacterial community typical of developed soils and indicating that the lithoid substrate of the bare moraine was here subjected to an accelerated colonization, driven by iron-oxidizing activity. PMID:20953598

  11. Method of synthesizing pyrite nanocrystals

    SciTech Connect

    Wadia, Cyrus; Wu, Yue

    2013-04-23

    A method of synthesizing pyrite nanocrystals is disclosed which in one embodiment includes forming a solution of iron (III) diethyl dithiophosphate and tetra-alkyl-ammonium halide in water. The solution is heated under pressure. Pyrite nanocrystal particles are then recovered from the solution.

  12. Surface electrochemical control for fine coal and pyrite separation. Final report

    SciTech Connect

    Wadsworth, M.E.; Bodily, D.M.; Hu, Weibai; Chen, Wanxiong; Huang, Qinping; Liang, Jun; Riley, A.M.; Li, Jun; Wann, Jyi-Perng; Zhong, Tingke; Zhu, Ximeng

    1993-01-20

    Laboratory flotation tests were carried out on three coals and on coal pyrite. Floatability measurements included natural floatability, flotation with a xanthate collector and salt flotation. The ranking of the floatability of the three coals were: Upper Freeport > Pittsburgh > Illinois. The floatability of mineral pyrite and coal pyrite increased markedly with xanthate concentration, but decreased with increased pH. In general, coal pyrite was more difficult to float than mineral pyrite. This was attributed to the presence of surface carbonaceous and mineral matter, since floatability of coal pyrite improved by acid pretreatment. Flotation tests demonstrated that the floatability of coal and mineral pyrite was greatly enhanced by the presence of an electrolyte. Flotation was also enhanced by the addition of modifiers such as CuSO{sub 4}, Na{sub 2}S, CO{sub 2} and EDTA. Lime additions markedly reduced the floatability of coal pyrite. Enhanced floatability of coal pyrite resulted when the pyrite was anodically oxidized in a specially constructed electrochemical flotation cell Pretreatment in potential ranges previously observed for polysulfide and sulfur film formation resulted in the enhanced floatability. While interesting trends and influences, both chemical and electrochemical, markedly improved the floatability of coal, there is little hope for reverse flotation as an effective technology for coal/coal-pyrite separations. The effects of poor liberation and entrainment appear overriding.

  13. Control of pyrite surface chemistry in physical coal cleaning

    SciTech Connect

    Luttrell, G.H.; Yoon, R.H.; Zachwieja, J.B.

    1992-06-24

    The removal of pyrite from coal by flotation or any other surface chemistry based separation process is often hampered by the apparent hydrophobicity of the mineral. Results obtained in this project suggest that corrosion processes are responsible for the apparent hydrophobicity of pyrite in aqueous environments. Characterization of the corrosion products of pyrite in acidic and alkaline solution has been performed using electrochemical (cyclic voltammetry and single-potential-step chronoamperometry) and spectroscopic techniques (X-ray photoelectron spectroscopy -- XPS). The nature of the surface products have been correlated with hydrophobicity determined from in-situ contact angle measurements. The results show that pyrite hydrophobicity is influenced by either the oxidation or reduction conditions of the system.

  14. Pyrite surface characterization and control for advanced fine coal desulfurization technologies. Fourth quarterly technical progress report, June 1, 1991--August 31, 1991

    SciTech Connect

    Wang, Xiang-Huai

    1991-12-31

    The objective of this project is to conduct extensive studies on the surfaces reactivity of pyrite by using electrochemical, surface analysis, potentiometric and calorimetric titration, and surface hydrophobicity characterization techniques and to correlate the alteration of the coal-pyrite surface with the efficiency of the pyrite rejection in coal flotation. The product as well as their structure, the mechanism and the kinetics of the oxidation of coal-pyrite surfaces and their interaction with various chemical reagents will be systematically studied and compared with that of mineral-pyrite and synthetic pyrite to determine the correlation between the surface reactivity of pyrite and the bulk chemical properties of pyrite and impurities. The surface chemical studies and the studies of floatability of coal-pyrite and the effect of various parameters such as grinding media and environment, aging under different atmospheres, etc., are directed at identifying the cause and possible solutions of the pyrite rejection problems in coal cleaning.

  15. Pyrite surface characterization and control for advanced fine coal desulfurization technologies. Third quarterly technical progress report, March 1, 1991--May 30, 1991

    SciTech Connect

    Wang, Xiang-Huai; Leonard, J.W.; Parekh, B.K.; Raichur, A.M.; Jiang, Chengliang

    1991-12-31

    The objective of this project is to conduct extensive studies on the surface reactivity of pyrite by using electrochemical, surface analysis, potentiometric and calorimetric titration, and surface hydrophobicity characterization techniques and to correlate the alteration of the coal-pyrite surface with the efficiency of pyrite rejection in coal flotation. The products as well as their structure, the mechanisms and the kinetics of the oxidation of coal-pyrite surfaces and their interaction with various chemical reagents will be systematically studied and compared with that of mineral-pyrite and synthetic pyrite to determine the correlation between the surface reactivity of pyrite and the bulk chemical properties of pyrite and impurities. The surface chemical studies and the studies of floatability of coal-pyrite and the effect of various parameters such as grinding media and environment, aging under different atmospheres, etc. on thereof will lead to identifying the causes and possible solutions of the pyrite rejection problems in coal cleaning.

  16. Can accelerated aqueous aging simulate in vivo oxidation of gamma-sterilized UHMWPE?

    PubMed

    Mazzucco, Daniel C; Dumbleton, John; Kurtz, Steven M

    2006-10-01

    Oxidation of ultrahigh molecular weight polyethylene (UHMWPE) gamma-sterilized arthroplasty components occurs in vivo. Though accelerated in vitro protocols have been developed to test the relative oxidation resistance of various types of UHMWPE, it is desirable to develop an accelerated aging protocol that more closely approximates the in vivo environment. The goal of this study was to investigate the effects of temperature, solute, and oxygen partial pressure in aqueous media on the oxidation of gamma-sterilized UHMWPE, as the basis for the development of improved accelerated aging protocols. The accelerated oxidation behavior of gamma-sterilized GUR 1150 was studied at 60 and 70 degrees C in an open vessel filled with distilled water or PBS in equilibrium with a controlled partial pressure of oxygen. The extent of oxidation was assessed using standardized mechanical and chemical evaluation techniques (small punch and Fourier transform infrared spectroscopy). Accelerated oxidation of UHMWPE was achieved in aqueous environments; however, both clinically relevant and nonrelevant oxidation species (e.g., aldehydes) were observed for long aging times at 60 degrees C, and for all aging times at 70 degrees C. These findings point the way to the development of an accelerated aging protocol. The current data, considered in conjunction with real-time aging studies, suggest that a temperature between body temperature and 60 degrees C may accelerate oxidative degradation without altering the oxidative patterns encountered in vivo.

  17. The rate of pyrite decomposition on the surface of Venus

    NASA Technical Reports Server (NTRS)

    Fegley, B., Jr.; Lodders, K.; Treiman, A. H.; Klingelhoefer, G.

    1995-01-01

    We report the results of a detailed experiment study of the kinetics and mechanism of pyrite (FeS2) chemical weathering under Venus surface conditions. Pyrite is thermodynamically unstable on the surface of Venus and will spontaneously decompose to pyrrhotite (Fe7S8) because the observed S2 partial pressure in the lower atmosphere of Venus is lower than the S2 vapor pressure over coexisting pyrite and pyrrhotite. Pyrite decomposition kinetics were studied in pure CO2 and CO2 gas mixtures along five isotherms in the temperature range 390-531 C. In all gas mixtures studied, pyrite thermally decomposes to pyrrhotite (Fe7S8), which on continued heating loses sulfur to form more Fe-rich pyrrhotites. During this process the pyrrhotites are also being oxidized to form magnetite (Fe3O4), which converts to maghemite (gamma-Fe2O3), and then to hematite (alpha-Fe2O3). The reaction rates for pyrite thermal decomposition to pyrrhotite were determined by measuring the weight loss. The thickness of the unreacted pyrite in the samples provided a second independent reaction rate measurement. Finally, Mossbauer spectra done on 42 of the 115 experimental samples provided a third set of independent reaction rate data. Pyrite decomposition follows zero-order kinetics and is independent of the amount of pyrite present. The rate of pyrite decomposition is apparently independent of the gas compositions used and of the CO2 number density over a range of a factor of 40. The derived activation energy of approximately 150 kJ/mole is the same in pure CO2, two different CO-CO2 mixtures, and a ternary CO-SO2-CO2 mixture. Based on data for a CO-CO2-SO2 gas mixture with a CO number density approximately 10 times higher than at the surface of Venus and a SO2 number density approximately equal to that at the surface of Venus, the rate of pyrite destruction on the surface of Venus varies from about 1225 +/- 238 days/cm at the top of Maxwell Montes (approximately 660 K) to about 233 +/- 133 days/cm in

  18. Pyrite surface characterization and control for advanced fine coal desulfurization technologies. Tenth quarterly technical progress report, January 1, 1993--March 31, 1993

    SciTech Connect

    Wang, X.H.; Leonard, J.W.; Parekh, B.K.; Jiang, C.L.

    1993-08-01

    The objective of the project is to conduct extensive fundamental studies on the surface chemistry of pyrite oxidation and flotation and to understand how the alteration of the coal-pyrite surface affects the efficiency of pyrite rejection in coal flotation. This report summarizes the studies in the following three aspects: (1) the effects of borate, used as pH buffer or electrolyte, on the pyrite surface oxidation and flotation; (2) the quantification of pyrite surface oxidation kinetics under different oxidation potentials; and (3) finding new coal-pyrite depressants. It has been demonstrated, for the first time, that borate, a pH buffer and electrolyte used by many previous investigators in studying pyrite oxidation, actively participates in the surface oxidation of pyrite. In high borate concentration solutions, the surface oxidation of pyrite is strongly enhanced. The anodic oxidation potential of pyrite is lowered by more than 0.4 volts. At low borate concentration, borate is chemisorbed on pyrite surfaces. In the intermediate concentration range, borate dissolves surface iron compounds. Consequently, the flotation of pyrite in borate solutions (using fuel oil as collector) displays depression-flotation-depression phenomena as the borate concentration is increased. The oxidation kinetics of pyrite surfaces has been determined by AC impedance spectroscopy. At low oxidation potentials, only capacitive behavior is observed. However, at high oxidation potentials, an inductive loop appears. The charge transfer resistance decreases with increasing potential, indicating that the oxidation rate increases with increasing potential. A chemical reagent has been found to be very effective in depressing the flotation of coal-pyrites from different sources, while it has little effects on the flotation of coal. The surface chemistry involved in the selective pyrite depression by this new reagent has been investigated by electrochemical studies and contact angle measurements.

  19. Comparison of dissolution under oxic acid drainage conditions for eight sedimentary and hydrothermal pyrite samples

    NASA Astrophysics Data System (ADS)

    Liu, Ran; Wolfe, Amy L.; Dzombak, David A.; Stewart, Brian W.; Capo, Rosemary C.

    2008-11-01

    The abiotic oxidative dissolution behaviors of eight natural pyrite samples, five sedimentary and three hydrothermal, from various geological environments were compared under oxic conditions at pH 3 and 6 in a highly controlled batch reactor dissolution system. The three sedimentary pyrite samples associated with coal had greater specific surface areas and also exhibited greater apparent dissolution rates and extent than the other two sedimentary and three hydrothermal samples under both pH conditions. However, after normalizing for surface area, the dissolution rate constants for the different pyrite samples were similar; the greatest difference was between the two non-coal sedimentary pyrite samples. Pyrite morphology and the presence of trace metals could contribute to the differences in dissolution behavior as reflected in the normalized dissolution rates. The sulfur:iron ratio observed in the aqueous solution at pH 3 increased with time, but was always less than 2.0 (predicted from the stoichiometry of dissolution) for all the pyrite samples during the 24-h experimental duration. This can be explained by the disproportionation dissociation of thiosulfate, an initial product of pyrite dissolution, to elemental sulfur and sulfate which does not occur in a 1:1 ratio. The results of this work indicate the importance of extracting and using the specific pyrite(s) relevant to particular mining areas in order to understand pyrite dissolution rates and the influence of environmental conditions on those rates.

  20. Control of pyrite surface chemistry in physical coal cleaning. Final report

    SciTech Connect

    Luttrell, G.H.; Yoon, R.H.; Richardson, P.E.

    1993-05-19

    In Part I, Surface Chemistry of Coal Pyrite the mechanisms responsible for the inefficient rejection of coal pyrite were investigated using a number of experimental techniques. The test results demonstrate that the hydrophobicity of coal pyrite is related to the surface products formed during oxidation in aqueous solutions. During oxidation, a sulfur-rich surface layer is produced in near neutral pH solutions. This surface layer is composed mainly of sulfur species in the form of an iron-polysulfide along with a smaller amount of iron oxide/hydroxides. The floatability coal pyrite increases dramatically in the presence of frothers and hydrocarbon collectors. These reagents are believed to absorb on the weakly hydrophobic pyrite surfaces as a result of hydrophobic interaction forces. In Part III, Developing the Best Possible Rejection Schemes, a number of pyrite depressants were evaluated in column and conventional flotation tests. These included manganese (Mn) metal, chelating agents quinone and diethylenetriamine (DETA), and several commercially-available organic depressants. Of these, the additives which serve as reducing agents were found to be most effective. Reducing agents were used to prevent pyrite oxidation and/or remove oxidation products present on previously oxidized surfaces. These data show that Mn is a significantly stronger depressant for pyrite than quinone or DETA. Important factors in determining the pyrite depression effect of Mn include the slurry solid content during conditioning, the addition of acid (HCl), and the amount of Mn. The acid helps remove the oxide layer from the surface of Mn and promotes the depression of pyrite by Mn.

  1. Semiconductor electrochemistry of coal pyrite. Technical progress report, October--December 1993

    SciTech Connect

    Osseo-Asare, K.; Wei, D.

    1994-03-01

    The effects of the semiconductor properties of pyrite on its electrochemical behavior have been explored with the aid of energy level diagram which illustrate the relationship between the energy levels of the solid land the equilibrium potentials of the redox couples in the aqueous solution. A novel approach to the study of pyrite electrochemistry was initiated. This approach is based on pyrite microelectrodes synthesized via aqueous phase precipitation. Preliminary results show that photocurrents can be generated by illumination of the pyrite particles synthesized in our laboratory. Central to this research is the recognition that pyrite is a semiconductor material. (Photo) electrochemical experiments are conducted to unravel the mechanisms of anodic and cathodic processes such as those associated with pyrite decomposition and the reduction of oxidants such as molecular oxygen and the ferric ion.

  2. Semiconductor electrochemistry of coal pyrite. Technical progress report, January--March 1992

    SciTech Connect

    Osseo-Asare, K.

    1992-05-01

    This project seeks to advance the fundamental understanding of the physicochemical processes occurring at the pyrite/aqueous interface, in the context of coal cleaning, coal desulfurization, and acid mine drainage. A novel approach to the study of pyrite aqueous electrochemistry is proposed, based on the use of both synthetic and natural (i.e. coal-derived) pyrite specimens, the utilization of pyrite both in the form of micro (i.e. colloidal and subcolloidal) and macro (i.e. rotating ring disk)-electrodes, and the application of in-situ direct electroanalytical and spectroelectrochemical characterization techniques. Central to this research is the recognition that pyrite is a semiconductor material. (Photo)electrochemical experiments will be conducted to unravel the mechanisms of anodic and cathodic processes such as those associated with pyrite decomposition and the reduction of oxidants such as molecular oxygen and the ferric ion.

  3. Lipid extraction and esterification for microalgae-based biodiesel production using pyrite (FeS2).

    PubMed

    Seo, Yeong Hwan; Sung, Mina; Oh, You-Kwan; Han, Jong-In

    2015-09-01

    In this study, pyrite (FeS2) was used for lipid extraction as well as esterification processes for microalgae-based biodiesel production. An iron-mediated oxidation reaction, Fenton-like reaction, produced an expected degree of lipid extraction, but pyrite was less effective than FeCl3 commercial powder. That low efficiency was improved by using oxidized pyrite, which showed an equivalent lipid extraction efficiency to FeCl3, about 90%, when 20 mM of catalyst was used. Oxidized pyrite was also employed in the esterification step, and converted free fatty acids to fatty acid methyl esters under acidic conditions; thus, the fatal problem of saponification during esterification with alkaline catalysts was avoided, and esterification efficiency over 90% was obtained. This study clearly showed that pyrite could be utilized as a cheap catalyst in the lipid extraction and esterification steps for microalgae-based biodiesel production.

  4. Thin film preparation of semiconducting iron pyrite

    NASA Astrophysics Data System (ADS)

    Smestad, Greg P.; Ennaoui, Ahmed; Fiechter, Sebastian; Hofmann, Wolfgang; Tributsch, Helmut; Kautek, Wolfgang

    1990-08-01

    Pyrite (Fe52) has been investigated as a promising new absorber material for thin film solar cell applications because of its high optical absorption coefficient of 1OL cm1, and its bandgap of 0.9 to 1.0 eV. Thin layers have been prepared by Metal Organic Chemical Vapor Deposition, MOCVD, Chemical Spray Pyrolysis, CSP, Chemical Vapor Transport, CVT, and Sulfurization of Iron Oxide films, 510. It is postulated that for the material FeS2, if x is not zero, a high point defect concentration results from replacing 2 dipoles by single S atoms. This causes the observed photovoltages and solar conversion efficiencies to be lower than expected. Using the Fe-O-S ternary phase diagram and the related activity plots, a thermodynamic understanding is formulated for the resulting composition of each of these types of films. It is found that by operating in the oxide portion of the phase diagram, the resulting oxidation state favors pyrite formation over FeS. By proper orientation of the grains relative to the film surface, and by control of pinholes and stoichiometry, an efficient thin film photovolatic solar cell material could be achieved.

  5. NOTE: Why Pyrite Is Unstable on the Surface of Venus

    NASA Astrophysics Data System (ADS)

    Fegley, Bruce

    1997-08-01

    The observed sulfur vapor abundance near Venus' surface is lower than the amount needed for pyrite to be stable. This conclusion is reached using either the observed S3abundance or the S2abundance calculated from the observations of S3. Furthermore, the atmosphere is too oxidizing for pyrite to be stable. Pyrite is unstable at Venus' modal radius of 6051.4 km (1992. P. G. Ford and G. H. Pettengill,J. Geophys. Res.97,13,103-13,114) whereT= 740 K andP= 95.6 bar (1986. A. Seiff, J. T. Schofield, A. J. Kliore, F. W. Taylor, S. S. Limaye, H. E. Revercomb, L. A. Sromovsky, V. I. Kerzhanovich, V. I. Moroz, and M. Ya. Marov, InThe Venus International Reference Atmosphere(A. J. Kliore, V. I. Moroz, and G. M. Keating, Eds.), pp. 3-58. Pergamon Press, Oxford). Pyrite is also unstable at 6056 km (T= 705 K,P= 71.2 bar), which is at 4.6 km altitude in the low radar emissivity region (Pettengillet al. 1996). Any pyrite on Venus' surface should decompose rapidly to iron oxides and sulfur vapor, as experimentally demonstrated by Fegleyet al.(1995. B. Fegley Jr., K. Lodders, A. H. Treiman, and G. Klingelhöfer.Icarus115,159-180).

  6. Electrochemistry of Thiobacillus ferrooxidans reactions with pyrite. Final report

    SciTech Connect

    Pesic, B.; Oliver, D.J.; Kim, Inbeum; De, G.C.

    1993-01-20

    A cyclic voltammetry technique was used to study the interactions of pyrite during bioleaching with the bacterium Thiobacillus ferrooxidans. Potential effects of heavy metals (silver and mercury) and varying the pH on the iron oxidizing ability of the bacterium are reported. Redox potential techniques were used to study effect of ferrous sulfate concentration and pH on bacterial growth.

  7. Iron monosulfide accumulation and pyrite formation in eutrophic estuarine sediments

    NASA Astrophysics Data System (ADS)

    Kraal, Peter; Burton, Edward D.; Bush, Richard T.

    2013-12-01

    This study investigates iron (Fe) and sulfur (S) cycling in sediments from the eutrophic Peel-Harvey Estuary in Western Australia, which is subject to localized accumulation of strongly reducing, organic- and sulfide-rich sediments. Sedimentary iron was mostly present in highly reactive form (on average 73% of total Fe) and showed extensive sulfidization even in surface sediments, despite being overlain by a well-mixed oxygenated water column. This indicates that, under eutrophic marine conditions, Fe sulfidization may be driven by reductive processes in the sediment without requiring oxygen depletion in the overlying waters. Strong enrichments in iron monosulfide (FeS > 300 μmol g-1) were observed in fine-grained sediment intervals up to 45 cm depth. This metastable Fe sulfide is commonly restricted to thin subsurface sediment intervals, below which pyrite (FeS2) dominates. Our findings suggest inhibition of the dissolution-precipitation processes that replace FeS with FeS2 in sediments. Rates of pyrite formation based on the FeS2 profiles were much lower than those predicted by applying commonly used kinetic equations for pyrite formation. Dissolved H2S was present at millimolar levels throughout the investigated sediment profiles. This may indicate that (i) pyrite formation via reaction between dissolved Fe (including Fe clusters) and H2S was limited by low availability of dissolved Fe or (ii) reaction kinetics of pyrite formation via the H2S pathway may be relatively slow in natural reducing sediments. We propose that rapid burial of the FeS under anoxic conditions in these organic-rich reducing sediments minimizes the potential for pyrite formation, possibly by preventing dissolution of FeS or by limiting the availability of oxidized sulfur species that are required for pyrite formation via the polysulfide pathway.

  8. Sedimentary pyrite formation: An update

    NASA Astrophysics Data System (ADS)

    Berner, Robert A.

    1984-04-01

    Sedimentary pyrite formation during early diagenesis is a major process for controlling the oxygen level of the atmosphere and the sulfate concentration in seawater over geologic time. The amount of pyrite that may form in a sediment is limited by the rates of supply of decomposable organic matter, dissolved sulfate, and reactive detrital iron minerals. Organic matter appears to be the major control on pyrite formation in normal (non-euxinic) terrigenous marine sediments where dissolved sulfate and iron minerals are abundant. By contrast, pyrite formation in non-marine, freshwater sediments is severely limited by low concentrations of sulfate and this characteristic can be used to distinguish ancient organic-rich fresh water shales from marine shales. Under marine euxinic conditions sufficient H 2S is produced that the dominant control on pyrite formation is the availability of reactive iron minerals. Calculations, based on a sulfur isotope model, indicate that over Phanerozoic time the worldwide average organic carbon-to-pyrite sulfur ratio of sedimentary rocks has varied considerably. High C/S ratios during Permo-Carboniferous time can be explained by a shift of major organic deposition from the oceans to the land which resulted in the formation of vast coal swamps at that time. Low C/S ratios, compared to today, during the early Paleozoic can be explained in terms of a greater abundance of euxinic basins combined with deposition of a more reactive type of organic matter in the remaining oxygenated portions of the ocean. The latter could have been due to lower oceanic oxygen levels and/or a lack of transportation of refractory terrestrial organic matter to the marine environment due to the absence of vascular land plants at that time.

  9. Speciation of arsenic in pyrite by micro-X-ray absorption fine- structure spectroscopy (XAFS)

    SciTech Connect

    Paktunc, D.

    2008-09-30

    Pyrite (FeS2) often contains variable levels of arsenic, regardless of the environment of formation. Arsenian pyrite has been reported in coals, sediments and ore deposits. Arsenian pyrite having As concentrations of up to 10 wt % in sedimentary rocks (Kolker et al. 1997), about 10 wt% in gold deposits (Fleet et al. 1993), 12 wt % in a refractory gold ore (Paktunc et al. 2006) and 20 wt % in a Carlin-type gold deposit in Nevada (Reich et al. 2005) have been reported. Arsenian pyrite is the carrier of gold in hydrothermal Carlin-type gold deposits, and gold concentrations of up to 0.9 wt % have been reported (Reich et al. 2005; Paktunc et al. 2006). In general, high Au concentrations correlate with As-rich zones in pyrite (Paktunc et al. 2006). Pyrite often ends up in mining and metallurgical wastes as an unwanted mineral and consititutes one of the primary sources of As in the wastes. Arsenic can be readily released to the environment due to rapid oxidative dissolution of host pyrite under atmospheric conditions. Pyrite is also the primary source of arsenic in emissions and dust resulting from combustion of bituminous coals. Despite the importance of arsenian pyrite as a primary source of anthropogenic arsenic in the environment and its economic significance as the primary carrier of gold in Carlin-type gold deposits, our understanding of the nature of arsenic in pyrite is limited. There are few papers dealing with the mode of occurrence of arsenic by bulk XAFS in a limited number of pyrite-bearing samples. The present study documents the analysis of pyrite particles displaying different morphologies and a range of arsenic and gold concentrations to determine the nature and speciation of arsenic.

  10. Control of pyrite surface chemistry in physical coal cleaning. Tenth quarterly progress report, December 1, 1991--February 29, 1992

    SciTech Connect

    Yoon, R.H.; Richardson, P.R.

    1992-06-24

    One of the most difficult separations in minerals processing involves the differential flotation of pyrite and coal. Under practical flotation conditions, they are both hydrophobic and no cost-effective method has been developed to efficiently reject the pyrite. The problem arises from inherent floatability of coal and pyrite. Coal is naturally hydrophobic and remains so under practical flotation. Although pyrite is believed to be naturally hydrophilic under practical flotation conditions it undergoes a relatively rapid incipient oxidation reaction that causes ``self-induced`` flotation. The oxidation product responsible for ``self-induced`` flotation is believed to be a metal polysulfide, excess sulfur in the lattice, or in some cases elemental sulfur. It is believed that if incipient oxidation of pyrite could be prevented, good pyrite rejection could be obtained. In order to gain a better understanding of how pyrite oxidizes, a new method of preparing fresh, unoxidized pyrite surfaces and a new method of studying pyrite oxidation have been developed this reporting period.

  11. Pyrite synthesis via polysulfide compounds

    NASA Astrophysics Data System (ADS)

    Luther, George W., III

    1991-10-01

    The reactions of Fe(II) and Fe(III) solutions with polysulfide solutions prepared from freshly synthesized Na 2S x ( x = 2, 4, 5) were studied at 25 and 100°C over the pH range 5.5 to 8. Direct and instantaneous pyrite formation was not observed in any reaction. High temperature reactions are nearly quantitative over periods of four hours with Fe(II) and polysulfide solutions. The rate of reaction at room temperature is comparable to that found by RICKARD (1975), and the observations reported here are in agreement with his mechanism of pyrite formation. Based on the polarographic results of these reactions and previous work, a refinement of the mechanism which includes dissolved iron sulfide complexes is proposed. Every reaction of equimolar amounts of polysulfide and Fe(II) gave the kinetic product "FeS" (an example of the Ostwald step rule). Polarographic results demonstrate that the "FeS" initially formed consists of (1) a complex of the form Fe(SH) + and (2) solid FeS. When excess polysulfide is present, a complex of form [Fe(SH) S x] - is present. This complex should readily allow for (1) the reduction of polysulfide by sulfide which produces S 22- in unprotonated form, and (2) the change of Fe(II) from high spin to low spin during the formation of pyrite. The reduction of polysulfide by sulfide was proposed by RICKARD (1975), but at the pH of the solutions studied herein, S 22- in solution should be protonated. The 22- ion is critical in the formation and structure of pyrite ( TOSSEL et al., 1981). The proposed complex allows for a cyclic intermediate which cleaves the reacting polysulfide to form S 22- unprotonated. As this process occurs, there is a change in the spin state of the Fe(II) from the high spin t 2g4e g2 to the low spin t 2g6 state which is an electron configuration exhibiting kinetic inertness. On change of the Fe(II) spin state, the complex irreversibly decomposes to form pyrite. The complex may be a cluster complex containing two or more

  12. Ferrous iron oxidation by Thiobacillus ferrooxidans: inhibition with benzoic acid, sorbic acid and sodium lauryl sulfate

    SciTech Connect

    Onysko, S.J.

    1984-07-01

    Acid mine drainage is formed by the weathering or oxidation of pyritic material exposed during coal mining. The rate of pyritic material oxidation can be greatly accelerated by certain acidophilic bacteria such as Thiobacillus ferrooxidans which catalyse the oxidation of ferrous to ferric iron. A number of organic compounds, under laboratory conditions, can apparently inhibit both the oxidation of ferrous to ferric iron by T. ferrooxidans and the weathering of pyritic material by mixed cultures of acid mine drainage micro-organisms. Sodium lauryl sulphate (SLS), an anionic surfactant has proved effective in this respect. Benzoic acid, sorbic acid and SLS at low concentrations, each effectively inhibited bacterial oxidation of ferrous iron in batch cultures of T. ferrooxidans. The rate of chemical oxidation of ferrous iron in low pH, sterile, batch reactors was not substantially affected at the tested concentrations of any of the compounds.

  13. Pyrite formation in two freshwater systems in the Netherlands

    SciTech Connect

    Marnette, E.C.L.; Van Breemen, N. ); Hordijk, K.A.; Cappenberg, T.E. )

    1993-09-01

    Cycling of Fe and S was investigated in sediments of Gerritsfles and Kliplo, two acidic shallow moorland pools in the Netherlands, in order to reveal the importance of pyrite as a pool of inorganic S. The porewater chemistry in both pool sediments is extremely dynamic as, e.g., Fe[sup 2+] concentrations may increase twentyfold within a time span of a month. Periodic oxidized conditions occur in the top several centimetres of the sediment. The redox status appeared to be a main factor in determining whether pyrite or a monosulfide, defined by the content of acid volatile sulfur (AVS), is formed. In Gerritsfles and Kliplo, pyrite was the most important iron sulfide phase; sedimentary FeS[sub 2]-S/AVS-S molar ratios were 32 and 55, respectively. In other lakes, where stratification caused anaerobic conditions in the hypolimmion, FeS[sub 2]/AVS ratios were <1. Morphological investigation by light and scanning electron microscopy indicated that pyrite was present as single crystals and as framboids. The framboids, mainly associated with organic matter, were thought to form in microsites where they may form slowly. The presence of a single crystal morphology point to a rapid formation of pyrite.

  14. Selenium speciation in framboidal and euhedral pyrites in shales.

    PubMed

    Matamoros-Veloza, Adriana; Peacock, Caroline L; Benning, Liane G

    2014-08-19

    The release of Se from shales is poorly understood because its occurrence, distribution, and speciation in the various components of shale are unknown. To address this gap we combined bulk characterization, sequential extractions, and spatially resolved μ-focus spectroscopic analyses and investigated the occurrence and distribution of Se and other associated elements (Fe, As, Cr, Ni, and Zn) and determined the Se speciation at the μ-scale in typical, low bulk Se containing shales. Our results revealed Se primarily correlated with the pyrite fraction with exact Se speciation highly dependent on pyrite morphology. In euhedral pyrites, we found Se(-II) substitutes for S in the mineral structure. However, we also demonstrate that Se is associated with framboidal pyrite grains as a discrete, independent FeSex phase. The presence of this FeSex species has major implications for Se release, because FeSex species oxidize much faster than Se substituted in the euhedral pyrite lattice. Thus, such an FeSex species will enhance and control the dynamics of Se weathering and release into the aqueous environment. PMID:25032506

  15. Selenium speciation in framboidal and euhedral pyrites in shales.

    PubMed

    Matamoros-Veloza, Adriana; Peacock, Caroline L; Benning, Liane G

    2014-08-19

    The release of Se from shales is poorly understood because its occurrence, distribution, and speciation in the various components of shale are unknown. To address this gap we combined bulk characterization, sequential extractions, and spatially resolved μ-focus spectroscopic analyses and investigated the occurrence and distribution of Se and other associated elements (Fe, As, Cr, Ni, and Zn) and determined the Se speciation at the μ-scale in typical, low bulk Se containing shales. Our results revealed Se primarily correlated with the pyrite fraction with exact Se speciation highly dependent on pyrite morphology. In euhedral pyrites, we found Se(-II) substitutes for S in the mineral structure. However, we also demonstrate that Se is associated with framboidal pyrite grains as a discrete, independent FeSex phase. The presence of this FeSex species has major implications for Se release, because FeSex species oxidize much faster than Se substituted in the euhedral pyrite lattice. Thus, such an FeSex species will enhance and control the dynamics of Se weathering and release into the aqueous environment.

  16. Surface electrochemical control for fine coal and pyrite separation

    SciTech Connect

    Hu, Weibai; Zhu, Ximeng; Bodily, D.M.; Wadsworth, M.E.

    1990-01-01

    Ongoing work includes the characterization of coal pyrites, the floatability evaluation typical US coal samples, the flotation behavior of coal pyrites, the electrochemical measurement of the surface properties of coal pyrites, and the characterization of species produced at pyrite surfaces.

  17. An ultrasonic-accelerated oxidation method for determining the oxidative stability of biodiesel.

    PubMed

    Avila Orozco, Francisco D; Sousa, Antonio C; Domini, Claudia E; Ugulino Araujo, Mario Cesar; Fernández Band, Beatriz S

    2013-05-01

    Biodiesel is considered an alternative energy because it is produced from fats and vegetable oils by means of transesterification. Furthermore, it consists of fatty acid alkyl esters (FAAS) which have a great influence on biodiesel fuel properties and in the storage lifetime of biodiesel itself. The biodiesel storage stability is directly related to the oxidative stability parameter (Induction Time - IT) which is determined by means of the Rancimat® method. This method uses condutimetric monitoring and induces the degradation of FAAS by heating the sample at a constant temperature. The European Committee for Standardization established a standard (EN 14214) to determine the oxidative stability of biodiesel, which requires it to reach a minimum induction period of 6h as tested by Rancimat® method at 110°C. In this research, we aimed at developing a fast and simple alternative method to determine the induction time (IT) based on the FAAS ultrasonic-accelerated oxidation. The sonodegradation of biodiesel samples was induced by means of an ultrasonic homogenizer fitted with an immersible horn at 480Watts of power and 20 duty cycles. The UV-Vis spectrometry was used to monitor the FAAS sonodegradation by measuring the absorbance at 270nm every 2. Biodiesel samples from different feedstock were studied in this work. In all cases, IT was established as the inflection point of the absorbance versus time curve. The induction time values of all biodiesel samples determined using the proposed method was in accordance with those measured through the Rancimat® reference method by showing a R(2)=0.998.

  18. 46 CFR 148.225 - Calcined pyrites (pyritic ash, fly ash).

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... be disposed of as prescribed in 33 CFR parts 151.55 through 151.77. ... 46 Shipping 5 2011-10-01 2011-10-01 false Calcined pyrites (pyritic ash, fly ash). 148.225 Section... § 148.225 Calcined pyrites (pyritic ash, fly ash). (a) This part does not apply to the shipment...

  19. 46 CFR 148.225 - Calcined pyrites (pyritic ash, fly ash).

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... be disposed of as prescribed in 33 CFR parts 151.55 through 151.77. ... 46 Shipping 5 2012-10-01 2012-10-01 false Calcined pyrites (pyritic ash, fly ash). 148.225 Section... § 148.225 Calcined pyrites (pyritic ash, fly ash). (a) This part does not apply to the shipment...

  20. 46 CFR 148.225 - Calcined pyrites (pyritic ash, fly ash).

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... be disposed of as prescribed in 33 CFR parts 151.55 through 151.77. ... 46 Shipping 5 2014-10-01 2014-10-01 false Calcined pyrites (pyritic ash, fly ash). 148.225 Section... § 148.225 Calcined pyrites (pyritic ash, fly ash). (a) This part does not apply to the shipment...

  1. 46 CFR 148.225 - Calcined pyrites (pyritic ash, fly ash).

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... be disposed of as prescribed in 33 CFR parts 151.55 through 151.77. ... 46 Shipping 5 2013-10-01 2013-10-01 false Calcined pyrites (pyritic ash, fly ash). 148.225 Section... § 148.225 Calcined pyrites (pyritic ash, fly ash). (a) This part does not apply to the shipment...

  2. Semiconductor electrochemistry of coal pyrite

    SciTech Connect

    Osseo-Asare, K.; Wei, D.

    1993-02-01

    This project seeks to advance the fundamental understanding of the physics-chemical processes occurring at the pyrite/aqueous interface, in the context of coal cleaning, coal desulfurization, and acid minedrainage. A novel approach to the study of pyrite aqueous electrochemistry is proposed, based on the use of both synthetic and natural ( i.e. coal-derived) pyrite specimens, the utilization of.pyrite both in the form of micro (i.e. colloidal and subcolloidal) and macro (i.e. rotating ring disk) electrodes, and the application of in-situ direct electroanalytical and spectroelectrochemical characterization techniques. The kinetic study of the reaction between sulfide and ferrous ions in solution suggested that the black species formed initially is FeHS[sup +] intermediate. To farther confirm this mechanism, the experiments aimed at establishing the stoichiometry for the intermediate were carried out thermodynamically with a stopped-flow spectrophotometric technique. The results showed that the mole ratio of H[sup [minus

  3. Reactivity of pyrites and dislocation density

    SciTech Connect

    Pollack, S.S.; Martello, D.V.; Diehl, J.R.; Tamilia, J.V. ); Graham, R.A. )

    1991-01-01

    Highly reactive coal pyrites and unstable museum specimens are easily distinguished from the stable pyrites by the growth of white crystals that cover samples exposed to room atmosphere for short periods of time. Continued exposure to the atmosphere will eventually cause the specimens to fall apart. The term rotten pyrite has been applied to museum specimens that fall apart in this way. SEM studies show that reactive (rotten) pyrites contain between 100 and 10,000 times more dislocations than stable pyrites. Shock-loading of a stable pyrite to 7.5 GPa and 17 GPa increased its reactivity by a factor of two, probably caused by an increase in the number of imperfections. However, shock-loading at 22 GPa decreased the reactivity of pyrite because the imperfections produced at the higher pressure were removed during annealing the sample received at the higher temperature. Although there was a factor of six difference between the most and least reactive shocked MCB (commercial pyrite) samples, shock-loading did not increase the reactivity of the MCB pyrite to that of the Queensland coal pyrite. The results in hand show that while shock-loading produces sufficient imperfections to increase the reactivity of pyrites, there is insufficient data to show that imperfections are the main reason why some coal pyrites are highly reactive. 9 refs., 1 fig., 1 tab.

  4. Nylon 6.6 accelerated aging studies : thermal-oxidative degradation and its interaction with hydrolysis.

    SciTech Connect

    Bernstein, Robert; Derzon, Dora Kay; Gillen, Kenneth T.

    2004-06-01

    Accelerated aging of Nylon 6.6 fibers used in parachutes has been conducted by following the tensile strength loss under both thermal-oxidative and 100% relative humidity conditions. Thermal-oxidative studies (air circulating ovens) were performed for time periods of weeks to years at temperatures ranging from 37 C to 138 C. Accelerated aging humidity experiments (100% RH) were performed under both an argon atmosphere to examine the 'pure' hydrolysis pathway, and under an oxygen atmosphere (oxygen partial pressure close to that occurring in air) to mimic true aging conditions. As expected the results indicated that degradation caused by humidity is much more important than thermal-oxidative degradation. Surprisingly when both oxygen and humidity were present the rate of degradation was dramatically enhanced relative to humidity aging in the absence of oxygen. This significant and previously unknown phenomena underscores the importance of careful accelerated aging that truly mimics real world storage conditions.

  5. Acceleration factors for oxidative aging of polymeric materials by oxygen detection.

    SciTech Connect

    Assink, Roger Alan; Celina, Mathias Christopher; Skutnik, Julie Michelle

    2005-01-01

    Three methods that were used to measure the chemical changes associated with oxidative degradation of polymeric materials are presented. The first method is based on the nuclear activation of {sup 18}O in an elastomer that was thermally aged in an {sup 18}O{sub 2} atmosphere. Second, the alcohol groups in a thermally aged elastomer were derivatized with trifluoroacetic anhydride and their concentration measured via {sup 19}F NMR spectroscopy. Finally, a respirometer was used to directly measure the oxidative rates of a polyurethane foam as a function of aging temperature. The measurement of the oxidation rates enabled acceleration factors for oxidative degradation of these materials to be calculated.

  6. Control of pyrite surface chemistry in physical coal cleaning. First quarterly progress report, September 1, 1989--November 30, 1989

    SciTech Connect

    Luttrell, G.H.; Yoon, R.H.; Zachwieja, J.; Lagno, M.

    1990-01-17

    To better understand the flotation behavior of coal pyrite, studies have been initiated to characterize the floatability of coal pyrite and mineral pyrite. The hydrophobicity of coal material pyrite was examined over a range of pH and oxidation times. The results indicate that surface oxidation plays an important role in coal and mineral pyrite hydrophobicity. The hydrophobicity of mineral pyrite decreases with increasing oxidation time (20 min. to 5 hr.) and increasing pH (pH 4.6 to 9.2), with maximum depression occurring at pH 9.2. However, coal pyrite exhibited low floatability, even at the lowest oxidation time, over the entire pH range. X-ray photoelectron spectroscopy (XPS) results suggest the growth of an oxidized iron layer as being responsible for the deterioration in floatability, while a sulfur-containing species present on the sample surfaces may promote floatability. Preliminary studies of the effect of frother indicate an enhancement in the floatability of both coal and mineral pyrite over the entire pH range.

  7. Interlaboratory reproducibility of standard accelerated aging methods for oxidation of UHMWPE.

    PubMed

    Kurtz, S M; Muratoglu, O K; Buchanan, F; Currier, B; Gsell, R; Greer, K; Gualtieri, G; Johnson, R; Schaffner, S; Sevo, K; Spiegelberg, S; Shen, F W; Yau, S S

    2001-07-01

    During accelerating aging, experimental uncertainty may arise due to variability in the oxidation process, or due to limitations in the technique that is ultimately used to measure oxidation. The purpose of the present interlaboratory study was to quantify the repeatability and reproducibility of standard accelerated aging methods for ultra-high molecular weight polyethylene (UHMWPE). Sections (200 microm thick) were microtomed from the center of an extruded rod of GUR 4150 HP, gamma irradiated in air or nitrogen, and circulated to 12 institutions in the United States and Europe for characterization of oxidation before and after accelerated aging. Specimens were aged for 3 weeks at 80 degrees C in an air circulating oven or for 2 weeks at 70 degrees C in an oxygen bomb (maintained at 503 kPa (5 atm.) of O2) in accordance with the two standard protocols described in ASTM F 2003-00. FTIR spectra were collected from each specimen within 24 h of the start and finish of accelerated aging, and oxidation indices were calculated by normalizing the peak area of the carbonyl region by the reference peak areas at 1370 or 2022 cm(-1). The mean relative interlaboratory uncertainty of the oxidation data was 78.5% after oven aging and 129.1% after bomb aging. The oxidation index measurement technique was not found to be a significant factor in the reproducibility. Comparable relative intrainstitutional uncertainty was observed after oven aging and bomb aging. For both aging methods, institutions successfully discriminated between air-irradiated and control specimens. However, the large interinstitutional variation suggests that absolute performance standards for the oxidation index of UHMWPE after accelerated aging may not be practical at the present time.

  8. Control of pyrite surface chemistry in physical coal cleaning. Third quarterly progress report, March 1, 1990--May 31, 1990

    SciTech Connect

    Luttrell, G.H.; Yoon, R.H.; Zachwieja, J.B.; Lagno, M.L.

    1992-06-24

    Correlation of the hydrophobicity measurements of coal and mineral pyrite with changes in the surface composition of the samples as determined by x-ray photoelectron spectroscopy (XPS) reveals that similar surface oxidation products are found on both mineral and coal pyrite samples. The surface oxidation layer of these samples is comprised of different amounts of hydrophilic species (iron hydroxy-oxides and/or iron oxides) and hydrophobic species (polysulfide or elemental sulfur). The resulting hydrophobicity of these samples may be attributed to the ratio of hydrophilic (surface oxides) to hydrophobic (sulfur-containing) species in the surface oxidation layer. Also, coal pyrite samples were found to exhibit a greater degree of superficial oxidation and a less hydrophobic character as compared to the mineral pyrite samples.

  9. Uranium in framboidal pyrite from a naturally bioreduced alluvial sediment.

    PubMed

    Qafoku, Nikolla P; Kukkadapu, Ravi K; McKinley, James P; Arey, Bruce W; Kelly, Shelly D; Wang, Chongmin; Resch, Charles T; Long, Philip E

    2009-11-15

    Samples of a naturally bioreduced, U-contaminated alluvial sediment were characterized with various microscopic and spectroscopic techniques and wet chemical extraction methods. The objective was to investigate U association and interaction with minerals of the sediment. Bioreduced sediment comprises approximately 10% of an alluvial aquifer adjacent to the Colorado River, in Rifle, CO, that was the site of a former U milling operation. Past and ongoing research has demonstrated that bioreduced sediment is elevated in solid-associated U, total organic carbon, and acid-volatile sulfide, and depleted in bioavailable Fe(III) confirming that sulfate and Fe(III) reduction have occurred naturally in the sediment. SEM/EDS analyses demonstrated that framboidal pyrites (FeS(2)) of different sizes ( approximately 10-20 microm in diameter), and of various microcrystal morphology, degree of surface weathering, and internal porosity were abundant in the <53 microm fraction (silt + clay) of the sediment and absent in adjacent sediments that were not bioreduced. SEM-EMPA, XRF, EXAFS, and XANES measurements showed elevated U was present in framboidal pyrite as both U(VI) and U(IV). This result indicates that U may be sequestered in situ under conditions of microbially driven sulfate reduction and pyrite formation. Conversely, such pyrites in alluvial sediments provide a long-term source of U under conditions of slow oxidation, contributing to the persistence of U of some U plumes. These results may also help in developing remedial measures for U-contaminated aquifers. PMID:20028047

  10. Uranium in framboidal pyrite from a naturally bioreduced alluvial sediment.

    PubMed

    Qafoku, Nikolla P; Kukkadapu, Ravi K; McKinley, James P; Arey, Bruce W; Kelly, Shelly D; Wang, Chongmin; Resch, Charles T; Long, Philip E

    2009-11-15

    Samples of a naturally bioreduced, U-contaminated alluvial sediment were characterized with various microscopic and spectroscopic techniques and wet chemical extraction methods. The objective was to investigate U association and interaction with minerals of the sediment. Bioreduced sediment comprises approximately 10% of an alluvial aquifer adjacent to the Colorado River, in Rifle, CO, that was the site of a former U milling operation. Past and ongoing research has demonstrated that bioreduced sediment is elevated in solid-associated U, total organic carbon, and acid-volatile sulfide, and depleted in bioavailable Fe(III) confirming that sulfate and Fe(III) reduction have occurred naturally in the sediment. SEM/EDS analyses demonstrated that framboidal pyrites (FeS(2)) of different sizes ( approximately 10-20 microm in diameter), and of various microcrystal morphology, degree of surface weathering, and internal porosity were abundant in the <53 microm fraction (silt + clay) of the sediment and absent in adjacent sediments that were not bioreduced. SEM-EMPA, XRF, EXAFS, and XANES measurements showed elevated U was present in framboidal pyrite as both U(VI) and U(IV). This result indicates that U may be sequestered in situ under conditions of microbially driven sulfate reduction and pyrite formation. Conversely, such pyrites in alluvial sediments provide a long-term source of U under conditions of slow oxidation, contributing to the persistence of U of some U plumes. These results may also help in developing remedial measures for U-contaminated aquifers.

  11. Interfacial activity and leaching patterns of Leptospirillum ferrooxidans on pyrite.

    PubMed

    Rojas-Chapana, José A; Tributsch, Helmut

    2004-01-01

    The leaching ability of Leptospirillum ferrooxidans goes beyond the mere oxidation of Fe(2+) to Fe(3+). Addition of these bacteria to pyrite triggers interfacial phenomena that lead to bacterial attachment and local forms of corrosion (surface pitting). As the leaching process proceeds, bacterial cells undergo changes, characterized by the release of extracellular polymeric substances (EPS) and the uptake and storage of electro-dense nanoparticles. The latter are embedded in an exopolymeric capsule, which coats the bacterial surface leading to distinctive biomineralized assemblages. High-resolution scanning electron microscopy (SEM) and transmission electron microscopy (TEM) analyses, quantitative energy-dispersive X-ray measurements and electron diffraction established that the embedded electron-dense nanoparticles comprise pyrite with a well-defined stoichiometry. Addition of Fe(3+) alone did not induce any form of local corrosion on pyrite, which indicates that the reactions taking place between the attached bacteria and the underlying pyrite surface are responsible for the leaching patterns observed in this study. The observed corrosion process resembles that of 'electrochemical machining', because it uses a corrosion promoter, namely the locally concentrated Fe(3+) in the biofilm environment, formed by the attached cells. PMID:19712343

  12. The coupled geochemistry of Au and As in pyrite from hydrothermal ore deposits

    NASA Astrophysics Data System (ADS)

    Deditius, Artur P.; Reich, Martin; Kesler, Stephen E.; Utsunomiya, Satoshi; Chryssoulis, Stephen L.; Walshe, John; Ewing, Rodney C.

    2014-09-01

    The ubiquity of Au-bearing arsenian pyrite in hydrothermal ore deposits suggests that the coupled geochemical behaviour of Au and As in this sulfide occurs under a wide range of physico-chemical conditions. Despite significant advances in the last 20 years, fundamental factors controlling Au and As ratios in pyrite from ore deposits remain poorly known. Here we explore these constraints using new and previously published EMPA, LA-ICP-MS, SIMS, and μ-PIXE analyses of As and Au in pyrite from Carlin-type Au, epithermal Au, porphyry Cu, Cu-Au, and orogenic Au deposits, volcanogenic massive sulfide (VHMS), Witwatersrand Au, iron oxide copper gold (IOCG), and coal deposits. Pyrite included in the data compilation formed under temperatures from ∼30 to ∼600 °C and in a wide variety of geological environments. The pyrite Au-As data form a wedge-shaped zone in compositional space, and the fact that most data points plot below the solid solubility limit defined by Reich et al. (2005) indicate that Au1+ is the dominant form of Au in arsenian pyrite and that Au-bearing ore fluids that deposit this sulfide are mostly undersaturated with respect to native Au. The analytical data also show that the solid solubility limit of Au in arsenian pyrite defined by an Au/As ratio of 0.02 is independent of the geochemical environment of pyrite formation and rather depends on the crystal-chemical properties of pyrite and post-depositional alteration. Compilation of Au-As concentrations and formation temperatures for pyrite indicates that Au and As solubility in pyrite is retrograde; Au and As contents decrease as a function of increasing temperature from ∼200 to ∼500 °C. Based on these results, two major Au-As trends for Au-bearing arsenian pyrite from ore deposits are defined. One trend is formed by pyrites from Carlin-type and orogenic Au deposits where compositions are largely controlled by fluid-rock interactions and/or can be highly perturbed by changes in temperature and

  13. Pyrite surface characterization and control for advanced fine coal desulfurization technologies. Eighth quarterly technical progress report, June 1, 1992--August 31, 1992

    SciTech Connect

    Wang, X.H.; Leonard, J.W.; Parekh, B.K.; Raichur, A.M.; Jiang, C.L.

    1992-12-01

    The objective of the project is to conduct extensive fundamental studies on the surface reactivity and surface hydrophobicity of coal-pyrites using various surface characterization techniques and to understand how the alteration of the coal-pyrite surface affects the efficiency of pyrite rejection in coal flotation. During this reporting period, the influence of the impurity content, particularly coal/carbon content, on the electrochemical oxidation of pyrite surfaces was investigated. The studies demonstrate that the coal/carbon content in coal-pyrite has a determining effect on the surface reactivity of pyrite. The oxidation behavior of high carbon-content coal-pyrite is completely different from that of purer coal-pyrite and ore-pyrite. The effects of flotation gases on the flotation behavior of coal and the surface hydrophobicity of various coal-pyrite were investigated. It was found from the lab-scale column flotation studies that among the various gases studied (air, oxygen, argon, nitrogen and carbon dioxide), carbon dioxide produced the best results with a combustible recovery of 90% and ash-content of less than 9 percent. Finally, the surface energetic studies revealed that the surfaces of pyrites and coals produced by wet grinding is more heterogenous than that prepared by dry grinding.

  14. Sulfide-driven arsenic mobilization from arsenopyrite and black shale pyrite

    NASA Astrophysics Data System (ADS)

    Zhu, Wenyi; Young, Lily Y.; Yee, Nathan; Serfes, Michael; Rhine, E. Danielle; Reinfelder, John R.

    2008-11-01

    We examined the hypothesis that sulfide drives arsenic mobilization from pyritic black shale by a sulfide-arsenide exchange and oxidation reaction in which sulfide replaces arsenic in arsenopyrite forming pyrite, and arsenide (As-1) is concurrently oxidized to soluble arsenite (As+3). This hypothesis was tested in a series of sulfide-arsenide exchange experiments with arsenopyrite (FeAsS), homogenized black shale from the Newark Basin (Lockatong formation), and pyrite isolated from Newark Basin black shale incubated under oxic (21% O 2), hypoxic (2% O 2, 98% N 2), and anoxic (5% H 2, 95% N 2) conditions. The oxidation state of arsenic in Newark Basin black shale pyrite was determined using X-ray absorption-near edge structure spectroscopy (XANES). Incubation results show that sulfide (1 mM initial concentration) increases arsenic mobilization to the dissolved phase from all three solids under oxic and hypoxic, but not anoxic conditions. Indeed under oxic and hypoxic conditions, the presence of sulfide resulted in the mobilization in 48 h of 13-16 times more arsenic from arsenopyrite and 6-11 times more arsenic from isolated black shale pyrite than in sulfide-free controls. XANES results show that arsenic in Newark Basin black shale pyrite has the same oxidation state as that in FeAsS (-1) and thus extend the sulfide-arsenide exchange mechanism of arsenic mobilization to sedimentary rock, black shale pyrite. Biologically active incubations of whole black shale and its resident microorganisms under sulfate reducing conditions resulted in sevenfold higher mobilization of soluble arsenic than sterile controls. Taken together, our results indicate that sulfide-driven arsenic mobilization would be most important under conditions of redox disequilibrium, such as when sulfate-reducing bacteria release sulfide into oxic groundwater, and that microbial sulfide production is expected to enhance arsenic mobilization in sedimentary rock aquifers with major pyrite-bearing, black

  15. Sulfide-driven arsenic mobilization from arsenopyrite and black shale pyrite

    USGS Publications Warehouse

    Zhu, W.; Young, L.Y.; Yee, N.; Serfes, M.; Rhine, E.D.; Reinfelder, J.R.

    2008-01-01

    We examined the hypothesis that sulfide drives arsenic mobilization from pyritic black shale by a sulfide-arsenide exchange and oxidation reaction in which sulfide replaces arsenic in arsenopyrite forming pyrite, and arsenide (As-1) is concurrently oxidized to soluble arsenite (As+3). This hypothesis was tested in a series of sulfide-arsenide exchange experiments with arsenopyrite (FeAsS), homogenized black shale from the Newark Basin (Lockatong formation), and pyrite isolated from Newark Basin black shale incubated under oxic (21% O2), hypoxic (2% O2, 98% N2), and anoxic (5% H2, 95% N2) conditions. The oxidation state of arsenic in Newark Basin black shale pyrite was determined using X-ray absorption-near edge structure spectroscopy (XANES). Incubation results show that sulfide (1 mM initial concentration) increases arsenic mobilization to the dissolved phase from all three solids under oxic and hypoxic, but not anoxic conditions. Indeed under oxic and hypoxic conditions, the presence of sulfide resulted in the mobilization in 48 h of 13-16 times more arsenic from arsenopyrite and 6-11 times more arsenic from isolated black shale pyrite than in sulfide-free controls. XANES results show that arsenic in Newark Basin black shale pyrite has the same oxidation state as that in FeAsS (-1) and thus extend the sulfide-arsenide exchange mechanism of arsenic mobilization to sedimentary rock, black shale pyrite. Biologically active incubations of whole black shale and its resident microorganisms under sulfate reducing conditions resulted in sevenfold higher mobilization of soluble arsenic than sterile controls. Taken together, our results indicate that sulfide-driven arsenic mobilization would be most important under conditions of redox disequilibrium, such as when sulfate-reducing bacteria release sulfide into oxic groundwater, and that microbial sulfide production is expected to enhance arsenic mobilization in sedimentary rock aquifers with major pyrite-bearing, black

  16. Surface electrochemical control for fine coal and pyrite separation

    SciTech Connect

    Hu, Weibai; Huang, Qinping; Li, Jun; Riley, A.; Turcotte, S.B.; Benner, R.E.; Zhu, Ximeng; Bodily, D.M.; Liang, Jun; Zhong, Tinghe; Wadsworth, M.E.

    1991-01-01

    The ongoing work includes the characterization of coal pyrites, the floatability evaluation of three typical US coal samples, the flotation behavior of coal pyrites, the electrochemical measurement of the surface properties of coal pyrites, and the characterization of species produced at pyrite surfaces. This report covers a Raman spectroscopy of species produced electrochemically on pyrite surfaces.

  17. Soft X-ray spectroscopic studies of the reaction of fractured pyrite surfaces with Cr(VI)-containing aqueous solutions

    NASA Astrophysics Data System (ADS)

    Doyle, Colin S.; Kendelewicz, Tom; Bostick, Benjamin C.; Brown, Gordon E.

    2004-11-01

    We have used synchrotron-based soft X-ray core-level photoemission and adsorption spectroscopies to study the reaction of aqueous sodium chromate solutions with freshly fractured pyrite surfaces. Pyrite surfaces were reacted with 50 μM sodium chromate solution at pH 7 for reaction times between 1 min and 37 hr. Additional experiments were performed at pH 2 and pH 4 with 50 μM sodium chromate solutions and at pH 7 with 5 mM solutions. At chromate concentrations of 50 μM, all chromium present on the pyrite surface was in the form of Cr(III), while at 5 mM, both Cr(III) and Cr(VI) were present at the pyrite surface. Minor quantities of oxidized sulfur species (sulfate, sulfite, and zero-valent sulfur) were identified as reaction products on the pyrite surface. The amount of oxidized sulfur species observed on the surface was greater when pyrite was reacted with 5 mM Cr(VI) solutions because the rate of chromium deposition exceeded the rate of dissolution of pyrite oxidation products, effectively trapping Cr(VI) and oxidized sulfur species in an overlayer of iron(III)-containing Cr(III)-hydroxide. This work shows that pyrite, an extremely cheap and readily available waste material, may be suitable for the removal of hexavalent chromium from acidic to circumneutral waste streams. The reduced chromium ultimately forms a coating on the pyrite surface, which passivates the pyrite surface towards further oxidation.

  18. Control of pyrite surface chemistry in physical coal cleaning. Twelfth quarterly technical progress report, June 1, 1992--August 31, 1992

    SciTech Connect

    Yoon, R.H.; Richardson, P.R.

    1992-12-31

    Over the past 10 years, much research has provided convincing evidence that one major difficulty in using froth flotation to separate pyrite from coal is the ``self-induced`` flotation of pyrite. Numerous studies have attempted to identify reactions that occur under moderate oxidizing conditions, which lead to self-induced flotation, and to identify the oxidization products. During the past two report periods, it was established that: (1) freshly fractured pyrite surfaces immediately assume, at fracture, an electrode potential several hundred millivolts more negative than the usual steady state mixed potentials. Within minutes after fracture, the electrodes oxidize and reach higher steady state potentials. It was also shown, by photocurrent measurements, that a negative surface charge (upward band bending) already exists on freshly fractured pyrite, and (2) particle bed electrodes can be used to control the oxidation of pyrite and to precisely determine the electrochemical conditions where flotation occurs, or is depressed. By circulating the solution phase to an ultraviolet spectrometer, soluble products produced on pyrite by oxidation and reduction can be determined, e.g., HS{sup {minus}} was identified as a soluble cathodic reduction product. These and other studies have provided considerable information concerning the anodic oxidation of pyrite. Much less is known about the mechanism and kinetics of oxygen reduction, the other half of the mixed potential reaction. To better understand pyrite oxidation kinetics and determine if oxygen reduction is rate determining, studies have been conducted during this report period on the oxygen reduction reaction with pyrite. In addition, to provide further support that the potential of particle bed electrodes can be controlled, the electro-adsorption and desorption of an organic surfactant was studied.

  19. Semiconductor electrochemistry of coal pyrite

    SciTech Connect

    Osseo-Asare, K.; Wei, D.

    1992-01-01

    Pyrite synthesis is of interest in many diverse fields, such as geology, fuel processing technology, chemistry, metallurgy, materials science, and so on. Based on fundamental studies of this process, the formation mechanisms of this important sulfide on the earth can be better understood. The studies can also help us to better understand the surface chemistry and electrochemistry of pyrite, thereby assisting in the development of more efficient processes for removal of the sulfide from coal. The work performed during this quarter focuses on the study of the reaction between aqueous sulfide ions and dissolved Fe(II) salts by using a stopped-flow spectrophotometric technique. At a wavelength of 500 mn, no absorption was observed with either aqueous sulfide or dissolved Fe(II) salt alone. However, when the two solutions were mixed, a strong absorbance appeared at the same wavelength. The absorbance-time curve showed that a black material formed at the first few seconds of the reaction, then this material decayed and changed gradually to a lighter dark material within the following several minutes. These processes were pH-dependent. It was more likely to form the black intermediate at the pH range from 7 to 8. This indicates that the reaction between Fe[sup 2+] and HS[sup [minus

  20. Control of pyrite addition in coal liquefaction process

    DOEpatents

    Schmid, Bruce K.; Junkin, James E.

    1982-12-21

    Pyrite addition to a coal liquefaction process (22, 26) is controlled (118) in inverse proportion to the calcium content of the feed coal to maximize the C.sub.5 --900.degree. F. (482.degree. C.) liquid yield per unit weight of pyrite added (110). The pyrite addition is controlled in this manner so as to minimize the amount of pyrite used and thus reduce pyrite contribution to the slurry pumping load and disposal problems connected with pyrite produced slag.

  1. Semiconductor electrochemistry of coal pyrite. Technical progress report, January--March 1993

    SciTech Connect

    Osseo-Asare, K.; Wei, D.

    1993-05-01

    This project seeks to advance the fundamental understanding of the physicochemical processes occurring at the pyrite/aqueous interface, in the context of coal cleaning, coal desulfurization, and acid mine drainage. A novel approach to the study of pyrite aqueous electrochemistry is proposed, based on the use of both synthetic and natural ( i.e. coal-derived) pyrite specimens, the utilization of pyrite both in the form of micro (i.e. colloidal and subcolloidal) and macro (i.e. rotating ring disk) electrodes, and the application of in-situ direct electroanalytical and spectroelectrochemical characterization techniques. The work performed during this quarter focuses on the synthesis of pyrite in aqueous solutions at room temperature and atmospheric pressure. The experimental results show that the initial product from the reaction between ferrous ions and sulfide ions is X-ray amorphous iron sulfide, and the final product is mackinawite from this reaction. Both amorphous iron sulfide and mackinawite in wet states are oxidized quickly in air to {gamma}-FeOOH. Pyrite can form in aqueous solution through a simple path from a reaction between ferric ions and sulfide ions at room temperature within 9 days. It is believed that a redox reaction occurs between ferric and sulfide ions to form ferrous ions and elemental sulfur. The Fe{sup 2+}, S{sup 2{minus}} ions and elemental sulfur, S{sup o}, in the system can then react with each other to form pyrite. This pathway of pyrite formation can be used in synthesizing nanoparticles of pyrite in microemulsions.

  2. Traumatic stress, oxidative stress and posttraumatic stress disorder: neurodegeneration and the accelerated-aging hypothesis

    PubMed Central

    Miller, Mark W.; Sadeh, Naomi

    2014-01-01

    Posttraumatic stress disorder (PTSD) is associated with elevated risk for a variety of age-related diseases and neurodegeneration. In this paper, we review evidence relevant to the hypothesis that chronic PTSD constitutes a form of persistent life stress that potentiates oxidative stress (OXS) and accelerates cellular aging. We provide an overview of empirical studies that have examined the effects of psychological stress on OXS, discuss the stress-perpetuating characteristics of PTSD, and then identify mechanisms by which PTSD might promote OXS and accelerated aging. We review studies on OXS-related genes and the role that they may play in moderating the effects of PTSD on neural integrity and conclude with a discussion of directions for future research on antioxidant treatments and biomarkers of accelerated aging in PTSD. PMID:25245500

  3. Control of pyrite surface chemistry in physical coal cleaning. Technical progress report for the ninth quarter, September 1--November 30, 1991

    SciTech Connect

    Yoon, R.H.; Luttrell, G.H.; Zachwieja, J.B.; Mielczarski, J.A.

    1992-03-18

    The separation of pyrite from coal by flotation is based on exploiting the wettability difference between coal and pyrite. There is evidence that the wettability of coal pyrite changes upon superficial oxidation. Therefore, the oxidation of coal pyrite has been studied under carefully controlled electrochemical conditions. In order to identify the species responsible for the changes in wettability, the surface products formed during oxidation have been identified by means of various surface analysis techniques, including X-ray photoelectron spectroscopy (XPS) and ion scattering spectroscopy (ISS). It has been found that pyrite oxidation creates a sulfur-rich surface along with iron oxides/hydroxides. The ratio between these hydrophobic and hydrophilic species correlates well with the results of the wettability measurements.

  4. Evidence for microbial dissolution of pyrite from the Lower Cambrian oolitic limestone, South China

    NASA Astrophysics Data System (ADS)

    Liu, W.; Zhang, X.-L.

    2011-03-01

    The oxidative dissolution of the sulphide mineral pyrite (FeS2) has been of significant interest since it affects global geochemical cycles, generates acid mine drainage, and is used in industrial metal extraction. Several different groups of prokaryotes are known to catalyze the dissolution of pyrite and use the free energy generated from the oxidation, which may result in the dissolution of the mineral and the precipitation of the secondary ferric iron minerals either on the cell surface or is separated from the cells. However, straightforward evidence for such metabolic process in the ancient sediments is rare. Here we report pyrite crystals from the Lower Cambrian oolitic limestones that show indications of microbial erosion in various degrees. Erosion pits and tubular micro-tunnels with characteristic shapes and sizes in our samples are generally similar to those obtained from the laboratory studies on the oxidative dissolution of pyrite by iron-oxidizing bacteria. Diagenetic examination demonstrates that the bioerosion predates the consolidation of the limestone. In addition, bacillus-sized and -shaped microfossils encrusted with iron oxides are present in our samples, which are very likely to be fossilized sheaths produced by iron-oxidizing bacteria. Our findings indicate that the microbial oxidative dissolution of pyrite existed in the Cambrian shallow marine carbonate sediments. Furthermore, we suggest that characteristic pitting patterns on the pyrite crystals from ancient sediments are an important clue to trace the evolution of life, in particular, the evolution of metabolism like microbial iron oxidation in the remote past on our planet, independent of biomarkers, isotopic signals and body fossils as well.

  5. Ultrasonic ash/pyrite liberation

    SciTech Connect

    Yungman, B.A.; Buban, K.S.; Stotts, W.F.

    1990-06-01

    The objective of this project was to develop a coal preparation concept which employed ultrasonics to precondition coal prior to conventional or advanced physical beneficiation processes such that ash and pyrite separation were enhanced with improved combustible recovery. Research activities involved a series of experiments that subjected three different test coals, Illinois No. 6, Pittsburgh No. 8, and Upper Freeport, ground to three different size fractions (28 mesh [times] 0, 200 mesh [times] 0, and 325 mesh [times] 0), to a fixed (20 kHz) frequency ultrasonic signal prior to processing by conventional and microbubble flotation. The samples were also processed by conventional and microbubble flotation without ultrasonic pretreatment to establish baseline conditions. Product ash, sulfur and combustible recovery data were determined for both beneficiation processes.

  6. Application of fuel cell for pyrite and heavy metal containing mining waste

    NASA Astrophysics Data System (ADS)

    Keum, H.; Ju, W. J.; Jho, E. H.; Nam, K.

    2015-12-01

    Once pyrite and heavy metal containing mining waste reacts with water and air it produces acid mine drainage (AMD) and leads to the other environmental problems such as contamination of surrounding soils. Pyrite is the major source of AMD and it can be controlled using a biological-electrochemical dissolution method. By enhancing the dissolution of pyrite using fuel cell technology, not only mining waste be beneficially utilized but also be treated at the same time by. As pyrite-containing mining waste is oxidized in the anode of the fuel cell, electrons and protons are generated, and electrons moves through an external load to cathode reducing oxygen to water while protons migrate to cathode through a proton exchange membrane. Iron-oxidizing bacteria such as Acidithiobacillus ferrooxidans, which can utilize Fe as an electron donor promotes pyrite dissolution and hence enhances electrochemical dissolution of pyrite from mining waste. In this study mining waste from a zinc mine in Korea containing 17 wt% pyrite and 9% As was utilized as a fuel for the fuel cell inoculated with A. ferrooxidans. Electrochemically dissolved As content and chemically dissolved As content was compared. With the initial pH of 3.5 at 23℃, the dissolved As concentration increased (from 4.0 to 13 mg/L after 20 d) in the fuel cell, while it kept decreased in the chemical reactor (from 12 to 0.43 mg/L after 20 d). The fuel cell produced 0.09 V of open circuit voltage with the maximum power density of 0.84 mW/m2. Dissolution of As from mining waste was enhanced through electrochemical reaction. Application of fuel cell technology is a novel treatment method for pyrite and heavy metals containing mining waste, and this method is beneficial for mining environment as well as local community of mining areas.

  7. Fe(III) oxides accelerate microbial nitrate reduction and electricity generation by Klebsiella pneumoniae L17.

    PubMed

    Liu, Tongxu; Li, Xiaomin; Zhang, Wei; Hu, Min; Li, Fangbai

    2014-06-01

    Klebsiella pneumoniae L17 is a fermentative bacterium that can reduce iron oxide and generate electricity under anoxic conditions, as previously reported. This study reveals that K. pneumoniae L17 is also capable of dissimilatory nitrate reduction, producing NO2(-), NH4(+), NO and N2O under anoxic conditions. The presence of Fe(III) oxides (i.e., α-FeOOH, γ-FeOOH, α-Fe2O3 and γ-Fe2O3) significantly accelerates the reduction of nitrate and generation of electricity by K. pneumoniae L17, which is similar to a previous report regarding another fermentative bacterium, Bacillus. No significant nitrate reduction was observed upon treatment with Fe(2+) or α-FeOOH+Fe(2+), but a slight facilitation of nitrate reduction and electricity generation was observed upon treatment with L17+Fe(2+). This result suggests that aqueous Fe(II) or mineral-adsorbed Fe(II) cannot reduce nitrate abiotically but that L17 can catalyze the reduction of nitrate and generation of electricity in the presence of Fe(II) (which might exist as cell surface-bound Fe(II)). To rule out the potential effect of Fe(II) produced by L17 during microbial iron reduction, treatments with the addition of TiO2 or Al2O3 instead of Fe(III) oxides also exhibited accelerated microbial nitrate reduction and electricity generation, indicating that cell-mineral sorption did account for the acceleration effect. However, the acceleration caused by Fe(III) oxides is only partially attributed to the cell surface-bound Fe(II) and cell-mineral sorption but may be driven by the iron oxide conduction band-mediated electron transfer from L17 to nitrate or an electrode, as proposed previously. The current study extends the diversity of bacteria of which nitrate reduction and electricity generation can be facilitated by the presence of iron oxides and confirms the positive role of Fe(III) oxides on microbial nitrate reduction and electricity generation by particular fermentative bacteria in anoxic environments.

  8. Surface electrochemical control for the fine coal and pyrite separation

    SciTech Connect

    Hu, Weibai; Huang, Qinping; Zhu, Ximeng; Li, Jun; Bodily, D.M.; Liang, Jun; Zhong, Tingke; Wadsworth, M.E.

    1992-01-01

    Ongoing work includes the characterization of coal pyrites, the floatability evaluation of typical US coal samples, the flotation behavior of coal pyrites, the electrochemical measurement of the surface properties of coal pyrites, and the characterization of species produced at pyrite surfaces.

  9. Surface electrochemical control for fine coal and pyrite separation

    SciTech Connect

    Chen, Wanxiong; Hu, Weibai; Wann, Jyi-Perng; Zhu, Ximeng; Bodily, D.M.; Wadsworth, M.E.

    1990-01-01

    Ongoing work includes the characterization of coal pyrites, the floatability evaluation of typical US coal samples, the flotation behavior of coal pyrites, the electrochemical measurement of the surface properties of coal pyrites, and the characterization of species produced at pyrite surfaces.

  10. Surface electrochemical control for the fine coal and pyrite separation

    SciTech Connect

    Chen, Wanxiong; Hu, Weibai; Wann, Jyi-Perng; Zhu, Ximeng; Wadsworth, M.E.

    1989-01-01

    Ongoing work includes the characterization of coal pyrites, the floatability evaluation of typical US coal samples, the flotation behavior of coal pyrites, the electrochemical measurement of the surface properties of coal pyrites, and the characterization of species produced at pyrite surfaces.

  11. Enhanced bioleaching on attachment of indigenous acidophilic bacteria to pyrite surface

    NASA Astrophysics Data System (ADS)

    Wi, D. W.; Cho, K. H.; Kim, B. J.; Choi, N. C.; Park, C. Y.

    2012-04-01

    In recent years, bioleaching has been widely applied on an industrial scale due to the advantages of low cost and environment friendliness. The direct contact mechanism of bioleaching assumes the action of a metal sulfide-attached cell oxidizing the mineral by an enzyme system with oxygen to sulfate and metal cations. Fundamental surface properties of sulfide particles and leaching-bacteria in bioleaching play the key role in the efficiency of this process. The aim of this work is to investigate of direct contact bioleaching mechanism on pyrite through attachment properties between indigenous acidophilic bacteria and pyrite surfaces. The bacteria were obtained from sulfur hot springs, Hatchobaru thermal electricity plant in Japan. And pyrite was collected from mine waste from Gwang-yang abandoned gold mines, Korea. In XRD analyses of the pyrite, x-ray diffracted d-value belong to pyrite was observed. The indigenous acidophilic bacteria grew well in a solution and over the course of incubation pH decreased and Eh increased. In relation to a bacterial growth-curve, the lag phase was hardly shown while the exponential phase was very fast. Bioleaching experiment result was showed that twenty days after the indigenous acidophilic bacteria were inoculated to a pyrite-leaching medium, the bacterial sample had a greater concentration of Fe and Zn than within the control sample. In SEM-EDS analyses, rod-shaped bacteria and round-shaped microbes were well attached to the surface of pyrite. The size of the rod-shaped bacteria ranged from 1.05~1.10 ? to 4.01~5.38 ?. Round-shaped microbes were more than 3.0 ? in diameter. Paired cells of rod-shaped bacteria were attached to the surface of pyrite linearly.

  12. The stability of thiosulfate in the presence of pyrite in low-temperature aqueous solutions

    NASA Astrophysics Data System (ADS)

    Xu, Yong; Schoonen, Martin A. A.

    1995-11-01

    The decomposition rate of thiosulfate (S 2O 32-) and the formation rates of its partial decomposition products, sulfite (SO 32-), sulfate (SO 42-), and tetrathionate (S 4O 62-), were measured in the absence and presence of pyrite in aqueous solution of pH 2.9-8.6 at 20°C. The pyrite-surface-catalyzed oxidation of S 2O 32- to S 40 62- by dissolved oxygen is the dominant S 2O 32- decomposition mechanism under the experimental conditions. The rate of tetrathionate formation is first order with respect to the pyrite surface concentration and has a fractional order (0 ≤ n ≤ 1) with respect to the S 20 32- concentration. This result is consistent with a surface-controlled heterogeneous mechanism and can be fitted with a Langmuir-Hinshelwood rate equation. The rate shows no pH dependence in the pH range between 2.9 and 6.6, but decreases in alkaline solution. The catalysis of pyrite in this reaction originates from its strong affinity for aqueous sulfur species and its semiconducting properties. Pyrite is thought to form an interfacial intermediate complex with the aqueous electron donor, S 2O 32-, on anodic sites, and the terminal electron acceptor, O 2, on cathodic sites. The electrons can transfer from the anodic site to the cathodic site via the conduction band of pyrite. In essence, the presence of pyrite eliminates a symmetry mismatch between the frontier orbitals of thiosulfate and oxygen. In the absence of pyrite, this symmetry overlap precludes the progress of this reaction and thiosulfate decomposes via disproportionation to yield sulfite and elemental sulfur.

  13. Pyrite cathode material for a thermal battery

    NASA Astrophysics Data System (ADS)

    Pemsler, J. P.; Litchfield, J. K.

    1991-02-01

    The present invention relates in general to a synthetic cathode material for a molten salt battery and, more particularly, to a process of providing and using synthetic pyrite for use as a cathode in a thermal battery. These batteries, which have been successfully used in a number of military applications, include iron disulfide cathode material obtained as benefacted or from natural occurring pyrite deposits, or as a byproduct of flotation concentrate from the processing of base or noble metal ores.

  14. Aqueous geochemistry and analysis of pyrite surfaces in sulfide-rich mine tailings

    NASA Astrophysics Data System (ADS)

    Al, T. A.; Blowes, D. W.; Martin, C. J.; Cabri, L. J.; Jambor, J. L.

    1997-06-01

    Aqueous geochemical techniques and analysis of pyrite surfaces have been used to study element partitioning between the aqueous and solid phase and to infer mechanisms that limit the concentrations of elements in porewater in a sulfide-rich mine tailings impoundment. Porewater samples and pyrite grains for surface analysis were collected from oxidized and unoxidized zones within the tailings. Surface analyses were conducted using a Time-of-Flight Laser-Ionization Mass Spectrometer (TOFLIMS). The porewater pH at the different sample locations varies from 3.85 to 6.98. High relative abundances of Na, K, Ca, Mg, Al, and Ni occur at the surfaces of the pyrite grains from all of the sample locations. The porewater concentrations of these elements in the low-pH zone may be controlled by precipitation or coprecipitation in secondary mineral coatings on the pyrite surface. Surface abundances of the metals Cu, Ag, Pb, Zn, and Cd are lowest, and porewater concentrations are highest, in the low-pH oxidized tailings. Surface abundances of As are greatest, and porewater concentrations are lowest, in the low-pH sulfide-oxidation zone. These trends vs. pH are consistent with an adsorption model for attenuation of Cu, Ag, Pb, Zn, Cd, and As from the porewater. The porewater Cu and Ag concentrations may be limited by replacement reactions that form secondary Cu and Ag sulfides at the pyrite surface. The highest abundance of C on the surface of the pyrite grains is in the shallow sulfide-oxidation zone; this interval coincides with large abundances of chemolithotrophic bacteria and may reflect populations of iron- and sulfur-oxidizing bacteria such as Thiobacilli.

  15. Influence of the sulfur species reactivity on biofilm conformation during pyrite colonization by Acidithiobacillus thiooxidans.

    PubMed

    Lara, René H; García-Meza, J Viridiana; Cruz, Roel; Valdez-Pérez, Donato; González, Ignacio

    2012-08-01

    Massive pyrite (FeS₂) electrodes were potentiostatically modified by means of variable oxidation pulse to induce formation of diverse surface sulfur species (S(n)²⁻, S⁰). The evolution of reactivity of the resulting surfaces considers transition from passive (e.g., Fe(1-x )S₂) to active sulfur species (e.g., Fe(1-x )S(2-y ), S⁰). Selected modified pyrite surfaces were incubated with cells of sulfur-oxidizing Acidithiobacillus thiooxidans for 24 h in a specific culture medium (pH 2). Abiotic control experiments were also performed to compare chemical and biological oxidation. After incubation, the attached cells density and their exopolysaccharides were analyzed by confocal laser scanning microscopy (CLMS) and atomic force microscopy (AFM) on bio-oxidized surfaces; additionally, S(n)²⁻/S⁰ speciation was carried out on bio-oxidized and abiotic pyrite surfaces using Raman spectroscopy. Our results indicate an important correlation between the evolution of S(n)²⁻/S⁰ surface species ratio and biofilm formation. Hence, pyrite surfaces with mainly passive-sulfur species were less colonized by A. thiooxidans as compared to surfaces with active sulfur species. These results provide knowledge that may contribute to establishing interfacial conditions that enhance or delay metal sulfide (MS) dissolution, as a function of the biofilm formed by sulfur-oxidizing bacteria.

  16. Influence of the sulfur species reactivity on biofilm conformation during pyrite colonization by Acidithiobacillus thiooxidans.

    PubMed

    Lara, René H; García-Meza, J Viridiana; Cruz, Roel; Valdez-Pérez, Donato; González, Ignacio

    2012-08-01

    Massive pyrite (FeS₂) electrodes were potentiostatically modified by means of variable oxidation pulse to induce formation of diverse surface sulfur species (S(n)²⁻, S⁰). The evolution of reactivity of the resulting surfaces considers transition from passive (e.g., Fe(1-x )S₂) to active sulfur species (e.g., Fe(1-x )S(2-y ), S⁰). Selected modified pyrite surfaces were incubated with cells of sulfur-oxidizing Acidithiobacillus thiooxidans for 24 h in a specific culture medium (pH 2). Abiotic control experiments were also performed to compare chemical and biological oxidation. After incubation, the attached cells density and their exopolysaccharides were analyzed by confocal laser scanning microscopy (CLMS) and atomic force microscopy (AFM) on bio-oxidized surfaces; additionally, S(n)²⁻/S⁰ speciation was carried out on bio-oxidized and abiotic pyrite surfaces using Raman spectroscopy. Our results indicate an important correlation between the evolution of S(n)²⁻/S⁰ surface species ratio and biofilm formation. Hence, pyrite surfaces with mainly passive-sulfur species were less colonized by A. thiooxidans as compared to surfaces with active sulfur species. These results provide knowledge that may contribute to establishing interfacial conditions that enhance or delay metal sulfide (MS) dissolution, as a function of the biofilm formed by sulfur-oxidizing bacteria. PMID:22113561

  17. Pyrite surface characterization and control for advanced fine coal desulfurization technologies. Ninth quarterly technical progress report, September 1, 1992-- December 31, 1992

    SciTech Connect

    Wang, X.H.; Leonard, J.W.; Parekh, B.K.; Jiang, C.L.

    1992-12-31

    This is the 9th quarterly technical progress report for the project entitled ``Pyrite surface characterization and control for advanced fine coal desulfurization technologies``, DE-FG22-90PC90295. The work presented in this report was performed from September 1, 1992 to November 31, 1992. The objective of the project is to conduct extensive fundamental studies on the surface chemistry of pyrite oxidation and flotation and to understand how the alteration of the coal-pyrite surface affects the efficiency of pyrite rejection in coal flotation. During this reporting period, the surface oxidation of pyrite in various electrolytes was investigated. It has been demonstrated, for the first time, that borate, a pH buffer and electrolyte used by many previous investigators in studying sulfide mineral oxidation, actively participates in the surface oxidation of pyrite. In borate solutions, the surface oxidation of pyrite is tronly enhanced. The anodic oxidation potential of pyrite is lowered by more than 0.4 volts. The initial reaction of the borate enhanced pyrite oxidation can be described by:FeS{sub 2} + B(OH){sub 4}{sup =} ------> [S{sub 2}Fe-B(OH){sub 4}]{sub surf} + e. This reaction is irreversible and is controlled by the mass-transfer of borate species from the solution to the surface. It has been shown that the above reaction inhibits the adsorption of xanthate on pyrite. Comparative studies have been made with other sulfide minerals. The solution chemistry of the iron-borate systems have been studied to understand the electrochemical results.

  18. Direct Detection of Fe(II) in Extracellular Polymeric Substances (EPS) at the Mineral-Microbe Interface in Bacterial Pyrite Leaching.

    PubMed

    Mitsunobu, Satoshi; Zhu, Ming; Takeichi, Yasuo; Ohigashi, Takuji; Suga, Hiroki; Jinno, Muneaki; Makita, Hiroko; Sakata, Masahiro; Ono, Kanta; Mase, Kazuhiko; Takahashi, Yoshio

    2016-01-01

    We herein investigated the mechanisms underlying the contact leaching process in pyrite bioleaching by Acidithiobacillus ferrooxidans using scanning transmission X-ray microscopy (STXM)-based C and Fe near edge X-ray absorption fine structure (NEXAFS) analyses. The C NEXAFS analysis directly showed that attached A. ferrooxidans produces polysaccharide-abundant extracellular polymeric substances (EPS) at the cell-pyrite interface. Furthermore, by combining the C and Fe NEXAFS results, we detected significant amounts of Fe(II), in addition to Fe(III), in the interfacial EPS at the cell-pyrite interface. A probable explanation for the Fe(II) in detected EPS is the leaching of Fe(II) from the pyrite. The detection of Fe(II) also indicates that Fe(III) resulting from pyrite oxidation may effectively function as an oxidizing agent for pyrite at the cell-pyrite interface. Thus, our results imply that a key role of Fe(III) in EPS, in addition to its previously described role in the electrostatic attachment of the cell to pyrite, is enhancing pyrite dissolution.

  19. Direct Detection of Fe(II) in Extracellular Polymeric Substances (EPS) at the Mineral-Microbe Interface in Bacterial Pyrite Leaching

    PubMed Central

    Mitsunobu, Satoshi; Zhu, Ming; Takeichi, Yasuo; Ohigashi, Takuji; Suga, Hiroki; Jinno, Muneaki; Makita, Hiroko; Sakata, Masahiro; Ono, Kanta; Mase, Kazuhiko; Takahashi, Yoshio

    2016-01-01

    We herein investigated the mechanisms underlying the contact leaching process in pyrite bioleaching by Acidithiobacillus ferrooxidans using scanning transmission X-ray microscopy (STXM)-based C and Fe near edge X-ray absorption fine structure (NEXAFS) analyses. The C NEXAFS analysis directly showed that attached A. ferrooxidans produces polysaccharide-abundant extracellular polymeric substances (EPS) at the cell-pyrite interface. Furthermore, by combining the C and Fe NEXAFS results, we detected significant amounts of Fe(II), in addition to Fe(III), in the interfacial EPS at the cell-pyrite interface. A probable explanation for the Fe(II) in detected EPS is the leaching of Fe(II) from the pyrite. The detection of Fe(II) also indicates that Fe(III) resulting from pyrite oxidation may effectively function as an oxidizing agent for pyrite at the cell-pyrite interface. Thus, our results imply that a key role of Fe(III) in EPS, in addition to its previously described role in the electrostatic attachment of the cell to pyrite, is enhancing pyrite dissolution. PMID:26947441

  20. The role of oxidative and nitrosative stress in accelerated aging and major depressive disorder.

    PubMed

    Maurya, Pawan Kumar; Noto, Cristiano; Rizzo, Lucas B; Rios, Adiel C; Nunes, Sandra O V; Barbosa, Décio Sabbatini; Sethi, Sumit; Zeni, Maiara; Mansur, Rodrigo B; Maes, Michael; Brietzke, Elisa

    2016-02-01

    Major depressive disorder (MDD) affects millions of individuals and is highly comorbid with many age associated diseases such as diabetes mellitus, immune-inflammatory dysregulation and cardiovascular diseases. Oxidative/nitrosative stress plays a fundamental role in aging, as well as in the pathogenesis of neurodegenerative/neuropsychiatric disorders including MDD. In this review, we critically review the evidence for an involvement of oxidative/nitrosative stress in acceleration of aging process in MDD. There are evidence of the association between MDD and changes in molecular mechanisms involved in aging. There is a significant association between telomere length, enzymatic antioxidant activities (SOD, CAT, GPx), glutathione (GSH), lipid peroxidation (MDA), nuclear factor κB, inflammatory cytokines with MDD. Major depression also is characterized by significantly lower concentration of antioxidants (zinc, coenzyme Q10, PON1). Since, aging and MDD share a common biological base in their pathophysiology, the potential therapeutic use of antioxidants and anti-aging molecules in MDD could be promising.

  1. Control of pyrite surface chemistry in physical coal cleaning. Second quarterly progress report, December 1, 1989--February 28, 1990

    SciTech Connect

    Luttrell, G.H.; Yoon, R.H.; Zachwieja, J.; Lagno, M.

    1992-06-24

    To better understand the surface chemical properties of coal and mineral pyrite, studies on the effect of flotation surfactants (frother and kerosene) on the degree of hydrophobicity have been conducted. The presence of either frother or kerosene enhanced the flotability of coal and mineral pyrite with a corresponding decrease in induction time over the pH range examined. Scanning electron microscopy (SEM) results indicate a correlation exists between the sample surface morphology and crystal structure and the observed hydrophobicity. As a result of the data obtained from the surface characterization studies, controlled surface oxidation was investigated as a possible pyrite rejection scheme in microbubble column flotation.

  2. A combined chemical, isotopic and microstructural study of pyrite from roll-front uranium deposits, Lake Eyre Basin, South Australia

    NASA Astrophysics Data System (ADS)

    Ingham, Edwina S.; Cook, Nigel J.; Cliff, John; Ciobanu, Cristiana L.; Huddleston, Adam

    2014-01-01

    The common sulfide mineral pyrite is abundant throughout sedimentary uranium systems at Pepegoona, Pepegoona West and Pannikan, Lake Eyre Basin, South Australia. Combined chemical, isotopic and microstructural analysis of pyrite indicates variation in fluid composition, sulfur source and precipitation conditions during a protracted mineralization event. The results show the significant role played by pyrite as a metal scavenger and monitor of fluid changes in low-temperature hydrothermal systems. In-situ micrometer-scale sulfur isotope analyses of pyrite demonstrated broad-scale isotopic heterogeneity (δ34S = -43.9 to +32.4‰VCDT), indicative of complex, multi-faceted pyrite evolution, and sulfur derived from more than a single source. Preserved textures support this assertion and indicate a genetic model involving more than one phase of pyrite formation. Authigenic pyrite underwent prolonged evolution and recrystallization, evidenced by a genetic relationship between archetypal framboidal aggregates and pyrite euhedra. Secondary hydrothermal pyrite commonly displays hyper-enrichment of several trace elements (Mn, Co, Ni, As, Se, Mo, Sb, W and Tl) in ore-bearing horizons. Hydrothermal fluids of magmatic and meteoric origins supplied metals to the system but the geochemical signature of pyrite suggests a dominantly granitic source and also the influence of mafic rock types. Irregular variation in δ34S, coupled with oscillatory trace element zonation in secondary pyrite, is interpreted in terms of continuous variations in fluid composition and cycles of diagenetic recrystallization. A late-stage oxidizing fluid may have mobilized selenium from pre-existing pyrite. Subsequent restoration of reduced conditions within the aquifer caused ongoing pyrite re-crystallization and precipitation of selenium as native selenium. These results provide the first qualitative constraints on the formation mechanisms of the uranium deposits at Beverley North. Insights into

  3. Oxygenation of a Cryogenian ocean (Nanhua Basin, South China) revealed by pyrite Fe isotope compositions

    NASA Astrophysics Data System (ADS)

    Zhang, Feifei; Zhu, Xiangkun; Yan, Bin; Kendall, Brian; Peng, Xi; Li, Jin; Algeo, Thomas J.; Romaniello, Stephen

    2015-11-01

    The nature of ocean redox chemistry between the Cryogenian Sturtian and Marinoan glaciations (ca. 663-654 Ma) is important for understanding the relationship between environmental conditions and the subsequent emergence and expansion of early animals. The Cryogenian-to-Ediacaran stratigraphic succession of the Nanhua Basin in South China provides a nearly complete sedimentary record of the Cryogenian, including a continuous record of interglacial sedimentation. Here, we present a high-resolution pyrite Fe isotope record for a ∼120-m-long drill-core (ZK105) through Sturtian glacial diamictites and the overlying interglacial sediments in the Nanhua Basin to explore changes in marine chemistry during the late Cryogenian. Our pyrite Fe isotope profile exhibits significant stratigraphic variation: Interval I, comprising middle to upper Tiesi'ao diamictites (correlative with the Sturtian glaciation), is characterized by light, modern seawater-like Fe isotope compositions; Interval II, comprising uppermost Tiesi'ao diamictites and the basal organic-rich Datangpo Formation, is characterized by an abrupt shift to heavier Fe isotope compositions; and Interval III, comprising organic-poor grey shales in the middle Datangpo Formation, is characterized by the return of lighter, seawater-like Fe isotope compositions. We infer that Interval I pyrite was deposited in a predominantly anoxic glacial Nanhua Basin through reaction of dissolved Fe2+ and H2S mediated by microbial sulfate reduction (MSR). The shift to heavier pyrite Fe isotope values in Interval II is interpreted as partial oxidation of ferrous iron to ferric iron and subsequent near-quantitative reduction and transformation of Fe-oxyhydroxides to pyrite through coupling with oxidation of organic matter in the local diagenetic environment. In Interval III, near-quantitative oxidation of ferrous iron to Fe-oxyhydroxides followed by near-quantitative reduction and conversion to pyrite in the local diagenetic environment

  4. Chemical composition and minerals in pyrite ash of an abandoned sulphuric acid production plant.

    PubMed

    Oliveira, Marcos L S; Ward, Colin R; Izquierdo, Maria; Sampaio, Carlos H; de Brum, Irineu A S; Kautzmann, Rubens M; Sabedot, Sydney; Querol, Xavier; Silva, Luis F O

    2012-07-15

    The extraction of sulphur produces a hematite-rich waste, known as roasted pyrite ash, which contains significant amounts of environmentally sensitive elements in variable concentrations and modes of occurrence. Whilst the mineralogy of roasted pyrite ash associated with iron or copper mining has been studied, as this is the main source of sulphur worldwide, the mineralogy, and more importantly, the characterization of submicron, ultrafine and nanoparticles, in coal-derived roasted pyrite ash remain to be resolved. In this work we provide essential data on the chemical composition and nanomineralogical assemblage of roasted pyrite ash. XRD, HR-TEM and FE-SEM were used to identify a large variety of minerals of anthropogenic origin. These phases result from highly complex chemical reactions occurring during the processing of coal pyrite of southern Brazil for sulphur extraction and further manufacture of sulphuric acid. Iron-rich submicron, ultrafine and nanoparticles within the ash may contain high proportions of toxic elements such as As, Se, U, among others. A number of elements, such as As, Cr, Cu, Co, La, Mn, Ni, Pb, Sb, Se, Sr, Ti, Zn, and Zr, were found to be present in individual nanoparticles and submicron, ultrafine and nanominerals (e.g. oxides, sulphates, clays) in concentrations of up to 5%. The study of nanominerals in roasted pyrite ash from coal rejects is important to develop an understanding on the nature of this by-product, and to assess the interaction between emitted nanominerals, ultra-fine particles, and atmospheric gases, rain or body fluids, and thus to evaluate the environmental and health impacts of pyrite ash materials.

  5. Coupling UV-H2O2 to accelerate dimethyl phthalate (DMP) biodegradation and oxidation.

    PubMed

    Chen, Bin; Song, Jiaxiu; Yang, Lihui; Bai, Qi; Li, Rongjie; Zhang, Yongming; Rittmann, Bruce E

    2015-11-01

    Dimethyl phthalate (DMP), an important industrial raw material, is an endocrine disruptor of concern for human and environmental health. DMP exhibits slow biodegradation, and its coupled treatment by means of advanced oxidation may enhance its biotransformation and mineralization. We evaluated two ways of coupling UV-H2O2 advanced oxidation to biodegradation: sequential coupling and intimate coupling in an internal circulation baffled biofilm reactor (ICBBR). During sequential coupling, UV-H2O2 pretreatment generated carboxylic acids that depressed the pH, and subsequent biodegradation generated phthalic acid; both factors inhibited DMP biodegradation. During intimately coupled UV-H2O2 with biodegradation, carboxylic acids and phthalic acid (PA) did not accumulate, and the biodegradation rate was 13 % faster than with biodegradation alone and 78 % faster than with biodegradation after UV-H2O2 pretreatment. Similarly, DMP oxidation with intimate coupling increased by 5 and 39 %, respectively, compared with biodegradation alone and sequential coupling. The enhancement effects during intimate coupling can be attributed to the rapid catabolism of carboxylic acids, which generated intracellular electron carriers that directly accelerated di-oxygenation of PA and relieved the inhibition effect of PA and low pH. Thus, intimate coupling optimized the impacts of energy input from UV irradiation used together with biodegradation.

  6. Skeletal Involution by Age-associated Oxidative Stress and Its Acceleration by Loss of Sex Steroids*

    PubMed Central

    Almeida, Maria; Han, Li; Martin-Millan, Marta; Plotkin, Lilian I.; Stewart, Scott A.; Roberson, Paula K.; Kousteni, Stavroula; O’Brien, Charles A.; Bellido, Teresita; Parfitt, A. Michael; Weinstein, Robert S.; Jilka, Robert L.; Manolagas, Stavros C.

    2011-01-01

    Both aging and loss of sex steroids have adverse effects on skeletal homeostasis, but whether and how they may influence each others negative impact on bone remains unknown. We report herein that both female and male C57BL/6 mice progressively lost strength (as determined by load-to-failure measurements) and bone mineral density in the spine and femur between the ages of 4 and 31 months. These changes were temporally associated with decreased rate of remodeling as evidenced by decreased osteoblast and osteoclast numbers and decreased bone formation rate; as well as increased osteoblast and osteocyte apoptosis, increased reactive oxygen species levels, and decreased glutathione reductase activity and a corresponding increase in the phosphorylation of p53 and p66shc, two key components of a signaling cascade that are activated by reactive oxygen species and influences apoptosis and lifespan. Exactly the same changes in oxidative stress were acutely reproduced by gonadectomy in 5-month-old females or males and reversed by estrogens or androgens in vivo as well as in vitro.We conclude that the oxidative stress that underlies physiologic organismal aging in mice may be a pivotal pathogenetic mechanism of the age-related bone loss and strength. Loss of estrogens or androgens accelerates the effects of aging on bone by decreasing defense against oxidative stress. PMID:17623659

  7. Reduction of Nitrite and Nitrate to Ammonium on Pyrite

    NASA Astrophysics Data System (ADS)

    Singireddy, Soujanya; Gordon, Alexander D.; Smirnov, Alexander; Vance, Michael A.; Schoonen, Martin A. A.; Szilagyi, Robert K.; Strongin, Daniel R.

    2012-08-01

    An important constraint on the formation of the building blocks of life in the Hadean is the availability of small, activated compounds such as ammonia (NH3) relative to its inert dinitrogen source. Iron-sulfur particles and/or mineral surfaces have been implicated to provide the catalytic active sites for the reduction of dinitrogen. Here we provide a combined kinetic, spectroscopic, and computational modeling study for an alternative source of ammonia from water soluble nitrogen oxide ions. The adsorption of aqueous nitrite (NO{2/-}) and nitrate (NO{3/-}) on pyrite (FeS2) and subsequent reduction chemistry to ammonia was investigated at 22°C, 70°C, and 120°C. Batch geochemical and in situ Attenuated Total Reflection - Fourier Transform Infrared (ATR-FTIR) spectroscopy experiments were used to determine the reduction kinetics to NH3 and to elucidate the identity of the surface complexes, respectively, during the reaction chemistry of NO{2/-} and NO{3/-}. Density functional theory (DFT) calculations aided the interpretation of the vibrational data for a representative set of surface species. Under the experimental conditions used in this study, we detected the adsorption of nitric oxide (NO) intermediate on the pyrite surface. NH3 production from NO{2/-} occurred at 70 and 120°C and from NO{3/-} occurred only at 120°C.

  8. Electrochemical accumulation of visible gold on pyrite and arsenopyrite surfaces

    NASA Astrophysics Data System (ADS)

    Möller, P.; Kersten, G.

    1994-09-01

    In galvanic cell arrangements gold is electrochemically deposited on semiconducting sulfide minerals (pyrite, arsenopyrite, chalcopyrite) from aerated as well as H2S-saturated, gold-bearing 1 M KCl solutions. Observed cell potential differences of about 0.4 0.6 V in setups with one sulfide in aerated (cathode) and the other in H2S-saturated (anode) solutions are comparable with known “self-potentials” of natural sulfide ore bodies. Gold preferentially accumulates on the cathode, i.e. under oxidizing conditions. Linked sulfides of variable composition in the same environment, either oxidizing or reducing, yield potential differences up to 20 mV. Such assemblages simulate conditions typically occurring at surfaces of chemically inhomogeneous single crystals (e.g. zonation). Depending on chemical composition, sulfide minerals show either n- or p-type conductivity. Visible gold is preferentially accumulated on individual domains of sulfide surfaces that act as cathodes, i.e. p-type conductors in n-p junctions. The experimental results are discussed in view of electrochemical accumulation of visible gold on sulfides in nature. Arsenic is the most important element in establishing p-type conductivity of pyrite and arsenopyrite. This feature may explain why As is such a powerful pathfinder in gold exploration.

  9. Organic Ligand Enhanced Cr(VI) Treatment in Pyrite Permeable Reactive Barriers

    NASA Astrophysics Data System (ADS)

    Kantar, Cetin; Ari, Cihan; Samet Bulbul, Muhammet

    2014-05-01

    Permeable reactive barriers (PRB), installed in subsurface in the path of flowing groundwater can offer a viable option for in situ remediation of Cr(VI)-contaminated subsurface systems. In this study, batch and column experiments were performed to determine the effects of organic ligands (L) on Cr(VI) treatment in PRBs containing pyrite. The organic ligands used include citrate, tartrate, oxalate, EDTA and salycilate. The results indicate that in the absence of organic ligands, the Cr(VI)removal by pyrite occurred only under acidic conditions (e.g., pH > 5). However, organic ligands led to a significant increase in Cr(VI) removal with pyrite depending on the type of organic ligand used, Cr(VI)/LT ratio and water chemistry (e.g., pH). While salicylate had no effect on Cr(VI) removal relative to non-ligand systems, the organic ligands including citrate, tartrate and oxalate significantly improved Cr(VI) removal under acidic to alkaline pH range. On the other hand, EDTA only improved Cr(VI) removal by pyrite under alkaline pH conditions relative to non-ligand conditions. In general, the efficiency of organic ligands on Cr(VI) removal decreased in the order: citrate > tartrate> oxalate>EDTA>salycilate. The X-ray photoelectron spectroscopy (XPS) and zeta potential measurements suggest that the Cr(VI) removal by pyrite occured due to the reduction of Cr(VI) to Cr(III), coupled with the oxidation of Fe(II) to Fe(III) and disulfide (S22-) to sulfate (SO42-) at the pyrite surface as well as in aqueous phase. However, the precipitation of sparingly soluble Fe(III-Cr(III)(oxy) hydroxide phases on pyrite surface led to surface passivation, which, then, inhibited further Cr(VI) reduction. The addition of organic ligands increased Cr(VI) reduction by pyrite due to: 1) the removal of the surface oxidation products by forming highly soluble Cr(III) and Fe(III)-ligand complexes as well as 2) the ligand promoted dissolution of Fe(II) from pyrite, which, subsequently, reduced Cr

  10. Distribution of arsenic, selenium, and other trace elements in high pyrite Appalachian coals: evidence for multiple episodes of pyrite formation

    USGS Publications Warehouse

    Diehl, S.F.; Goldhaber, M.B.; Koenig, A.E.; Lowers, H.A.; Ruppert, L.F.

    2012-01-01

    Pennsylvanian coals in the Appalachian Basin host pyrite that is locally enriched in potentially toxic trace elements such as As, Se, Hg, Pb, and Ni. A comparison of pyrite-rich coals from northwestern Alabama, eastern Kentucky, and West Virginia reveals differences in concentrations and mode of occurrence of trace elements in pyrite. Pyrite occurs as framboids, dendrites, or in massive crystalline form in cell lumens or crosscutting veins. Metal concentrations in pyrite vary over all scales, from microscopic to mine to regional, because trace elements are inhomogeneously distributed in the different morphological forms of pyrite, and in the multiple generations of sulfide mineral precipitates. Early diagenetic framboidal pyrite is usually depleted in As, Se, and Hg, and enriched in Pb and Ni, compared to other pyrite forms. In dendritic pyrite, maps of As distribution show a chemical gradient from As-rich centers to As-poor distal branches, whereas Se concentrations are highest at the distal edges of the branches. Massive crystalline pyrite that fills veins is composed of several generations of sulfide minerals. Pyrite in late-stage veins commonly exhibits As-rich growth zones, indicating a probable epigenetic hydrothermal origin. Selenium is concentrated at the distal edges of veins. A positive correlation of As and Se in pyrite veins from Kentucky coals, and of As and Hg in pyrite-filled veins from Alabama coals, suggests coprecipitation of these elements from the same fluid. In the Kentucky coal samples (n = 18), As and Se contents in pyrite-filled veins average 4200 ppm and 200 ppm, respectively. In Alabama coal samples, As in pyrite-filled veins averages 2700 ppm (n = 34), whereas As in pyrite-filled cellular structures averages 6470 ppm (n = 35). In these same Alabama samples, Se averages 80 ppm in pyrite-filled veins, but was below the detection limit in cell structures. In samples of West Virginia massive pyrite, As averages 1700 ppm, and Se averages 270

  11. Direct interspecies electron transfer accelerates syntrophic oxidation of butyrate in paddy soil enrichments.

    PubMed

    Li, Huijuan; Chang, Jiali; Liu, Pengfei; Fu, Li; Ding, Dewen; Lu, Yahai

    2015-05-01

    Syntrophic interaction occurs during anaerobic fermentation of organic substances forming methane as the final product. H2 and formate are known to serve as the electron carriers in this process. Recently, it has been shown that direct interspecies electron transfer (DIET) occurs for syntrophic CH4 production from ethanol and acetate. Here, we constructed paddy soil enrichments to determine the involvement of DIET in syntrophic butyrate oxidation and CH4 production. The results showed that CH4 production was significantly accelerated in the presence of nanoFe3 O4 in all continuous transfers. This acceleration increased with the increase of nanoFe3 O4 concentration but was dismissed when Fe3 O4 was coated with silica that insulated the mineral from electrical conduction. NanoFe3 O4 particles were found closely attached to the cell surfaces of different morphology, thus bridging cell connections. Molecular approaches, including DNA-based stable isotope probing, revealed that the bacterial Syntrophomonadaceae and Geobacteraceae, and the archaeal Methanosarcinaceae, Methanocellales and Methanobacteriales, were involved in the syntrophic butyrate oxidation and CH4 production. Among them, the growth of Geobacteraceae strictly relied on the presence of nanoFe3 O4 and its electrical conductivity in particular. Other organisms, except Methanobacteriales, were present in enrichments regardless of nanoFe3 O4 amendment. Collectively, our study demonstrated that the nanoFe3 O4 -facilitated DIET occurred in syntrophic CH4 production from butyrate, and Geobacter species played the key role in this process in the paddy soil enrichments.

  12. Pyrite nanoparticles as a Fenton-like reagent for in situ remediation of organic pollutants

    PubMed Central

    Losa-Adams, Elisabeth; F.-Dávila, Alfonso; Gago-Duport, Luis

    2014-01-01

    Summary The Fenton reaction is the most widely used advanced oxidation process (AOP) for wastewater treatment. This study reports on the use of pyrite nanoparticles and microparticles as Fenton reagents for the oxidative degradation of copper phthalocyanine (CuPc) as a representative contaminant. Upon oxidative dissolution in water, pyrite (FeS2) particles can generate H2O2 at their surface while simultaneously promoting recycling of Fe3+ into Fe2+ and vice versa. Pyrite nanoparticles were synthesized by the hot injection method. The use of a high concentration of precursors gave individual nanoparticles (diameter: 20 nm) with broader crystallinity at the outer interfaces, providing a greater number of surface defects, which is advantageous for generating H2O2. Batch reactions were run to monitor the kinetics of CuPc degradation in real time and the amount of H2O2. A markedly greater degradation of CuPc was achieved with nanoparticles as compared to microparticles: at low loadings (0.08 mg/L) and 20 h reaction time, the former enabled 60% CuPc removal, whereas the latter enabled only 7% removal. These results confirm that the use of low concentrations of synthetic nanoparticles can be a cost effective alternative to conventional Fenton procedures for use in wastewater treatment, avoiding the potential risks caused by the release of heavy metals upon dissolution of natural pyrites. PMID:24991522

  13. Pyrite nanoparticles as a Fenton-like reagent for in situ remediation of organic pollutants.

    PubMed

    Gil-Lozano, Carolina; Losa-Adams, Elisabeth; F-Dávila, Alfonso; Gago-Duport, Luis

    2014-01-01

    The Fenton reaction is the most widely used advanced oxidation process (AOP) for wastewater treatment. This study reports on the use of pyrite nanoparticles and microparticles as Fenton reagents for the oxidative degradation of copper phthalocyanine (CuPc) as a representative contaminant. Upon oxidative dissolution in water, pyrite (FeS2) particles can generate H2O2 at their surface while simultaneously promoting recycling of Fe(3+) into Fe(2+) and vice versa. Pyrite nanoparticles were synthesized by the hot injection method. The use of a high concentration of precursors gave individual nanoparticles (diameter: 20 nm) with broader crystallinity at the outer interfaces, providing a greater number of surface defects, which is advantageous for generating H2O2. Batch reactions were run to monitor the kinetics of CuPc degradation in real time and the amount of H2O2. A markedly greater degradation of CuPc was achieved with nanoparticles as compared to microparticles: at low loadings (0.08 mg/L) and 20 h reaction time, the former enabled 60% CuPc removal, whereas the latter enabled only 7% removal. These results confirm that the use of low concentrations of synthetic nanoparticles can be a cost effective alternative to conventional Fenton procedures for use in wastewater treatment, avoiding the potential risks caused by the release of heavy metals upon dissolution of natural pyrites. PMID:24991522

  14. Pyrite nanoparticles as a Fenton-like reagent for in situ remediation of organic pollutants.

    PubMed

    Gil-Lozano, Carolina; Losa-Adams, Elisabeth; F-Dávila, Alfonso; Gago-Duport, Luis

    2014-01-01

    The Fenton reaction is the most widely used advanced oxidation process (AOP) for wastewater treatment. This study reports on the use of pyrite nanoparticles and microparticles as Fenton reagents for the oxidative degradation of copper phthalocyanine (CuPc) as a representative contaminant. Upon oxidative dissolution in water, pyrite (FeS2) particles can generate H2O2 at their surface while simultaneously promoting recycling of Fe(3+) into Fe(2+) and vice versa. Pyrite nanoparticles were synthesized by the hot injection method. The use of a high concentration of precursors gave individual nanoparticles (diameter: 20 nm) with broader crystallinity at the outer interfaces, providing a greater number of surface defects, which is advantageous for generating H2O2. Batch reactions were run to monitor the kinetics of CuPc degradation in real time and the amount of H2O2. A markedly greater degradation of CuPc was achieved with nanoparticles as compared to microparticles: at low loadings (0.08 mg/L) and 20 h reaction time, the former enabled 60% CuPc removal, whereas the latter enabled only 7% removal. These results confirm that the use of low concentrations of synthetic nanoparticles can be a cost effective alternative to conventional Fenton procedures for use in wastewater treatment, avoiding the potential risks caused by the release of heavy metals upon dissolution of natural pyrites.

  15. Control of pyrite surface chemistry in physical coal cleaning. Seventh quarterly progress report, March 1, 1991--May 31, 1991

    SciTech Connect

    Luttrell, G.H.; Yoon, R.H.; Zachwieja, J.B.

    1992-06-24

    The removal of pyrite from coal by flotation or any other surface chemistry based separation process is often hampered by the apparent hydrophobicity of the mineral. Results obtained in this project suggest that corrosion processes are responsible for the apparent hydrophobicity of pyrite in aqueous environments. Characterization of the corrosion products of pyrite in acidic and alkaline solution has been performed using electrochemical (cyclic voltammetry and single-potential-step chronoamperometry) and spectroscopic techniques (X-ray photoelectron spectroscopy -- XPS). The nature of the surface products have been correlated with hydrophobicity determined from in-situ contact angle measurements. The results show that pyrite hydrophobicity is influenced by either the oxidation or reduction conditions of the system.

  16. Surface electrochemical control for fine coal and pyrite separation

    SciTech Connect

    Hu, Weibai; Huang, Qinping; Riley, A.; Zhu, Ximeng; Bodily, D.M.; Liang, Jun; Zhong, Tinghe; Wadsworth, M.E.

    1991-01-01

    This technical progress report, prepared in accordance with the reporting requirements of DOE Project No. DE-AC22-89PC89758, covers the work performed from April 1, 1991 to June 30, 1991. The ongoing work includes the characterization of coal pyrites, the floatability evaluation of three typical US coal samples, the flotation behavior of coal pyrites, the electrochemical measurement of the surface properties of coal pyrites, and the characterization of species produced at pyrite surfaces. 6 refs., 20 figs.

  17. Nucleic acid interactions with pyrite surfaces

    NASA Astrophysics Data System (ADS)

    Mateo-Martí, E.; Briones, C.; Rogero, C.; Gomez-Navarro, C.; Methivier, Ch.; Pradier, C. M.; Martín-Gago, J. A.

    2008-09-01

    The study of the interaction of nucleic acid molecules with mineral surfaces is a field of growing interest in organic chemistry, origin of life, material science and biotechnology. We have characterized the adsorption of single-stranded peptide nucleic acid (ssPNA) on a natural pyrite surface, as well as the further adsorption of ssDNA on a PNA-modified pyrite surface. The characterization has been performed by means of reflection absorption infrared spectroscopy (RAIRS), atomic force microscopy (AFM) and X-ray photoemission spectroscopy (XPS) techniques. The N(1s) and S(2p) XPS core level peaks of PNA and PNA + DNA have been decomposed in curve-components that we have assigned to different chemical species. RAIRS spectra recorded for different concentrations show the presence of positive and negative adsorption bands, related to the semiconducting nature of the surface. The combination of the information gathered by these techniques confirms that PNA adsorbs on pyrite surface, interacting through nitrogen-containing groups of the nucleobases and the iron atoms of the surface, instead of the thiol group of the molecule. The strong PNA/pyrite interaction inhibits further hybridization of PNA with complementary ssDNA, contrary to the behavior reported on gold surfaces.

  18. Particulate Pyrite Autotrophic Denitrification (PPAD) for Remediation of Nitrate-contaminated Groundwater

    NASA Astrophysics Data System (ADS)

    Tong, S.; Rodriguez-Gonzalez, L. C.; Henderson, M.; Feng, C.; Ergas, S. J.

    2015-12-01

    The rapid movement of human civilization towards urbanization, industrialization, and increased agricultural activities has introduced a large amount of nitrate into groundwater. Nitrate is a toxic substance discharged from groundwater to rivers and leads to decreased dissolved oxygen and eutrophication. For this experiment, an electron donor is needed to convert nitrate into non-toxic nitrogen gas. Pyrite is one of the most abundant minerals in the earth's crust making it an ideal candidate as an electron donor. The overall goal of this research was to investigate the potential for pyrite to be utilized as an electron donor for autotrophic denitrification of nitrate-contaminated groundwater. Batch studies of particulate pyrite autotrophic denitrification (PPAD) of synthetic groundwater (100 mg NO3--N L-1) were set up with varying biomass concentration, pyrite dose, and pyrite particle size. Reactors were seeded with mixed liquor volatile suspended solids (VSS) from a biological nitrogen removal wastewater treatment facility. PPAD using small pyrite particles (<0.45mm) resulted in a favorable nitrate removal. The nitrate removal rate increased from 0.26 to 0.34 mg L-1h-1 and then to 0.86 mg L-1h-1, approaching that of the sulfur oxidizing denitrification (SOD) rate of 1.19 mg L-1h-1. Based on Box-Behnken design (BBD) and response surface methodology (RSM), the optimal amount of biomass concentration, pyrite dose, and pyrite particle size were 1,250 mg VSS L-1, 125 g L-1, and 0.815-1.015 mm, respectively. PPAD exhibited substantial nitrate removal rate, lower sulfate accumulation (5.46 mg SO42-/mg NO3--N) and lower alkalinity consumption (1.70 mg CaCO3/mg NO3--N) when compared to SOD (7.54 mg SO42-/mg NO3--N, 4.57 mg CaCO3/mg NO3--N based on stoichiometric calculation). This research revealed that the PPAD process is a promising technique for nitrate-contaminated groundwater treatment and promoted the utilization of pyrite in the field of environmental remediation.

  19. Statistical relationship between pyrite grain size distribution and pyritic sulfur reduction in Ohio coal

    USGS Publications Warehouse

    Mazumdar, M.; Carlton, R.W.; Irdi, G.A.

    1988-01-01

    This paper presents a statistical relationship between the pyrite particle size distribution and the potential amount of pyritic sulfur reduction achieved by specific-gravity-based separation. This relationship is obtained from data on 26 Ohio coal samples crushed to 14 ?? 28 mesh. In this paper a prediction equation is developed that considers the complete statistical distribution of all the pyrite particle sizes in the coal sample. Assuming that pyrite particles occurring in coal have a lognormal distribution, the information about the particle size distribution can be encapsulated in terms of two parameters only, the mean and the standard deviation of the logarithms of the grain diameters. When the pyritic sulfur reductions of the 26 coal samples are related to these two parameters, a very satisfactory regression equation (R2 = 0.91) results. This equation shows that information on both these parameters is needed for an accurate prediction of potential sulfur reduction, and that the mean and the standard deviation interact negatively insofar as their influence on pyritic sulfur reduction is concerned. ?? 1988.

  20. Combined nitric oxide-releasing poly(vinyl alcohol) film/F127 hydrogel for accelerating wound healing.

    PubMed

    Schanuel, Fernanda Seabra; Raggio Santos, Karen Slis; Monte-Alto-Costa, Andréa; de Oliveira, Marcelo G

    2015-06-01

    Nitric oxide (NO) releasing biomaterials represent a potential strategy for use as active wound dressings capable of accelerating wound healing. Topical NO-releasing poly(vinyl alcohol) (PVA) films and Pluronic F127 hydrogels (F127) have already exhibited effective skin vasodilation and wound healing actions. In this study, we functionalized PVA films with SNO groups via esterification with a mixture of mercaptosucinic acid (MSA) and thiolactic acid (TLA) followed by S-nitrosation of the SH moieties. These films were combined with an underlying layer of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide), i.e., PEO-PPO-PEO (Pluronic F127) hydrogel and used for the topical treatment of skin lesions in an animal model. The mixed esterification of PVA with MSA and TLA led to chemically crosslinked PVA-SNO films with a high swelling capacity capable of spontaneously releasing NO. Real time NO-release measurements revealed that the hydrogel layer reduces the initial NO burst from the PVA-SNO films. We demonstrate that the combination of PVA-SNO films with F127 hydrogel accelerates wound contraction, decreases wound gap and cellular density and accelerates the inflammatory phase of the lesion. These results were reflected in an increase in myofibroblastic differentiation and collagen type III expression in the cicatricial tissue. Therefore, PVA-SNO films combined with F127 hydrogel may represent a new approach for active wound dressings capable of accelerating wound healing. PMID:25907598

  1. Binding of oxygen on vacuum fractured pyrite surfaces: Reactivity of iron and sulfur surface sites

    NASA Astrophysics Data System (ADS)

    Berlich, A. G.; Nesbitt, H. W.; Bancroft, G. M.; Szargan, R.

    2013-05-01

    Synchrotron radiation excited photoelectron spectroscopy (SXPS) has been used to study the interaction of oxygen with vacuum fractured pyrite surfaces. Especially valence band spectra obtained with 30 eV photon energy were analyzed to provide a mechanism of the incipient steps of pyrite oxidation. These spectra are far more sensitive to the oxidation than sulfur or iron core level spectra. It is shown that oxygen is adsorbed on Fe(II) surface sites restoring the octahedral coordination of the Fe(II) sites. This process leads to the removal of two surface states in the valence band which are located at the low and high binding energy sides of the outer valence band, respectively. The existence of these surface states which have been proposed by calculations is experimentally proven. Furthermore, it is shown, that the sulfur sites are more reactive than expected. Sulfite like species are already formed after the lowest oxygen exposure of 10 L. This oxidation occurs at sulfur sites neighboring the Fe(II) surface sites. Oxidation of the S2 - surface sites which were considered as the most reactive species in former studies is second. No iron(III) oxides are formed during oxygen exposure, supporting the assumption that water plays an important role in the oxidation mechanism of pyrite surfaces.

  2. Control of pyrite surface chemistry in physical coal cleaning

    SciTech Connect

    Luttrell, G.H.; Yoon, R.H.; Zachwieja, J.B.; Lagno, M.L.

    1990-01-01

    Several pyrite depressants have been evaluated for their effectiveness in depressing coal pyrite. A novel reagent, NVT, has been synthesized and shown to be selective for the separation of coal from coal pyrite by froth flotation. This organic reagent contains no sulfur group in its structure and exhibits a stronger affinity toward pyrite than toward coal. The effects of a number of parameters such as pH, reagent concentration and flotation time on flotation response were investigated in a microflotation cell and a bench-scale Denver flotation cell. The reagent has demonstrated good performance at relatively low concentrations when compared to the commercially available sulfur-based pyrite depressants. 8 figs.

  3. The senescence-accelerated mouse (SAM): a higher oxidative stress and age-dependent degenerative diseases model.

    PubMed

    Chiba, Yoichi; Shimada, Atsuyoshi; Kumagai, Naoko; Yoshikawa, Keisuke; Ishii, Sanae; Furukawa, Ayako; Takei, Shiro; Sakura, Masaaki; Kawamura, Noriko; Hosokawa, Masanori

    2009-04-01

    The SAM strain of mice is actually a group of related inbred strains consisting of a series of SAMP (accelerated senescence-prone) and SAMR (accelerated senescence-resistant) strains. Compared with the SAMR strains, the SAMP strains show a more accelerated senescence process, a shorter lifespan, and an earlier onset and more rapid progress of age-associated pathological phenotypes similar to human geriatric disorders. The higher oxidative stress status observed in SAMP mice is partly caused by mitochondrial dysfunction, and may be a cause of this senescence acceleration and age-dependent alterations in cell structure and function. Based on our recent observations, we discuss a possible mechanism for mitochondrial dysfunction resulting in the excessive production of reactive oxygen species, and a role for the hyperoxidative stress status in neurodegeneration in SAMP mice. These SAM strains can serve as a useful tool to understand the cellular mechanisms of age-dependent degeneration, and to develop clinical interventions. PMID:18688709

  4. Degradation of Anthraquinone Dye Reactive Blue 4 in Pyrite Ash Catalyzed Fenton Reaction

    PubMed Central

    Becelic-Tomin, Milena; Dalmacija, Bozo; Rajic, Ljiljana; Tomasevic, Dragana; Kerkez, Djurdja; Watson, Malcolm; Prica, Miljana

    2014-01-01

    Pyrite ash (PA) is created by burning pyrite in the chemical production of sulphuric acid. The high concentration of iron oxide, mostly hematite, present in pyrite ash, gives the basis for its application as a source of catalytic iron in a modified Fenton process for anthraquinone dye reactive blue 4 (RB4) degradation. The effect of various operating variables such as catalyst and oxidant concentration, initial pH and RB4 concentration on the abatement of total organic carbon, and dye has been assessed in this study. Here we show that degradation of RB4 in the modified Fenton reaction was efficient under the following conditions: pH = 2.5; [PA]0 = 0.2 g L−1; [H2O2]0 = 5 mM and initial RB4 concentration up to 100 mg L−1. The pyrite ash Fenton reaction can overcome limitations observed from the classic Fenton reaction, such as the early termination of the Fenton reaction. Metal (Pb, Zn, and Cu) content of the solution after the process suggests that an additional treatment step is necessary to remove the remaining metals from the water. These results provide basic knowledge to better understand the modified, heterogeneous Fenton process and apply the PA Fenton reaction for the treatment of wastewaters which contains anthraquinone dyes. PMID:24526885

  5. Evaluation of oxidative behavior of polyolefin geosynthetics utilizing accelerated aging tests based on temperature and pressure

    NASA Astrophysics Data System (ADS)

    Li, Mengjia

    Polyolefin geosynthetics are susceptible to oxidation, which eventually leads to the reduction in their engineering properties. In the application of polyolefin geosynthetics, a major issue is an estimate of the materials durability (i.e. service lifetime) under various aging conditions. Antioxidant packages are added to the polyolefin products to extend the induction time, during which antioxidants are gradually depleted and polymer oxidation reactions are prevented. In this PhD study, an improved laboratory accelerating aging method under elevated and high pressure environments was applied to evaluate the combined effect of temperature and pressure on the depletion of the antioxidants and the oxidation of polymers. Four types of commercial polyolefn geosynthetic materials selected for aging tests included HDPE geogrid, polypropylene woven and nonwoven geotextiles. A total of 33 different temperature/pressure aging conditions were used, with the incubation duration up to 24 months. The applied oven temperature ranged from 35°C to 105°C and the partial oxygen pressure ranged from 0.005 MPa to 6.3 MPa. Using the Oxidative Induction Time (OIT) test, the antioxidant depletion, which is correlated to the decrease of the OIT value, was found to follow apparent first-order decay. The OIT data also showed that, the antioxidant depletion rate increased with temperature according to the Arrhenius equation, while under constant temperatures, the rate increased exponentially with the partial pressure of oxygen. A modified Arrhenius model was developed to fit the antioxidant depletion rate as a function of temperature and pressure and to predict the antioxidant lifetime under various field conditions. This study has developed new temperature/pressure incubation aging test method with lifetime prediction models. Using this new technique, the antioxidant lifetime prediction results are close to regular temperature aging data while the aging duration can be reduced considerably

  6. Element mobility during pyrite weathering: implications for acid and heavy metal pollution at mining-impacted sites

    NASA Astrophysics Data System (ADS)

    Lu, Long; Wang, Rucheng; Chen, Fanrong; Xue, Jiyue; Zhang, Peihua; Lu, Jianjun

    2005-11-01

    Based on back scattered electron images and electron micro-probe analysis results, four alteration layers, including a transition layer, a reticulated ferric oxide layer, a nubby ferric oxide layer and a cellular ferric oxide layer, were identified in the naturally weathering products of pyrite. These layers represent a progressive alteration sequence of pyrite under weathering conditions. The cellular ferric oxide layer correlates with the strongest weathering phase and results from the dissolution of nubby ferric oxide by acidic porewater. Leaching coefficient was introduced to better express the response of element mobility to the degree of pyrite weathering. Its variation shows that the mobility of S, Co and Bi is stronger than As, Cu and Zn. Sulfur in pyrite is oxidized to sulfuric acid and sulfate that are basically released into to porewater, and heavy metals Co and Bi are evidently released by acid dissolution. As, Cu and Zn are enriched in ferric oxide by adsorption and by co-precipitation, but they would re-release to the environment via desorption or dissolution when porewater pH becomes low enough. Consequently, Co, Bi, As, Cu and Zn may pose a substantial impact on water quality. Considering that metal mobility and its concentration in mine waste are two important factors influencing heavy metal pollution at mining-impacted sites, Bi and Co are more important pollutants in this case.

  7. Soluble sulfur species extracted from coal by chemical leaching. [MS thesis; mineral and coal-derived pyrite; 114 references

    SciTech Connect

    Stephenson, M.D.

    1982-07-01

    The nature of the soluble sulfur-containing reaction products from the desulfurization of pyrite was studied. The rate of oxydesulfurization of the two varieties of pyrite was studied under the leaching conditions of the Ames process. Concentrations of soluble sulfur species were determined for oxydesulfurization using leach solutions of sodium carbonate, sodium bicarbonate, distilled water, and dilute sulfuric acid and for alkaline leaching without oxygen using sodium carbonate. Mineral grade pyrite was found to be much less reactive towards oxydesulfurization than coal-derived pyrite, although the mechanism of sulfur removal was apparently the same. The sulfur containing products of oxydesulfurization were found to be thiosulfate, sulfite, and sulfate for alkaline leach solutions, and elemental sulfur and sulfuric acid when neutral or acidic solutions were used. For the Ames process, thiosulfate was usually the major sulfur containing product, although oxidation to sulfite and sulfate was found to take place. Oxidation of thiosulfate did not occur with oxygen alone, but did occur in the presence of oxygen and partially reacted pyrite. Higher temperatures and higher oxygen partial pressures favored formation of sulfate at the expense of both thiosulfate and sulfite. With neutral and acidic leach solutions, sulfuric acid accounted for most of the sulfur, although measurable quantities of elemental sulfur were present.Higher oxygen partial pressures and higher temperatures favored the formation of sulfuric acid at the expense of elemental sulfur. Pyrite oxidized faster under alkaline conditions than under neutral or acidic conditions. Pyrite was also leached at high temperatures in a sodium carbonate solution in the absence of oxygen.

  8. Zinc stable isotope fractionation upon accelerated oxidative weathering of sulfidic mine waste.

    PubMed

    Matthies, R; Krahé, L; Blowes, D W

    2014-07-15

    Accelerated oxidative weathering in a reaction cell (ASTM D 5744 standard protocol) was performed over a 33 week period on well characterized, sulfidic mine waste from the Kidd Creek Cu-Zn volcanogenic massive sulfide deposit, Canada. The cell leachate was monitored for physicochemical parameters, ion concentrations and stable isotope ratios of zinc. Filtered zinc concentrations (<0.45 μm) in the leachate ranged between 4.5 mg L(-1) and 1.9 g L(-1)-potentially controlled by pH, mineral solubility kinetics and (de)sorption processes. The zinc stable isotope ratios varied mass-dependently within +0.1 and +0.52‰ relative to IRMM 3702, and were strongly dependent on the pH (rpH-d66Zn=0.65, p<0.005, n=31). At a pH below 5, zinc mobilization was governed by sphalerite oxidation and hydroxide dissolution-pointing to the isotope signature of sphalerite (+0.1 to +0.16‰). Desorption processes resulted in enrichment of (66)Zn in the leachate reaching a maximum offset of +0.32‰ compared to the proposed sphalerite isotope signature. Over a period characterized by pH=6.1 ± 0.6, isotope ratios were significantly more enriched in (66)Zn with an offset of ≈ 0.23‰ compared to sphalerite, suggesting that zinc release may have been derived from a second zinc source, such as carbonate minerals, which compose 8 wt.% of the tailings. This preliminary study confirms the benefit of applying zinc isotopes alongside standard monitoring parameters to track principal zinc sources and weathering processes in complex multi-phase matrices.

  9. High-resolution (SIMS) versus bulk sulfur isotope patterns of pyrite in Proterozoic microbialites with diverse mat textures

    NASA Astrophysics Data System (ADS)

    Gomes, M. L.; Fike, D. A.; Bergmann, K.; Knoll, A. H.

    2015-12-01

    Sulfur (S) isotope signatures of sedimentary pyrite preserved in marine rocks provide a rich suite of information about changes in biogeochemical cycling associated with the evolution of microbial metabolisms and oxygenation of Earth surface environments. Conventionally, these S isotope records are based on bulk rock measurements. Yet, in modern microbial mat environments, S isotope compositions of sulfide can vary by up to 40‰ over a spatial range of ~ 1 mm. Similar ranges of S isotope variability have been found in Archean pyrite grains using both Secondary Ion Mass Spectrometry and other micro-analytical techniques. These micron-scale patterns have been linked to changes in rates of microbial sulfate reduction and/or sulfide oxidation, isotopic distillation of the sulfate reservoir due to microbial sulfate reduction, and post-depositional alteration. Fine-scale mapping of S isotope compositions of pyrite can thus be used to differentiate primary environmental signals from post-depositional overprinting - improving our understanding of both. Here, we examine micron-scale S isotope patterns of pyrite in microbialites from the Mesoproterozoic-Neoproterozoic Sukhaya Tunguska Formation and Neoproterozoic Draken Formation in order to explore S isotope variability associated with different mat textures and pyrite grain morphologies. A primary goal is to link modern observations of how sulfide spatial isotope distributions reflect active microbial communities present at given depths in the mats to ancient processes driving fine-sale pyrite variability in microbialites. We find large (up to 60‰) S isotope variability within a spatial range of less than 2.5cm. The micron-scale S isotope measurements converge around the S isotope composition of pyrite extracted from bulk samples of the same microbialites. These micron-scale pyrite S isotope patterns have the potential to reveal important information about ancient biogeochemical cycling in Proterozoic mat environments

  10. Arsenic chemistry with sulfide, pyrite, zero-valent iron, and magnetite

    NASA Astrophysics Data System (ADS)

    Sun, Fenglong

    The aim of this thesis is to study the immobilization reactions of arsenic in water. Since compounds containing iron or sulfide are common in most natural and engineered systems, the research focused on the redox reactions and adsorption of arsenic with sulfide, pyrite, zero-valent iron (ZVI), and magnetite which were studied through wet chemistry methods and spectroscopic techniques. The kinetic and thermodynamic information of the reactions of As(V) with S(-II), As(V)/As(III) with pyrite and surface-oxidized pyrite, As(V) with ZVI and acid-treated ZVI, As(III) with magnetite was used to identify mechanisms. The necessity to maintain strictly anoxic conditions was emphasized for the study of arsenic redox chemistry with sulfides and ZVI. The major findings of this research can be stated as follows. First, dissolved sulfide reduced As(V) to lower valences to form a yellow precipitate at acidic pH. The reaction involved the formation of thioarsenic intermediate species. Dissolved O2, granular activated carbon (GAC) and dissolved Fe(II) inhibited the removal of As(V) by sulfide. Elemental sulfur catalyzed the reduction of As(V) by sulfide, which implied the possible benefit of using sulfur-loaded GAC for arsenic removal. Possible reaction mechanisms were discussed. Second, As(III) adsorbed on pristine pyrite over a broader pH range than on surface-oxidized pyrite, while As(V) adsorbed over a narrower pH range with pristine pyrite. As(V) was completely reduced to As(III) on pristine pyrite at acidic pH but not at higher pH. The reduction was first-order with respect to As(V). As(V) was not reduced on surface-oxidized pyrite at pH = 4--11. The different behaviors of As(V) and As(III) on pristine and surface oxidized pyrite determines the toxicity and mobility of arsenic under oxic/anoxic environments. Third, commercial ZVI reduced As(V) to As(III) at low pH (<9) but not at higher pH. Acid-treated ZVI reduced As(V) to As(0), indicated by wet chemical analyses and by

  11. Coffee Silverskin Extract Protects against Accelerated Aging Caused by Oxidative Agents.

    PubMed

    Iriondo-DeHond, Amaia; Martorell, Patricia; Genovés, Salvador; Ramón, Daniel; Stamatakis, Konstantinos; Fresno, Manuel; Molina, Antonio; Del Castillo, Maria Dolores

    2016-01-01

    Nowadays, coffee beans are almost exclusively used for the preparation of the beverage. The sustainability of coffee production can be achieved introducing new applications for the valorization of coffee by-products. Coffee silverskin is the by-product generated during roasting, and because of its powerful antioxidant capacity, coffee silverskin aqueous extract (CSE) may be used for other applications, such as antiaging cosmetics and dermaceutics. This study aims to contribute to the coffee sector's sustainability through the application of CSE to preserve skin health. Preclinical data regarding the antiaging properties of CSE employing human keratinocytes and Caenorhabditis elegans are collected during the present study. Accelerated aging was induced by tert-butyl hydroperoxide (t-BOOH) in HaCaT cells and by ultraviolet radiation C (UVC) in C. elegans. Results suggest that the tested concentrations of coffee extracts were not cytotoxic, and CSE 1 mg/mL gave resistance to skin cells when oxidative damage was induced by t-BOOH. On the other hand, nematodes treated with CSE (1 mg/mL) showed a significant increased longevity compared to those cultured on a standard diet. In conclusion, our results support the antiaging properties of the CSE and its great potential for improving skin health due to its antioxidant character associated with phenols among other bioactive compounds present in the botanical material. PMID:27258247

  12. Accelerated creep in solid oxide fuel cell anode supports during reduction

    NASA Astrophysics Data System (ADS)

    Frandsen, H. L.; Makowska, M.; Greco, F.; Chatzichristodoulou, C.; Ni, D. W.; Curran, D. J.; Strobl, M.; Kuhn, L. T.; Hendriksen, P. V.

    2016-08-01

    To evaluate the reliability of solid oxide fuel cell (SOFC) stacks during operation, the stress field in the stack must be known. During operation the stress field will depend on time as creep processes relax stresses. The creep of reduced Ni-YSZ anode support at operating conditions has been studied previously. In this work a newly discovered creep phenomenon taking place during the reduction is reported. This relaxes stresses at a much higher rate (∼×104) than creep during operation. The phenomenon was studied both in three-point bending and uniaxial tension. Differences between the two measurements could be explained by newly observed stress promoted reduction. Finally, samples exposed to a small tensile stress (∼0.004 MPa) were observed to expand during reduction, which is in contradiction to previous literature. These observations suggest that release of internal residual stresses between the NiO and the YSZ phases occurs during reduction. The accelerated creep should practically eliminate any residual stress in the anode support in an SOFC stack, as has previously been indirectly observed. This phenomenon has to be taken into account both in the production of stacks and in the simulation of the stress field in a stack based on anode supported SOFCs.

  13. Coffee Silverskin Extract Protects against Accelerated Aging Caused by Oxidative Agents.

    PubMed

    Iriondo-DeHond, Amaia; Martorell, Patricia; Genovés, Salvador; Ramón, Daniel; Stamatakis, Konstantinos; Fresno, Manuel; Molina, Antonio; Del Castillo, Maria Dolores

    2016-01-01

    Nowadays, coffee beans are almost exclusively used for the preparation of the beverage. The sustainability of coffee production can be achieved introducing new applications for the valorization of coffee by-products. Coffee silverskin is the by-product generated during roasting, and because of its powerful antioxidant capacity, coffee silverskin aqueous extract (CSE) may be used for other applications, such as antiaging cosmetics and dermaceutics. This study aims to contribute to the coffee sector's sustainability through the application of CSE to preserve skin health. Preclinical data regarding the antiaging properties of CSE employing human keratinocytes and Caenorhabditis elegans are collected during the present study. Accelerated aging was induced by tert-butyl hydroperoxide (t-BOOH) in HaCaT cells and by ultraviolet radiation C (UVC) in C. elegans. Results suggest that the tested concentrations of coffee extracts were not cytotoxic, and CSE 1 mg/mL gave resistance to skin cells when oxidative damage was induced by t-BOOH. On the other hand, nematodes treated with CSE (1 mg/mL) showed a significant increased longevity compared to those cultured on a standard diet. In conclusion, our results support the antiaging properties of the CSE and its great potential for improving skin health due to its antioxidant character associated with phenols among other bioactive compounds present in the botanical material.

  14. Arsenic release from pyrite ashes: kinetic studies.

    PubMed

    Lodolo, Andrea; Antonini, Paolo; Bukovec, Peter

    2013-01-01

    Arsenic mobility in pyrite ashes was studied because of the possible effects on water systems. The batch extraction method was used to assess kinetics and extent of As release induced by contact of the material either with rainwater or groundwater. Self-established pH-Eh range of pyrite ashes/water mixtures brought both As(III) and As(V) to be present in the water phase, as neutral arsenite H3AsO3 and anionic arsenate HAsO42-, respectively. Tests in reagent water showed both rate and extent of arsenite release higher than arsenate; total As concentration ([As] = 12 µg/L) at equilibrium little exceeded its EU Maximum Concentration Level (MCL) for surface and groundwater ([As] = 10 µg/L). Tests in groundwater, instead, showed a much higher release rate and extent for arsenate than for arsenite and the chemistry of groundwater mainly influenced arsenate mobility; total As almost instantly exceeded its MCL and it was markedly higher ([As] = 31 µg/L) at equilibrium. Overall, the study has shown the environmental implications of As mobility in the pyrite ashes, also casting light on some limits of the environmental representativeness of leaching tests in reagent water.

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

    SciTech Connect

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

    1997-12-31

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

  16. Cinnabar, arsenian pyrite and thallium-enrichment in active shallow submarine hydrothermal vents at Paleochori Bay, Milos Island, Greece

    NASA Astrophysics Data System (ADS)

    Kati, Marianna; Voudouris, Panagiotis; Valsami-Jones, Eugenia; Magganas, Andreas; Baltatzis, Emmanouil; Kanellopoulos, Christos; Mavrogonatos, Constantinos

    2015-04-01

    We herein report the discovery of active cinnabar-depositing hydrothermal vents in a submarine setting at Paleochori Bay, within the offshore southeastern extension of the Milos Island Geothermal Field, South Aegean Active Volcanic Arc. Active, low temperature (up to 115 °C) hydrothermal venting through volcaniclastic material has led to a varied assemblage of sulfide and alteration mineral phases in an area of approximately 1 km2. Our samples recovered from Paleochori Bay are hydrothermal edifices composed of volcaniclastic detrital material cemented by pyrite, or pure sulfide (mainly massive pyrite) mounts. Besides pyrite and minor marcasite, the hydrothermal minerals include cinnabar, amorphous silica, hydrous ferric oxides, carbonates (aragonite and calcite), alunite-jarosite solid solution and Sr-rich barite. Among others, growth textures, sieve-textured pyrite associated with barite, alunite-jarosite solid solution and hydrous ferric oxides rims colloform-banded pyrite layers. Overgrowths of arsenian pyrite layers (up to 3.2 wt. % As and/or up to 1.1 wt. % Mn) onto As-free pyrite indicate fluctuation in As content of the hydrothermal fluid. Mercury, in the form of cinnabar, occurs in up to 5 μm grains within arsenian pyrite layers, usually forming distinct cinnabar-enriched micro-layers. Hydrothermal Sr-rich barite (barite-celestine solid solution), pseudocubic alunite-jarosite solid solution and Mn- and Sr-enriched carbonates occur in various amounts and closely associated with pyrite and/or hydrous ferric oxides. Thallium-bearing sulfides and/or sulfosalts were not detected during our study; however, hydrous ferric oxides show thallium content of up to 0.5 wt. % Tl. The following scenarios may have played a role in pyrite precipitation at Paleochori: (a) H2S originally dissolved in the deep fluid but separated upon boiling could have reacted with oxygenated seawater under production of sulphuric acid, thus causing leaching and dissolution of primary iron

  17. Coupled pyrite concentration and sulfur isotopic insight into the paleo sulfate-methane transition zone (SMTZ) in the northern South China Sea

    NASA Astrophysics Data System (ADS)

    Lin, Qi; Wang, Jiasheng; Taladay, Katie; Lu, Hongfeng; Hu, Gaowei; Sun, Fei; Lin, Rongxiao

    2016-01-01

    The sulfate-methane transition zone (SMTZ) is an important diagenetic redox boundary within marine sediments where the anaerobic oxidation of methane (AOM), coupled with bacterial sulfate reduction, can promote sulfur isotopic enrichments in several solid phase minerals including pyrite (FeS2). Authigenic pyrite can form in concentrated abundances within the SMTZ and as such, can be used as a proxy to identify paleo-SMTZs. This study uses enrichments in 34S and anomalously high abundances of authigenic pyrites in 287 samples from the northern South China Sea (SCS) to determine the paleo-SMTZ. The pyrite samples were collected from sediment cores acquired at three sites, each of which are known to be located in natural gas hydrate-bearing regions. We assess the relative abundances of authigenic pyrites, the types of pyrite morphologies recovered in the cored sediments, and the sulfur isotopic values of recovered pyrite samples using two methods: (1) handpicked sample analysis using a binocular microscope, and (2) the chromium reduction method. Our results show that pyrite concentrations and sulfur isotopic compositions exhibit synchronous fluctuations, particularly from 6.8 m below seafloor (mbsf) to 8.4 mbsf at all three study sites. There is a significant increase in the occurrence of rod-like pyrite morphology within this key interval. We define the position of the paleo-SMTZ by the presence of anomalously high accumulations of pyrites at greater than 5.0 wt.% using the handpicking method or greater than 0.5 wt.% via the chromium reduction method, along with positive Δδ34S excursions greater than 10.0‰ VCDT. We discovered a regional paleo-SMTZ that is shallower than the modern SMTZ, suggesting a previous period of elevated methane flux from depth, possibly related to widespread gas hydrate dissociation.

  18. Potential of using cerium oxide nanoparticles for protecting healthy tissue during accelerated partial breast irradiation (APBI)

    PubMed Central

    Ouyang, Zi; Mainali, Madan Kumar; Sinha, Neeharika; Strack, Guinevere; Altundal, Yucel; Hao, Yao; Winningham, Thomas Andrew; Sajo, Erno; Celli, Jonathan; Ngwa, Wilfred

    2016-01-01

    The purpose of this study is to investigate the feasibility of using cerium oxide nanoparticles (CONPs) as radical scavengers during accelerated partial breast irradiation (APBI) to protect normal tissue. We hypothesize that CONPs can be slowly released from the routinely used APBI balloon applicators—via a degradable coating—and protect the normal tissue on the border of the lumpectomy cavity over the duration of APBI. To assess the feasibility of this approach, we analytically calculated the initial concentration of CONPs required to protect normal breast tissue from reactive oxygen species (ROS) and the time required for the particles to diffuse to various distances from the lumpectomy wall. Given that cerium has a high atomic number, we took into account the possible inadvertent dose enhancement that could occur due to the photoelectric interactions with radiotherapy photons. To protect against a typical MammoSite treatment fraction of 3.4 Gy, 5 ng-g−1 of CONPs is required to scavenge hydroxyl radicals and hydrogen peroxide. Using 2 nm sized NPs, with an initial concentration of 1 mg-g−1, we found that 2–10 days of diffusion is required to obtain desired concentrations of CONPs in regions 1–2 cm away from the lumpectomy wall. The resultant dose enhancement factor (DEF) is less than 1.01 under such conditions. Our results predict that CONPs can be employed for radioprotection during APBI using a new design in which balloon applicators are coated with the NPs for sustained/controlled in-situ release from within the lumpectomy cavity. PMID:27053452

  19. Potential of using cerium oxide nanoparticles for protecting healthy tissue during accelerated partial breast irradiation (APBI).

    PubMed

    Ouyang, Zi; Mainali, Madan Kumar; Sinha, Neeharika; Strack, Guinevere; Altundal, Yucel; Hao, Yao; Winningham, Thomas Andrew; Sajo, Erno; Celli, Jonathan; Ngwa, Wilfred

    2016-04-01

    The purpose of this study is to investigate the feasibility of using cerium oxide nanoparticles (CONPs) as radical scavengers during accelerated partial breast irradiation (APBI) to protect normal tissue. We hypothesize that CONPs can be slowly released from the routinely used APBI balloon applicators-via a degradable coating-and protect the normal tissue on the border of the lumpectomy cavity over the duration of APBI. To assess the feasibility of this approach, we analytically calculated the initial concentration of CONPs required to protect normal breast tissue from reactive oxygen species (ROS) and the time required for the particles to diffuse to various distances from the lumpectomy wall. Given that cerium has a high atomic number, we took into account the possible inadvertent dose enhancement that could occur due to the photoelectric interactions with radiotherapy photons. To protect against a typical MammoSite treatment fraction of 3.4Gy, 5ng·g(-1) of CONPs is required to scavenge hydroxyl radicals and hydrogen peroxide. Using 2nm sized NPs, with an initial concentration of 1mg·g(-1), we found that 2-10days of diffusion is required to obtain desired concentrations of CONPs in regions 1-2cm away from the lumpectomy wall. The resultant dose enhancement factor (DEF) is less than 1.01 under such conditions. Our results predict that CONPs can be employed for radioprotection during APBI using a new design in which balloon applicators are coated with the NPs for sustained/controlled in-situ release from within the lumpectomy cavity. PMID:27053452

  20. A higher oxidative status accelerates senescence and aggravates age-dependent disorders in SAMP strains of mice.

    PubMed

    Hosokawa, Masanori

    2002-11-01

    The SAM strain of mice is actually a group of related inbred strains consisting of series of SAMP (accelerated senescence-prone, short-lived) and SAMR (accelerated senescence-resistant, longer-lived) strains. Comparing with the SAMR strains, the SAMP strains of mice show a more accelerated senescence process, shorter lifespan, and an earlier onset and more rapid progress of age-associated pathological phenotypes similar to several geriatric disorders observed in humans, including senile osteoporosis, degenerative joint disease, age-related deficits in learning and memory, olfactory bulb and forebrain atrophy, presbycusis and retinal atrophy, senile amyloidosis, immunosenescence, senile lungs, and diffuse medial thickening of the aorta. The higher oxidative stress observed in the SAMP strains of mice are partly caused by mitochondrial dysfunction, and may be one cause of the senescence acceleration and age-dependent alterations in cell structure and function, including neuronal cell degeneration. This senescence acceleration is also observed during senescence/crisis in cultures of isolated fibroblast-like cells from SAMP strains of mice, and was associated with a hyperoxidative status. These observations suggest that the SAM strains are useful tools in the attempt to understand the mechanisms of age-dependent degeneration of cells and tissues, and their aggravation, and to develop clinical interventions. PMID:12470893

  1. Ultrafine pyrite desulfurization by selective flocculation

    SciTech Connect

    Cai, Z.; Liu, H.; Wu, J.; Wang, X.

    1997-12-31

    Selective flocculation is introduced for the separation of ultrafine pyrite from coal. Selective flocculation refers to the process in which high molecule weight polymer reagents bridge the fine particles of one component in a mixture. According to the differences in physico-chemical properties, the reagent can be adsorbed on one component which can be flocculated but not on others which cannot be flocculated. A number of selective flocculation separation tests under different conditions have been performed and the results are very encouraging. The results also show that desulfurization and deashing can be obtained simultaneously in the selective flocculation process.

  2. Geochemistry of pyrite from diamictites of the Hamersley Basin, Western Australia with implications for the GOE and Paleoproterozoic ice ages.

    NASA Astrophysics Data System (ADS)

    Swanner, Elizabeth; Cates, Nicole; Pecoits, Ernesto; Bekker, Andrey; Konhauser, Kurt O.; Mojzsis, Stephen J.

    2013-04-01

    Sediments of the ca. 2400 Ma Turee Creek Group of Western Australia span the oxygenation of Earth's surface resulting from the 'Great Oxidation Event' (GOE). Diamictite within the Boolgeeda Iron Formation from the Boundary Ridge section at Duck Creek Syncline have been correlated to the glaciogenic Meteorite Bore Member of the Turee Creek Group at Hardey Syncline (Martin, 1999). The Meteorite Bore Member is thought to be correlative and time-equivalent with the Paleoproterozoic glacial diamictites of North America. If diamictite units at Boundary Ridge represent worldwide Paleoproterozoic glaciations, they should record the disappearance of mass independently fractionated (MIF) sulfur. Triple S-isotope compositions for pyrites from the Boundary Ridge sections measured by in situ multi-collector ion microprobe yielded both mass-dependent and mass-independently fractionated (MIF) S isotope values (Δ33S values from -0.65 to 6.27). Trace element heterogeneities were found by measurements at multiple spatial scales within rounded pyrites in the Boundary Ridge section, signifying multiple generations of pyrite from sulfur processed in an anoxic atmosphere. S-isotope data from pyrite in the Boundary Ridge diamictites analyzed in this study and previous work (Williford et al., 2011) define multiple δ34S vs. δ33S arrays, linked to a source of detrital pyrite from the overlying Hamersley and Fortescue groups. Authigenic pyrite in an overlying shale unit from Boundary Ridge plot along the terrestrial fractionation line but retain positive MIF-S and detrital pyrite, results that are incompatible with a correlation to North American Paleoproterozoic glacially-influenced successions where the MIF-S signal permanently disappears. The diamictites at the Duck Creek Syncline are older than the Meteorite Bore Member because of their stratigraphic position within the Boolgeeda Iron Formation underlying the Turee Creek Group, which is separated from the Meteorite Bore Member by

  3. Pyritic ash-flow tuff, Yucca Mountain, Nevada -- A discussion

    SciTech Connect

    Weiss, S.I.; Larson, L.T.; Noble, D.C.

    1994-12-31

    Textural and mineralogic evidence exists for at least one episode of widespread hydrothermal alteration of volcanic rocks deep in Yucca Mountain, Nevada. Despite this evidence, Castor et al. infer that most of the pyrite found in tuffs at Yucca Mountain was introduced as ejecta (lithic fragments) incorporated during the eruptions of the tuffs, rather than by in-situ hydrothermal activity. Their conclusions appear to be based on their observation that most of the pyrite resides in unaltered to variably altered and veined lithic fragments, whereas pyrite-bearing veins are absent in the tuff matrix, titanomagnetite and mafic phenocrysts in the matrix are generally not replaced by pyrite, and feldspar phenocrysts in the pyritic tuff matrix are generally unaltered. Castor et al. dismiss the much smaller quantities of pyrite disseminated in the tuff matrix, including relatively rare pyritized hornblende and biotite grains, as xenolithic as well. The pyritic tuffs belong to large-volume, subalkaline rhyolite ash-flow units (ca. > 150 to 250 km{sup 3} each). The interpretation of Castor et al. has broad implications for the temperature, fO{sub 2} and fS{sub 2} of major ash flow eruptions. Pyrite origin also bears on the nature of past fluid flow and water-rock reactions at Yucca Mountain, which in turn are important factors in assessing the potential for currently undiscovered mineral resources in the area of the proposed nuclear waste repository. We have studied core and cuttings from the same drill holes studied by Castor et al., as well as other drill holes. It is our contention that the inconsistent lateral and stratigraphic distribution of the pyrite, textural features of the pyrite, and phase stability considerations are incompatible with the {open_quotes}lithic{close_quotes} origin of Castor et al., and are more reasonably explained by in-situ formation from hydrothermal fluids containing low, but geochemically significant, concentrations of reduced sulfur.

  4. Poor maternal nutrition and accelerated postnatal growth induces an accelerated aging phenotype and oxidative stress in skeletal muscle of male rats

    PubMed Central

    Fernandez-Twinn, Denise S.; Chen, Jian Hua; Hargreaves, Iain P.; Neergheen, Viruna; Aiken, Catherine E.; Ozanne, Susan E.

    2016-01-01

    ABSTRACT ‘Developmental programming’, which occurs as a consequence of suboptimal in utero and early environments, can be associated with metabolic dysfunction in later life, including an increased incidence of cardiovascular disease and type 2 diabetes, and predisposition of older men to sarcopenia. However, the molecular mechanisms underpinning these associations are poorly understood. Many conditions associated with developmental programming are also known to be associated with the aging process. We therefore utilized our well-established rat model of low birth weight and accelerated postnatal catch-up growth (termed ‘recuperated’) in this study to establish the effects of suboptimal maternal nutrition on age-associated factors in skeletal muscle. We demonstrated accelerated telomere shortening (a robust marker of cellular aging) as evidenced by a reduced frequency of long telomeres (48.5-8.6 kb) and an increased frequency of short telomeres (4.2-1.3 kb) in vastus lateralis muscle from aged recuperated offspring compared to controls. This was associated with increased protein expression of the DNA-damage-repair marker 8-oxoguanine-glycosylase (OGG1) in recuperated offspring. Recuperated animals also demonstrated an oxidative stress phenotype, with decreased citrate synthase activity, increased electron-transport-complex activities of complex I, complex II-III and complex IV (all markers of functional mitochondria), and increased xanthine oxidase (XO), p67phox and nuclear-factor kappa-light-chain-enhancer of activated B-cells (NF-κB). Recuperated offspring also demonstrated increased antioxidant defense capacity, with increased protein expression of manganese superoxide dismutase (MnSOD), copper-zinc superoxide dismutase (CuZnSOD), catalase and heme oxygenase-1 (HO1), all of which are known targets of NF-κB and can be upregulated as a consequence of oxidative stress. Recuperated offspring also had a pro-inflammatory phenotype, as evidenced by

  5. A thermodynamic study of pyrite and pyrrhotite

    USGS Publications Warehouse

    Toulmin, P.; Barton, P.B.

    1964-01-01

    Through the use of the electrum-tarnish method the following equation has been found to interrelate the composition of pyrrhotite, fugacity of sulfur, and temperature: In this equation fs2 is the fugacity of sulfur relative to the ideal diatomic gas at 1 atm, N is the mol fraction of FeS in pyrrhotite (in the system FeS-S2), and T the absolute temperature. The experimental uncertainty in the equation is 0-003 in N. The activity of FeS (aFeS) in pyrrhotite relative to the pure substance at the temperature of consideration follows from the above equation by virtue of the Gibbs-Duhem relation; it is given by:. The electrum-tarnish method has permitted us to determine the fs2 vs. T curve for the univariant assemblage pyrrhotite-pyrite-vapor from 743 to 325??C. Our determinations of the composition of pyrrhotite are in excellent agreement with the results of Arnold. The activity of FeS in pyrite-saturated pyrrhotite is very different from unity, a fact that greatly influences the interpretation of some other phase equilibrium studies involving pyrrhotite and their application to sulfide mineral assemblages, but has little effect on the more general calculations of composition of hydrothermal or magmatic fluids. Pressure effects calculated from available volumetric data on the phases are small. ?? 1964.

  6. Changes in oxidative stress parameters and neurodegeneration markers in the brain of the senescence-accelerated mice SAMP-8.

    PubMed

    Sureda, Francesc X; Gutierrez-Cuesta, Javier; Romeu, Marta; Mulero, Miquel; Canudas, Anna Maria; Camins, Antoni; Mallol, Jordi; Pallàs, Mercè

    2006-04-01

    The senescence-accelerated strains of mice (SAMP) are well-characterized animal models of senescence. Senescence may be related to enhanced production or defective control of reactive oxygen species, which lead to neuronal damage. Therefore, the activity of various oxidative-stress related enzymes was determined in the cortex of 5 months-old senescence-accelerated mice prone-8 (SAMP-8) of both sexes and compared with senescence-accelerated mice-resistant-1 (SAMR-1). Glutathione reductase and peroxidase activities in SAMP-8 male mice were lower than in male SAMR-1, and a decreased catalase activity was found in both male and female SAMP-8 mice, which correlates with the lower catalase expression found by Western blotting. Nissl staining showed marked loss of neuronal cells in the cerebral cortex of five month-old SAMP-8 mice. SAMP-8 mice also had marked astrogliosis and microgliosis. We also found an increase in caspase-3 and calpain activity in the cortex. In addition, we observed morphological changes in the immunostaining of tau protein in SAMP-8, indicative of a loss of their structural function. Altogether, these results show that, at as early as 5 months of age, SAMP-8 mice have cytological and molecular alterations indicative of neurodegeneration in the cerebral cortex and suggestive of altered control of the production of oxidative species and hyper-activation of calcium-dependent enzymes. PMID:16542809

  7. Controlled colloidal synthesis of iron pyrite FeS2 nanorods and quasi-cubic nanocrystal agglomerates

    NASA Astrophysics Data System (ADS)

    Zhu, Leize; Richardson, Beau J.; Yu, Qiuming

    2013-12-01

    Earth-abundant and nontoxic pyrite iron disulfide (FeS2) is very promising for photovoltaic applications but the phase purity and the morphology of iron pyrite nanocrystals (NCs) have a significant impact on the solar cell performance. In this work, we systematically investigated reaction conditions and the local chemical environment on the phase purity and morphology of iron pyrite NCs synthesized via the hot injection method. By using different solvents to dissolve iron and sulfur agents, varying reactant concentrations, and adding trioctylphosphine oxide (TOPO) or 1,2-hexadecanediol (Diol) into the reaction solution, iron pyrite short, branched and chromosome-like rods were obtained with a diameter of ~10 nm and a length of ~20-30 nm as well as quasi-cubic NC agglomerates with a size of ~200 nm. Our experimental results show that the molar ratio of sulfur to iron and the reaction temperature are two critical factors in determining the crystalline phase of the synthesized materials. A mechanism involving the generation of H2S is proposed to explain the phase purity observed. The as-synthesized iron pyrite NCs can be dispersed well in chloroform, chlorobenzene, toluene, and hexane and thus are promising in solution-processable photovoltaic applications.

  8. Photoeffects in cobalt doped pyrite (FeS 2) films

    NASA Astrophysics Data System (ADS)

    Thomas, B.; Ellmer, K.; Bohne, W.; Röhrich, J.; Kunst, M.; Tributsch, H.

    1999-07-01

    By indiffusion of a thin metallic cobalt layer into a pyrite film deposited by metal organic chemical vapour deposition (MOCVD), cobalt doped pyrite (FeS 2) films have been prepared. The cobalt in these films acts as a donor and transforms the originally p-type into n-type conductivity. To our knowledge this is the first time that n-type pyrite films have been prepared. Compared to the undoped p-type pyrite films, the cobalt-diffused films exhibit a much higher photoconductivity, as revealed by time resolved microwave conductivity analysis. From Hall and conductivity measurements a charge carrier concentration of about 10 20 cm -3 and a Hall mobility of about 1.5 cm 2/(V s) was calculated. This has to be compared with p-type pyrite films which do not show a Hall mobility above 0.1 cm 2/(V s), the detection limit of our Hall system. By analytical techniques (Rutherford backscattering and photoelectron spectroscopy) it was confirmed that the increase of the photoactivity is a bulk property of the pyrite films and not merely due to a surface passivation (for instance, due to metallic CoS 2). The presented results stimulate further experiments on in-situ-doping of pyrite by MOCVD and open the opportunity for the preparation of pn-junctions and pn-solar cells with pyrite.

  9. Process for removing pyritic sulfur from bituminous coals

    DOEpatents

    Pawlak, Wanda; Janiak, Jerzy S.; Turak, Ali A.; Ignasiak, Boleslaw L.

    1990-01-01

    A process is provided for removing pyritic sulfur and lowering ash content of bituminous coals by grinding the feed coal, subjecting it to micro-agglomeration with a bridging liquid containing heavy oil, separating the microagglomerates and separating them to a water wash to remove suspended pyritic sulfur. In one embodiment the coal is subjected to a second micro-agglomeration step.

  10. Quantitative proteomics analysis of specific protein expression and oxidative modification in aged senescence-accelerated-prone 8 mice brain.

    PubMed

    Poon, H F; Castegna, A; Farr, S A; Thongboonkerd, V; Lynn, B C; Banks, W A; Morley, J E; Klein, J B; Butterfield, D A

    2004-01-01

    The senescence-accelerated mouse (SAM) is a murine model of accelerated senescence that was established using phenotypic selection. The SAMP series includes nine substrains, each of which exhibits characteristic disorders. SAMP8 is known to exhibit age-dependent learning and memory deficits. In our previous study, we reported that brains from 12-month-old SAMP8 have greater protein oxidation, as well as lipid peroxidation, compared with brains from 4-month-old SAMP8 mice. In order to investigate the relation between age-associated oxidative stress on specific protein oxidation and age-related learning and memory deficits in SAMP8, we used proteomics to identify proteins that are expressed differently and/or modified oxidatively in aged SAMP8 brains. We report here that in 12 month SAMP8 mice brains the expressions of neurofilament triplet L protein, lactate dehydrogenase 2 (LDH-2), heat shock protein 86, and alpha-spectrin are significantly decreased, while the expression of triosephosphate isomerase (TPI) is increased compared with 4-month-old SAMP8 brains. We also report that the specific protein carbonyl levels of LDH-2, dihydropyrimidinase-like protein 2, alpha-spectrin and creatine kinase, are significantly increased in the brain of 12-month-old SAMP8 mice when compared with the 4-month-old SAMP8 brain. These findings are discussed in reference to the effect of specific protein oxidation and changes of expression on potential mechanisms of abnormal alterations in metabolism and neurochemicals, as well as to the learning and memory deficits in aged SAMP8 mice.

  11. Ambient pyrite in precambrian chert: new evidence and a theory.

    PubMed

    Knoll, A H; Barghoorn, E S

    1974-06-01

    Ambient pyrites of two distinct types were described from middle Precambrian rocks of the Lake Superior area. A new class of this phenomenon is here described from middle Precambrian chert from western Australia. The newly found ambient pyrites are quite minute and characteristically occur in groups forming a "starburst" pattern. All three types of ambient pyrite may be explained in terms of pressure solution initiated by gas evolution from organic material attached to the pyrite. Thermal degradation of the kerogen produces the gases which, due to the impermeability of the encompassing chert, build up the pressures necessary to initiate solution. Pyrite appendages bear a striking resemblance to micro-organisms and, thus, constitute the smallest pseudofossils known. PMID:16592159

  12. The hidden life of pyrite: how low can it go?

    NASA Astrophysics Data System (ADS)

    Boyle, Alan; Barrie, Craig; Salter, Michael

    2010-05-01

    Pyrite is the most abundant sulphide mineral in the Earth's crust, being present in most rock units but only volumetrically important in sulphide ore deposits. Thus, rheological behaviour of pyrite does not have significant implications for crustal deformation as a whole, but it does for deformation of ore deposits. Therefore, understanding pyrite behaviour in ore deposits may help understanding of deformation in rocks where it is of low abundance. Pyrite is a difficult mineral to study because it is both opaque and cubic, two properties that hide most of its microstructure when studied using optical microscopy as well as standard SEM back-scattered electron imaging. Etching can reveal some of the internal secrets of pyrite, but the technique is not universally applicable. The generally accepted view from such studies, coupled with experimental deformation and some TEM studies, is that pyrite is a robust mineral, which, under typical geological strain-rates, deforms by plastic deformation mechanisms above ~425 °C and by brittle or pressure-solution diffusive mechanisms below. Over the last decade or so, the advent of reliable and fast SEM-based electron backscattered diffraction (EBSD) systems, coupled with orientation contrast (OC) imaging techniques, has revolutionised study of microstructure in cubic minerals. Plastic deformation can now be readily identified in pyrite; it is no longer hidden. Freitag et al (2004) documented relatively low temperature (~350 °C) plastic deformation of pyrite from Green's Creek, Alaska, raising the possibility that pyrite deforms plastically at lower temperatures than is generally accepted. In this presentation we describe pyrite microstructures from a series of pyrite-rich polymetallic ore deposits (Parys Mountain, Anglesey; Løkken, Norway; Baia Borsa, Romania), deformed at low temperature metamorphic conditions (~200-420 °C). Our results (Barrie et al. 2009) indicate that pyrite grains in all of the ore deposits studied

  13. Ambient pyrite in precambrian chert: new evidence and a theory.

    PubMed

    Knoll, A H; Barghoorn, E S

    1974-06-01

    Ambient pyrites of two distinct types were described from middle Precambrian rocks of the Lake Superior area. A new class of this phenomenon is here described from middle Precambrian chert from western Australia. The newly found ambient pyrites are quite minute and characteristically occur in groups forming a "starburst" pattern. All three types of ambient pyrite may be explained in terms of pressure solution initiated by gas evolution from organic material attached to the pyrite. Thermal degradation of the kerogen produces the gases which, due to the impermeability of the encompassing chert, build up the pressures necessary to initiate solution. Pyrite appendages bear a striking resemblance to micro-organisms and, thus, constitute the smallest pseudofossils known.

  14. Ambient Pyrite in Precambrian Chert: New Evidence and a Theory

    PubMed Central

    Knoll, Andrew H.; Barghoorn, Elso S.

    1974-01-01

    Ambient pyrites of two distinct types were described from middle Precambrian rocks of the Lake Superior area. A new class of this phenomenon is here described from middle Precambrian chert from western Australia. The newly found ambient pyrites are quite minute and characteristically occur in groups forming a “starburst” pattern. All three types of ambient pyrite may be explained in terms of pressure solution initiated by gas evolution from organic material attached to the pyrite. Thermal degradation of the kerogen produces the gases which, due to the impermeability of the encompassing chert, build up the pressures necessary to initiate solution. Pyrite appendages bear a striking resemblance to micro-organisms and, thus, constitute the smallest pseudofossils known. Images PMID:16592159

  15. Surface electrochemical control for fine coal and pyrite separation. Technical progress report, April 1, 1990--June 30, 1990

    SciTech Connect

    Hu, Weibai; Zhu, Ximeng; Bodily, D.M.; Wadsworth, M.E.

    1990-12-31

    Ongoing work includes the characterization of coal pyrites, the floatability evaluation typical US coal samples, the flotation behavior of coal pyrites, the electrochemical measurement of the surface properties of coal pyrites, and the characterization of species produced at pyrite surfaces.

  16. Cr(VI) removal from aqueous systems using pyrite as the reducing agent: Batch, spectroscopic and column experiments

    NASA Astrophysics Data System (ADS)

    Kantar, Cetin; Ari, Cihan; Keskin, Selda; Dogaroglu, Zeynep Gorkem; Karadeniz, Aykut; Alten, Akin

    2015-03-01

    Laboratory batch and column experiments, in conjunction with geochemical calculations and spectroscopic analysis, were performed to better understand reaction mechanisms and kinetics associated with Cr(VI) removal from aqueous systems using pyrite as the reactive material under both static and dynamic flow conditions similar to those observed in in situ permeable reactive barriers (PRBs). The X-ray photoelectron spectroscopy (XPS) and geochemical calculations suggest that the Cr(VI) removal by pyrite occurred due to the reduction of Cr(VI) to Cr(III), coupled with the oxidation of Fe(II) to Fe(III) and S22 - to SO42 - at the pyrite surface. Zeta potential measurements indicate that although the pyrite surface was negatively charged under a wide pH range in the absence of Cr(VI), it behaved more like a "metal oxide" surface with the surface potential shifting from positive to negative values at pH values > pH 6 in the presence of Cr(VI). Batch experiments show that increasing solution pH led to a significant decrease in Cr(VI) removal. The decrease in Cr(VI) removal at high Cr(VI) concentrations and pH values can be explained through the precipitation of sparingly soluble Cr(OH)3(s), Fe(OH)3(s) and Fe(III)-Cr(III) (oxy) hydroxides onto pyrite surface which may, then, lead to surface passivation for further Cr(VI) reduction. Batch results also suggest that the reaction kinetics follow a first order model with rate constants decreasing with increasing solution pH, indicating proton consumption during Cr(VI) reduction by pyrite. Column experiments indicate that nearly 100% of total Fe in the column effluent was in the form of Fe(II) species with a [SO42 -]/[Fe2 +] stoichiometric ratio of 2.04, indicating that the reduction of Cr(VI) by pyrite produced about 2 mol of sulfate per mole of Fe (II) release under excess surface sites relative to Cr(VI) concentration. Column experiments provide further evidence on the accumulation of oxidation products which consequently led

  17. Cr(VI) removal from aqueous systems using pyrite as the reducing agent: batch, spectroscopic and column experiments.

    PubMed

    Kantar, Cetin; Ari, Cihan; Keskin, Selda; Dogaroglu, Zeynep Gorkem; Karadeniz, Aykut; Alten, Akin

    2015-03-01

    Laboratory batch and column experiments, in conjunction with geochemical calculations and spectroscopic analysis, were performed to better understand reaction mechanisms and kinetics associated with Cr(VI) removal from aqueous systems using pyrite as the reactive material under both static and dynamic flow conditions similar to those observed in in situ permeable reactive barriers (PRBs). The X-ray photoelectron spectroscopy (XPS) and geochemical calculations suggest that the Cr(VI) removal by pyrite occurred due to the reduction of Cr(VI) to Cr(III), coupled with the oxidation of Fe(II) to Fe(III) and S2(2-) to SO4(2-) at the pyrite surface. Zeta potential measurements indicate that although the pyrite surface was negatively charged under a wide pH range in the absence of Cr(VI), it behaved more like a "metal oxide" surface with the surface potential shifting from positive to negative values at pH values >pH 6 in the presence of Cr(VI). Batch experiments show that increasing solution pH led to a significant decrease in Cr(VI) removal. The decrease in Cr(VI) removal at high Cr(VI) concentrations and pH values can be explained through the precipitation of sparingly soluble Cr(OH)(3(s)), Fe(OH)(3(s)) and Fe(III)-Cr(III) (oxy) hydroxides onto pyrite surface which may, then, lead to surface passivation for further Cr(VI) reduction. Batch results also suggest that the reaction kinetics follow a first order model with rate constants decreasing with increasing solution pH, indicating proton consumption during Cr(VI) reduction by pyrite. Column experiments indicate that nearly 100% of total Fe in the column effluent was in the form of Fe(II) species with a [SO4(2-)]/[Fe(2+)] stoichiometric ratio of 2.04, indicating that the reduction of Cr(VI) by pyrite produced about 2 mol of sulfate per mole of Fe (II) release under excess surface sites relative to Cr(VI) concentration. Column experiments provide further evidence on the accumulation of oxidation products which

  18. Hydrosilane and bismuth-accelerated palladium catalyzed aerobic oxidative esterification of benzylic alcohols with air.

    PubMed

    Bai, Xing-Feng; Ye, Fei; Zheng, Long-Sheng; Lai, Guo-Qiao; Xia, Chun-Gu; Xu, Li-Wen

    2012-09-01

    In a palladium-catalyzed oxidative esterification, hydrosilane can serve as an activator of palladium catalyst with bismuth, thus leading to a novel ligand- and silver-free palladium catalyst system for facile oxidative esterification of a variety of benzylic alcohols in good yields.

  19. Hydrosilane and bismuth-accelerated palladium catalyzed aerobic oxidative esterification of benzylic alcohols with air.

    PubMed

    Bai, Xing-Feng; Ye, Fei; Zheng, Long-Sheng; Lai, Guo-Qiao; Xia, Chun-Gu; Xu, Li-Wen

    2012-09-01

    In a palladium-catalyzed oxidative esterification, hydrosilane can serve as an activator of palladium catalyst with bismuth, thus leading to a novel ligand- and silver-free palladium catalyst system for facile oxidative esterification of a variety of benzylic alcohols in good yields. PMID:22814568

  20. Accelerator Magnet Plugging By Metal Oxides: A Theoretical Investigation, Remediation, and Preliminary Results

    SciTech Connect

    William W. Rust

    2003-05-01

    The Thomas Jefferson National Accelerator Facility has experienced magnet overheating at high power. Overheating is caused by cooling water passages becoming plugged and is a direct result of the Dean Effect deposition of corrosion products suspended in the water. Salving simplified dynamic model equations of the flow in the magnet tubing bends yielded a relationship for plugging rate as a function of particle size, concentration, velocity, channel width and bend radius. Calculated deposition rates using data from a previous study are promising. Remediation has consisted of submicron filtration, magnet cleaning, and dissolved oxygen removal. Preliminary results are good: no accelerator outages have been attributed to magnet plugging since the remediation has been completed.

  1. Greigite: a true intermediate on the polysulfide pathway to pyrite

    PubMed Central

    Hunger, Stefan; Benning, Liane G

    2007-01-01

    The formation of pyrite (FeS2) from iron monosulfide precursors in anoxic sediments has been suggested to proceed via mackinawite (FeS) and greigite (Fe3S4). Despite decades of research, the mechanisms of pyrite formation are not sufficiently understood because solid and dissolved intermediates are oxygen-sensitive and poorly crystalline and therefore notoriously difficult to characterize and quantify. In this study, hydrothermal synchrotron-based energy dispersive X-ray diffraction (ED-XRD) methods were used to investigate in situ and in real-time the transformation of mackinawite to greigite and pyrite via the polysulfide pathway. The rate of formation and disappearance of specific Bragg peaks during the reaction and the changes in morphology of the solid phases as observed with high resolution microscopy were used to derive kinetic parameters and to determine the mechanisms of the reaction from mackinawite to greigite and pyrite. The results clearly show that greigite is formed as an intermediate on the pathway from mackinawite to pyrite. The kinetics of the transformation of mackinawite to greigite and pyrite follow a zero-order rate law indicating a solid-state mechanism. The morphology of greigite and pyrite crystals formed under hydrothermal conditions supports this conclusion and furthermore implies growth of greigite and pyrite by oriented aggregation of nanoparticulate mackinawite and greigite, respectively. The activation enthalpies and entropies of the transformation of mackinawite to greigite, and of greigite to pyrite were determined from the temperature dependence of the rate constants according to the Eyring equation. Although the activation enthalpies are uncharacteristic of a solid-state mechanism, the activation entropies indicate a large increase of order in the transition state, commensurate with a solid-state mechanism. PMID:17376247

  2. Preventing the accelerated low-temperature oxidation of MoSi{sub 2} (pesting) by the application of superficial alkali-salt layers

    SciTech Connect

    Cockeram, B.V.; Wang, G.; Rapp, R.A.

    1996-02-01

    Previous work showed that MoSi{sub 2} diffusion coatings formed by a NaF-activated pack cementation process did not pest. A Na-Al-oxide by-product layer resulting from the NaF activator formed a Na-silicate layer to passivate MoSi{sub 2}. Superficial NaF layers were then used to prevent the pesting of MoSi{sub 2} diffusion coatings that were otherwise susceptible to pest disintegration. In this study, the use of superficial alkali-salt layers to prevent the accelerated oxidation of bulk MoSi{sub 2} at 500{degrees}C is investigated more broadly. The application of Na-halide, KF, LiF, Na{sub 2}B{sub 4}O{sub 7}, or Na-silicate layers prior to oxidation prevented accelerated oxidation and pesting for at least 2000 hr at 500{degrees}C in air. The formation of a fast-growing, Na-silicate layer passivates MoSi{sub 2}. The MoO{sub 3} that forms during oxidation absorbs sodium by intercalation to form stable Na-molybdate precipitates. Na{sub 2}B{sub 4}O{sub 7}, Na-silicate, LiF, and KF prevented accelerated oxidation at 500{degrees}C by a similar mechanism. The application of alkali-halide salts is a simple, effective solution to prevent the accelerated oxidation and pesting of MoSi{sub 2}.

  3. Oxidation resistance of Y-implanted steel using accelerator based techniques

    NASA Astrophysics Data System (ADS)

    Noli, F.; Lagoyannis, A.; Misaelides, P.

    2008-05-01

    The thermal oxidation behavior in air of Y-implanted (fluence 2 × 1017 ions/cm2) and non-implanted stainless steel AISI-321 samples was investigated using the 16O(d,p)17O nuclear reaction and Rutherford backscattering spectrometry (RBS). The oxidation temperature was 650 and 900 °C and the duration of the thermal treatment 48 hours. The influence of the implantation energy (40, 55 and 80 keV) on the oxidation behavior of stainless steel was also studied. An improvement of the oxidation resistance of the Y-implanted samples with increasing implantation energy was observed. Additional secondary ion mass spectroscopy (SIMS) measurements of the samples implanted by 40 keV Y-ions also indicated a slight chromium depletion of their near-surface layers. Mechanisms attempting to explain the experimental results are proposed.

  4. Deciphering a multistage history affecting U-Cu(-Fe) mineralization in the Singhbhum Shear Zone, eastern India, using pyrite textures and compositions in the Turamdih U-Cu(-Fe) deposit

    NASA Astrophysics Data System (ADS)

    Pal, Dipak C.; Barton, Mark D.; Sarangi, A. K.

    2009-01-01

    The ˜200-km-long intensely deformed Singhbhum Shear Zone (SSZ) in eastern India hosts India’s largest U and Cu deposits and related Fe mineralization. The SSZ separates an Archaean cratonic nucleus to the south from a Mesoproterozoic fold belt in the North and has a complex geologic history that obscures the origin of the contained iron-oxide-rich mineral deposits. This study investigates aspects of the history of mineralization in the SSZ by utilizing new petrographic and electron microprobe observations of pyrite textures and zoning in the Turamdih U-Cu(-Fe) deposit. Mineralization at Turamdih is hosted in intensively deformed quartz-chlorite schist. Sulfides and oxides include, in inferred order of development: (a) magmatic Fe(-Ti-Cr) oxide and Fe-Cu(-Ni) sulfide minerals inferred to be magmatic (?) in origin; followed by (b) uranium, Fe-oxide, and Fe-Cu(-Co) sulfide minerals that predate most or all ductile deformation, and are inferred to be of hydrothermal origin; and (c) Fe-Cu sulfides that were generated during and postdating ductile deformation. These features are associated with the formation of three compositionally and texturally distinct pyrites. Pyrite (type-A), typically in globular-semiglobular composite inclusions of pyrite plus chalcopyrite in magnetite, is characterized by very high Ni content (up to 30,700 ppm) and low Co to Ni ratios (0.01-0.61). The textural and compositional characteristics of associated chalcopyrite and rare pyrrhotite suggest that this pyrite could be linked to the magmatic event via selective replacement of magmatic pyrrhotite. Alternatively, this pyrite and associated sulfide inclusions might be cogenetic with hydrothermal Fe-oxide. Type-B pyrite that forms elongate grains and irregular relics and cores of pyrite with high Co contents (up to 23,630 ppm) and high Co to Ni ratios (7.2-140.9) are interpreted to be related to hydrothermal mineralization predating ductile deformation. A third generation of pyrite (type C

  5. Arsenopyrite and pyrite bioleaching: evidence from XPS, XRD and ICP techniques.

    PubMed

    Fantauzzi, Marzia; Licheri, Cristina; Atzei, Davide; Loi, Giovanni; Elsener, Bernhard; Rossi, Giovanni; Rossi, Antonella

    2011-10-01

    In this work, a multi-technical bulk and surface analytical approach was used to investigate the bioleaching of a pyrite and arsenopyrite flotation concentrate with a mixed microflora mainly consisting of Acidithiobacillus ferrooxidans. X-ray diffraction, X-ray photoelectron spectroscopy (XPS) and X-ray-induced Auger electron spectroscopy mineral surfaces investigations, along with inductively coupled plasma-atomic emission spectroscopy and carbon, hydrogen, nitrogen and sulphur determination (CHNS) analyses, were carried out prior and after bioleaching. The flotation concentrate was a mixture of pyrite (FeS(2)) and arsenopyrite (FeAsS); after bioleaching, 95% of the initial content of pyrite and 85% of arsenopyrite were dissolved. The chemical state of the main elements (Fe, As and S) at the surface of the bioreactor feed particles and of the residue after bioleaching was investigated by X-ray photoelectron and X-ray excited Auger electron spectroscopy. After bioleaching, no signals of iron, arsenic and sulphur originating from pyrite and arsenopyrite were detected, confirming a strong oxidation and the dissolution of the particles. On the surfaces of the mineral residue particles, elemental sulphur as reaction intermediate of the leaching process and precipitated secondary phases (Fe-OOH and jarosite), together with adsorbed arsenates, was detected. Evidence of microbial cells adhesion at mineral surfaces was also produced: carbon and nitrogen were revealed by CHNS, and nitrogen was also detected on the bioleached surfaces by XPS. This was attributed to the deposition, on the mineral surfaces, of the remnants of a bio-film consisting of an extra-cellular polymer layer that had favoured the bacterial action.

  6. Pyrite as a proxy for the identification of former coastal lagoons in semiarid NE Brazil

    NASA Astrophysics Data System (ADS)

    Ferreira, Tiago O.; Nóbrega, Gabriel N.; Albuquerque, Antonia G. B. M.; Sartor, Lucas R.; Gomes, Irlene S.; Artur, Adriana G.; Otero, Xosé L.

    2015-10-01

    This work aimed to test the suitability of pyrite (FeS2) as a proxy for reconstructing past marine environmental conditions along the semiarid coast of Brazil. Morphological description combined with physicochemical analyses including Fe partitioning were conducted for soil depth profiles (30 and 60 cm depths) at three sites in two contrasting lagoons of the state of Ceará: a suspected former lagoon that would have been transformed into a freshwater "lake" at a site vegetated by Juncus effusus (site P1), and another lagoon with connection to the sea at sites vegetated by J. effusus (site P2) or Portulaca oleracea (site P3). Soil samples were collected in September 2010. Site P3 had more reducing conditions, reaching Eh values of -132 mV in the surface layer (0-10 cm), whereas minimum values for the P1 and P2 sites were +219 and +85 mV, respectively. Lower pyritic Fe values were found at site P1, with a degree of pyritization (DOP) ranging from 10 to 13%. At sites P2 and P3, DOP ranged from 9 to 67% and from 55 to 72%, respectively. These results are consistent with an interruption of tidal channels by eolian dune migration inducing strong changes in the hydrodynamics and physicochemical characteristics (lower salinity, oxidizing conditions) of these sites, causing the dieback of suspected former mangroves and a succession to freshwater marshes with an intermediate salt marsh stage. Together with other physicochemical signatures, pyrite can evidently serve as a useful proxy in tracking environmental changes in such ecotones, with implications for coastal management.

  7. Parahalogenated phenols accelerate the photochemical release of nitrogen oxides from frozen solutions containing nitrate.

    PubMed

    Abida, Otman; Osthoff, Hans D

    2012-06-21

    The photolysis of nitrate anion (NO(3)(-)) contained in surface ice and snow can be a regionally significant source of gas-phase nitrogen oxides and affect the composition of the planetary boundary layer. In this study, the photochemical release of nitrogen oxides from frozen solutions containing NO(3)(-) in the presence of organic compounds was investigated. Gas-phase nitrogen oxides were quantified primarily by NO-O(3) chemiluminescence detection of NO and NO(y) (=NO + NO(2) + HONO + HNO(3) + ∑PAN + ∑AN ...) and cavity ring-down spectroscopy of NO(2) and total alkyl nitrates (∑AN). The photochemical production of gas-phase NO(y) was suppressed by the presence of formate, methanesulfonate, toluene, or phenol. In contrast, para-halogenated phenols (in the order of Cl > Br > F) promoted the conversion of NO(3)(-) to gas-phase NO(y), rationalized by acidification of the ice surface.

  8. Reactive oxygen species accelerate degradation of anion exchange membranes based on polyphenylene oxide in alkaline environments.

    PubMed

    Parrondo, Javier; Wang, Zhongyang; Jung, Min-Suk J; Ramani, Vijay

    2016-07-20

    Anion exchange membranes (AEM) based on polyphenylene oxide (PPO) suffered quaternary-ammonium-cation-site degradation in alkaline environments. Surprisingly, the degradation rate was considerably faster in the presence of molecular oxygen. We postulated that the AEM cation-site catalyzes the reduction of dioxygen by hydroxide ions to yield the superoxide anion radical and the highly reactive hydroxyl free radical. We substantiated our hypothesis by using a phosphorous-containing spin trap (5-diisopropoxy-phosphoryl-5-methyl-1-pyrroline-N-oxide) to detect the adducts for both free radicals in situ using (31)P-NMR spectroscopy. PMID:27381009

  9. Microstructural evolution and trace element mobility in Witwatersrand pyrite

    NASA Astrophysics Data System (ADS)

    Reddy, Steven M.; Hough, Robert M.

    2013-11-01

    Microstructural analysis of pyrite from a single sample of Witwatersrand conglomerate indicates a complex deformation history involving components of both plastic and brittle deformation. Internal deformation associated with dislocation creep is heterogeneously developed within grains, shows no systematic relationship to bulk rock strain or the location of grain boundaries and is interpreted to represent an episode of pyrite deformation that predates the incorporation of detrital pyrite grains into the Central Rand conglomerates. In contrast, brittle deformation, manifest by grain fragmentation that transects dislocation-related microstructures, is spatially related to grain contacts and is interpreted to represent post-depositional deformation of the Central Rand conglomerates. Analysis of the low-angle boundaries associated with the early dislocation creep phase of deformation indicates the operation of <010>{100} slip systems. However, some orientation boundaries have geometrical characteristics that are not consistent with simple <010>{100} deformation. These boundaries may represent the combination of multiple slip systems or the operation of the previously unrecognized <001>{120} slip system. These boundaries are associated with order of magnitude enrichments in As, Ni and Co that indicate a deformation control on the remobilization of trace elements within pyrite and a potential slip system control on the effectiveness of fast-diffusion pathways. The results confirm the importance of grain-scale elemental remobilization within pyrite prior to their incorporation into the Witwatersrand gold-bearing conglomerates. Since the relationship between gold and pyrite is intimately related to the trace element geochemistry of pyrite, the results have implications for the application of minor element geochemistry to ore deposit formation, suggest a reason for heterogeneous conductivity and localized gold precipitation in natural pyrite and provide a framework for

  10. Degradation of tyrosol by a novel electro-Fenton process using pyrite as heterogeneous source of iron catalyst.

    PubMed

    Ammar, Salah; Oturan, Mehmet A; Labiadh, Lazhar; Guersalli, Amor; Abdelhedi, Ridha; Oturan, Nihal; Brillas, Enric

    2015-05-01

    Tyrosol (TY) is one of the most abundant phenolic components of olive oil mill wastewaters. Here, the degradation of synthetic aqueous solutions of 0.30 mM TY was studied by a novel heterogeneous electro-Fenton (EF) process, so-called EF-pyrite, in which pyrite powder was the source of Fe(2+) catalyst instead of a soluble iron salt used in classical EF. Experiments were performed with a cell equipped with a boron-doped diamond anode and a carbon-felt cathode, where TY and its products were destroyed by hydroxyl radicals formed at the anode surface from water oxidation and in the bulk from Fenton's reaction between Fe(2+) and H2O2 generated at the cathode. Addition of 1.0 g L(-1) pyrite provided an easily adjustable pH to 3.0 and an appropriate 0.20 mM Fe(2+) to optimize the EF-pyrite treatment. The effect of current on mineralization rate, mineralization current efficiency and specific energy consumption was examined under comparable EF and EF-pyrite conditions. The performance of EF-pyrite was 8.6% superior at 50 mA due to self-regulation of soluble Fe(2+) by pyrite. The TY decay in this process followed a pseudo-first-order kinetics. The absolute rate constant for TY hydroxylation was 3.57 × 10(9) M(-1) s(-1), as determined by the competition kinetics method. Aromatic products like 3,4-dihydroxyphenylethanol, 4-hydroxyphenylacetic acid, 4-hydroxybenzoic acid, 3,4-dihydroxybenzoic acid and catechol, as well as o-benzoquinone, were identified by GC-MS and reversed-phase HPLC. Short-chain aliphatic carboxylic acids like maleic, glycolic, acetic, oxalic and formic were quantified by ion-exclusion HPLC. Oxalic acid was the major and most persistent product found. Based on detected intermediates, a plausible mineralization pathway for TY by EF-pyrite was proposed. PMID:25720669

  11. Effect of the presence of pyrite traces on silver behavior in natural porous media.

    PubMed

    Charrière, Delphine; Hernández Cortázar, Manuel de A; Behra, Philippe

    2015-05-15

    In order to better understand the fate of the toxic element Ag(I), sorption of Ag(I) was studied from batch experiments, at different pHs (2-8) and at 298 K. A pure quartz sand (99.999% SiO2) and "natural" quartz sand (99% SiO2, and traces of Fe, Al, Mn (hydr)oxides, of clays and of pyrite) were used as sorbents. The Ag(I) sorption behavior depends strongly on pH with isotherm shapes characteristic of Langmuir-type relationship for initial Ag concentration [Ag(I)], range between 5.0×10(-7) and 1.0×10(-3) M. Even if the Ag (I) sorption capacity on pure quartz sand is very low compared to the natural quartz sands, its affinity is rather high. From speciation calculations, several sites were proposed: at pHi 4, 6 and 8, the first surface site is assumed to be due to iron (hydr)oxides while the second surface site is attributed to silanols. At pHi 2, sorption of Ag(I) was assumed to be on two surface sites of iron (hydr)oxides and a third surface site on silanol groups. Even if the sand is mainly composed of silica, the trace minerals play an important role in sorption capacity compared to silica. The conditional surface complexation constants of Ag(I) depend on pH. On the other hand, it is shown that the Ag speciation depends strongly on the history of "natural" quartz sand due to initial applied treatment, little rinsing or longer washing. In the presence of low amount of pyrite, strong complexes between Ag(I) and sulfur compounds such as thiosulfates due to oxidative dissolution of pyrite are formed what decreases Ag sorption capability. SEM-EDS analyses highlighted the surface complexation-precipitation of Ag2S and Ag(0) colloids which confirmed the important role of pyrite on Ag(I) speciation.

  12. Conductive iron oxide minerals accelerate syntrophic cooperation in methanogenic benzoate degradation.

    PubMed

    Zhuang, Li; Tang, Jia; Wang, Yueqiang; Hu, Min; Zhou, Shungui

    2015-08-15

    Recent studies have suggested that conductive iron oxide minerals can facilitate syntrophic metabolism of the methanogenic degradation of organic matter, such as ethanol, propionate and butyrate, in natural and engineered microbial ecosystems. This enhanced syntrophy involves direct interspecies electron transfer (DIET) powered by microorganisms exchanging metabolic electrons through electrically conductive minerals. Here, we evaluated the possibility that conductive iron oxides (hematite and magnetite) can stimulate the methanogenic degradation of benzoate, which is a common intermediate in the anaerobic metabolism of aromatic compounds. The results showed that 89-94% of the electrons released from benzoate oxidation were recovered in CH4 production, and acetate was identified as the only carbon-bearing intermediate during benzoate degradation. Compared with the iron-free controls, the rates of methanogenic benzoate degradation were enhanced by 25% and 53% in the presence of hematite and magnetite, respectively. This stimulatory effect probably resulted from DIET-mediated methanogenesis in which electrons transfer between syntrophic partners via conductive iron minerals. Phylogenetic analyses revealed that Bacillaceae, Peptococcaceae, and Methanobacterium are potentially involved in the functioning of syntrophic DIET. Considering the ubiquitous presence of iron minerals within soils and sediments, the findings of this study will increase the current understanding of the natural biological attenuation of aromatic hydrocarbons in anaerobic environments.

  13. Solution-based Syntheses of Iron Pyrite Thin Films for Photovoltaic and Protein Foot-printing Applications

    NASA Astrophysics Data System (ADS)

    El Makkaoui, Mohammed

    Iron pyrite (cubic FeS2) is a non-toxic, earth abundant semiconductor possessing a set of excellent optical/electronic properties for serving as an absorber layer in PV devices. Additionally, pyrite is a very efficient hydroxyl radical generator via Fenton chemistry and has shown promise in oxidative protein and DNA foot-printing application. The main focus of this thesis is on fabricating phase and elementally pure iron pyrite thin films using a solution-based approach that employs hydrazine as a solvent. A precursor ink is formed at room temperature by mixing elemental iron and sulfur in anhydrous hydrazine and then deposited on Mo-coated glass substrates, via spin coating, to yield amorphous iron sulfide films that are then annealed in H2S (340°C) and sulfur gas (≤ 500 °C) to form uniform, polycrystalline and phase pure pyrite films with densely packed grains. This approach is likely to yield the most elementally pure pyrite thin films made to date, through a very simple and scalable process. The ink has shown to be very sensitive to environmental conditions and has a very short shelf life (˜1 day). Additionally, the film microstructure is greatly influenced by the S:Fe concentration ratio that when tuned to 3:1, yielded uniform, robust and optically flat iron sulfide thin films with an optimal thickness (˜320 nm) for PV application. The results however were not reproducible, mainly due to failure in applying multiple layers without compromising film morphology. Thinner (< 100 nm) iron sulfide films, on the other hand, are reproducibly produced, but are too thin to be employed in PV devices. Direct annealing in sulfur gas at 475°C for 4 hours, bypassing the > 12 hour H2S annealing step, yielded phase pure pyrite films, with good morphology, at lower processing time and annealing temperatures (< 500°C). The latter part of this thesis regards the use of pyrite nano-crystals in conjunction with high surface area polymer laminates for protein foot

  14. [Study on phase distribution and release of heavy metal in pyrite using sequential extraction procedure and ICP-MS].

    PubMed

    Zhang, Ping; Qi, Jian-Ying; Yang, Chun-Xia; Chen, Yong-Heng

    2007-06-01

    Heavy metal elements of V, Cr, Mn, Co, Ni, Cu, Zn, Sr, Mo, Cd, Sb, Ba and Pb were determined by ICP-MS. The linear ranges of determination for these elements were obtained, and the correlation coefficients were larger than 0.997. The detection limit ranges were from 0.005 to 0.01 microg x L(-1) and the RSDs were lower than 5%. Phase distributions of heavy metals in pyrite were analyzed by ICP-MS with sequential extraction procedure. The result showed that Pb was the main heavy metal in pyrite and its total content was 830 mg x kg(-1). Pb existed mostly in carbonate or galena (PbS) phase of pyrite and the proportion was 56.9%. Pb existed less in iron oxides with 29.7% in proportion, and least in sulfide and silicate with 3.5% and 9.9%, respectively. The release of Pb in pyrite was primary in natural environment, but the release of Cr and Cd was not be ignorable, too. PMID:17763794

  15. Computational Chemistry Study of Accelerated Oxidation Mechanism of IGSCC of Structural Materials in LWR Environments and Theoretical Design of SCC Resistant Alloys

    SciTech Connect

    Ken Suzuki; Yo-ichi Takeda; Zhanpeng Lu; Tetsuo Shoji

    2004-07-01

    Computational chemistry has been used to investigate the mechanism of accelerated oxidation of IGSCC. It has been found that the iron atoms along the grain boundary were oxidized more easily than those at other sites. Moreover, success has been achieved in the examination of the effects of element additions to Fe-based alloys. The results indicated that the Ti, Mn, Sr, Y, Ce, and Hf could be used as such additional elements to obtain improvements in the SCC resistance. (authors)

  16. Nobiletin, a citrus flavonoid, ameliorates cognitive impairment, oxidative burden, and hyperphosphorylation of tau in senescence-accelerated mouse.

    PubMed

    Nakajima, Akira; Aoyama, Yuki; Nguyen, Thuy-Ty Lan; Shin, Eun-Joo; Kim, Hyoung-Chun; Yamada, Shinnosuke; Nakai, Tsuyoshi; Nagai, Taku; Yokosuka, Akihito; Mimaki, Yoshihiro; Ohizumi, Yasushi; Yamada, Kiyofumi

    2013-08-01

    Senescence-accelerated mouse prone 8 (SAMP8) is a model of aging characterized by the early onset of learning and memory impairment and various pathological features of Alzheimer's disease (AD). Our recent studies have demonstrated that nobiletin, a polymethoxylated flavone from citrus peels, ameliorates learning and memory impairment in olfactory-bulbectomized mice, amyloid precursor protein transgenic mice, and NMDA receptor antagonist-treated mice. Here, we present evidence that this natural compound improves age-related cognitive impairment and reduces oxidative stress and tau phosphorylation in SAMP8 mice. Treatment with nobiletin (10 or 50mg/kg) reversed the impairment of recognition memory and context-dependent fear memory in SAMP8 mice. Treatment with nobiletin also restored the decrease in the GSH/GSSG ratio in the brain of SAMP8 mice. In addition, increases in glutathione peroxidase and manganese-superoxide dismutase activities, as well as a decrease in protein carbonyl level, were observed in the brain of nobiletin-treated SAMP8 mice. Furthermore, nobiletin reduced tau phosphorylation in the hippocampus of SAMP8 mice. Together, the markedly beneficial effects of nobiletin represent a potentially useful treatment for ameliorating the learning and memory deficits, oxidative stress, and hyperphosphorylation of tau in aging as well as age-related neurodegenerative diseases such as AD.

  17. Oxidized high-density lipoprotein accelerates atherosclerosis progression by inducing the imbalance between treg and teff in LDLR knockout mice.

    PubMed

    Ru, Ding; Zhiqing, He; Lin, Zhu; Feng, Wu; Feng, Zhang; Jiayou, Zhang; Yusheng, Ren; Min, Fan; Chun, Liang; Zonggui, Wu

    2015-05-01

    High density lipoprotein (HDL) dysfunction has been widely reported in clinic, and oxidation of HDL (ox-HDL) was shown to be one of the most common modifications in vivo and participate in the progression of atherosclerosis. But the behind mechanisms are still elusive. In this study, we firstly analyzed and found strong relationship between serum ox-HDL levels and risk factors of coronary artery diseases in clinic, then the effects of ox-HDL in initiation and progression of atherosclerosis in LDLR knockout mice were investigated by infusion of ox-HDL dissolved in chitosan hydrogel before the formation of lesions in vivo. Several new evidence were shown: (i) the serum levels of ox-HDL peaked early before the formation of lesions in LDLR mice fed with high fat diet similar to oxidative low density lipoprotein, (ii) the formation of atherosclerotic lesions could be accelerated by infusion of ox-HDL, (iii) the pro-atherosclerotic effects of ox-HDL were accompanied by imbalanced levels of effector and regulatory T cells and relative gene expressions, which implied that imbalance of teff and treg might contribute to the pro-atherosclerosis effects of ox-HDL.

  18. Conductive Fe3O4 Nanoparticles Accelerate Syntrophic Methane Production from Butyrate Oxidation in Two Different Lake Sediments

    PubMed Central

    Zhang, Jianchao; Lu, Yahai

    2016-01-01

    Syntrophic methanogenesis is an essential link in the global carbon cycle and a key bioprocess for the disposal of organic waste and production of biogas. Recent studies suggest direct interspecies electron transfer (DIET) is involved in electron exchange in methanogenesis occurring in paddy soils, anaerobic digesters, and specific co-cultures with Geobacter. In this study, we evaluate the possible involvement of DIET in the syntrophic oxidation of butyrate in the enrichments from two lake sediments (an urban lake and a natural lake). The results showed that the production of CH4 was significantly accelerated in the presence of conductive nanoscale Fe3O4 or carbon nanotubes in the sediment enrichments. Observations made with fluorescence in situ hybridization and scanning electron microscope indicated that microbial aggregates were formed in the enrichments. It appeared that the average cell-to-cell distance in aggregates in nanomaterial-amended enrichments was larger than that in aggregates in the non-amended control. These results suggested that DIET-mediated syntrophic methanogenesis could occur in the lake sediments in the presence of conductive materials. Microbial community analysis of the enrichments revealed that the genera of Syntrophomonas, Sulfurospirillum, Methanosarcina, and Methanoregula were responsible for syntrophic oxidation of butyrate in lake sediment samples. The mechanism for the conductive-material-facilitated DIET in butyrate syntrophy deserves further investigation.

  19. Conductive Fe3O4 Nanoparticles Accelerate Syntrophic Methane Production from Butyrate Oxidation in Two Different Lake Sediments

    PubMed Central

    Zhang, Jianchao; Lu, Yahai

    2016-01-01

    Syntrophic methanogenesis is an essential link in the global carbon cycle and a key bioprocess for the disposal of organic waste and production of biogas. Recent studies suggest direct interspecies electron transfer (DIET) is involved in electron exchange in methanogenesis occurring in paddy soils, anaerobic digesters, and specific co-cultures with Geobacter. In this study, we evaluate the possible involvement of DIET in the syntrophic oxidation of butyrate in the enrichments from two lake sediments (an urban lake and a natural lake). The results showed that the production of CH4 was significantly accelerated in the presence of conductive nanoscale Fe3O4 or carbon nanotubes in the sediment enrichments. Observations made with fluorescence in situ hybridization and scanning electron microscope indicated that microbial aggregates were formed in the enrichments. It appeared that the average cell-to-cell distance in aggregates in nanomaterial-amended enrichments was larger than that in aggregates in the non-amended control. These results suggested that DIET-mediated syntrophic methanogenesis could occur in the lake sediments in the presence of conductive materials. Microbial community analysis of the enrichments revealed that the genera of Syntrophomonas, Sulfurospirillum, Methanosarcina, and Methanoregula were responsible for syntrophic oxidation of butyrate in lake sediment samples. The mechanism for the conductive-material-facilitated DIET in butyrate syntrophy deserves further investigation. PMID:27597850

  20. Conductive Fe3O4 Nanoparticles Accelerate Syntrophic Methane Production from Butyrate Oxidation in Two Different Lake Sediments.

    PubMed

    Zhang, Jianchao; Lu, Yahai

    2016-01-01

    Syntrophic methanogenesis is an essential link in the global carbon cycle and a key bioprocess for the disposal of organic waste and production of biogas. Recent studies suggest direct interspecies electron transfer (DIET) is involved in electron exchange in methanogenesis occurring in paddy soils, anaerobic digesters, and specific co-cultures with Geobacter. In this study, we evaluate the possible involvement of DIET in the syntrophic oxidation of butyrate in the enrichments from two lake sediments (an urban lake and a natural lake). The results showed that the production of CH4 was significantly accelerated in the presence of conductive nanoscale Fe3O4 or carbon nanotubes in the sediment enrichments. Observations made with fluorescence in situ hybridization and scanning electron microscope indicated that microbial aggregates were formed in the enrichments. It appeared that the average cell-to-cell distance in aggregates in nanomaterial-amended enrichments was larger than that in aggregates in the non-amended control. These results suggested that DIET-mediated syntrophic methanogenesis could occur in the lake sediments in the presence of conductive materials. Microbial community analysis of the enrichments revealed that the genera of Syntrophomonas, Sulfurospirillum, Methanosarcina, and Methanoregula were responsible for syntrophic oxidation of butyrate in lake sediment samples. The mechanism for the conductive-material-facilitated DIET in butyrate syntrophy deserves further investigation. PMID:27597850

  1. Oxidized high-density lipoprotein accelerates atherosclerosis progression by inducing the imbalance between treg and teff in LDLR knockout mice.

    PubMed

    Ru, Ding; Zhiqing, He; Lin, Zhu; Feng, Wu; Feng, Zhang; Jiayou, Zhang; Yusheng, Ren; Min, Fan; Chun, Liang; Zonggui, Wu

    2015-05-01

    High density lipoprotein (HDL) dysfunction has been widely reported in clinic, and oxidation of HDL (ox-HDL) was shown to be one of the most common modifications in vivo and participate in the progression of atherosclerosis. But the behind mechanisms are still elusive. In this study, we firstly analyzed and found strong relationship between serum ox-HDL levels and risk factors of coronary artery diseases in clinic, then the effects of ox-HDL in initiation and progression of atherosclerosis in LDLR knockout mice were investigated by infusion of ox-HDL dissolved in chitosan hydrogel before the formation of lesions in vivo. Several new evidence were shown: (i) the serum levels of ox-HDL peaked early before the formation of lesions in LDLR mice fed with high fat diet similar to oxidative low density lipoprotein, (ii) the formation of atherosclerotic lesions could be accelerated by infusion of ox-HDL, (iii) the pro-atherosclerotic effects of ox-HDL were accompanied by imbalanced levels of effector and regulatory T cells and relative gene expressions, which implied that imbalance of teff and treg might contribute to the pro-atherosclerosis effects of ox-HDL. PMID:25912129

  2. Quantitative analysis of volatiles in edible oils following accelerated oxidation using broad spectrum isotope standards

    PubMed Central

    Gómez-Cortés, Pilar; Sacks, Gavin L.; Brenna, J. Thomas

    2014-01-01

    Analysis of food volatiles generated by processing are widely reported but comparisons across studies is challenging in part because most reports are inherently semi-quantitative for most analytes due to limited availability of chemical standards. We recently introduced a novel strategy for creation of broad spectrum isotopic standards for accurate quantitative food chemical analysis. Here we apply the principle to quantification of 25 volatiles in seven thermally oxidized edible oils. After extended oxidation, total volatiles of high n-3 oils (flax, fish, cod liver) were 120-170 mg/kg while low n-3 vegetable oils were <50 mg/kg. Separate experiments on thermal degradation of d5-ethyl linolenate indicate that off-aroma volatiles originate throughout the n-3 molecule and not solely the n-3 terminal end. These data represent the first report using broad-spectrum isotopically labeled standards for quantitative characterization of processing-induced volatile generation across related foodstuffs, and verify the origin of specific volatiles from parent n-3 fatty acids. PMID:25529686

  3. Linseed oil presents different patterns of oxidation in real-time and accelerated aging assays.

    PubMed

    Douny, Caroline; Razanakolona, Rina; Ribonnet, Laurence; Milet, Jérôme; Baeten, Vincent; Rogez, Hervé; Scippo, Marie-Louise; Larondelle, Yvan

    2016-10-01

    This study aimed at verifying if the hypothesis that one day at 60°C is equivalent to one month at 20°C could be confirmed during linseed oil aging for 6months at 20°C and 6days at 60°C using the "Schaal oven stability test". Tests were conducted with linseed oil supplemented or not with myricetin or butyl-hydroxytoluene as antioxidants. Oxidation was evaluated with the peroxide and p-anisidine values, as well as the content in conjugated dienes and aldehydes. All four indicators of oxidation showed very different kinetic behaviors at 20 and 60°C. The hypothesis is thus not verified for linseed oil, supplemented or not with antioxidant. In the control oil, the conjugated dienes and the peroxide value observed were respectively of 41.8±0.8 Absorbance Unit (AU)/g oil and 254.3±5.8meq.O2/kg oil after 6months at 20°C. These values were of 18.2±1.3AU/g oil and 65.2±20.3meq.O2/kg after 6days at 60°C.

  4. Iberian Pyrite Belt Subsurface Life (IPBSL), a drilling project in a geochemical Mars terrestrial analogue

    NASA Astrophysics Data System (ADS)

    Amils, R.; Fernández-Remolar, D. C.; Parro, V.; Manfredi, J. A.; Timmis, K.; Oggerin, M.; Sánchez-Román, M.; López, F. J.; Fernández, J. P.; Omoregie, E.; Gómez-Ortiz, D.; Briones, C.; Gómez, F.; García, M.; Rodríguez, N.; Sanz, J. L.

    2012-09-01

    Iberian Pyrite Belt Subsurface Life (IPBSL) is a drilling project specifically designed to characterize the subsurface ecosystems operating in the Iberian Pyrite Belt (IPB), in the area of Peña de Hierro, and responsible of the extreme acidic conditions existing in the Rio Tinto basin [1]. Rio Tinto is considered a good geochemical terrestrial analogue of Mars [2, 3]. A dedicated geophysical characterization of the area selected two drilling sites (4) due to the possible existence of water with high ionic content (low resistivity). Two wells have been drilled in the selected area, BH11 and BH10, of depths of 340 and 620 meters respectively, with recovery of cores and generation of samples in anaerobic and sterile conditions. Preliminary results showed an important alteration of mineral structures associated with the presence of water, with production of expected products from the bacterial oxidation of pyrite (sulfates and ferric iron). Ion chromatography of water soluble compounds from uncontaminated samples showed the existence of putative electron donors (ferrous iron, nitrite in addition of the metal sulfides), electron acceptors (sulfate, nitrate, ferric iron) as well as variable concentration of metabolic organic acids (mainly acetate, formate, propionate and oxalate), which are strong signals of the presence of active subsurface ecosystem associated to the high sulfidic mineral content of the IPB. The system is driven by oxidants that appear to be provided by the rock matrix, only groundwater is needed to launch microbial metabolism. The geological, geomicrobiological and molecular biology analysis which are under way, should allow the characterization of this ecosystem of paramount interest in the design of an astrobiological underground Mars exploration mission in the near future.

  5. Multiscale characterization of pyritized plant tissues in blueschist facies metamorphic rocks

    NASA Astrophysics Data System (ADS)

    Bernard, Sylvain; Benzerara, Karim; Beyssac, Olivier; Brown, Gordon E., Jr.

    2010-09-01

    Pyritized plant tissues with well-preserved morphology were studied in rocks from Vanoise (western Alps, France) that experienced high-pressure, low-temperature metamorphic conditions in the blueschist facies during the Alpine orogeny. Organic and inorganic phases composing these fossils were characterized down to the nanometer scale by Raman microspectroscopy, scanning transmission X-ray microscopy and transmission electron microscopy. The graphitic but disordered organic matter composing these fossils is chemically and structurally homogeneous and mostly contains aromatic functional groups. Its original chemistry remains undefined likely because it was significantly transformed by diagenetic processes and/or thermal degradation during metamorphism. Various mineral phases are closely associated with this organic matter, including sulphides such as pyrite and pyrrhotite, carbonates such as ankerite and calcite, and iron oxides. A tentative time sequence of formation of these diverse mineral phases relative to organic matter decay is proposed. The absence of traces of organic matter sulphurization, the pervasive pyritization of the vascular tissues and the presence of ankerite suggest that the depositional/diagenetic environment of these metasediments was likely rich in reactive iron. Fe-sulphides and ankerite likely precipitated early and might have promoted the preservation of the fossilized biological soft tissues by providing mechanical resistance to compaction during diagenesis and subsequent metamorphism. In contrast, iron oxides which form rims of 100-nm in thickness at the interface between organic matter and Fe-sulphides may result from metamorphic processes. This study illustrates that it may be possible in some instances to deconvolve metamorphic from diagenetic imprints and opens new avenues to better constrain processes that may allow the preservation of organic fossils during diagenesis and metamorphism.

  6. Zinc oxide nanoparticles induce migration and adhesion of monocytes to endothelial cells and accelerate foam cell formation

    SciTech Connect

    Suzuki, Yuka; Tada-Oikawa, Saeko; Ichihara, Gaku; Yabata, Masayuki; Izuoka, Kiyora; Suzuki, Masako; Sakai, Kiyoshi; Ichihara, Sahoko

    2014-07-01

    Metal oxide nanoparticles are widely used in industry, cosmetics, and biomedicine. However, the effects of exposure to these nanoparticles on the cardiovascular system remain unknown. The present study investigated the effects of nanosized TiO{sub 2} and ZnO particles on the migration and adhesion of monocytes, which are essential processes in atherosclerogenesis, using an in vitro set-up of human umbilical vein endothelial cells (HUVECs) and human monocytic leukemia cells (THP-1). We also examined the effects of exposure to nanosized metal oxide particles on macrophage cholesterol uptake and foam cell formation. The 16-hour exposure to ZnO particles increased the level of monocyte chemotactic protein-1 (MCP-1) and induced the migration of THP-1 monocyte mediated by increased MCP-1. Exposure to ZnO particles also induced adhesion of THP-1 cells to HUVECs. Moreover, exposure to ZnO particles, but not TiO{sub 2} particles, upregulated the expression of membrane scavenger receptors of modified LDL and increased cholesterol uptake in THP-1 monocytes/macrophages. In the present study, we found that exposure to ZnO particles increased macrophage cholesterol uptake, which was mediated by an upregulation of membrane scavenger receptors of modified LDL. These results suggest that nanosized ZnO particles could potentially enhance atherosclerogenesis and accelerate foam cell formation. - Highlights: • Effects of metal oxide nanoparticles on foam cell formation were investigated. • Exposure to ZnO nanoparticles induced migration and adhesion of monocytes. • Exposure to ZnO nanoparticles increased macrophage cholesterol uptake. • Expression of membrane scavenger receptors of modified LDL was also increased. • These effects were not observed after exposure to TiO{sub 2} nanoparticles.

  7. ACCELERATED CELL DEATH2 suppresses mitochondrial oxidative bursts and modulates cell death in Arabidopsis

    PubMed Central

    Pattanayak, Gopal K.; Venkataramani, Sujatha; Hortensteiner, Stefan; Kunz, Lukas; Christ, Bastien; Moulin, Michael; Smith, Alison G.; Okamoto, Yukihiro; Tamiaki, Hitoshi; Sugishima, Masakazu; Greenberg, Jean T.

    2012-01-01

    SUMMARY The Arabidopsis ACCELERATED CELL DEATH 2 (ACD2) protein protects cells from programmed cell death (PCD) caused by endogenous porphyrin-related molecules like red chlorophyll catabolite or exogenous protoporphyrin IX. We previously found that during bacterial infection, ACD2, a chlorophyll breakdown enzyme, localizes to both chloroplasts and mitochondria in leaves. Additionally, acd2 cells show mitochondrial dysfunctions. In plants with acd2 and ACD2+ sectors, ACD2 functions cell autonomously, implicating a pro-death ACD2 substrate as cell non-autonomous in promoting spreading PCD. ACD2 targeted solely to mitochondria can reduce the accumulation of an ACD2 substrate that originates in chloroplasts, indicating that ACD2 substrate molecules are likely mobile within cells. Two different light-dependent reactive oxygen bursts in mitochondria play prominent and causal roles in the acd2 PCD phenotype. Finally, ACD2 can complement acd2 when targeted to mitochondria or chloroplasts, respectively, as long as it is catalytically active; the ability to bind substrate is not sufficient for ACD2 to function in vitro or in vivo. Together the data suggest that ACD2 localizes dynamically during infection to protect cells from pro-death mobile substrate molecules, some of which may originate in chloroplasts, but have major effects on mitochondria. PMID:21988537

  8. Accelerated cell death 2 suppresses mitochondrial oxidative bursts and modulates cell death in Arabidopsis.

    PubMed

    Pattanayak, Gopal K; Venkataramani, Sujatha; Hortensteiner, Stefan; Kunz, Lukas; Christ, Bastien; Moulin, Michael; Smith, Alison G; Okamoto, Yukihiro; Tamiaki, Hitoshi; Sugishima, Masakazu; Greenberg, Jean T

    2012-02-01

    The Arabidopsis ACCELERATED CELL DEATH 2 (ACD2) protein protects cells from programmed cell death (PCD) caused by endogenous porphyrin-related molecules like red chlorophyll catabolite or exogenous protoporphyrin IX. We previously found that during bacterial infection, ACD2, a chlorophyll breakdown enzyme, localizes to both chloroplasts and mitochondria in leaves. Additionally, acd2 cells show mitochondrial dysfunction. In plants with acd2 and ACD2 (+) sectors, ACD2 functions cell autonomously, implicating a pro-death ACD2 substrate as being cell non-autonomous in promoting the spread of PCD. ACD2 targeted solely to mitochondria can reduce the accumulation of an ACD2 substrate that originates in chloroplasts, indicating that ACD2 substrate molecules are likely to be mobile within cells. Two different light-dependent reactive oxygen bursts in mitochondria play prominent and causal roles in the acd2 PCD phenotype. Finally, ACD2 can complement acd2 when targeted to mitochondria or chloroplasts, respectively, as long as it is catalytically active: the ability to bind substrate is not sufficient for ACD2 to function in vitro or in vivo. Together, the data suggest that ACD2 localizes dynamically during infection to protect cells from pro-death mobile substrate molecules, some of which may originate in chloroplasts, but have major effects on mitochondria.

  9. Final Technical Report. Reactivity of Iron-Bearing Minerals and CO2 Sequestration and Surface Chemistry of Pyrite. An Interdisciplinary Approach

    SciTech Connect

    Strongin, Daniel

    2014-12-31

    Over the course of the scientific program, two areas of research were pursued: reactions of iron oxides with supercritical CO2 and sulfide and surface reactivity of pyrite. The latter area of interest was to understand the chemistry that results when supercritical CO2 (scCO2 ) with H2 S and/or SO2 in deep saline formations (DFS) contacts iron bearing minerals. Understanding the complexities the sulfur co-injectants introduce is a critical step in developing CO2 sequestration as a climate-mitigating strategy. The research strategy was to understand macroscopic observations of this chemistry with an atomic/molecular level view using surface analytical techniques. Research showed that the exposure of iron (oxyhdr)oxides (which included ferrihydrite, goethite, and hematite) to scCO2 in the presence of sulfide led to reactions that formed siderite (FeCO3). The results have important implications for the sequestration of CO2 via carbonation reactions in the Earth’s subsurface. An earlier area of focus in the project was to understand pyrite oxidation in microscopic detail. This understanding was used to understand macroscopic observations of pyrite reactivity. Results obtained from this research led to a better understanding how pyrite reacts in a range of chemical environments. Geochemical and modern surface science techniques were used to understand the chemistry of pyrite in important environmental conditions. The program relied on a strong integration the results of these techniques to provide a fundamental understanding to the macroscopic chemistry exhibited by pyrite in the environment. Major achievements during these studies included developing an understanding of the surface sites on pyrite that controlled its reactivity under oxidizing conditions. In particular sulfur anion vacancies and/or ferric sites were sites of reactivity. Studies also showed that the

  10. Surface electrochemical control for fine coal and pyrite separation. Technical progress report, July 1, 1991--September 30, 1991

    SciTech Connect

    Hu, Weibai; Huang, Qinping; Li, Jun; Riley, A.; Turcotte, S.B.; Benner, R.E.; Zhu, Ximeng; Bodily, D.M.; Liang, Jun; Zhong, Tinghe; Wadsworth, M.E.

    1991-12-31

    The ongoing work includes the characterization of coal pyrites, the floatability evaluation of three typical US coal samples, the flotation behavior of coal pyrites, the electrochemical measurement of the surface properties of coal pyrites, and the characterization of species produced at pyrite surfaces. This report covers a Raman spectroscopy of species produced electrochemically on pyrite surfaces.

  11. Curcumin Mitigates Accelerated Aging after Irradiation in Drosophila by Reducing Oxidative Stress

    PubMed Central

    Yu, Mira; Park, Sunhoo; Jin, Young Woo; Min, Kyung-Jin

    2015-01-01

    Curcumin, belonging to a class of natural phenol compounds, has been extensively studied due to its antioxidative, anticancer, anti-inflammatory, and antineurodegenerative effects. Recently, it has been shown to exert dual activities after irradiation, radioprotection, and radiosensitization. Here, we investigated the protective effect of curcumin against radiation damage using D. melanogaster. Pretreatment with curcumin (100 μM) recovered the shortened lifespan caused by irradiation and increased eclosion rate. Flies subjected to high-dose irradiation showed a mutant phenotype of outstretched wings, whereas curcumin pretreatment reduced incidence of the mutant phenotype. Protein carbonylation and formation of γH2Ax foci both increased following high-dose irradiation most likely due to generation of reactive oxygen species. Curcumin pretreatment reduced the amount of protein carbonylation as well as formation of γH2Ax foci. Therefore, we suggest that curcumin acts as an oxidative stress reducer as well as an effective protective agent against radiation damage. PMID:25815315

  12. Pyrite surface characterization and control for advanced fine coal desulfurization technologies

    SciTech Connect

    Wang, Xiang-Huai; Leonard, J.W.; Parekh, B.K.; Jiang, Chengliang; Raichur, A.M.

    1992-07-14

    The objective of this project is to conduct extensive studies on the surface reactivity and surface hydrophobicity of coal-pyrites using various surface characterization techniques and to correlate the alteration of the coal-pyrite surface with the efficiency of pyrite rejection in coal flotation. The flotation characteristics of coal-pyrites under various conditions was studied and compared with ore-pyrite and coal to determine the causes of pyrite rejection difficulties in coal flotation. Both the native and induced floatabilities of pyrites were investigated. It was found that both coal- and ore-pyrites, ff prepared by dry-grinding, show little or no floatability in the absence of any chemical reagents. After ultrasonic pretreatment, ore-pyrite floats effectively in the acidic to neutral pH range. Kentucky No. 9 coal-pyrite (KYPY) shows significant flotation in the pH range 7--10. With ethyl xanthate as collector, ore-pyrite floats well up to pH = 10; while coal-pyrite reveals no flotation above pH = 6. For the first time, the effect of coal collector on the floatability of coal-pyrite has been studied. It was shown that in the presence of fuel oil--a widely used collector for promoting coal flotation, coal-pyrite, particularly for the fine sizes, shows good flotation below pH = 11, whereas ore-pyrite has no or little floatability. These studies demonstrate that one of the main causes of the coal-pyrite flotation in coal separation is the oil-induced floatability due to adsorption/attachment of oil droplets on the coal-pyrite surfaces, the native'' or self-induced'' floatability of pyrite is no as profound as the oil-induced flotation.

  13. Pyrite discs in coal: evidence for fossilized bacterial colonies

    USGS Publications Warehouse

    Southam, G.; Donald, R.; Rostad, A.; Brock, C.

    2001-01-01

    Discs of pyrite from 1 to 3 mm in diameter and ∼100 μm thick were observed within fracture planes in coal from the Black Mesa coal deposit in northeastern Arizona. The pyrite discs were composed of aggregates of crystals, which suggested that sulfide mineral diagenesis had initiated at multiple nucleation sites and occurred prior to the compaction forces occurring during coal formation. Stable sulfur isotope analysis of the discs (δ34S = −31.7‰) supports a bacterial origin resulting from dissimilatory sulfate reduction. Fossilized bacteria on the disc surfaces (average = 27/100 μm2) appeared as halos when viewed using reflected light microscopy, but were lenticular by scanning electron microscopy, each microfossil being 2–3 μm in length. A fossilized bacterial colony (pyrite disc), 1 mm in diameter, would contain ∼2.1 × 107 microfossils. These microfossils were not observed on hydrothermal pyrite. Coating and in-filling of sulfate-reducing bacteria with iron disulfide during in vitro sulfide mineral diagenesis provide mechanisms to explain the preservation of the three-dimensional lenticular microfossils observed on the pyrite discs.

  14. Arsenic incorporation into authigenic pyrite, Bengal Basin sediment, Bangladesh

    USGS Publications Warehouse

    Lowers, H.A.; Breit, G.N.; Foster, A.L.; Whitney, J.; Yount, J.; Uddin, Md. N.; Muneem, Ad. A.

    2007-01-01

    Sediment from two deep boreholes (???400 m) approximately 90 km apart in southern Bangladesh was analyzed by X-ray absorption spectroscopy (XAS), total chemical analyses, chemical extractions, and electron probe microanalysis to establish the importance of authigenic pyrite as a sink for arsenic in the Bengal Basin. Authigenic framboidal and massive pyrite (median values 1500 and 3200 ppm As, respectively), is the principal arsenic residence in sediment from both boreholes. Although pyrite is dominant, ferric oxyhydroxides and secondary iron phases contain a large fraction of the sediment-bound arsenic between approximately 20 and 100 m, which is the depth range of wells containing the greatest amount of dissolved arsenic. The lack of pyrite in this interval is attributed to rapid sediment deposition and a low sulfur flux from riverine and atmospheric sources. The ability of deeper aquifers (>150 m) to produce ground water with low dissolved arsenic in southern Bangladesh reflects adequate sulfur supplies and sufficient time to redistribute the arsenic into pyrite during diagenesis.

  15. Synthesis and characterization of pyrite (FeS{sub 2}) using microwave irradiation

    SciTech Connect

    Kim, Eun Jung; Batchelor, Bill

    2009-07-01

    A procedure using microwave irradiation was studied to develop a fast and reliable method for synthesizing pyrite. Pyrite was successfully synthesized within a few minutes via reaction of ferric iron and hydrogen sulfide under the influence of irradiation by a conventional microwave oven. The SEM-EDX study revealed that the nucleation and growth of pyrite occurred on the surface of elemental sulfur, where polysulfides are available. Compared to conventional heating, using microwave energy results in rapid (<1 min) formation of smaller particulates of pyrite. Higher levels of microwave power can form pyrite even faster, but faster reaction can lead to the formation of pyrite with defects.

  16. Nanoscale-alumina induces oxidative stress and accelerates amyloid beta (Aβ) production in ICR female mice

    NASA Astrophysics Data System (ADS)

    Shah, Shahid Ali; Yoon, Gwang Ho; Ahmad, Ashfaq; Ullah, Faheem; Amin, Faiz Ul; Kim, Myeong Ok

    2015-09-01

    The adverse effects of nanoscale-alumina (Al2O3-NPs) have been previously demonstrated in both in vitro and in vivo studies, whereas little is known about their mechanism of neurotoxicity. It is the goal of this research to determine the toxic effects of nano-alumina on human neuroblastoma SH-SY5Y and mouse hippocampal HT22 cells in vitro and on ICR female mice in vivo. Nano-alumina displayed toxic effects on SH-SY5Y cell lines in three different concentrations also increased aluminium abundance and induced oxidative stress in HT22 cells. Nano-alumina peripherally administered to ICR female mice for three weeks increased brain aluminium and ROS production, disturbing brain energy homeostasis, and led to the impairment of hippocampus-dependent memory. Most importantly, these nano-particles induced Alzheimer disease (AD) neuropathology by enhancing the amyloidogenic pathway of Amyloid Beta (Aβ) production, aggregation and implied the progression of neurodegeneration in the cortex and hippocampus of these mice. In conclusion, these data demonstrate that nano-alumina is toxic to both cells and female mice and that prolonged exposure may heighten the chances of developing a neurodegenerative disease, such as AD.

  17. Electrochemical mineralization of the antibiotic levofloxacin by electro-Fenton-pyrite process.

    PubMed

    Barhoumi, Natija; Labiadh, Lazhar; Oturan, Mehmet A; Oturan, Nihal; Gadri, Abdellatif; Ammar, Salah; Brillas, Enric

    2015-12-01

    Levofloxacin is a large spectrum antibiotic from fluoroquinolones family, widely used and detected in natural waters. Here, this drug was degraded by a novel heterogeneous electro-Fenton (EF) process, so-called EF-pyrite, in which pyrite powder in suspension regulates the solution pH to 3.0 and supplies 0.2mM Fe(2+) as catalyst to the solution. Trials were performed with a stirred boron-doped diamond (BDD)/carbon-felt cell under O2 bubbling for cathodic H2O2 generation. Hydroxyl radicals formed from water oxidation at the BDD anode and in the bulk from Fenton's reaction between Fe(2+) and H2O2 were the main oxidizing agents. The effect of applied current and antibiotic concentration over the mineralization rate and degree, mineralization current efficiency and specific energy consumption was studied. An almost total mineralization was achieved for a 0.23mM drug solution operating at 300mA for 8h. The kinetic decay of the drug was followed by reversed-phase HPLC and obeyed a pseudo-first-order reaction. Ion-exclusion HPLC analysis of treated solutions revealed that oxalic and oxamic acids, the most persistent final products, were the predominant pollutants remaining in solution at long electrolysis time. Ion chromatography analysis confirmed the release of F(-), NO3(-) and NH4(+) ions during levofloxacin mineralization. PMID:26291910

  18. Kinetics of the Removal of Iron Pyrite from Coal by Microbial Catalysis

    PubMed Central

    Hoffmann, Michael R.; Faust, Bruce C.; Panda, Fern A.; Koo, Hong H.; Tsuchiya, Henry M.

    1981-01-01

    Different strains of Thiobacillus ferrooxidans and Thiobacillus thiooxidans were used to catalyze the oxidative dissolution of iron pyrite, FeS2, in nine different coal samples. Kinetic variables and parametric factors that were determined to have a pronounced effect on the rate and extent of oxidative dissolution at a fixed Po2 were: the bacterial strain, the nitrogen/phosphorus molar ratio, the partial pressure of CO2, the coal source, and the total reactive surface area of FeS2. The overall rate of leaching, which exhibited a first-order dependence on the total surface area of FeS2, was analyzed mathematically in terms of the sum of a biochemical rate, ν1, and a chemical rate, ν2. Results of this study show that bacterial desulfurization (90 to 98%) of coal samples which are relatively high in pyritic sulfur can be achieved within a time-frame of 8 to 12 days when pulp densities are ≤20% and particle sizes are ≤74 μm. The most effective strains of T. ferrooxidans were those that were isolated from natural systems, and T. ferrooxidans ATCC 19859 was the most effective pure strain. The most effective nutrient media contained relatively low phosphate concentrations, with an optimal N/P molar ratio of 90:1. These results suggest that minimal nutrient additions may be required for a commercial desulfurization process. PMID:16345826

  19. Pyrite in contact with supercritical water: the desolation of steam.

    PubMed

    Stirling, András; Rozgonyi, Tamás; Krack, Matthias; Bernasconi, Marco

    2015-07-14

    The supercritical water-pyrite interface has been studied by ab initio molecular dynamics simulation. Extreme conditions are relevant in the iron-sulfur world (ISW) theory where prebiotic chemical reactions are postulated to occur at the mineral-water interface. We have investigated the properties of this interface under such conditions. We have come to the conclusion that hot-pressurized water on pyrite leads to an interface where a dry pyrite surface is in contact with the nearby SC water without significant chemical interactions. This picture is markedly different from that under ambient conditions where the surface is fully covered with adsorbed water molecules which is of relevance for the surface reactions of the ISW hypothesis.

  20. Pyrite in contact with supercritical water: the desolation of steam.

    PubMed

    Stirling, András; Rozgonyi, Tamás; Krack, Matthias; Bernasconi, Marco

    2015-07-14

    The supercritical water-pyrite interface has been studied by ab initio molecular dynamics simulation. Extreme conditions are relevant in the iron-sulfur world (ISW) theory where prebiotic chemical reactions are postulated to occur at the mineral-water interface. We have investigated the properties of this interface under such conditions. We have come to the conclusion that hot-pressurized water on pyrite leads to an interface where a dry pyrite surface is in contact with the nearby SC water without significant chemical interactions. This picture is markedly different from that under ambient conditions where the surface is fully covered with adsorbed water molecules which is of relevance for the surface reactions of the ISW hypothesis. PMID:26077541

  1. Comparison of methods to determine degree of pyritization

    USGS Publications Warehouse

    Leventhal, J.; Taylor, C.

    1990-01-01

    Degree of pyritization (DOP) is a measure of the ratio pyrite iron/(pyrite iron + reactive iron) that can be related to the depositional environment of a sediment. Several methods of DOP determination have been used but not systematically evaluated. The determination/extraction of reactive (usually acid soluble) iron is critical to the DOP determination, and the method generally used is reaction of the sample for 1 to 2 min with hot 12 N HCl. We present results for timed experiments with 1 N, 6 N, and 12 N HCl on three different samples. We also show that a 24 h room temperature treatment with 1 N HCl is equivalent to the 24 h treatment with Na-dithionite. Experiments with several suites of samples show that all three of these methods leach comparable amounts of iron; therefore, the DOP values are similar. However, the 1 N HCl, 24 h procedure is preferable because laboratory handling is less and easier. ?? 1990.

  2. Electrochemical Evaluation of Pyrite Films Prepared by Plasma Spraying

    SciTech Connect

    Guidotti, R.A.; Reinhardt, F.W.

    1998-10-30

    Thermally activated batteries use electrodes that are typically fabricated by cold pressing of powder. In the LiSi/FeS2 system, natural (mineral) pyrite is used for the cathode. In an effort to increase the energy density and specific energy of these batteries, flame and plasma spraying to form thin films of pyrite cathodes were evaluated. The films were deposited on a 304 stainless steel substrate (current collector) and were characterized by scanning electron microscopy and x-ray dlfllaction. The films were electrochemically tested in single cells at 5000C and the petiormance compared to that of standard cells made with cold-pressed powders. The best results were obtained with material deposited by de-arc plasma spraying with a proprietq additive to suppress thermal decomposion of the pyrite.

  3. Biogenic syngenetic pyrite from tuffaceous sedimentary RF3-V rocks

    NASA Astrophysics Data System (ADS)

    Kozyreva, Irina; Nikulova, Natalia

    2015-04-01

    Biogenic framboidal pyrite was found in intraformational tuffaceous sedimentary gravelites, within basic volcanites (RF3-V) in Subpolar Urals (Sablya Ridge). Pyrite grains (Fe 44.07-44,33, S 50.22-53.31 wt. %) are composed of ball-like microconcretions, sometimes intergrown with crystals of pentagondodecahedron and cubic habit. The microconcretions (20 to 40 mcm) are roundish and composed of microcrystals, which end faces form spherical surface. The nuclei of the microconcretions are represented by frambohedrons 4-5 mcm in size, which are pyritized cells of sulphate-reducing colonial coccoid microfossils. The formation of the frambohedrons occurred synchronously to sedimentation in stagnant reducing environment at interaction of biogenic hydrogen sulphide with water-dissolved iron. The biogenic hydrogen sulphide is reduced by microorganisms in the conditions of free and unrestricted access of dissolved sulphate ions sourced from sulphur of fumarole gases. Iron came from washed-out basic volcanites. The growth of outer radial parts of microconcretions occurred during compaction of sediments in diagenetic stage. The quantity of dissolved sulphate and iron during pyrite formation exceeded possibilitites of bacterial "starters" which resulted in the formation of pyrites of other morphological varieties. This is confirmed by the accretion of concentric rays of the concretions and cubic microcrystals of pyrite in the aggregate grains. The formation of tuffaceous sediments occurred during temporary decrease of volcanic activity in a continuous linear water flow with stagnant areas composed of water-displaced pebbles from underlying metaterrigenous rocks (RF 1-2), which were exposed beyond the development area of volcanic strata, unchanged clasts of recent and synchronously formed basic and medium volcanites with participation of air-driven ashes and influence of volcanic gases in the presence of sulphate-reducing bacteria. The work is financially supported by the Program

  4. Graphene oxide scaffold accelerates cellular proliferative response and alveolar bone healing of tooth extraction socket

    PubMed Central

    Nishida, Erika; Miyaji, Hirofumi; Kato, Akihito; Takita, Hiroko; Iwanaga, Toshihiko; Momose, Takehito; Ogawa, Kosuke; Murakami, Shusuke; Sugaya, Tsutomu; Kawanami, Masamitsu

    2016-01-01

    Graphene oxide (GO) consisting of a carbon monolayer has been widely investigated for tissue engineering platforms because of its unique properties. For this study, we fabricated a GO-applied scaffold and assessed the cellular and tissue behaviors in the scaffold. A preclinical test was conducted to ascertain whether the GO scaffold promoted bone induction in dog tooth extraction sockets. For this study, GO scaffolds were prepared by coating the surface of a collagen sponge scaffold with 0.1 and 1 µg/mL GO dispersion. Scaffolds were characterized using scanning electron microscopy (SEM), physical testing, cell seeding, and rat subcutaneous implant testing. Then a GO scaffold was implanted into a dog tooth extraction socket. Histological observations were made at 2 weeks postsurgery. SEM observations show that GO attached to the surface of collagen scaffold struts. The GO scaffold exhibited an interconnected structure resembling that of control subjects. GO application improved the physical strength, enzyme resistance, and adsorption of calcium and proteins. Cytocompatibility tests showed that GO application significantly increased osteoblastic MC3T3-E1 cell proliferation. In addition, an assessment of rat subcutaneous tissue response revealed that implantation of 1 µg/mL GO scaffold stimulated cellular ingrowth behavior, suggesting that the GO scaffold exhibited good biocompatibility. The tissue ingrowth area and DNA contents of 1 µg/mL GO scaffold were, respectively, approximately 2.5-fold and 1.4-fold greater than those of the control. Particularly, the infiltration of ED2-positive (M2) macrophages and blood vessels were prominent in the GO scaffold. Dog bone-formation tests showed that 1 µg/mL GO scaffold implantation enhanced bone formation. New bone formation following GO scaffold implantation was enhanced fivefold compared to that in control subjects. These results suggest that GO was biocompatible and had high bone-formation capability for the scaffold

  5. Graphene oxide scaffold accelerates cellular proliferative response and alveolar bone healing of tooth extraction socket.

    PubMed

    Nishida, Erika; Miyaji, Hirofumi; Kato, Akihito; Takita, Hiroko; Iwanaga, Toshihiko; Momose, Takehito; Ogawa, Kosuke; Murakami, Shusuke; Sugaya, Tsutomu; Kawanami, Masamitsu

    2016-01-01

    Graphene oxide (GO) consisting of a carbon monolayer has been widely investigated for tissue engineering platforms because of its unique properties. For this study, we fabricated a GO-applied scaffold and assessed the cellular and tissue behaviors in the scaffold. A preclinical test was conducted to ascertain whether the GO scaffold promoted bone induction in dog tooth extraction sockets. For this study, GO scaffolds were prepared by coating the surface of a collagen sponge scaffold with 0.1 and 1 µg/mL GO dispersion. Scaffolds were characterized using scanning electron microscopy (SEM), physical testing, cell seeding, and rat subcutaneous implant testing. Then a GO scaffold was implanted into a dog tooth extraction socket. Histological observations were made at 2 weeks postsurgery. SEM observations show that GO attached to the surface of collagen scaffold struts. The GO scaffold exhibited an interconnected structure resembling that of control subjects. GO application improved the physical strength, enzyme resistance, and adsorption of calcium and proteins. Cytocompatibility tests showed that GO application significantly increased osteoblastic MC3T3-E1 cell proliferation. In addition, an assessment of rat subcutaneous tissue response revealed that implantation of 1 µg/mL GO scaffold stimulated cellular ingrowth behavior, suggesting that the GO scaffold exhibited good biocompatibility. The tissue ingrowth area and DNA contents of 1 µg/mL GO scaffold were, respectively, approximately 2.5-fold and 1.4-fold greater than those of the control. Particularly, the infiltration of ED2-positive (M2) macrophages and blood vessels were prominent in the GO scaffold. Dog bone-formation tests showed that 1 µg/mL GO scaffold implantation enhanced bone formation. New bone formation following GO scaffold implantation was enhanced fivefold compared to that in control subjects. These results suggest that GO was biocompatible and had high bone-formation capability for the scaffold

  6. Phanerozoic atmosphere oxygen cycles revealed by trace elements in marine pyrite

    NASA Astrophysics Data System (ADS)

    Large, R. R.; Halpin, J.

    2014-12-01

    It is generally accepted that oxygen in the atmosphere rose in two major steps at around 2.4-2.2 and 0.7-0.5 billion years ago. The variation in atmosphere oxygen over the last 500 million years, is considered to have been relatively minor by comparison. Sedimentary pyrite from marine shales efficiently captures many trace elements from the oceans, providing a novel proxy for seawater chemistry. Here we use temporal changes in the selenium and cobalt content of Phanerozoic marine pyrite, coupled with the 87Sr/86Sr ratio in marine carbonate, to argue for five dramatic pO2 cycles, each starting with a period of oxygenation, followed by a period of de-oxygenation. The selenium proxy is based on the premise that increased erosion of continental rocks leads to the release of selenium as both the selenate and selenite species. Under neutral to alkaline, oxygenated conditions the selenate species remains highly soluble, where it can be readily transported via river systems to the ocean. Cobalt on the other hand becomes less soluble under increasing pO2 as the oxidized species Co2+ and CoO are immobilised by Fe and Mn oxyhydroxides, that form during weathering. Thus variations in the Se and Co composition of marine pyrite enable us to propose a new oxygenation proxy; the ratio Se/Co, which increases in marine pyrite during periods of increasing pO2 (oxygenation) and decreases during periods of decreasing pO2 (deoxygenation). The first half of each of the five Phanerozoic pO2 cycles involves an increase in atmosphere/ocean oxygenation driven initially by supercontinent dispersal, increased continental erosion and nutrient trace element flux to the oceans. Increased marine productivity leads to carbon and sulphur sequestration, producing metalliferous black shales, and further drives oxygenation to the peak of the cycle. The cycle downside suggests decreasing oxidative erosion and nutrient delivery, resulting in a drop in productivity. Continued drawdown of ocean trace

  7. Effect of various coal contaminants on the performance of solid oxide fuel cells: Part I. Accelerated testing

    NASA Astrophysics Data System (ADS)

    Bao, JianEr; Krishnan, Gopala N.; Jayaweera, Palitha; Perez-Mariano, Jordi; Sanjurjo, Angel

    The contaminants that are potentially present in the coal-derived gas stream and their thermochemical nature are discussed. Accelerated testing was carried out on Ni-YSZ/YSZ/LSM solid oxide fuel cells (YSZ: yttria stabilized zirconia and LSM: lanthanum strontium manganese oxide) for eight main kind of contaminants: CH 3Cl, HCl, As, P, Zn, Hg, Cd and Sb at the temperature range of 750-850 °C. The As and P species, at 10 and 35 ppm, respectively, resulted in severe power density degradation at temperatures 800 °C and below. SEM and EDX analysis indicated that As attacked the Ni region of the anode surface and the Ni current collector, caused the break of the current collector and the eventual cell failure at 800 °C. The phosphorous containing species were found in the bulk of the anode, they were segregated and formed "grain boundary" like phases separating large Ni patches. These species are presumably nickel phosphide/phosphate and zirconia phosphate, which could break the Ni network for electron transport and inhibit the YSZ network for oxygen ion transport. The presence of 40 ppm CH 3Cl and 5 ppm Cd only affected the cell power density at above 800 °C and Cd caused significant performance loss. Whereas the presence of 9 ppm Zn, 7 ppm Hg and 8 ppm Sb only degraded the cell power density by less than 1% during the 100 h test in the temperature range of 750-850 °C.

  8. Chemistry and mineralogy of pyrite-enriched sediments at a passive margin sulfide brine seep: abyssal Gulf of Mexico

    USGS Publications Warehouse

    Commeau, R.F.; Paull, C.K.; Commeau, J.A.; Poppe, L.J.

    1987-01-01

    Pyrite is rapidly accumulating at the contact between the Cretaceous limestones of the Florida Platform and the hemipelagic sediments of the abyssal Gulf of Mexico. Sediments sampled with the submersible "Alvin" in 3266 m of water are associated with a dense community of organisms that depend on chemosynthetic primary production as a food source. Analysis of the chemistry, mineralogy, and textural composition of these sediments indicate that iron sulfide mineralization is occurring at the seafloor within an anoxic micro-habitat sustained by the advection of hydrogen sulfide-charged saline brines from the adjacent platform. The chemosynthetic bacteria that directly overlie the sediments oxidize hydrogen sulfide for energy and provide elemental sulfur that reacts with iron monosulfide to form some of the pyrite. The sediments are mixtures of pyrite (??? 30 wt.%), BaSr sulfates (??? 4 wt.%), clays, and locally derived biogenic carbonates and are progressively being cemented by iron sulfides. Oxidation of hydrogen sulfide produces locally acidic conditions that corrode the adjacent limestones. Potential sources of S, H2S, Fe, Ba, and Sr are discussed. ?? 1987.

  9. Magnetic field-induced acceleration of the accumulation of magnetic iron oxide nanoparticles by cultured brain astrocytes.

    PubMed

    Lamkowsky, Marie-Christin; Geppert, Mark; Schmidt, Maike M; Dringen, Ralf

    2012-02-01

    Magnetic iron oxide nanoparticles (Fe-NPs) are considered for various biomedical and neurobiological applications that involve the presence of external magnetic fields. However, little is known on the effects of a magnetic field on the uptake of such particles by brain cells. Cultured brain astrocytes accumulated dimercaptosuccinate-coated Fe-NP in a time-, temperature-, and concentration-dependent manner. This accumulation was strongly enhanced by the presence of the magnetic field generated by a permanent neodymium iron boron magnet that had been positioned below the cells. The magnetic field-induced acceleration of the accumulation of Fe-NP increased almost proportional to the strength of the magnetic field applied, increasing the cellular-specific iron content from an initial 10 nmol/mg protein within 4 h of incubation at 37°C to up to 12,000 nmol/mg protein. However, presence of a magnetic field also increased the amounts of iron that attached to the cells during incubation with Fe-NP at 4°C. These results suggest that the presence of an external magnetic field promotes in cultured astrocytes both the binding of Fe-NP to the cell membrane and the internalization of Fe-NP.

  10. Size and maceral association of pyrite in Illinois coals and their float-sink fractions

    USGS Publications Warehouse

    Harvey, R.D.; DeMaris, P.J.

    1987-01-01

    The amount of pyrite (FeS2) removed by physical cleaning varies with differences in the amount of pyrite enclosed within minerals and of free pyrite in feed coals. A microscopic procedure for characterizing the size and maceral association of pyrite grains was developed and evaluate by testing three coals and their washed products. The results yield an index to the cleanability of pyrite. The index is dependent upon particle size and has intermediate values for feed coals, lower values for cleaned fractions, and higher values for refuse fractions; furthermore, it correlates with pyritic sulfur content. In the coals examined, the summed percentage of grain diameters of pyrite enclosed in vitrinite, liptinite, and bi- and trimacerite provides a quantitative measure of the proportion of early diagenetic deposition of pyrite. ?? 1987.

  11. Isolation and characterization of a novel Acidithiobacillus ferrivorans strain from the Chilean Altiplano: attachment and biofilm formation on pyrite at low temperature.

    PubMed

    Barahona, Sergio; Dorador, Cristina; Zhang, Ruiyong; Aguilar, Pablo; Sand, Wolfgang; Vera, Mario; Remonsellez, Francisco

    2014-11-01

    Microorganisms are used to aid the extraction of valuable metals from low-grade sulfide ores in mines worldwide, but relatively little is known about this process in cold environments. This study comprises a preliminary analysis of the bacterial diversity of the polyextremophilic acid River Aroma located in the Chilean Altiplano, and revealed that Betaproteobacteria was the most dominant bacterial group (Gallionella-like and Thiobacillus-like). Taxa characteristic of leaching environments, such Acidithiobacillus and Leptospirillum, were detected at low abundances. Also, bacteria not associated with extremely acidic, metal-rich environments were found. After enrichment in iron- and sulfur-oxidizing media, we isolated and identified a novel psychrotolerant Acidithiobacillus ferrivorans strain ACH. This strain can grow using ferrous iron, sulfur, thiosulfate, tetrathionate and pyrite, as energy sources. Optimal growth was observed in the presence of pyrite, where cultures reached a cell number of 6.5 · 10(7) cells mL(-1). Planktonic cells grown with pyrite showed the presence of extracellular polymeric substances (10 °C and 28 °C), and a high density of cells attached to pyrite grains were observed at 10 °C by electron microscopy. The attachment of cells to pyrite coupons and the presence of capsular polysaccharides were visualized by using epifluorescence microscopy, through nucleic acid and lectin staining with Syto(®)9 and TRITC-Con A, respectively. Interestingly, we observed high cell adhesion including the formation of microcolonies within 21 days of incubation at 4 °C, which was correlated with a clear induction of capsular polysaccharides production. Our data suggests that attachment to pyrite is not temperature-dependent in At. ferrivorans ACH. The results of this study highlight the potential of this novel psychrotolerant strain in oxidation and attachment to minerals under low-temperature conditions.

  12. Capture of molybdenum in pyrite-forming sediments: role of ligand-induced reduction by polysulfides 1

    NASA Astrophysics Data System (ADS)

    Vorlicek, Trent P.; Kahn, Mani D.; Kasuya, Yasuhiro; Helz, George R.

    2004-02-01

    Capture of Mo by FeS 2 is an important sink for marine Mo. X-ray spectroscopy has shown that Mo forms Mo-Fe-S cuboidal clusters on pyrite. Reduction of Mo VI must occur to stabilize these structures. Sulfide alone is a poor reductant for Mo, producing instead a series of Mo VI thioanions (MoO xS 4-x2-, x = 0-3). In solutions that contain both H 2S and S 0-donors (i.e. polysulfides; dissolved S 8), Mo is transformed to Mo IV or Mo V2 polysulfide/sulfide anions. This intramolecular reduction requires no external reducing agent. Remarkably, an oxidizing agent (S 0 donor), rather than a reducing agent, stabilizes the reducible Mo VI complex. Thiomolybdates and their reduction products do not precipitate spontaneously; solutions supersaturated by 10 9 with respect to molybdenite, MoS 2, produce no precipitate in 40 days. In 10-minute exposures, pyrite can scavenge MoOS 32- and MoS 42- weakly at mildly alkaline pH but can scavenge an unidentified product of the S 0-induced reduction of MoOS 32- very strongly. On the basis of these observations, a reaction pathway for Mo capture by pyrite is proposed. Conditions that favor Mo capture by this pathway also favor pyrite growth. Ascribing Mo capture simply to low redox potential is too simplistic and neglects the likely role of oxidizing S 0-donors. The aqueous speciation of Mo in anoxic environments will be a function of the activity of zero-valent sulfur as well as the activity of H 2S(aq).

  13. TRANSFORMATION OF CARBON TETRACHLORIDE BY PYRITE IN AQUEOUS SOLUTION

    EPA Science Inventory

    The reactivity of Cc4 with pyrite was investigated by measuring the CC14 transformation rates and products under aerobic and anaerobic conditions. Under all reaction conditions, >90% of the CC14 was transformed within 12- 36 days in the presence o...

  14. Effects of Surfactants on Chlorobenzene Absorption on Pyrite Surface

    NASA Astrophysics Data System (ADS)

    Hoa, P. T.; Suto, K.; Inoue, C.; Hara, J.

    2007-03-01

    Recently, both surfactant extraction of chlorinated compounds from contaminated soils and chemical reduction of chlorinated compounds by pyrite have had received a lot of attention. The reaction of the natural mineral pyrite was found as a surface controlling process which strongly depends on absorption of contaminants on the surface. Surfactants were not only aggregated into micelle which increase solubility of hydrophobic compounds but also tend to absorb on the solid surface. This study investigated effects of different kinds of Surfactants on absorption of chlorobenzene on pyrite surface in order to identify coupling potential of surfactant application and remediation by pyrite. Surfactants used including non-ionic, anionic and cationic which were Polyoxyethylene (23) Lauryl Ether (Brij35), Sodium Dodecyl Sulfate (SDS) and Cetyl TrimethylAmmonium Bromide (CTAB) respectively were investigated with a wide range of surfactant concentration up to 4 times of each critical micelle concentration (CMC). Chlorobenzene was chosen as a representative compound. The enhancement or competition effects of Surfactants on absorption were discussed.

  15. Polygenetic pyritic gold occurrences in Bousquet Township, Quebec

    SciTech Connect

    Valliant, R.I.; Stone, W.E.

    1985-01-01

    Bousquet Township contains stratiform and stratabound pyritic gold deposits and gold-bearing quartz veins within volcaniclastic sedimentary rocks, felsic volcanic rocks and a granitoid stock on the south side of the Abitibi Greenstone Belt, 50 km east of Noranda, Quebec. Bousquet number3 is a large stratiform lens of fine grained gold in layered disseminated and massive pyrite with minor telluride and base metal sulfide minerals. The enclosing rock consists of quartz and muscovite with accessory andalusite, corundum, paragonite, chloritoid, and manganiferous garnet. Bousquet number5 and Doyon number2 are large stratabound lenses of fine grained gold with disseminated pyrite on a cleavage penetrating a rock of quartz, muscovite, chlorite and carbonate. The vein deposits are relatively small and have gold with quartz, pyrite, and chalcopyrite which crosscut the Doyon number2 lens and the granitoid stock. The stratiform, stratabound, and vein deposits record a progressive metallogenic event coeval with deposition and deformation of the enveloping rocks. The stratiform deposits are interpreted as products of exhalative activity accompanying felsic volcanism. Stratabound occurrences are interpreted as successively modified variations of the stratiform deposits or, as gold introduced during deformation which is synchronous with or after volcanism. The vein deposits represent waning stages of hydrothermal fluid circulation accompanying crystallization of the granitoid stock toward the end of volcanic activity in the district.

  16. Semiconductor electrochemistry of coal pyrite. Final technical report, September 1990--September 1995

    SciTech Connect

    Osseo-Asare, K.; Wei, D.

    1996-01-01

    This project is concerned with the physiochemical processes occuring at the pyrite/aqueous interface, in the context of coal cleaning, desulfurization, and acid mine drainage. The use of synthetic particles of pyrite as model electrodes to investigate the semiconductor electrochemistry of pyrite is employed.

  17. Arsenic incorporation into FeS 2 pyrite and its influence on dissolution: A DFT study

    NASA Astrophysics Data System (ADS)

    Blanchard, Marc; Alfredsson, Maria; Brodholt, John; Wright, Kate; Catlow, C. Richard A.

    2007-02-01

    FeS 2 pyrite can incorporate large amounts of arsenic (up to ca. 10 wt%) and hence has a strong impact on the mobility of this toxic metalloid. Focussing on the lowest arsenic concentrations for which the incorporation occurs in solid solution, the substitution mechanisms involved have been investigated by assuming simple incorporation reactions in both oxidising and reducing conditions. The solution energies were calculated by Density Functional Theory (DFT) calculations and we predict that the formation of AsS dianion groups is the most energetically favourable mechanism. The results also suggest that the presence of arsenic will accelerate the dissolution and thus the generation of acid drainage, when the crystal dissolves in oxidising conditions.

  18. Sulfidation Roasting of Hemimorphite with Pyrite for the Enrichment of Zn and Pb

    NASA Astrophysics Data System (ADS)

    Min, Xiao-Bo; Xue, Ke; Ke, Yong; Zhou, Bo-Sheng; Li, Yang-Wen-Jun; Wang, Qing-Wei

    2016-06-01

    With the increasing consumption of zinc and the depletion of zinc sulfide ores, the exploitation of low-grade zinc oxide ores may be important for the sustainability of the zinc industry. Hemimorphite, a zinc hydroxyl silicate hydrate, is a significant source of Zn and Pb. It is difficult to obtain Zn and Pb from the hemimorphite using traditional technology. In this work, for the first time, sulfidation roasting of hemimorphite with pyrite was studied for the enrichment of Zn and Pb by a flotation process. Four stages of sulfidation roasting were determined based on x-ray diffraction and thermogravimetry analysis. Then, the effects of sulfidation temperature, pyrite dosage and reaction time on the sulfidation percentages were investigated at the laboratory scale. The experimental results showed that the sulfidation percentages of Pb and Zn were as high as 98.08% and 90.55% under optimum conditions, respectively. Finally, a flotation test was performed to enrich Zn and Pb in the sulfidation product. A flotation concentrate with 8.78% Zn and 9.25% Pb was obtained, and the recovery of Zn and Pb reached 56.14% and 75.94%, respectively.

  19. Sulfidation Roasting of Hemimorphite with Pyrite for the Enrichment of Zn and Pb

    NASA Astrophysics Data System (ADS)

    Min, Xiao-Bo; Xue, Ke; Ke, Yong; Zhou, Bo-Sheng; Li, Yang-Wen-Jun; Wang, Qing-Wei

    2016-09-01

    With the increasing consumption of zinc and the depletion of zinc sulfide ores, the exploitation of low-grade zinc oxide ores may be important for the sustainability of the zinc industry. Hemimorphite, a zinc hydroxyl silicate hydrate, is a significant source of Zn and Pb. It is difficult to obtain Zn and Pb from the hemimorphite using traditional technology. In this work, for the first time, sulfidation roasting of hemimorphite with pyrite was studied for the enrichment of Zn and Pb by a flotation process. Four stages of sulfidation roasting were determined based on x-ray diffraction and thermogravimetry analysis. Then, the effects of sulfidation temperature, pyrite dosage and reaction time on the sulfidation percentages were investigated at the laboratory scale. The experimental results showed that the sulfidation percentages of Pb and Zn were as high as 98.08% and 90.55% under optimum conditions, respectively. Finally, a flotation test was performed to enrich Zn and Pb in the sulfidation product. A flotation concentrate with 8.78% Zn and 9.25% Pb was obtained, and the recovery of Zn and Pb reached 56.14% and 75.94%, respectively.

  20. The rate of chemical weathering of pyrite on the surface of Venus

    NASA Technical Reports Server (NTRS)

    Fegley, B., Jr.; Lodders, K.

    1993-01-01

    This abstract reports results of an experimental study of the chemical weathering of pyrite (FeS2) under Venus-like conditions. This work, which extends the earlier study by Fegley and Treiman, is part of a long range research program to experimentally measure the rates of thermochemical gas-solid reactions important in the atmospheric-lithospheric sulfur cycle on Venus. The objectives of this research are (1) to measure the kinetics of thermochemical gas-solid reactions responsible for both the production (e.g., anhydrite formation) and destruction (e.g., pyrrhotite oxidation) of sulfur-bearing minerals on the surface of Venus and (2) to incorporate these and other constraints into holistic models of the chemical interactions between the atmosphere and surface of Venus. Experiments were done with single crystal cubes of natural pyrite (Navajun, Logrono, Spain) that were cut and polished into slices of known weight and surface area. The slices were isothermally heated at atmospheric pressure in 99.99 percent CO2 (Coleman Instrument Grade) at either 412 C (685 K) or 465 C (738 K) for time periods up to 10 days. These two isotherms correspond to temperatures at about 6 km and 0 km altitude, respectively, on Venus. The reaction rate was determined by measuring the weight loss of the reacted slices after removal from the furnace. The reaction products were characterized by X-ray diffraction, scanning electron microscopy, and energy dispersive spectroscopy on the SEM.

  1. Sulfur isotope variability in biogenic pyrite: Reflections of heterogeneous bacterial colonization?

    SciTech Connect

    Kohn, M.J.; Riciputi, L.R.; Stakes, D.; Orange, D.L.

    1998-11-01

    The top 20 cm of sediments at active cold seeps in Monterey Bay, coastal California, contain framboidal pyrite that occurs as infillings and pseudomorphs of the chambers of the tests of foraminifera and rarely as irregularly shaped grains. Sulfur isotope compositions obtained with the ion microprobe show depletions in {sup 34}S and large variations both within and among these pyrite grains. Backscattered-electron imaging reveals three types of pyrite: isolated framboids in a porous aggregation, agglomerated framboids with cementing interstitial pyrite, and recrystallized pyrite with isolated relicts of framboids. In individual grains, RF-pyrite cores grade into F+I-pyrite toward grain rims, and F+I-pyrite grades into PF-pyrite at the grain edges. These textures are consistent with a paragenetic sequence whereby framboids first agglomerate (PF-pyrite), then cement (F+I-pyrite), and finally recrystallize (RF-pyrite). The {delta}{sup 34}S values of RF-pyrite are generally lower than that of F+I-pyrite; if the paragenetic sequence is correct, then this trend parallels the regular core-rim isotopic zoning observed in some grains. The implied increase in {delta}{sup 14}S with time is consistent with Rayleigh fractionation of sulfur in a closed system. Bacteria are intimately involved in the production of pyrite from the samples, and heterogeneous colonization by bacteria provides a simple explanation for the sulfur isotope heterogeneity among and within grains: The foraminifera provide open space for colonization and local nutrients for bacterial growth, whereas the cell walls of the bacteria may provide a local nucleation site for sulfides.

  2. Trace-element characteristics of different pyrite types in Mesoarchaean to Palaeoproterozoic placer deposits

    NASA Astrophysics Data System (ADS)

    Koglin, Nikola; Frimmel, Hartwig E.; Lawrie Minter, W. E.; Brätz, Helene

    2010-03-01

    A comparative in situ LA-ICP MS trace-element study on pyrite from three different, variably auriferous, Archaean to Palaeoproterozoic palaeoplacer deposits in the Ouro Fino Syncline (Quadrilátero Ferrífero; Brazil), the Elliot Lake area north of Lake Huron (SE Canada) and several deposits within the Witwatersrand Basin (South Africa) revealed systematic differences between morphologically different pyrite types and between the various palaeoplacer deposits. Especially the Ni and Au concentrations as well as Co/Ni and Mo/Ni ratios were found to be systematically different in detrital compact, detrital porous and post-sedimentary/hydrothermal pyrite grains from different source areas. High Co/Ni ratios and low Au concentrations are typical of post-sedimentary pyrite, which is hydrothermal in origin. In contrast, relatively low Co/Ni ratios and high Au contents characterise detrital porous banded and concentric pyrite grains (Au > 1 ppm), which are syn-sedimentary in origin. In the Elliot Lake area and the Witwatersrand Basin, detrital compact rounded pyrite is characterised by high Co/Ni ratios, which is in agreement with derivation from a hydrothermal source. Low Au concentrations in this pyrite type support the contention of the gold and the pyrite in these deposits coming from different source rocks. In contrast, derivation from an originally diagenetic pyrite is suggested for the detrital compact pyrite in the Ouro Fino Syncline because of low to intermediate Co/Ni ratios. High Au contents may indicate a genetic relationship between pyrite and gold there. Systematic differences exist between the three areas with respect to Au, Ni, Co, Mo and Cu distributions in detrital pyrite, which reflects differences in the provenance. A predominantly mafic/ultramafic source is indicated for the Ouro Fino, a felsic source for the Elliot Lake, and a mixed felsic-mafic provenance for the Witwatersrand pyrite populations. Independently of pyrite type, the higher Au endowment

  3. Surface electrochemical control for fine coal and pyrite separation. Technical progress report, January 1, 1990--March 31, 1990

    SciTech Connect

    Chen, Wanxiong; Hu, Weibai; Wann, Jyi-Perng; Zhu, Ximeng; Bodily, D.M.; Wadsworth, M.E.

    1990-12-31

    Ongoing work includes the characterization of coal pyrites, the floatability evaluation of typical US coal samples, the flotation behavior of coal pyrites, the electrochemical measurement of the surface properties of coal pyrites, and the characterization of species produced at pyrite surfaces.

  4. Surface electrochemical control for the fine coal and pyrite separation. Technical progress report, July 21, 1989--September 30, 1989

    SciTech Connect

    Chen, Wanxiong; Hu, Weibai; Wann, Jyi-Perng; Zhu, Ximeng; Wadsworth, M.E.

    1989-12-31

    Ongoing work includes the characterization of coal pyrites, the floatability evaluation of typical US coal samples, the flotation behavior of coal pyrites, the electrochemical measurement of the surface properties of coal pyrites, and the characterization of species produced at pyrite surfaces.

  5. Surface electrochemical control for the fine coal and pyrite separation. Technical progress report, January 1, 1992--March 31, 1992

    SciTech Connect

    Hu, Weibai; Huang, Qinping; Zhu, Ximeng; Li, Jun; Bodily, D.M.; Liang, Jun; Zhong, Tingke; Wadsworth, M.E.

    1992-07-01

    Ongoing work includes the characterization of coal pyrites, the floatability evaluation of typical US coal samples, the flotation behavior of coal pyrites, the electrochemical measurement of the surface properties of coal pyrites, and the characterization of species produced at pyrite surfaces.

  6. Surface electrochemical control for the fine coal and pyrite separation. Technical progress report, October 1, 1989--December 31, 1989

    SciTech Connect

    Chen, Wanxiong; Hu, Weibai; Wann, Jyi-Perng; Zhu, Ximeng; Wadsworth, M.E.; Bodily, D.M.

    1989-12-31

    Ongoing work includes the characterization of coal pyrites, the floatability evaluation of typical US coal samples, the flotation behavior of coal pyrites, the electrochemical measurement of the surface properties of coal pyrites, and the characterization of species produced at pyrite surfaces.

  7. Assessing the influence of reacting pyrite and carbonate minerals on the geochemistry of drainage in the Coeur d'Alene mining district

    USGS Publications Warehouse

    Balistrieri, L.S.; Box, S.E.; Bookstrom, A.A.; Ikramuddin, M.

    1999-01-01

    The relative abundance of minerals that react to generate or consume acid in mineralized areas is critical in determining the quality of water draining from such areas. This work examines the fundamental reactions that influence the pH and composition of drainage from mine adits and tailings piles. We construct triangle diagrams that predict stoichiometric relationships between concentrations of dissolved SO4 dissolved Ca and Mg, and either alkalinity or acidity by considering reactions involving the oxidation of pyrite, dissolution of carbonate minerals, and precipitation of iron oxide and iron hydroxysulfate minerals. Drainage data from the Coeur d'Alene mining district are used to test our stoichiometric approach. Comparisons between theoretical predictions and drainage data indicate that the range of pH values in the mining district is due to reacting pyrite to carbonate mineral ratios that range from near 0/1 to 1/1. Calcite and ankerite are the dominant carbonate minerals that buffer the acid produced during pyrite oxidation and ferrihydrite or schwertmannite precipitation.The relative abundance of minerals that react to generate or consume acid in mineralized areas is critical in determining the quality of water draining from such areas. This work examines the fundamental reactions that influence the pH and composition of drainage from mine adits and tailings piles. We construct triangle diagrams that predict stoichiometric relationships between concentrations of dissolved SO4, dissolved Ca and Mg, and either alkalinity or acidity by considering reactions involving the oxidation of pyrite, dissolution of carbonate minerals, and precipitation of iron oxide and iron hydroxysulfate minerals. Drainage data from the Coeur d'Alene mining district are used to test our stoichiometric approach. Comparisons between theoretical predictions and drainage data indicate that the range of pH values in the mining district is due to reacting pyrite to carbonate mineral ratios

  8. Heavy minerals and sedimentary organic matter in Pleistocene and Cretaceous sediments on Long Island, New York, with emphasis on pyrite and marcasite in the Magothy aquifer

    USGS Publications Warehouse

    Brown, Craig J.; Rakovan, John; Schoonen, Martin A.A.

    2000-01-01

    Abundance and distribution of iron-bearing and other heavy minerals in sediments of Long Island, N.Y., were examined to identify sources and sinks of dissolved iron and other ground-water constituents along a deep flow path from the ground-water divide to the southern shore along the Nassau-Suffolk County border. The occurrence and reactivity of many iron-bearing minerals in the aquifer system are affected by terminal electron-accepting processes, which are a function of depth below land surface, distance from the ground-water divide, and organic-matter content of the sediment. The lateral distribution of heavy minerals within lithologic sediments is not uniform throughout Long Island, or even along the 30-kilometer study section at the Nassau-Suffolk County border. Mineralogy and mineral abundance in Pleistocene units differ from those in Cretaceous sediments, and some of the trends vary with depth as well as from north to south. Major heavy minerals in the Cretaceous sediments at the study sites include pyrite, marcasite, muscovite, leucoxene, ilmenite, rutile, staurolite, chloritoid, and aluminosilicates (Al2SiO5); those in the overlying Pleistocene deposits at one site include iron oxides, leucoxene, zircon, garnet, ilmenite, aluminosilicates, and hornblende. Pyrite, marcasite, garnet, hornblende, and tourmaline were found locally in the Cretaceous sediments. Pyrite and marcasite were detected less frequently in borehole samples from near the ground-water divide, where the ground water is generally oxic, than in those from near the southern shore of Long Island, but were found in sulfate- reducing zones throughout the Magothy aquifer. Glauconite was present in Cretaceous and Pleistocene deposits, but only in the marine or transitional units. The most abundant and potentially reactive of the iron-bearing minerals found were iron (hydr)oxides, leucoxene, glauconite, chlorite, pyrite, and marcasite. The presence and morphology of pyrite and marcasite can be

  9. Hydrodynamics of electrofluidization: Separation of pyrites from coal

    SciTech Connect

    Shih, Y.T.; Gidaspow, D.; Wasan, D.

    1987-08-01

    Dry, electrostatic separation is a potentially efficient method of removing pyrites from coal. However, progress in the past was hampered by a lack of a quantitative analysis of the process. To help design better separation equipment, the authors developed a hydrodynamic model of separation of pyrites from coal in a batch electrofluidized bed. The simulations were done on a Cray-2 computer. The input variables include the surface charge of the particles and the solids stress, which were measured. Realistic shapes and sizes of bubbles were computed with and without an applied electric field for a two-dimensional bed with a central jet. The bubble sizes and the rising velocities were smaller with an applied field, consistent with observations. Computed electrophoretic mobilities in the fluidized bed will be useful for a better design of continuous beds.

  10. Thermoluminescence kinetics of pyrite (FeS sub 2 )

    SciTech Connect

    Silverman, A.N; Levy, P.W.; Kierstead, J.A.

    1990-01-01

    Thermoluminescence of pyrite (FeS{sub 2}) has been investigated to study the kinetics of single peak glow curves. The material used normally exhibits one large and four small peaks. However a glow curve can be obtained with only the large single peak that is suitable for testing thermoluminescence kinetics. Glow curves from aliquots of a single natural pyrite crystal studied in detail contain two low intensity thermoluminescence (TL) peaks at {approx}90{degree} and {approx}250{degree}C, and two chemiluminescence (CL) peaks at {approx}350{degree} and {approx}430{degree}C. The CL peaks are largely removable by initially heating the sample chamber under vacuum, pumping through liquid nitrogen traps, and recording glow curves immediately after helium is introduced, procedures which reduce system contaminants that react with pyrite. The shape, the variation of the temperature of the peak maximum (T{sub max}) with dose, and the retrapping to recombination cross section ratio {sigma} of the large 250{degree}C peak are better described by the general one trap (GOT) kinetic equation, the basic equation from which the 1st and 2nd order kinetic equations are obtained as special cases (see text), than by the 1st and 2nd order equations. 12 refs., 7 figs.

  11. Uranium in Framboidal Pyrite from a Naturally Bioreduced Alluvial Sediment

    SciTech Connect

    Qafoku, Nikolla; Kukkadapu, Ravi K.; McKinley, James P.; Arey, Bruce W.; Kelly, Shelly D.; Wang, Chong M.; Resch, Charles T.; Long, Philip E.

    2009-10-07

    Samples of a naturally bioreduced, U contaminated aquifer sediment from Rifle, CO were characterized with various microscopic and spectroscopic techniques and wet chemical extraction methods. The objective was to investigate U association and interaction with the soil minerals of the sediment. The naturally bioreduced sediment was elevated in solid-phase U, total organic carbon and acid-volatile sulfide, and depleted in bioavailable Fe(III) indicating that sulfate and Fe(III) reduction have occurred naturally in the sediment. XRD and SEM/EDS analyses demonstrated that framboidal pyrites (FeS2) of different sizes (~10 – 20 μm in diameter), and of various microcrystal morphology, degree of surface weathering and internal porosity were abundant in the < 53 μm fraction (silt+clay) of the sediment. EMP, XRF, EXAFS, and XANES measurements confirmed that U interacted mostly with framboidal pyrite and that both U(VI) and U(IV) were associated with the framboids indicating partial reduction of surface bounded U(VI). Results demonstrated that U(VI) may be sorbed and reduced on framboidal pyrite, and both sorption and reduction were important pathways of U(VI) attenuation in this naturally bioreduced sediment. A fuller understanding of U(VI) fate in this unique system could help in developing remedial measures for other U contaminated aquifers.

  12. Source of arsenic-bearing pyrite in southwestern Vermont, USA: sulfur isotope evidence.

    PubMed

    Mango, Helen; Ryan, Peter

    2015-02-01

    Arsenic-bearing pyrite is the source of arsenic in groundwater produced in late Cambrian and Ordovician gray and black slates and phyllites in the Taconic region of southwestern Vermont, USA. The aim of this study is to analyze the sulfur isotopic composition of this pyrite and determine if a relationship exists between pyrite δ(34)S and arsenic content. Pyrite occurs in both sedimentary/diagenetic (bedding-parallel layers and framboids) and low-grade metamorphic (porphyroblast) forms, and contains up to >2000 ppm As. The sulfur isotopic composition of arsenic-bearing pyrite ranges from -5.2‰ to 63‰. In the marine environment, the sulfur in sedimentary pyrite becomes increasingly enriched in (34)S as the geochemical environment becomes increasingly anoxic. There is a positive correlation between δ(34)S and arsenic content in the Taconic pyrite, suggesting that uptake of arsenic by pyrite increased as the environment became more reducing. This increased anoxia may have been due to a rise in sea level and/or tectonic activity during the late Cambrian and Ordovician. Low-grade metamorphism appears to have little effect on sulfur isotope composition, but does correlate with lower arsenic content in pyrite. New groundwater wells drilled in this region should therefore avoid gray and black slates and phyllites that contain sedimentary/diagenetic pyrite with heavy δ(34)S values.

  13. Source of arsenic-bearing pyrite in southwestern Vermont, USA: sulfur isotope evidence.

    PubMed

    Mango, Helen; Ryan, Peter

    2015-02-01

    Arsenic-bearing pyrite is the source of arsenic in groundwater produced in late Cambrian and Ordovician gray and black slates and phyllites in the Taconic region of southwestern Vermont, USA. The aim of this study is to analyze the sulfur isotopic composition of this pyrite and determine if a relationship exists between pyrite δ(34)S and arsenic content. Pyrite occurs in both sedimentary/diagenetic (bedding-parallel layers and framboids) and low-grade metamorphic (porphyroblast) forms, and contains up to >2000 ppm As. The sulfur isotopic composition of arsenic-bearing pyrite ranges from -5.2‰ to 63‰. In the marine environment, the sulfur in sedimentary pyrite becomes increasingly enriched in (34)S as the geochemical environment becomes increasingly anoxic. There is a positive correlation between δ(34)S and arsenic content in the Taconic pyrite, suggesting that uptake of arsenic by pyrite increased as the environment became more reducing. This increased anoxia may have been due to a rise in sea level and/or tectonic activity during the late Cambrian and Ordovician. Low-grade metamorphism appears to have little effect on sulfur isotope composition, but does correlate with lower arsenic content in pyrite. New groundwater wells drilled in this region should therefore avoid gray and black slates and phyllites that contain sedimentary/diagenetic pyrite with heavy δ(34)S values. PMID:24726513

  14. The senescence-accelerated mouse-prone 8 is not a suitable model for the investigation of cardiac inflammation and oxidative stress and their modulation by dietary phytochemicals.

    PubMed

    Schiborr, Christina; Schwamm, Dorothea; Kocher, Alexa; Rimbach, Gerald; Eckert, Gunter P; Frank, Jan

    2013-08-01

    Aging is associated with chronic inflammation and oxidative stress, which both may promote age-associated disorders including cardiovascular diseases. The cardiovascular system suffers from the life-long impact of stressors, such as reactive oxygen and nitrogen species. A diet rich in vegetables and fruits, and thus phytochemicals, may extend healthy lifespan in humans, in part by improving heart health by lowering of oxidative stress and modulating signal transduction pathways. To investigate the potential impact of dietary anthocyanin-rich bilberry extract and curcumin on oxidative stress and inflammatory markers in the heart, two groups of senescence-accelerated mouse-resistant 1 (SAMR1) and senescence-accelerated mouse-prone 8 (SAMP8) mice, respectively, were fed a Western-type diet (normal control and aged control, respectively) and two groups of SAMP8 mice were fed either bilberry extract (20g/kg diet) or curcumin (500mg/kg diet) over a period of 5 months. An activation of the transcription factor nuclear factor κ B (NFκB), but no differences in the gene and protein expression of NFκB-regulated pro-inflammatory mediators, was observed in the hearts of SAMP8 compared to SAMR1 control mice. Cardiac concentrations of protein and lipid oxidation parameters were similar in SAMR1 and SAMP8 control mice and the phytochemical-fed SAMP8 mice. Our data question the suitability of the SAMP8 and SAMR1 strains as a model for age-dependent changes of pro-inflammatory cytokines and oxidative stress in the heart.

  15. Autoxidation and acetylene-accelerated oxidation of NO in a 2-phase system; implications for the expression of denitrification in ex situ experiments

    NASA Astrophysics Data System (ADS)

    Nadeem, Shahid; Dörsch, Peter; Bakken, Lars

    2013-04-01

    Denitrification allows microorganisms to sustain respiration under anoxic conditions. The typical niche for denitrification is an environment with fluctuating oxygen concentrations such as soils and borders between anoxic and oxic zones of biofilms and sediments. In such environments, the organisms need adequate regulation of denitrification in response to changing oxygen availability to tackle both oxic and anoxic spells. The regulation of denitrification in soils has environmental implications, since it affects the proportions of N2, N2O and NO emitted to the atmosphere. The expression of denitrification enzymes is regulated by a complex regulatory network involving one or several positive feedback loops via the intermediate nitrogen oxides. Nitric oxide (NO) is known to induce denitrification in model organisms, but the quantitative effect of NO and its concentration dependency has not been assessed for denitrification in soils. NO is chemically unstable in the presence of oxygen due to autoxidation, and the oxidation of NO is accelerated by acetylene (C2H2) which is commonly used as an inhibitor of N2O reductase in denitrification studies. As a first step to a better understanding of NO's role in soil denitrification, we investigated NO oxidation kinetics for a closed "two phase" system (i.e. liquid phase + headspace) typically used for denitrification experiments with soil slurries, with and without acetylene present. Models were developed to adequately predict autoxidation and acetylene-accelerated oxidation. The minimum oxygen concentration in the headspace ([O2]min, mL L-1) for acetylene-accelerated NO oxidation was found to increase linearly with the NO concentration ([NO], mL L-1); [O2]min= 0.192 + [NO]*0.1 (r2=0.978). The models for NO oxidation were then used to assess NO-oxidation rates in denitrification experiments with batches of bacterial cells extracted from soil. The batches were exposed to low initial oxygen concentrations in gas tight serum

  16. Simultaneous oxidation of arsenic and antimony at low and circumneutral pH, with and without microbial catalysis

    USGS Publications Warehouse

    Asta, M.P.; Kirk, Nordstrom D.; Blaine, McCleskey R.

    2012-01-01

    Arsenic and Sb are common mine-water pollutants and their toxicity and fate are strongly influenced by redox processes. In this study, simultaneous Fe(II), As(III) and Sb(III) oxidation experiments were conducted to obtain rates under laboratory conditions similar to those found in the field for mine waters of both low and circumneutral pH. Additional experiments were performed under abiotic sterile conditions to determine the biotic and abiotic contributions to the oxidation processes. The results showed that under abiotic conditions in aerated Fe(III)-H 2SO 4 solutions, Sb(III) oxidizes slightly faster than As(III). The oxidation rates of both elements were accelerated by increasing As(III), Sb(III), Fe(III), and Cl - concentrations in the presence of light. For unfiltered circumneutral water from the Giant Mine (Yellowknife, NWT, Canada), As(III) oxidized at 15-78??mol/L/h whereas Sb(III) oxidized at 0.03-0.05??mol/L/h during microbial exponential growth. In contrast, As(III) and Sb(III) oxidation rates of 0.01-0.03 and 0.01-0.02??mol/L/h, respectively, were obtained in experiments performed with acid unfiltered mine waters from the Iberian Pyritic Belt (SW Spain). These results suggest that the Fe(III) formed from microbial oxidation abiotically oxidized As(III) and Sb(III). After sterile filtration of both mine water samples, neither As(III), Sb(III), nor Fe(II) oxidation was observed. Hence, under the experimental conditions, bacteria were catalyzing As and Sb oxidation in the Giant Mine waters and Fe oxidation in the acid waters of the Iberian Pyrite Belt. ?? 2011 Elsevier Ltd.

  17. Coenzyme Q10 prevents hepatic fibrosis, inflammation, and oxidative stress in a male rat model of poor maternal nutrition and accelerated postnatal growth1

    PubMed Central

    Tarry-Adkins, Jane L; Fernandez-Twinn, Denise S; Hargreaves, Iain P; Neergheen, Viruna; Aiken, Catherine E; Martin-Gronert, Malgorzata S; McConnell, Josie M; Ozanne, Susan E

    2016-01-01

    Background: It is well established that low birth weight and accelerated postnatal growth increase the risk of liver dysfunction in later life. However, molecular mechanisms underlying such developmental programming are not well characterized, and potential intervention strategies are poorly defined. Objectives: We tested the hypotheses that poor maternal nutrition and accelerated postnatal growth would lead to increased hepatic fibrosis (a pathological marker of liver dysfunction) and that postnatal supplementation with the antioxidant coenzyme Q10 (CoQ10) would prevent this programmed phenotype. Design: A rat model of maternal protein restriction was used to generate low-birth-weight offspring that underwent accelerated postnatal growth (termed “recuperated”). These were compared with control rats. Offspring were weaned onto standard feed pellets with or without dietary CoQ10 (1 mg/kg body weight per day) supplementation. At 12 mo, hepatic fibrosis, indexes of inflammation, oxidative stress, and insulin signaling were measured by histology, Western blot, ELISA, and reverse transcriptase–polymerase chain reaction. Results: Hepatic collagen deposition (diameter of deposit) was greater in recuperated offspring (mean ± SEM: 12 ± 2 μm) than in controls (5 ± 0.5 μm) (P < 0.001). This was associated with greater inflammation (interleukin 6: 38% ± 24% increase; P < 0.05; tumor necrosis factor α: 64% ± 24% increase; P < 0.05), lipid peroxidation (4-hydroxynonenal, measured by ELISA: 0.30 ± 0.02 compared with 0.19 ± 0.05 μg/mL per μg protein; P < 0.05), and hyperinsulinemia (P < 0.05). CoQ10 supplementation increased (P < 0.01) hepatic CoQ10 concentrations and ameliorated liver fibrosis (P < 0.001), inflammation (P < 0.001), some measures of oxidative stress (P < 0.001), and hyperinsulinemia (P < 0.01). Conclusions: Suboptimal in utero nutrition combined with accelerated postnatal catch-up growth caused more hepatic fibrosis in adulthood, which was

  18. Coupled Geochemical and Reactive Transport Modeling of Organic Contaminants in a Pyrite-Rich Aquifer

    NASA Astrophysics Data System (ADS)

    Sarioglu, S. M.; Copty, N. K.

    2004-12-01

    Although pH is recognized as a key factor influencing bacterial activity, existing groundwater transport models generally do not directly account for the effect of pH on the biodegradation of organic compounds. The purpose of this study is to develop a coupled reactive transport and geochemical model that explicitly incorporates the effect of spatial and temporal variations of the pH on the biodegradation of organic contaminants. The model consists of two modules: a transport module and a geochemical module. The transport module uses a Crank-Nicholson finite-difference formulation to solve the groundwater flow and transport equations for the hydrocarbon, dissolved oxygen, microbial mass and all reactive groundwater species influencing the hydrocarbon biodegradation and pH distribution. The geochemical module allows for the simulation of both kinetically defined as well as geochemical equilibrium reactions. The governing non-linear system of equations is solved using an iterative multi-step operator-splitting algorithm. Both modules account for heterogeneity in the definition of the hydrogeological and biochemical parameters. For demonstration, the model is applied to a hypothetical pyrite-rich aquifer contaminated with petroleum hydrocarbons. A commonly used practice for the remediation of aquifers contaminated with petroleum hydrocarbons is the delivery of oxygen for the enhanced aerobic biodegradation of the organic contaminant. However, the presence of pyrite may interfere with the intended purpose of the supplied oxygen, leading to undesirable side effects. Specifically, oxygen readily reacts with the sulfide minerals leading to depletion of oxygen and acidification of the subsurface environment and, subsequently, the inadvertent inhibition of the microbial activity. The developed coupled geochemical and reactive transport model is used to quantify these processes and assess the dominance of the various chemical reactions. Both abiotic and biotic pyrite

  19. Comparison Analysis of Coal Biodesulfurization and Coal's Pyrite Bioleaching with Acidithiobacillus ferrooxidans

    PubMed Central

    Hong, Fen-Fen; He, Huan; Liu, Jin-Yan; Tao, Xiu-Xiang; Zheng, Lei; Zhao, Yi-Dong

    2013-01-01

    Acidithiobacillus ferrooxidans (A. ferrooxidans) was applied in coal biodesulfurization and coal's pyrite bioleaching. The result showed that A. ferrooxidans had significantly promoted the biodesulfurization of coal and bioleaching of coal's pyrite. After 16 days of processing, the total sulfur removal rate of coal was 50.6%, and among them the removal of pyritic sulfur was up to 69.9%. On the contrary, after 12 days of processing, the coal's pyrite bioleaching rate was 72.0%. SEM micrographs showed that the major pyrite forms in coal were massive and veinlets. It seems that the bacteria took priority to remove the massive pyrite. The sulfur relative contents analysis from XANES showed that the elemental sulfur (28.32%) and jarosite (18.99%) were accumulated in the biotreated residual coal. However, XRD and XANES spectra of residual pyrite indicated that the sulfur components were mainly composed of pyrite (49.34%) and elemental sulfur (50.72%) but no other sulfur contents were detected. Based on the present results, we speculated that the pyrite forms in coal might affect sulfur biooxidation process. PMID:24288464

  20. FTIR and XPS studies of surface chemistry of pyrite in flotation

    SciTech Connect

    Leppinen, J.; Laajalehto, K.; Kartio, I.; Suoninen, E.

    1995-12-31

    Efficient separation of pyrite is of great importance for the metallurgical performance of flotation processes. Presently, separation of pyrite by flotation is becoming more and more important for reduction of sulfur in coal. In this work Fourier Transform Infrared Spectroscopy (FTIR) and X-ray Photoelectron Spectroscopy (XPS) were used to study the surface chemistry of pyrite in depression, activation and xanthate adsorption under conditions of controlled potential. Modifications of pyrite surfaces after treatment with depressants (lime, sulfur dioxide, sodium cyanide) and after activation with metal ions (Cu, Pb) were studied. The principal adsorption product identified on pyrite was dixanthogen whose formation started at about +0.15 V and +0.25 V (vs, SHE) in ethyl and amyl xanthate solutions, respectively. Copper xanthate was formed on copper(II) activated pyrite. Activation mechanism of pyrite by copper(II) salts is likely to be electrochemical where copper occurs as copper(I) on the surface of pyrite. Effective depression is achieved by sulfur dioxide and sodium cyanide. Depression at high pH is due to formation of iron(III) hydroxides. Calcium ions do not affect the electrochemistry but adsorb on pyrite and reduce the surface sites for dixanthogen adsorption.

  1. Comparison analysis of coal biodesulfurization and coal's pyrite bioleaching with Acidithiobacillus ferrooxidans.

    PubMed

    Hong, Fen-Fen; He, Huan; Liu, Jin-Yan; Tao, Xiu-Xiang; Zheng, Lei; Zhao, Yi-Dong

    2013-01-01

    Acidithiobacillus ferrooxidans (A. ferrooxidans) was applied in coal biodesulfurization and coal's pyrite bioleaching. The result showed that A. ferrooxidans had significantly promoted the biodesulfurization of coal and bioleaching of coal's pyrite. After 16 days of processing, the total sulfur removal rate of coal was 50.6%, and among them the removal of pyritic sulfur was up to 69.9%. On the contrary, after 12 days of processing, the coal's pyrite bioleaching rate was 72.0%. SEM micrographs showed that the major pyrite forms in coal were massive and veinlets. It seems that the bacteria took priority to remove the massive pyrite. The sulfur relative contents analysis from XANES showed that the elemental sulfur (28.32%) and jarosite (18.99%) were accumulated in the biotreated residual coal. However, XRD and XANES spectra of residual pyrite indicated that the sulfur components were mainly composed of pyrite (49.34%) and elemental sulfur (50.72%) but no other sulfur contents were detected. Based on the present results, we speculated that the pyrite forms in coal might affect sulfur biooxidation process.

  2. Arsenic poisoning in dairy cattle from naturally occurring arsenic pyrites.

    PubMed

    Hopkirk, R G

    1987-10-01

    An outbreak of arsenic poisoning occurred in which most of a 200 cow dairy herd were affected and six died. The source of the arsenic was naturally occurring arsenic pyrites from the Waiotapu Stream, near Rotorua. Arsenic levels in the nearby soil were as high as 6618 ppm. There was little evidence to suggest that treatment affected the course of the disease. Haematology was of little use in diagnosis, post-mortem signs were not always consistent and persistence of the element in the liver appeared short. Control of further outbreaks have been based on practical measures to minimise the intake of contaminated soil and free laying water by the stock. PMID:16031332

  3. Arsenic poisoning in dairy cattle from naturally occurring arsenic pyrites.

    PubMed

    Hopkirk, R G

    1987-10-01

    An outbreak of arsenic poisoning occurred in which most of a 200 cow dairy herd were affected and six died. The source of the arsenic was naturally occurring arsenic pyrites from the Waiotapu Stream, near Rotorua. Arsenic levels in the nearby soil were as high as 6618 ppm. There was little evidence to suggest that treatment affected the course of the disease. Haematology was of little use in diagnosis, post-mortem signs were not always consistent and persistence of the element in the liver appeared short. Control of further outbreaks have been based on practical measures to minimise the intake of contaminated soil and free laying water by the stock.

  4. Petrographic and SIMS pyrite sulfur isotope analyses of Ediacaran chert nodules: Implications for microbial processes in pyrite rim formation, silicification, and exceptional fossil preservation

    NASA Astrophysics Data System (ADS)

    Xiao, Shuhai; Schiffbauer, James D.; McFadden, Kathleen A.; Hunter, Jerry

    2010-09-01

    The lower Ediacaran Doushantuo Formation in the Yangtze Gorges area contains exceptionally preserved microfossils, including the earliest known animal resting eggs and embryos. These fossils are preserved in cm-sized chert nodules, which typically have a microbial mat fragment in the center, a silica cortex, a pyrite rim, and an outer rim of blocky calcite. Petrographic analysis indicates that the formation of the blocky calcite rim postdates that of the pyrite rim and silica cortex. The pyrite rim grew centripetally during early diagenesis, representing a reaction front that was determined by the dynamics between ambient Fe 2+ and H 2S, the latter of which was derived from bacterial sulfate reduction (BSR) of mat fragment in nodule center. The silica cortex was formed pervasively through replacement of carbonate sediments prior to compaction. Secondary ion mass spectroscopy (SIMS) sulfur isotopes of individual pyrite crystals (δ 34S py - SIMS) in pyrite rims and matrices show highly positive values (15.2-39.8‰). The pyrite rims do not show an isotopic gradient between small crystals formed in outer rim during early diagenesis and large crystals formed in inner rim during subsequent overgrowth. Although rim pyrite in the same chert nodule has consistent δ 34S py - SIMS values, there are significant spatial and stratigraphic variations in δ 34S py - SIMS values of both matrix and rim pyrite. Overall, isotopic fractionation between pyrite and carbonate associated sulfate (CAS) is small (< 22‰). The isotopic and petrographic data can be interpreted as evidence for rapid BSR of highly metabolizable organic matter in a diagenetic environment with limited sulfate availability, local anoxia, high Fe 2+ concentration, and low sedimentation rate. The embryonic nodules nucleated on microbial mat fragments and stayed in the BSR zone during early diagenesis, when rapid BSR in the nodule center generated outward-diffusing H 2S that was confined by readily available Fe 2

  5. Simultaneous oxidation of arsenic and antimony at low and circumneutral pH, with and without microbial catalysis

    USGS Publications Warehouse

    Asta, Maria P.; Nordstrom, D. Kirk; McCleskey, R. Blaine

    2012-01-01

    Arsenic and Sb are common mine-water pollutants and their toxicity and fate are strongly influenced by redox processes. In this study, simultaneous Fe(II), As(III) and Sb(III) oxidation experiments were conducted to obtain rates under laboratory conditions similar to those found in the field for mine waters of both low and circumneutral pH. Additional experiments were performed under abiotic sterile conditions to determine the biotic and abiotic contributions to the oxidation processes. The results showed that under abiotic conditions in aerated Fe(III)–H2SO4 solutions, Sb(III) oxidizes slightly faster than As(III). The oxidation rates of both elements were accelerated by increasing As(III), Sb(III), Fe(III), and Cl- concentrations in the presence of light. For unfiltered circumneutral water from the Giant Mine (Yellowknife, NWT, Canada), As(III) oxidized at 15–78 μmol/L/h whereas Sb(III) oxidized at 0.03–0.05 μmol/L/h during microbial exponential growth. In contrast, As(III) and Sb(III) oxidation rates of 0.01–0.03 and 0.01–0.02 μmol/L/h, respectively, were obtained in experiments performed with acid unfiltered mine waters from the Iberian Pyritic Belt (SW Spain). These results suggest that the Fe(III) formed from microbialoxidation abiotically oxidized As(III) and Sb(III). After sterile filtration of both mine water samples, neither As(III), Sb(III), nor Fe(II) oxidation was observed. Hence, under the experimental conditions, bacteria were catalyzing As and Sb oxidation in the Giant Mine waters and Fe oxidation in the acid waters of the Iberian Pyrite Belt.

  6. Antisense directed against PS-1 gene decreases brain oxidative markers in aged senescence accelerated mice (SAMP8) and reverses learning and memory impairment: a proteomics study.

    PubMed

    Fiorini, Ada; Sultana, Rukhsana; Förster, Sarah; Perluigi, Marzia; Cenini, Giovanna; Cini, Chiara; Cai, Jian; Klein, Jon B; Farr, Susan A; Niehoff, Michael L; Morley, John E; Kumar, Vijaya B; Allan Butterfield, D

    2013-12-01

    Amyloid β-peptide (Aβ) plays a central role in the pathophysiology of Alzheimer's disease (AD) through the induction of oxidative stress. This peptide is produced by proteolytic cleavage of amyloid precursor protein (APP) by the action of β- and γ-secretases. Previous studies demonstrated that reduction of Aβ, using an antisense oligonucleotide (AO) directed against the Aβ region of APP, reduced oxidative stress-mediated damage and prevented or reverted cognitive deficits in senescence-accelerated prone mice (SAMP8), a useful animal model for investigating the events related to Aβ pathology and possibly to the early phase of AD. In the current study, aged SAMP8 were treated by AO directed against PS-1, a component of the γ-secretase complex, and tested for learning and memory in T-maze foot shock avoidance and novel object recognition. Brain tissue was collected to identify the decrease of oxidative stress and to evaluate the proteins that are differently expressed and oxidized after the reduction in free radical levels induced by Aβ. We used both expression proteomics and redox proteomics approaches. In brain of AO-treated mice a decrease of oxidative stress markers was found, and the proteins identified by proteomics as expressed differently or nitrated are involved in processes known to be impaired in AD. Our results suggest that the treatment with AO directed against PS-1 in old SAMP8 mice reverses learning and memory deficits and reduces Aβ-mediated oxidative stress with restoration to the normal condition and identifies possible pharmacological targets to combat this devastating dementing disease.

  7. Oxidative stress and age-related changes in T cells: is thalassemia a model of accelerated immune system aging?

    PubMed Central

    Ghatreh-Samani, Mahdi; Esmaeili, Nafiseh; Soleimani, Masoud; Asadi-Samani, Majid; Ghatreh-Samani, Keihan

    2016-01-01

    Iron overload in β-thalassemia major occurs mainly due to blood transfusion, an essential treatment for β-thalassemia major patients, which results in oxidative stress. It has been thought that oxidative stress causes elevation of immune system senescent cells. Under this condition, cells normally enhance in aging, which is referred to as premature immunosenescence. Because there is no animal model for immunosenescence, most knowledge on the immunosenescence pattern is based on induction of immunosenescence. In this review, we describe iron overload and oxidative stress in β-thalassemia major patients and how they make these patients a suitable human model for immunosenescence. We also consider oxidative stress in some kinds of chronic virus infections, which induce changes in the immune system similar to β-thalassemia major. In conclusion, a therapeutic approach used to improve the immune system in such chronic virus diseases, may change the immunosenescence state and make life conditions better for β-thalassemia major patients. PMID:27095931

  8. Oxidative stress and age-related changes in T cells: is thalassemia a model of accelerated immune system aging?

    PubMed

    Ghatreh-Samani, Mahdi; Esmaeili, Nafiseh; Soleimani, Masoud; Asadi-Samani, Majid; Ghatreh-Samani, Keihan; Shirzad, Hedayatolah

    2016-01-01

    Iron overload in β-thalassemia major occurs mainly due to blood transfusion, an essential treatment for β-thalassemia major patients, which results in oxidative stress. It has been thought that oxidative stress causes elevation of immune system senescent cells. Under this condition, cells normally enhance in aging, which is referred to as premature immunosenescence. Because there is no animal model for immunosenescence, most knowledge on the immunosenescence pattern is based on induction of immunosenescence. In this review, we describe iron overload and oxidative stress in β-thalassemia major patients and how they make these patients a suitable human model for immunosenescence. We also consider oxidative stress in some kinds of chronic virus infections, which induce changes in the immune system similar to β-thalassemia major. In conclusion, a therapeutic approach used to improve the immune system in such chronic virus diseases, may change the immunosenescence state and make life conditions better for β-thalassemia major patients.

  9. Screening of microRNAs associated with Alzheimer's disease using oxidative stress cell model and different strains of senescence accelerated mice.

    PubMed

    Zhang, Rui; Zhang, Qingfu; Niu, Jingya; Lu, Kang; Xie, Bing; Cui, Dongsheng; Xu, Shunjiang

    2014-03-15

    Oxidative stress plays a critical role in the etiology and pathogenesis of Alzheimer's disease (AD), and the molecular mechanisms that control the neuron response to oxidative stress have been extensively studied. However, the effects of oxidative stress on miRNA expression in hippocampal neurons has not been investigated, and little is known about the roles of ROS-modulated miRNAs in cell function as yet. In this study, miRNA microarray technology was used to analyze the expression of miRNAs in the oxidative stressed primary hippocampal neurons, hippocampus of senescence accelerated mouse prone 8 (SAMP8) and prone 10 (SAMP10). The targets of co-regulated microRNAs were also selected for computational prediction using miRWalk software and functional analysis by the DAVID software. In addition, the changes of co-regulated microRNA expression were validated by quantitative real-time PCR. The results of microarray analysis showed that miR-329, miR-193b, miR-20a, miR-296, and miR-130b were all upregulated in H2O2-induced primary hippocampal neurons and different strains of senescence accelerated mice. The Kyoto Encyclopedia of Genes and Genomes (KEGG) pathway analysis showed that these co-regulated microRNAs may be involved in the regulation of cell growth, apoptosis, signal transmission and cancer development. In which, mitogen-activated protein kinase (MAPK) signaling pathway was one of the most significant pathways to be affected by 83 target genes of miR-329, miR-193b, miR-20a miR-296, and miR-130b. The quantitative real-time PCR data confirmed the alterations of the co-upregulated miRNAs. These results suggested that oxidative stress alters the miRNA expression profile of hippocampal neurons, and the deregulated miRNAs might play potential roles in the pathogenesis of neurodegenerative diseases, such as Alzheimer's disease (AD). This study provided a strong basis for the future study aiming at contributions of miRNAs induced by oxidative stress in AD.

  10. Enabling Earth-Abundant Pyrite (FeS2) Semiconductor Nanostructures for High Performance Photovoltaic Devices

    SciTech Connect

    Jin, Song

    2014-11-18

    This project seeks to develop nanostructures of iron pyrite, an earth-abundant semiconductor, to enable their applications in high-performance photovoltaic (PV) devices. Growth of high purity iron pyrite nanostructures (nanowires, nanorods, and nanoplates), as well as iron pyrite thin films and single crystals, has been developed and their structures characterized. These structures have been fundamentally investigated to understand the origin of the low solar energy conversion efficiency of iron pyrite and various passivation strategies and doping approaches have been explored in order to improve it. By taking advantage of the high surface-to-bulk ratio in nanostructures and effective electrolyte gating, we fully characterized both the surface inversion and bulk electrical transport properties for the first time through electrolyte-gated Hall measurements of pyrite nanoplate devices and show that pyrite is n-type in the bulk and p-type near the surface due to strong inversion, which has important consequences to using nanocrystalline pyrite for efficient solar energy conversion. Furthermore, through a comprehensive investigation on n-type iron pyrite single crystals, we found the ionization of high-density bulk deep donor states, likely resulting from bulk sulfur vacancies, creates a non-constant charge distribution and a very narrow surface space charge region that limits the total barrier height, thus satisfactorily explains the limited photovoltage and poor photoconversion efficiency of iron pyrite single crystals. These findings suggest new ideas on how to improve single crystal pyrite and nanocrystalline or polycrystalline pyrite films to enable them for high performance solar applications.

  11. The effect of a thiol-containing organic molecule on molybdenum adsorption onto pyrite

    NASA Astrophysics Data System (ADS)

    Freund, Carla; Wishard, Anthony; Brenner, Ryan; Sobel, Marisa; Mizelle, Jack; Kim, Alex; Meyer, Drew A.; Morford, Jennifer L.

    2016-02-01

    The effect of a small thiol-containing organic molecule on the adsorption of Mo to pyrite was investigated through the use of equilibration experiments with molybdate (MoO42-), tetrathiomolybdate (MoS42-), and 2-mercaptopropionic acid (2MPA). MoO42-, MoS42-, and 2MPA individually adsorb to pyrite through the formation of specific interactions with the mineral surface. In select combination experiments, 2MPA effectively out-competes MoO42- for pyrite surface sites, which is indicative of the relatively weaker MoO42--pyrite interactions. Results suggest that the presence of 2MPA on the pyrite surface would inhibit MoO42- access to catalytic mineral surface sites for the transformation of MoO42- to MoS42-. In contrast, thiols are not expected to be an obstacle to Mo uptake once the "switch point", or the critical H2S concentration required for the formation of MoS42-, has been surpassed. This is due to the stronger adsorption of MoS42- to the pyrite surface. EXAFS results support weak specific interactions with little change to the MoO42- environment upon adsorption to pyrite. In contrast, larger changes to the Mo-S internuclear distances during MoS42- adsorption to pyrite support a more substantial structural change upon adsorption. MoS42- is able to bind to both the pyrite surface and a thiol-containing organic molecule to form a ternary structure on the pyrite surface, and may provide for a molecular-level connection between Mo and thiol-containing organic molecules. Mo(VI) is reduced to Mo(IV) during MoS42- adsorption to pyrite as a result of ligand-induced reduction, thereby confirming that the thiolated form of Mo is necessary for Mo reduction.

  12. Linear Accelerators

    SciTech Connect

    Sidorin, Anatoly

    2010-01-05

    In linear accelerators the particles are accelerated by either electrostatic fields or oscillating Radio Frequency (RF) fields. Accordingly the linear accelerators are divided in three large groups: electrostatic, induction and RF accelerators. Overview of the different types of accelerators is given. Stability of longitudinal and transverse motion in the RF linear accelerators is briefly discussed. The methods of beam focusing in linacs are described.

  13. Fe@Fe2O3 core-shell nanowires enhanced Fenton oxidation by accelerating the Fe(III)/Fe(II) cycles.

    PubMed

    Shi, Jingu; Ai, Zhihui; Zhang, Lizhi

    2014-08-01

    In this study we demonstrate Fe@Fe2O3 core-shell nanowires can improve Fenton oxidation efficiency by two times with rhodamine B as a model pollutant at pH > 4. Active species trapping experiments revealed that the rhodamine B oxidation enhancement was attributed to molecular oxygen activation induced by Fe@Fe2O3 core-shell nanowires. The molecular oxygen activation process could generate superoxide radicals to assist iron core for the reduction of ferric ions to accelerate the Fe(III)/Fe(II) cycles, which favored the H2O2 decomposition to produce more hydroxyl radicals for the rhodamine B oxidation. The combination of Fe@Fe2O3 core-shell nanowires and ferrous ions (Fe@Fe2O3/Fe(2+)) offered a superior Fenton catalyst to decompose H2O2 for producing OH. We employed benzoic acid as a probe reagent to check the generation of OH and found the OH generation rate of Fe@Fe2O3/Fe(2+) was 2-4 orders of magnitude larger than those of commonly used iron based Fenton catalysts and 38 times that of Fe(2+). The reusability and the stability of Fe@Fe2O3 core-shell nanowires were studied. Total organic carbon and ion chromatography analyses revealed the mineralization of rhodamine B and the releasing of nitrate ions. Gas chromatograph-mass spectrometry was used to investigate the degradation intermediates to propose the possible rhodamine B Fenton oxidation pathway in the presence of Fe@Fe2O3 nanowires. This study not only provides a new Fenton oxidation system for pollutant control, but also widen the application of molecular oxygen activation induced by nanoscale zero valent iron.

  14. Thermal stability and mechanism of decomposition of emulsion explosives in the presence of pyrite.

    PubMed

    Xu, Zhi-Xiang; Wang, Qian; Fu, Xiao-Qi

    2015-12-30

    The reaction of emulsion explosives (ammonium nitrate) with pyrite was studied using techniques of TG-DTG-DTA. TG-DSC-MS was also used to analyze samples thermal decomposition process. When a mixture of pyrite and emulsion explosives was heated at a constant heating rate of 10K/min from room temperature to 350°C, exothermic reactions occurred at about 200°C. The essence of reaction between emulsion explosives and pyrite is the reaction between ammonium nitrate and pyrite. Emulsion explosives have excellent thermal stability but it does not mean it showed the same excellent thermal stability when pyrite was added. Package emulsion explosives were more suitable to use in pyrite shale than bulk emulsion explosives. The exothermic reaction was considered to take place between ammonium nitrate and pyrite where NO, NO2, NH3, SO2 and N2O gases were produced. Based on the analysis of the gaseous, a new overall reaction was proposed, which was thermodynamically favorable. The results have significant implication in the understanding of stability of emulsion explosives in reactive mining grounds containing pyrite minerals.

  15. Surfactant-Assisted Hydrothermal Synthesis of Single Phase Pyrite FeS2 Nanocrystals

    SciTech Connect

    Wadia, Cyrus; Wu, Yue; Gul, Sheraz; Volkman, Steven; Guo, Jinghua; Alivisatos, Paul

    2009-03-27

    Iron pyrite nanocrystals with high purity have been synthesized through a surfactant-assisted hydrothermal reaction under optimum pH value. These pyrite nanocrystals represent a new group of well-defined nanoscale structures for high-performance photovoltaic solar cells based on non-toxic and earth abundant materials.

  16. Treatment of Actual Chemical Wastewater by a Heterogeneous Fenton Process Using Natural Pyrite

    PubMed Central

    Sun, Liang; Li, Yan; Li, Aimin

    2015-01-01

    Wastewater from chemical plants has remarkable antibiotic effects on the microorganisms in traditional biological treatment processes. An enhanced Fenton system catalyzed by natural pyrite was developed to degrade this kind of wastewater. Approximately 30% chemical oxygen demand (COD) was removed within 120 min when 50 mmol/L H2O2 and 10 g/L natural pyrite were used at initial pH from 1.8 to 7. A BOD5/COD enhancement efficiency of 210% and an acute biotoxicity removal efficiency of 84% were achieved. The COD removal efficiency was less sensitive to initial pH than was the classic Fenton process. Excessive amounts of pyrite and H2O2 did not negatively affect the pyrite Fenton system. The amount of aniline generated indicated that nitrobenzene reduction by pyrite was promoted using a low initial concentration of H2O2 (<5 mmol/L). Fluorescence excitation emission matrix analyses illustrated that H2O2 facilitated the reduction by natural pyrite of organic molecules containing an electron-withdrawing group to electron-donating group. Thus, the Fenton-like process catalyzed by pyrite can remediate wastewater containing organic pollutants under mild reaction conditions and provide an alternative environmentally friendly method by which to reuse natural pyrite. PMID:26516893

  17. Pyrite-based autotrophic denitrification for remediation of nitrate contaminated groundwater.

    PubMed

    Pu, Jiaoyang; Feng, Chuanping; Liu, Ying; Li, Rui; Kong, Zhe; Chen, Nan; Tong, Shuang; Hao, Chunbo; Liu, Ye

    2014-12-01

    In this study, pyrite-based denitrification using untreated pyrite (UP) and acid-pretreated pyrite (AP) was evaluated as an alternative to elemental sulfur based denitrification. Pyrite-based denitrification resulted in a favorable nitrate removal rate constant (0.95 d(-1)), sulfate production of 388.00 mg/L, and a stable pH. The pretreatment of pyrite with acid led to a further increase in the nitrate removal rate constant (1.03 d(-1)) and reduction in initial sulfate concentration (224.25±7.50 mg/L). By analyzing the microbial community structure using Denaturing Gradient Gel Electrophoresis, it was confirmed that Sulfurimonas denitrificans (S. denitrificans) could utilize pyrite as an electron donor. A stable pH was observed over the entire experimental period, indicating that the use of a pH buffer reagent would not be necessary for pyrite-based denitrification. Therefore, pyrite could effectively replace elemental sulfur as an electron donor in autotrophic denitrification for nitrate-contaminated groundwater remediation.

  18. Treatment of Actual Chemical Wastewater by a Heterogeneous Fenton Process Using Natural Pyrite.

    PubMed

    Sun, Liang; Li, Yan; Li, Aimin

    2015-11-01

    Wastewater from chemical plants has remarkable antibiotic effects on the microorganisms in traditional biological treatment processes. An enhanced Fenton system catalyzed by natural pyrite was developed to degrade this kind of wastewater. Approximately 30% chemical oxygen demand (COD) was removed within 120 min when 50 mmol/L H₂O₂ and 10 g/L natural pyrite were used at initial pH from 1.8 to 7. A BOD₅/COD enhancement efficiency of 210% and an acute biotoxicity removal efficiency of 84% were achieved. The COD removal efficiency was less sensitive to initial pH than was the classic Fenton process. Excessive amounts of pyrite and H₂O₂ did not negatively affect the pyrite Fenton system. The amount of aniline generated indicated that nitrobenzene reduction by pyrite was promoted using a low initial concentration of H₂O₂ (<5 mmol/L). Fluorescence excitation emission matrix analyses illustrated that H₂O₂ facilitated the reduction by natural pyrite of organic molecules containing an electron-withdrawing group to electron-donating group. Thus, the Fenton-like process catalyzed by pyrite can remediate wastewater containing organic pollutants under mild reaction conditions and provide an alternative environmentally friendly method by which to reuse natural pyrite. PMID:26516893

  19. Sulphur isotope geochemistry of pyrite from the Upper Cretaceous Marshybank Formation, Western Interior Basin

    NASA Astrophysics Data System (ADS)

    McKay, J. L.; Longstaffe, F. J.

    2003-04-01

    Variations in the texture and sulphur isotopic composition of pyrite in the Upper Cretaceous Marshybank Formation are linked to depositional environment. Abundant, framboidal (and lesser euhedral) pyrite precipitated in offshore marine rocks. Moderate quantities of pyrite also crystallized in brackish, coastal plain rocks. However, in contrast to marine pyrite, coastal plain pyrite is dominantly euhedral in texture, reflecting direct precipitation from a porewater with a relatively low dissolved sulphide concentration. In the marine rocks, pyrite δ34S values range from -35.7‰ to +27.4‰ (avg. -4.8‰ Canyon Diablo Troilite, CDT). Pyrite within carbonate concretions hosted in these marine rocks has a similar isotopic composition (-49.8‰ to +10.6‰ CDT). However, isotopic values are often highly variable within individual concretions as a result of the heterogeneous nature of sulphate reduction and pyrite formation within marine sediments. Pyrite in coastal plain rocks is characterized by relatively high δ34S values (-4.2‰ to +35.5‰, avg. +13.2‰ CDT), while the overlying sideritized conglomerates have the lowest δ34S values reported for Cretaceous rocks from the Western Interior Basin of North America (-49.8‰ to -41.7‰ CDT). Very low δ34S values, which are only observed in the marine rocks, are indicative of microbial sulphate reduction and pyrite formation in a sulphate-replete (i.e., open) system. Higher δ34S values (up to +18‰), which were obtained for both the marine and coastal plain rocks, are indicative of progressive pyrite crystallization in a sulphate-limited (i.e., closed) system. Such conditions are expected in marine sediments as burial occurs, and in brackish (i.e., low sulphate) sediments. Pyrite with very high δ34S values (>+18‰) is common in the coastal plain rocks. These high values are the result of influx of 34S-enriched, residual sulphide derived from overlying marine units. A minor amount of 34S-enriched pyrite is also

  20. Semiconductor electrochemistry of coal pyrite. Technical progress report, July--September, 1994

    SciTech Connect

    Osseo-Asare, K.; Wei, D.

    1994-10-01

    This project seeks to advance the fundamental understanding of the physicochemical processes occurring at the pyrite/aqueous interface, in the context of coal cleaning, coal desulfurization, and acid mine drainage. Pyrite particles were synthesized by aqueous precipitation and purified by means of solvent extraction to remove elemental sulfur. A purified pyrite sample containing 98.35% FeS{sub 2} was obtained and used in photoelectrochemical experiments. Illumination of pyrite microelectrodes increased both the anodic current and the dissolution rate dramatically, but it had little effect on the cathodic current and the cathodic dissolution. These results indicate that pyrite, as an n-type semiconductor, dissolves anodically through a hole transfer pathway, while cathodic dissolution involves only electron reaction.

  1. Novel microorganism for selective separation of coal from ash and pyrite. Fifth quarterly technical progress report, October 1--December 31, 1994

    SciTech Connect

    Misra, M.; Smith, R.W.; Raichur, A.M.

    1994-12-31

    The objective of this project is to study the effectiveness of a novel hydrophobic microorganism, Mycobacterium phlei (M. phlei), for the selective flocculation of coal from pyrite and ash forming minerals. During the reporting period, the flocculation efficiencies of Illinois No.6 coal with M. phlei and with polymeric flocculants such as polyethylene oxide and polyacrylamide were investigated. Results indicated that good flocculation efficiencies were obtained with M. phlei as opposed to synthetic flocculants at an acidic pH value. Floc separation studies were conducted using column flotation. It was found that very good recovery of coal with a high rejection of pyrite and ash could be obtained using M. phlei when compared with synthetic flocculants. DLVO calculations for coal/M. phlei interface showed that minimum interaction energy occurs at acidic pH values thus facilitating the adhesion of M. phlei. A good correlation between the interaction energy and adhesion, contact angle and flocculation results were noticed.

  2. Remnant colloform pyrite at the haile gold deposit, South Carolina: A textural key to genesis

    USGS Publications Warehouse

    Foley, N.; Ayuso, R.A.; Seal, R.R.

    2001-01-01

    Auriferous iron sulfide-bearing deposits of the Carolina slate belt have distinctive mineralogical and textural features-traits that provide a basis to construct models of ore deposition. Our identification of paragenetically early types of pyrite, especially remnant colloform, crustiform, and layered growth textures of pyrite containing electrum and pyrrhotite, establishes unequivocally that gold mineralization was coeval with deposition of host rocks and not solely related to Paleozoic tectonic events. Ore horizons at the Haile deposit, South Carolina, contain many remnants of early pyrite: (1) fine-grained cubic pyrite disseminated along bedding; (2) fine- grained spongy, rounded masses of pyrite that may envelop or drape over pyrite cubes; (3) fragments of botryoidally and crustiform layered pyrite, and (4) pyritic infilling of vesicles and pumice. Detailed mineral chemistry by petrography, microprobe, SEM, and EDS analysis of replaced pumice and colloform structures containing both arsenic compositional banding and electrum points to coeval deposition of gold and the volcanic host rocks and, thus, confirms a syngenetic origin for the gold deposits. Early pyrite textures are present in other major deposits of the Carolina slate belt, such as Ridgeway and Barite Hill, and these provide strong evidence for models whereby the sulfide ores formed prior to tectonism. The role of Paleozoic metamorphism was to remobilize and concentrate gold and other minerals in structurally prepared sites. Recognizing the significance of paragenetically early pyrite and gold textures can play an important role in distinguishing sulfide ores that form in volcanic and sedimentary environments from those formed solely by metamorphic processes. Exploration strategies applied to the Carolina slate belt and correlative rocks in the eastern United States in the Avalonian basement will benefit from using syngenetic models for gold mineralization.

  3. Semiconductor electrochemistry of coal pyrite. Final technical report, September 1990--September 1995

    SciTech Connect

    Osseo-Asare, K.; Wei, Dawei

    1996-01-01

    This project seeks to advance the fundamental understanding of the physico-chemical processes occurring at the pyrite/aqueous interface, in the context of coal cleaning, coal desulfurization, and acid mine drainage. Central to this research is the use of synthetic microsize particles of pyrite as model microelectrodes to investigate the semiconductor electrochemistry of pyrite. The research focuses on: (a) the synthesis of microsize particles of pyrite in aqueous solution at room temperature, (b) the formation of iron sulfide complex, the precursor of FeS or FeS{sub 2}, and (c) the relationship between the semiconductor properties of pyrite and its interfacial electrochemical behavior in the dissolution process. In Chapter 2, 3 and 4, a suitable protocol for preparing microsize particles of pyrite in aqueous solution is given, and the essential roles of the precursors elemental sulfur and ``FeS`` in pyrite formation are investigated. In Chapter 5, the formation of iron sulfide complex prior to the precipitation of FeS or FeS{sub 2} is investigated using a fast kinetics technique based on a stopped-flow spectrophotometer. The stoichiometry of the iron sulfide complex is determined, and the rate and formation constants are also evaluated. Chapter 6 provides a summary of the semiconductor properties of pyrite relevant to the present study. In Chapters 7 and 8, the effects of the semiconductor properties on pyrite dissolution are investigated experimentally and the mechanism of pyrite dissolution in acidic aqueous solution is examined. Finally, a summary of the conclusions from this study and suggestions for future research are presented in Chapter 9.

  4. Can Accelerators Accelerate Learning?

    NASA Astrophysics Data System (ADS)

    Santos, A. C. F.; Fonseca, P.; Coelho, L. F. S.

    2009-03-01

    The 'Young Talented' education program developed by the Brazilian State Funding Agency (FAPERJ) [1] makes it possible for high-schools students from public high schools to perform activities in scientific laboratories. In the Atomic and Molecular Physics Laboratory at Federal University of Rio de Janeiro (UFRJ), the students are confronted with modern research tools like the 1.7 MV ion accelerator. Being a user-friendly machine, the accelerator is easily manageable by the students, who can perform simple hands-on activities, stimulating interest in physics, and getting the students close to modern laboratory techniques.

  5. Can Accelerators Accelerate Learning?

    SciTech Connect

    Santos, A. C. F.; Fonseca, P.; Coelho, L. F. S.

    2009-03-10

    The 'Young Talented' education program developed by the Brazilian State Funding Agency (FAPERJ)[1] makes it possible for high-schools students from public high schools to perform activities in scientific laboratories. In the Atomic and Molecular Physics Laboratory at Federal University of Rio de Janeiro (UFRJ), the students are confronted with modern research tools like the 1.7 MV ion accelerator. Being a user-friendly machine, the accelerator is easily manageable by the students, who can perform simple hands-on activities, stimulating interest in physics, and getting the students close to modern laboratory techniques.

  6. A pyritized polychaete from the Devonian of Ontario

    PubMed Central

    Farrell, Úna C; Briggs, Derek E.G

    2006-01-01

    A polychaete from the Middle Devonian Arkona Shale at Hungry Hollow, Arkona, Ontario is preserved in three dimensions in pyrite. The prostomium bears a single median antenna, a pair of lateral antennae and a pair of ventral palps. It is assumed to be fused to a reduced peristomium. The anteriormost three pairs of trunk appendages are modified as tentacular cirri, the third long and biramous. The remainder of the finely annulated trunk bears at least 21 similar biramous parapodia, some of which preserve evidence of chaetae. The postsegmental pygidium is very small and may bear up to two pairs of cirri. The polychaete, Arkonips topororum, falls within the Palpata, Aciculata, among the crown group Phyllodocida. Its remarkable preservation highlights the potential of the Arkona Shale to yield other examples of soft-tissue preservation. PMID:17476769

  7. Surface electrochemical control for fine coal and pyrite separation

    SciTech Connect

    Hu, Weibai; Huang, Qinping; Zhu, Ximeng; Li, Jun; Bodily, D.M; Zhong, Tingke; Wadsworth, M.E.

    1992-01-01

    A series of fine coal kinetic tests were carried out on three coals. It was found that the rank of flotation rates for the three coals tested were: Upper Freeport > Pittsburgh No. 8 > Illinois No. 6. In the case of Pittsburgh No. 8, the contained coal-pyrite was found to float more slowly than the coal itself when xanthate was used as the collector. In kinetic modeling, first order kinetic models produced large errors for long flotation times. It was found that a modified first order kinetic-model with slow and fast rate constants was appropriate for fine coal flotation. A log-log plot of 1(R{sub j} -R) versus t forms a straight line for the test conditions of this study. The Lai proportionality flotation model was found to apply from the start and extending over a very broad time range.

  8. Ultrasonic ash/pyrite liberation. Final technical report

    SciTech Connect

    Yungman, B.A.; Buban, K.S.; Stotts, W.F.

    1990-06-01

    The objective of this project was to develop a coal preparation concept which employed ultrasonics to precondition coal prior to conventional or advanced physical beneficiation processes such that ash and pyrite separation were enhanced with improved combustible recovery. Research activities involved a series of experiments that subjected three different test coals, Illinois No. 6, Pittsburgh No. 8, and Upper Freeport, ground to three different size fractions (28 mesh {times} 0, 200 mesh {times} 0, and 325 mesh {times} 0), to a fixed (20 kHz) frequency ultrasonic signal prior to processing by conventional and microbubble flotation. The samples were also processed by conventional and microbubble flotation without ultrasonic pretreatment to establish baseline conditions. Product ash, sulfur and combustible recovery data were determined for both beneficiation processes.

  9. Accelerated Biodegradation of Cement by Sulfur-Oxidizing Bacteria as a Bioassay for Evaluating Immobilization of Low-Level Radioactive Waste

    PubMed Central

    Aviam, Orli; Bar-Nes, Gabi; Zeiri, Yehuda; Sivan, Alex

    2004-01-01

    Disposal of low-level radioactive waste by immobilization in cement is being evaluated worldwide. The stability of cement in the environment may be impaired by sulfur-oxidizing bacteria that corrode the cement by producing sulfuric acid. Since this process is so slow that it is not possible to perform studies of the degradation kinetics and to test cement mixtures with increased durability, procedures that accelerate the biodegradation are required. Semicontinuous cultures of Halothiobacillus neapolitanus and Thiomonas intermedia containing thiosulfate as the sole energy source were employed to accelerate the biodegradation of cement samples. This resulted in a weight loss of up to 16% after 39 days, compared with a weight loss of 0.8% in noninoculated controls. Scanning electron microscopy of the degraded cement samples revealed deep cracks, which could be associated with the formation of low-density corrosion products in the interior of the cement. Accelerated biodegradation was also evident from the leaching rates of Ca2+ and Si2+, the major constituents of the cement matrix, and Ca exhibited the highest rate (up to 20 times greater than the control rate) due to the reaction between free lime and the biogenic sulfuric acid. Leaching of Sr2+ and Cs+, which were added to the cement to simulate immobilization of the corresponding radioisotopes, was also monitored. In contrast to the linear leaching kinetics of calcium, silicon, and strontium, the leaching pattern of cesium produced a saturation curve similar to the control curve. Presumably, the leaching of cesium is governed by the diffusion process, whereas the leaching kinetics of the other three ions seems to governed by dissolution of the cement. PMID:15466547

  10. Increase of theaflavin gallates and thearubigins by acceleration of catechin oxidation in a new fermented tea product obtained by the tea-rolling processing of loquat ( Eriobotrya japonica ) and green tea leaves.

    PubMed

    Tanaka, Takashi; Miyata, Yuji; Tamaya, Kei; Kusano, Rie; Matsuo, Yosuke; Tamaru, Shizuka; Tanaka, Kazunari; Matsui, Toshiro; Maeda, Masamichi; Kouno, Isao

    2009-07-01

    In a project to produce a new fermented tea product from non-used tea leaves harvested in the summer, we found that kneading tea leaves ( Camellia sinensis ) with fresh loquat leaves ( Eriobotrya japonica ) accelerated the enzymatic oxidation of tea catechins. The fermented tea obtained by tea-rolling processing of tea and loquat leaves had a strong, distinctive flavor and a plain aftertaste, which differed from usual black, green, and oolong teas. The phenolic constituents were similar to those of black tea. However, the concentrations of theaflavin 3-O-gallate, theaflavin 3,3'-di-O-gallate, and thearubigins were higher in the tea leaves kneaded with loquat leaves than in tea leaves kneaded without loquat leaves. The results from in vitro experiments suggested that acceleration of catechin oxidation was caused by the strong oxidation activity of loquat leaf enzymes and a coupled oxidation mechanism with caffeoyl quinic acids, which are the major phenolic constituents of loquat leaves.

  11. Mineralogical and chemical changes in pyrite after traditional processing for use in medicines.

    PubMed

    Hwang, Jeong; Hur, Soon Do; Seo, Young Bae

    2004-01-01

    Pyrite has been the most commonly used medicinal mineral, and its toxicity was reduced by traditional processing operations including heating and quenching in vinegar. To verify the scientific effects of this process, pyrite was processed at temperatures up to 850 degrees C and through as many as five processing cycles. A metal extraction test was carried out from the processed pyrites on the assumption that pyrite medicines with the lowest toxic metal content would be most desirable. Increasing temperature and the number of processing cycles promoted phase change of pyrite to hematite, reduction of toxic metals in pyrite and their concentrations in the extraction solutions. However, the relationships between variations in extracted elements and the number of processing cycles at the same processing temperature were not clearly defined. Heating temperature is more important than the number of processing cycles for effective processing, and pyrite should be processed at the highest possible temperature in order to diminish highly toxic metals such as As and Pb. PMID:15673196

  12. DFT study of interactions between calcium hydroxyl ions and pyrite, marcasite, pyrrhotite surfaces

    NASA Astrophysics Data System (ADS)

    Zhao, Cuihua; Chen, Jianhua; Li, Yuqiong; Huang, De wei; Li, Weizhou

    2015-11-01

    The interaction between CaOH+ ions and pyrite, marcasite and pyrrhotite surfaces was studied using density functional theory (DFT) calculations. The calculated results show that the adsorption energy of CaOH+ on the marcasite surface is the largest, -384.65 kJ/mol; then pyrrhotite, -346.61 kJ/mol; pyrite, -276.62 kJ/mol. After CaOH+ adsorption, oxygen atom is bonded to one iron atom, calcium atom is bonded to two sulfur atoms of pyrite surface. And there exists a Casbnd Fe2 anti-bonding on the pyrite surface. For marcasite, oxygen atom is bonded to one iron atom, calcium atom is bonded to two sulfur atoms of marcasite surface. As for pyrrhotite, calcium atom is only attached to three sulfur atoms of pyrrhotite surface. The charge transfers occur from CaOH+ to sulfides surfaces. The value of charge transfer from CaOH+ to marcasite surface is the largest, then pyrite, pyrrhotite in order. However, formation of Casbnd Fe2 anti-bonding on the pyrite surface weakens the reaction of CaOH+ with pyrite.

  13. Mineralogical and chemical changes in pyrite after traditional processing for use in medicines.

    PubMed

    Hwang, Jeong; Hur, Soon Do; Seo, Young Bae

    2004-01-01

    Pyrite has been the most commonly used medicinal mineral, and its toxicity was reduced by traditional processing operations including heating and quenching in vinegar. To verify the scientific effects of this process, pyrite was processed at temperatures up to 850 degrees C and through as many as five processing cycles. A metal extraction test was carried out from the processed pyrites on the assumption that pyrite medicines with the lowest toxic metal content would be most desirable. Increasing temperature and the number of processing cycles promoted phase change of pyrite to hematite, reduction of toxic metals in pyrite and their concentrations in the extraction solutions. However, the relationships between variations in extracted elements and the number of processing cycles at the same processing temperature were not clearly defined. Heating temperature is more important than the number of processing cycles for effective processing, and pyrite should be processed at the highest possible temperature in order to diminish highly toxic metals such as As and Pb.

  14. Biogeochemistry of sulfur in a sediment core from the west-central Baltic Sea: Evidence from stable isotopes and pyrite textures

    NASA Astrophysics Data System (ADS)

    Böttcher, Michael E.; Lepland, Aivo

    2000-07-01

    The biogeochemistry of the sulfur cycle in a ca. 5-m-long sediment core from the eastern slope (221 m water depth) of the Landsort Deep in the west-central Baltic Sea was investigated by analyzing the solid phase records of sulfur isotopes and pyrite textures, besides selected main and minor elements. The sediments were deposited during post-glacial history of the Baltic Sea when the basin experienced alteration of brackish (Yoldia Sea, Littorina Sea) and freshwater (Baltic Ice Lake, Ancylus Lake) conditions. The stable isotopic composition of total sulfur was analyzed as a function of depth. In selected samples pyrite (FeS 2), greigite (Fe 3S 4), and barite (BaSO 4) fractions were separated for isotope analyses. Pyrite textures were analyzed by SEM and optical microscopy. Microbial reactions associated with the oxidation of organic matter resulted in assemblages of authigenic sulfide minerals which for the post-Ancylus Lake brackish water environment are dominated by pyrite and for freshwater environments by Fe-monosulfides. The sulfur isotopic composition of the brackish water Littorina Sea sediments ( δ34S between -40 and -27‰ vs. V-CDT) is believed to be determined by cellular sulfate reduction rates and reactions involving intermediate sulfur species. The availability of reactive iron and decomposable organic matter as well as sedimentation rate and the chemocline position are important variables upon the δ34S values of sulfides in brackish water environment. The syn-depositional abundance of sulfur and organic matter, and transport of dissolved sulfur species vs. rates of microbial reactions determine δ34S in the freshwater sediments. The upper part of the Ancylus Lake sediments is sulfidized by downward diffusing H 2S and/or sulfate from overlying brackish water sediments. Minor concretionary barite formation in the freshwater sediments is most likely due to the reaction of pore water sulfate diffusing downward from brackish water sediments with barium

  15. Synthesis of hierarchical NiCo2O4 hollow nanorods via sacrificial-template accelerate hydrolysis for electrochemical glucose oxidation.

    PubMed

    Yang, Jiao; Cho, Misuk; Lee, Youngkwan

    2016-01-15

    Hierarchical NiCo2O4 hollow nanorods (HR) were directly grown on stainless steel via a sacrificial template accelerated hydrolysis and post calcination using ZnO nanorod as a template. The composition of the NiCo2O4 HR electrode was determined using X-ray diffraction and X-ray photoelectron spectroscopy. The morphology of the NiCo2O4 HR is comprised of nanoflakes that were characterized with scanning electron microscopy and transmission electron microscopy. The mixed-valence metal oxide and hollow structure provided high chemical reactivity and a large surface area for glucose oxidation in an alkaline solution. Under an optimal applied potential of +0.6 V, the developed NiCo2O4 HR electrode showed a broad detection range of 0.0003–1.0 mM, a sensitivity of 1685.1 μA mM−1 cm−2, and a low detection limit of 0.16 μM. These results represent a significant improvement over both NiO and Co3O4 HR. The developed NiCo2O4 HR electrode not only demonstrated excellent selectivity in the presence of several electro-active species, but also exhibited high stability following a 200 cycles voltammetry test. PMID:26281005

  16. Abundances and isotopic compositions of rhenium and osmium in pyrite samples from the Huaibei coalfield, Anhui, China

    USGS Publications Warehouse

    Liu, Gaisheng; Chou, C.-L.; Peng, Z.; Yang, G.

    2008-01-01

    Two pyrite samples from the Shihezi Formation (Lower Permian), Huaibei coalfield, Anhui, China, have been analyzed for abundances and isotopic compositions of rhenium and osmium using negative thermal ion mass spectrometry. The Re-Os ages of the pyrites are 64.4 and 226 Ma, which are younger than the formation age of the coal seam. The pyrite samples may consist of pyrite formed at various stages during the history of coal formation. The ??Osvalues of the two pyrite samples are +17 and +18, respectively. Such high ??Osvalues are reported for the first time for recycles crustal materials from a sedimentary basin. ?? Springer-Verlag 2007.

  17. Accelerated migration and invasion of prostate cancer cells after a photodynamic therapy-like challenge: Role of nitric oxide.

    PubMed

    Fahey, Jonathan M; Girotti, Albert W

    2015-09-15

    Employing an in vitro model for 5-aminolevulinic acid (ALA)-based photodynamic therapy (PDT), we recently reported that human prostate cancer PC3 cells rapidly and persistently overexpressed inducible nitric oxide synthase (iNOS) and nitric oxide (NO) after a moderate ALA/light challenge. The upregulated iNOS/NO was shown to play a key role in cell resistance to apoptotic photokilling and also in the dramatic growth spurt observed in surviving cells. In the present study, we found that PC3 cells surviving an ALA/light insult not only proliferated faster than non-stressed controls, but migrated and invaded faster as well, these effects being abrogated by an iNOS inhibitor or NO scavenger. Photostressed prostate DU145 cells exhibited similar behavior. Using in-gel zymography, we showed that PC3 extracellular matrix metalloproteinase-9 (MMP-9) was strongly activated 24 h after ALA/light treatment and that MMP-9 inhibitor TIMP-1 was downregulated, consistent with MMP-9 involvement in enhanced invasiveness. We also observed a photostress-induced upregulation of α6 and β1 integrins, implying their involvement as well. The MMP-9, TIMP-1, and integrin effects were strongly attenuated by iNOS inhibition, confirming NO's role in photostress-enhanced migration/invasion. This study reveals novel, potentially tumor-promoting, side-effects of prostate cancer PDT which may be averted through use of iNOS inhibitors as PDT adjuvants.

  18. Complexation of the vulcanization accelerator tetramethylthiuram disulfide and related molecules with zinc compounds including zinc oxide clusters (Zn4O4).

    PubMed

    Steudel, Ralf; Steudel, Yana; Wong, Ming Wah

    2008-01-01

    Zinc chemicals are used as activators in the vulcanization of organic polymers with sulfur to produce elastic rubbers. In this work, the reactions of Zn(2+), ZnMe(2), Zn(OMe)(2), Zn(OOCMe)(2), and the heterocubane cluster Zn(4)O(4) with the vulcanization accelerator tetramethylthiuram disulfide (TMTD) and with the related radicals and anions Me(2)NCS(2)(*), Me(2)NCS(3)(*), Me(2)NCS(2)(-), and Me(2)NCS(3)(-) have been studied by quantum chemical methods at the MP2/6-31+G(2df,p)//B3LYP/6-31+G* level of theory. More than 35 zinc complexes have been structurally characterized and the energies of formation from their components calculated for the first time. The binding energy of TMTD as a bidendate ligand increases in the order ZnMe(2)oxide used as an activator in rubber vulcanization by sulfur. The further uptake of sulfur atoms by the various complexes from S(8) or TMTD with formation of species derived from the radical Me(2)NCS(3)(*) or the trithiocarbamate anion Me(2)NCS(3)(-) is endothermic for mono- and dinuclear zinc dithiocarbamate (dtc) complexes such as [Zn(dtc)(2)] and [Zn(2)(dtc)(4)], but exothermic in the case of polynuclear zinc oxide species containing bridging ligands as in [Zn(4)O(4)(mu-S(2)CNMe(2))] and [Zn(4)O(4)(mu-dtc)]. Therefore, zinc oxide as a polynuclear species is predicted to promote the formation of trisulfido complexes, which are generally assumed to serve as catalysts for the transfer of

  19. A Combination of Mitochondrial Oxidative Stress and Excess Fat/Calorie Intake Accelerates Steatohepatitis by Enhancing Hepatic CC Chemokine Production in Mice.

    PubMed

    Moro, Tadashi; Nakao, Sachie; Sumiyoshi, Hideaki; Ishii, Takamasa; Miyazawa, Masaki; Ishii, Naoaki; Sato, Tadayuki; Iida, Yumi; Okada, Yoshinori; Tanaka, Masayuki; Hayashi, Hideki; Ueha, Satoshi; Matsushima, Kouji; Inagaki, Yutaka

    2016-01-01

    Mitochondrial oxidative stress is considered as a key accelerator of fibrosis in various organs including the liver. However, the production of oxidative stress and progression of liver fibrosis may merely represent the independent consequences of hepatocellular injury caused by the primary disease. Because of a lack of appropriate experimental models to evaluate the sole effects of oxidative stress, it is virtually unknown whether this stress is causatively linked to the progression of liver fibrosis. Here, we examined the direct effects of mitochondrial reactive oxygen species (ROS) on the progression of high fat/calorie diet-induced steatohepatitis using Tet-mev-1 mice, in which a mutated succinate dehydrogenase transgene impairs the mitochondrial electron transport and generates an excess amount of ROS in response to doxycycline administration. Wild type and Tet-mev-1 mice that had been continuously given doxycycline-containing water were subsequently fed either normal chow or a cholesterol-free high-fat/high-sucrose diet for 4 months at approximately 1 or 2 years of age. Histopathological examinations indicated that neither the mitochondrial ROS induced in Tet-mev-1 mice nor the feeding of wild type animals with high-fat/high-sucrose diet alone caused significant liver fibrosis. Only when the Tet-mev-1 mice were fed a high-fat/high-sucrose diet, it induced lipid peroxidation in hepatocytes and enhanced hepatic CC chemokine expression. These events were accompanied by increased infiltration of CCR5-positive cells and activation of myofibroblasts, resulting in extensive liver fibrosis. Interestingly, this combinatorial effect of mitochondrial ROS and excess fat/calorie intake on liver fibrosis was observed only in 2-year-old Tet-mev-1 mice, not in the 1-year-old animals. Collectively, these results indicate that mitochondrial ROS in combination with excess fat/calorie intake accelerates liver fibrosis by enhancing CC chemokine production in aged animals. We have

  20. Complexation of the vulcanization accelerator tetramethylthiuram disulfide and related molecules with zinc compounds including zinc oxide clusters (Zn4O4).

    PubMed

    Steudel, Ralf; Steudel, Yana; Wong, Ming Wah

    2008-01-01

    Zinc chemicals are used as activators in the vulcanization of organic polymers with sulfur to produce elastic rubbers. In this work, the reactions of Zn(2+), ZnMe(2), Zn(OMe)(2), Zn(OOCMe)(2), and the heterocubane cluster Zn(4)O(4) with the vulcanization accelerator tetramethylthiuram disulfide (TMTD) and with the related radicals and anions Me(2)NCS(2)(*), Me(2)NCS(3)(*), Me(2)NCS(2)(-), and Me(2)NCS(3)(-) have been studied by quantum chemical methods at the MP2/6-31+G(2df,p)//B3LYP/6-31+G* level of theory. More than 35 zinc complexes have been structurally characterized and the energies of formation from their components calculated for the first time. The binding energy of TMTD as a bidendate ligand increases in the order ZnMe(2)oxide used as an activator in rubber vulcanization by sulfur. The further uptake of sulfur atoms by the various complexes from S(8) or TMTD with formation of species derived from the radical Me(2)NCS(3)(*) or the trithiocarbamate anion Me(2)NCS(3)(-) is endothermic for mono- and dinuclear zinc dithiocarbamate (dtc) complexes such as [Zn(dtc)(2)] and [Zn(2)(dtc)(4)], but exothermic in the case of polynuclear zinc oxide species containing bridging ligands as in [Zn(4)O(4)(mu-S(2)CNMe(2))] and [Zn(4)O(4)(mu-dtc)]. Therefore, zinc oxide as a polynuclear species is predicted to promote the formation of trisulfido complexes, which are generally assumed to serve as catalysts for the transfer of

  1. A Combination of Mitochondrial Oxidative Stress and Excess Fat/Calorie Intake Accelerates Steatohepatitis by Enhancing Hepatic CC Chemokine Production in Mice.

    PubMed

    Moro, Tadashi; Nakao, Sachie; Sumiyoshi, Hideaki; Ishii, Takamasa; Miyazawa, Masaki; Ishii, Naoaki; Sato, Tadayuki; Iida, Yumi; Okada, Yoshinori; Tanaka, Masayuki; Hayashi, Hideki; Ueha, Satoshi; Matsushima, Kouji; Inagaki, Yutaka

    2016-01-01

    Mitochondrial oxidative stress is considered as a key accelerator of fibrosis in various organs including the liver. However, the production of oxidative stress and progression of liver fibrosis may merely represent the independent consequences of hepatocellular injury caused by the primary disease. Because of a lack of appropriate experimental models to evaluate the sole effects of oxidative stress, it is virtually unknown whether this stress is causatively linked to the progression of liver fibrosis. Here, we examined the direct effects of mitochondrial reactive oxygen species (ROS) on the progression of high fat/calorie diet-induced steatohepatitis using Tet-mev-1 mice, in which a mutated succinate dehydrogenase transgene impairs the mitochondrial electron transport and generates an excess amount of ROS in response to doxycycline administration. Wild type and Tet-mev-1 mice that had been continuously given doxycycline-containing water were subsequently fed either normal chow or a cholesterol-free high-fat/high-sucrose diet for 4 months at approximately 1 or 2 years of age. Histopathological examinations indicated that neither the mitochondrial ROS induced in Tet-mev-1 mice nor the feeding of wild type animals with high-fat/high-sucrose diet alone caused significant liver fibrosis. Only when the Tet-mev-1 mice were fed a high-fat/high-sucrose diet, it induced lipid peroxidation in hepatocytes and enhanced hepatic CC chemokine expression. These events were accompanied by increased infiltration of CCR5-positive cells and activation of myofibroblasts, resulting in extensive liver fibrosis. Interestingly, this combinatorial effect of mitochondrial ROS and excess fat/calorie intake on liver fibrosis was observed only in 2-year-old Tet-mev-1 mice, not in the 1-year-old animals. Collectively, these results indicate that mitochondrial ROS in combination with excess fat/calorie intake accelerates liver fibrosis by enhancing CC chemokine production in aged animals. We have

  2. A Combination of Mitochondrial Oxidative Stress and Excess Fat/Calorie Intake Accelerates Steatohepatitis by Enhancing Hepatic CC Chemokine Production in Mice

    PubMed Central

    Moro, Tadashi; Nakao, Sachie; Sumiyoshi, Hideaki; Ishii, Takamasa; Miyazawa, Masaki; Ishii, Naoaki; Sato, Tadayuki; Iida, Yumi; Okada, Yoshinori; Tanaka, Masayuki; Hayashi, Hideki; Ueha, Satoshi; Matsushima, Kouji; Inagaki, Yutaka

    2016-01-01

    Mitochondrial oxidative stress is considered as a key accelerator of fibrosis in various organs including the liver. However, the production of oxidative stress and progression of liver fibrosis may merely represent the independent consequences of hepatocellular injury caused by the primary disease. Because of a lack of appropriate experimental models to evaluate the sole effects of oxidative stress, it is virtually unknown whether this stress is causatively linked to the progression of liver fibrosis. Here, we examined the direct effects of mitochondrial reactive oxygen species (ROS) on the progression of high fat/calorie diet-induced steatohepatitis using Tet-mev-1 mice, in which a mutated succinate dehydrogenase transgene impairs the mitochondrial electron transport and generates an excess amount of ROS in response to doxycycline administration. Wild type and Tet-mev-1 mice that had been continuously given doxycycline-containing water were subsequently fed either normal chow or a cholesterol-free high-fat/high-sucrose diet for 4 months at approximately 1 or 2 years of age. Histopathological examinations indicated that neither the mitochondrial ROS induced in Tet-mev-1 mice nor the feeding of wild type animals with high-fat/high-sucrose diet alone caused significant liver fibrosis. Only when the Tet-mev-1 mice were fed a high-fat/high-sucrose diet, it induced lipid peroxidation in hepatocytes and enhanced hepatic CC chemokine expression. These events were accompanied by increased infiltration of CCR5-positive cells and activation of myofibroblasts, resulting in extensive liver fibrosis. Interestingly, this combinatorial effect of mitochondrial ROS and excess fat/calorie intake on liver fibrosis was observed only in 2-year-old Tet-mev-1 mice, not in the 1-year-old animals. Collectively, these results indicate that mitochondrial ROS in combination with excess fat/calorie intake accelerates liver fibrosis by enhancing CC chemokine production in aged animals. We have

  3. Exploration and local forecast of gold-ore deposits based on typomorphic properties of pyrite

    NASA Astrophysics Data System (ADS)

    Pshenichkin, A. Ya; Ananyev, Yu S.; Bushmano, A. I.; Abramova, R. N.

    2015-11-01

    The article describes the data in exploration and local forecast of gold-ore deposits based on typomorphic pyrite properties. The pyrite properties: crystal shape, impurity-elements and thermal EMF change in relation to the deposit formation conditions are consistent with the mineralogical and geochemical zoning of ore bodies and deposits. In this case, it is possible to evaluate the ore zone erosion, prospectivity and productivity of the ore bodies at depth and flanks. Mineralogical sampling on pyrite and gold should be conducted on the basis of other methods during exploration and mining.

  4. Protein oxidation and aggregation in UVA-irradiated Escherichia coli cells as signs of accelerated cellular senescence.

    PubMed

    Bosshard, Franziska; Riedel, Kathrin; Schneider, Thomas; Geiser, Carina; Bucheli, Margarete; Egli, Thomas

    2010-11-01

    Solar disinfection (SODIS) is a simple drinking water treatment method that improves microbiological water quality where other means are unavailable. It makes use of the deleterious effect of solar irradiation on pathogenic microbes and viruses. A positive impact on health has been documented in several epidemiological studies. However, the molecular mechanisms damaging cells during this simple treatment are not yet fully understood. Here we show that protein damage is crucial in the process of inactivation by sunlight. Protein damages in UVA-irradiated Escherichia coli cells have been evaluated by an immunoblot method for carbonylated proteins and an aggregation assay based on semi-quantitative proteomics. A wide spectrum of structural and enzymatic proteins within the cell is affected by carbonylation and aggregation. Vital cellular functions like the transcription and translation apparatus, transport systems, amino acid synthesis and degradation, respiration, ATP synthesis, glycolysis, the TCA cycle, chaperone functions and catalase are targeted by UVA irradiation. The protein damage pattern caused by SODIS strongly resembles the pattern caused by reactive oxygen stress. Hence, sunlight probably accelerates cellular senescence and leads to the inactivation and finally death of UVA-irradiated cells.

  5. Composition and spectra of copper-carotenoid sediments from a pyrite mine stream in Spain.

    PubMed

    Garcia-Guinea, Javier; Furio, Marta; Sanchez-Moral, Sergio; Jurado, Valme; Correcher, Virgilio; Saiz-Jimenez, Cesareo

    2015-01-25

    Mine drainages of La Poderosa (El Campillo, Huelva, Spain), located in the Rio Tinto Basin (Iberian Pyrite Belt) generate carotenoid complexes mixed with copper sulfates presenting good natural models for the production of carotenoids from microorganisms. The environmental conditions of Rio Tinto Basin include important environmental stresses to force the microorganisms to accumulate carotenoids. Here we show as carotenoid compounds in sediments can be analyzed directly in the solid state by Raman and Luminescence spectroscopy techniques to identify solid carotenoid, avoiding dissolution and pre-concentration treatments, since the hydrous copper-salted paragenesis do not mask the Raman emission of carotenoids. Raman spectra recorded from one of these specimens' exhibit major features at approximately 1006, 1154, and 1520 cm(-1). The bands at 1520 cm(-1) and 1154 cm(-1) can be assigned to in-phase C=C (γ(-1)) and C-C stretching (γ(-2)) vibrations of the polyene chain in carotenoids. The in-plane rocking deformations of CH3 groups linked to this chain coupled with C-C bonds are observed in the 1006 cm(-1) region. X-irradiation pretreatments enhance the cathodoluminescence spectra emission of carotenoids enough to distinguish organic compounds including hydroxyl and carboxyl groups. Carotenoids in copper-sulfates could be used as biomarkers and useful proxies for understanding remote mineral formations as well as for terrestrial environmental investigations related to mine drainage contamination including biological activity and photo-oxidation processes. PMID:25064504

  6. Composition and spectra of copper-carotenoid sediments from a pyrite mine stream in Spain

    NASA Astrophysics Data System (ADS)

    Garcia-Guinea, Javier; Furio, Marta; Sanchez-Moral, Sergio; Jurado, Valme; Correcher, Virgilio; Saiz-Jimenez, Cesareo

    2015-01-01

    Mine drainages of La Poderosa (El Campillo, Huelva, Spain), located in the Rio Tinto Basin (Iberian Pyrite Belt) generate carotenoid complexes mixed with copper sulfates presenting good natural models for the production of carotenoids from microorganisms. The environmental conditions of Rio Tinto Basin include important environmental stresses to force the microorganisms to accumulate carotenoids. Here we show as carotenoid compounds in sediments can be analyzed directly in the solid state by Raman and Luminescence spectroscopy techniques to identify solid carotenoid, avoiding dissolution and pre-concentration treatments, since the hydrous copper-salted paragenesis do not mask the Raman emission of carotenoids. Raman spectra recorded from one of these specimens' exhibit major features at approximately 1006, 1154, and 1520 cm-1. The bands at 1520 cm-1 and 1154 cm-1 can be assigned to in-phase Cdbnd C (γ-1) and Csbnd C stretching (γ-2) vibrations of the polyene chain in carotenoids. The in-plane rocking deformations of CH3 groups linked to this chain coupled with Csbnd C bonds are observed in the 1006 cm-1 region. X-irradiation pretreatments enhance the cathodoluminescence spectra emission of carotenoids enough to distinguish organic compounds including hydroxyl and carboxyl groups. Carotenoids in copper-sulfates could be used as biomarkers and useful proxies for understanding remote mineral formations as well as for terrestrial environmental investigations related to mine drainage contamination including biological activity and photo-oxidation processes.

  7. Iron Pyrite/Titanium Dioxide Photoanode for Extended Near Infrared Light Harvesting in a Photoelectrochemical Cell

    PubMed Central

    Wang, Di-Yan; Li, Cheng-Hung; Li, Shao-Sian; Kuo, Tsung-Rong; Tsai, Chin-Ming; Chen, Tin-Reui; Wang, Ying-Chiao; Chen, Chun-Wei; Chen, Chia-Chun

    2016-01-01

    The design of active and stable semiconducting composites with enhanced photoresponse from visible light to near infrared (NIR) is a key to improve solar energy harvesting for photolysis of water in photoelectrochemical cell. In this study, we prepared earth abundant semiconducting composites consisting of iron pyrite and Titanium oxide as a photoanode (FeS2/TiO2 photoanode) for photoelectrochemical applications. The detailed structure and atomic compositions of FeS2/TiO2 photoanode was characterized by high-resolution transmission electron microscopy (HRTEM), energy-dispersive X-ray spectroscopy (EDS), powder X-ray diffraction (XRD), inductively coupled plasma with atomic emission spectroscopy (ICPAES) and Raman spectroscopy. Through the proper sulfurization treatment, the FeS2/TiO2 photoanode exhibited high photoresponse from visible light extended to near infrared range (900 nm) as well as stable durability test for 4 hours. We found that the critical factors to enhance the photoresponse are on the elimination of surface defect of FeS2 and on the enhancement of interface charge transfer between FeS2 and TiO2. Our overall results open a route for the design of sulfur-based binary compounds for photoelectrochemical applications. PMID:26852670

  8. Pyrite formation and trace metal enrichment patterns reflect past environmental conditions on the Peru-Chile continental margin

    NASA Astrophysics Data System (ADS)

    Böning, Philipp; Böttcher, Michael E.; Brumsack, Hans-Jürgen

    2010-05-01

    The stable sulfur isotopes of pyrite and porewater sulfate as well as data on porewater sulfate/H2S and trace metals (e.g. Mn, Co, Mo) were used to deduce information about paleo-depositional conditions and early diagenesis in two long cores (0-5 m) from within and below the oxgen minimum zone off Huacho (Peru) and three long cores from the bay and shelf off Concepcion (Chile). These cores were retrieved on cruises with R/Vs Vidal Gormaz, Kay Kay, and Sonne. The shallow Peruvian core (127 m water depth) and the Chilean cores (24 - 88 m water depth) are fine-grained organic-rich sediments and show almost complete sulfate depletion within the first meter of sediment. The turbiditic deep core off Peru (1278 m depth) comprises coarse phosphorite-rich sediments deposited on an organic-rich section. Only in the latter, net sulfate depletion is significant and Mo is extremely enriched (140 ppm on average). Such high Mo values are only attained within the OMZ, hence, this section must represent a former downslope event. In cores off Peru, the Mn and Co depletion hints to the dissolution of Mn-oxides and to a substantial release of Mn and Co from particles settling through the OMZ before reaching the sediment surface. Sulfate reduction leads to a depletion of 34S in pyrite compared to bottom water sulfate of up to 53 per mil (shallow Peruvian and Chilean cores) and 67 per mil (turbiditic core). Isotopic variation with sediment depth for the shallow Peruvian core is small (-32±2 per mil on average) indicating pyrite formation close to the sediment-water interface and control by sedimentation and corresponding microbial activity during the Holocene. For the phosphorite-rich section of the deep core the extreme isotope discrimination (-45 per mil on average) is due to processes in the oxidative part of the sulfur cycle in addition to sulfate reduction. However, in the deep organic-rich section d34Spyrite of -15 per mil represents a mixture of a pre- and post sedimentation

  9. Accelerated Fatty Acid Oxidation in Muscle Averts Fasting-induced Hepatic Steatosis in SJL/J Mice*

    PubMed Central

    Guan, Hong-Ping; Goldstein, Joseph L.; Brown, Michael S.; Liang, Guosheng

    2009-01-01

    The accumulation of triglycerides (TG) in the liver, designated hepatic steatosis, is characteristically associated with obesity and insulin resistance, but it can also develop after fasting. Here, we show that fasting-induced hepatic steatosis is under genetic control in inbred mice. After a 24-h fast, C57BL/6J mice and SJL/J mice both lost more than 20% of body weight and ∼60% of total body TG. In C57BL/6J mice, TG accumulated in liver, producing frank steatosis. In striking contrast, SJL/J mice failed to accumulate any hepatic TG even though they lost nearly as much adipose tissue mass as the C57BL/6J mice. Mice from five other inbred strains developed fasting-induced steatosis like the C57BL/6J mice. Measurements of the uptake of free fatty acids (FA) in vivo and in vitro demonstrated that SJL/J mice were protected from steatosis because their heart and skeletal muscle took up and oxidized twice as much FA as compared with C57BL/6J mice. As a result of this muscle diversion, serum-free FA and ketone bodies rose much less after fasting in SJL/J mice as compared with C57BL/6J mice. When livers of SJL/J and C57BL/6J mice were perfused with similar concentrations of FA, the livers took up and esterified similar amounts. We conclude that SJL/J mice express one or more variant genes that lead to enhanced FA uptake and oxidation in muscle, thereby sparing the liver from FA overload in the fasting state. PMID:19581301

  10. Aerobic and Anaerobic Thiosulfate Oxidation by a Cold-Adapted, Subglacial Chemoautotroph

    PubMed Central

    Harrold, Zoë R.; Skidmore, Mark L.; Hamilton, Trinity L.; Desch, Libby; Amada, Kirina; van Gelder, Will; Glover, Kevin; Roden, Eric E.

    2015-01-01

    Geochemical data indicate that protons released during pyrite (FeS2) oxidation are important drivers of mineral weathering in oxic and anoxic zones of many aquatic environments, including those beneath glaciers. Oxidation of FeS2 under oxic, circumneutral conditions proceeds through the metastable intermediate thiosulfate (S2O32−), which represents an electron donor capable of supporting microbial metabolism. Subglacial meltwaters sampled from Robertson Glacier (RG), Canada, over a seasonal melt cycle revealed concentrations of S2O32− that were typically below the limit of detection, despite the presence of available pyrite and concentrations of the FeS2 oxidation product sulfate (SO42−) several orders of magnitude higher than those of S2O32−. Here we report on the physiological and genomic characterization of the chemolithoautotrophic facultative anaerobe Thiobacillus sp. strain RG5 isolated from the subglacial environment at RG. The RG5 genome encodes genes involved with pathways for the complete oxidation of S2O32−, CO2 fixation, and aerobic and anaerobic respiration with nitrite or nitrate. Growth experiments indicated that the energy required to synthesize a cell under oxygen- or nitrate-reducing conditions with S2O32− as the electron donor was lower at 5.1°C than 14.4°C, indicating that this organism is cold adapted. RG sediment-associated transcripts of soxB, which encodes a component of the S2O32−-oxidizing complex, were closely affiliated with soxB from RG5. Collectively, these results suggest an active sulfur cycle in the subglacial environment at RG mediated in part by populations closely affiliated with RG5. The consumption of S2O32− by RG5-like populations may accelerate abiotic FeS2 oxidation, thereby enhancing mineral weathering in the subglacial environment. PMID:26712544

  11. Aerobic and Anaerobic Thiosulfate Oxidation by a Cold-Adapted, Subglacial Chemoautotroph.

    PubMed

    Harrold, Zoë R; Skidmore, Mark L; Hamilton, Trinity L; Desch, Libby; Amada, Kirina; van Gelder, Will; Glover, Kevin; Roden, Eric E; Boyd, Eric S

    2016-03-01

    Geochemical data indicate that protons released during pyrite (FeS2) oxidation are important drivers of mineral weathering in oxic and anoxic zones of many aquatic environments, including those beneath glaciers. Oxidation of FeS2 under oxic, circumneutral conditions proceeds through the metastable intermediate thiosulfate (S2O3 (2-)), which represents an electron donor capable of supporting microbial metabolism. Subglacial meltwaters sampled from Robertson Glacier (RG), Canada, over a seasonal melt cycle revealed concentrations of S2O3 (2-) that were typically below the limit of detection, despite the presence of available pyrite and concentrations of the FeS2 oxidation product sulfate (SO4 (2-)) several orders of magnitude higher than those of S2O3 (2-). Here we report on the physiological and genomic characterization of the chemolithoautotrophic facultative anaerobe Thiobacillus sp. strain RG5 isolated from the subglacial environment at RG. The RG5 genome encodes genes involved with pathways for the complete oxidation of S2O3 (2-), CO2 fixation, and aerobic and anaerobic respiration with nitrite or nitrate. Growth experiments indicated that the energy required to synthesize a cell under oxygen- or nitrate-reducing conditions with S2O3 (2-) as the electron donor was lower at 5.1°C than 14.4°C, indicating that this organism is cold adapted. RG sediment-associated transcripts of soxB, which encodes a component of the S2O3 (2-)-oxidizing complex, were closely affiliated with soxB from RG5. Collectively, these results suggest an active sulfur cycle in the subglacial environment at RG mediated in part by populations closely affiliated with RG5. The consumption of S2O3 (2-) by RG5-like populations may accelerate abiotic FeS2 oxidation, thereby enhancing mineral weathering in the subglacial environment. PMID:26712544

  12. Aerobic and Anaerobic Thiosulfate Oxidation by a Cold-Adapted, Subglacial Chemoautotroph.

    PubMed

    Harrold, Zoë R; Skidmore, Mark L; Hamilton, Trinity L; Desch, Libby; Amada, Kirina; van Gelder, Will; Glover, Kevin; Roden, Eric E; Boyd, Eric S

    2015-12-28

    Geochemical data indicate that protons released during pyrite (FeS2) oxidation are important drivers of mineral weathering in oxic and anoxic zones of many aquatic environments, including those beneath glaciers. Oxidation of FeS2 under oxic, circumneutral conditions proceeds through the metastable intermediate thiosulfate (S2O3 (2-)), which represents an electron donor capable of supporting microbial metabolism. Subglacial meltwaters sampled from Robertson Glacier (RG), Canada, over a seasonal melt cycle revealed concentrations of S2O3 (2-) that were typically below the limit of detection, despite the presence of available pyrite and concentrations of the FeS2 oxidation product sulfate (SO4 (2-)) several orders of magnitude higher than those of S2O3 (2-). Here we report on the physiological and genomic characterization of the chemolithoautotrophic facultative anaerobe Thiobacillus sp. strain RG5 isolated from the subglacial environment at RG. The RG5 genome encodes genes involved with pathways for the complete oxidation of S2O3 (2-), CO2 fixation, and aerobic and anaerobic respiration with nitrite or nitrate. Growth experiments indicated that the energy required to synthesize a cell under oxygen- or nitrate-reducing conditions with S2O3 (2-) as the electron donor was lower at 5.1°C than 14.4°C, indicating that this organism is cold adapted. RG sediment-associated transcripts of soxB, which encodes a component of the S2O3 (2-)-oxidizing complex, were closely affiliated with soxB from RG5. Collectively, these results suggest an active sulfur cycle in the subglacial environment at RG mediated in part by populations closely affiliated with RG5. The consumption of S2O3 (2-) by RG5-like populations may accelerate abiotic FeS2 oxidation, thereby enhancing mineral weathering in the subglacial environment.

  13. Pulmonary alveolar lipoproteinosis in rats following intratracheal injection of pyrite particles.

    PubMed

    Governa, M; Valentino, M; Tosi, P; Luzi, P; Miracco, C; Sartorelli, E; Loi, F; Franzinelli, A; Gori, R

    1986-01-01

    Wistar rats were injected intratracheally with pyrite particles and after 6 and 12 mo, lungs were evaluated for histological changes. Results were compared with rats that were given particles of galena, lead silicate, travertine, and quartz. Under the light microscope no significant changes were observed in the lungs from animals treated with galena, lead silicate, and travertine. In the lungs from animals that received quartz, a typical nodular fibrosis was observed. Moreover, both pyrite-treated rats and quartz-treated rats developed pulmonary alveolar lipoproteinosis; the lesions were much less prominent and severe in animals injected with pyrite than with quartz. These results indicate that pyrite, like only a few other types of dust that are different from quartz, can evoke the development of pulmonary alveolar lipoproteinosis in rats. PMID:3772986

  14. Selective flocculation of pyrite and/or silica in the presence of coal

    SciTech Connect

    Venkatadri, R.; Markuszevski, R.; Wheelock, T.D. ); Walters, A.B. )

    1988-06-01

    Two cationic surfactants, Arquad T-50 and Duomac T, were investigated as possible selective flocculants or coagulants for iron pyrite or silica particles in the presence of particles of eastern bituminous coal. Although these surfactants were adsorbed by all three materials, they were found to promote the flocculation of pyrite and silica much more than the flocculation of coal when the solid materials were flocculated separately. In subsequent selective flocculation tests involving binary mixtures of the solid components, a good separation of coal and silica was achieved with Duomac T by agitating the flocculating suspension for a prolonged time. However, the separation of coal and pyrite proved more elusive. While some separation was achieved with Arquad T-50 because pyrite was flocculated more extensively than coal, the separation was marginal at best.

  15. The 57Fe Mössbauer parameters of pyrite and marcasite with different provenances

    USGS Publications Warehouse

    Evans, B.J.; Johnson, R.G.; Senftle, F.E.; Cecil, C.B.; Dulong, F.

    1982-01-01

    The Mössbauer parameters of pyrite and marcasite exhibit appreciable variations, which bear no simple relationship to the geological environment in which they occur but appear to be selectively influenced by impurities, especially arsenic, in the pyrite lattice. Quantitative and qualitative determinations of pyrite/marcasite mechanical mixtures are straightforward at 298 K and 77 K but do require least-squares computer fittings and are limited to accuracies ranging from ±5 to ±15 per cent by uncertainties in the parameter values of the pure phases. The methodology and results of this investigation are directly applicable to coals for which the presence and relative amounts of pyrite and marcasite could be of considerable genetic significance.

  16. Chalcophile Siderophile Trace Element Systematics of Hydrothermal Pyrite from Martian Regolith Breccia NWA 7533

    NASA Astrophysics Data System (ADS)

    Lorand, J.-P.; Hewins, R. H.; Humayun, M.; Remusat, L.; Zanda, B.; La, C.; Pont, S.

    2016-08-01

    Martian impact breccia NWA 7533 contains hydrothermal pyrite. Laser ablation ICPMS analyses show that its chalcophile siderophile element content was inherited from both early meteorite bombardment and later hydrothermal inputs from H2S fluids.

  17. A method for generating uniform size-segregated pyrite particle fractions

    PubMed Central

    Wolfe, Amy L; Liu, Ran; Stewart, Brian W; Capo, Rosemary C; Dzombak, David A

    2007-01-01

    Background Standardized sample preparation techniques allow comparison of pyrite dissolution experiments under diverse conditions. Our objective was to assess dry and wet sieving preparation methodologies, and to develop a reproducible technique that yields uniformly size-distributed material within a limited size range of interest. Results Here, we describe a wet sieving preparation method that successfully concentrates pyrite particles within a 44–75 μm diameter range. In addition, this technique does not require a post-processing cleanup step to remove adhering particles, as those particles are removed during the procedure. We show that sample preparation methods not only affect the pyrite size distribution, but also apparent dissolution rates. Conclusion The presented methodology is non-destructive to the sample, uses readily available chemical equipment within the laboratory, and could be applied to minerals other than pyrite. PMID:17927834

  18. Phase-pure iron pyrite nanocrystals for low-cost photodetectors

    PubMed Central

    2014-01-01

    Earth-abundant iron pyrite (FeS2) shows great potential as a light absorber for solar cells and photodetectors due to their high absorption coefficient (>105 cm-1). In this paper, high-quality phase-pure and single crystalline pyrite nanocrystals were synthesized via facile, low-cost, and environment friendly hydrothermal method. The molar ratio of sulphur to iron and the reaction time play a crucial role in determining the quality and morphology of FeS2 nanocrystals. X-ray diffraction and high-resolution transmission electron microscopy confirm that phase-pure and single crystalline pyrite nanocrystals can be synthesized with high sulphur to iron molar ratio and sufficient reaction time. For the first time, a crystalline nanogap pyrite photodetector with promising photocurrent and UV-visible photoresponse has been fabricated. This work further demonstrates a facile route to synthesize high-quality FeS2 nanomaterials and their potential in optoelectronic applications. PMID:25317102

  19. Do sulfur isotope compositions of sulfate minerals and occurrence of framboidal pyrite indicate the subvent biosphere at the Suiyo Seamount in Japan?

    NASA Astrophysics Data System (ADS)

    Kakegawa, T.

    2002-12-01

    Detailed morphological studies and sulfur isotope analyses were performed on sulfides and sulfates in the drilled core samples from the Suiyo Seamount in Japan. Petrographic studies indicate that drilled samples were extremely altered by the submarine hydrothermal process. Notable feature of the examined samples is the high abundance of sulfide (e.g., FeS2, CuFeS2, ZnS and PbS) and sulfate minerals (e.g., CaSO4, BaSO4). The euhedral shape of sulfides is most common morphology in the examined samples. Sulfur isotope compositions of these sulfides are ranging from +1 to +6 per mil, suggesting that sulfides were directly precipitated from isotopically homogeneous H2S in hydrothermal fluids. On the contrary, framboidal form of pyrite was found in subsurface samples (2 m depth) of APSK 03 site (drilled site near eastern edge of caldera wall). Detailed SEM observation indicates that the framboidal pyrite is aggregate (ca. 100 micro-meter in diameter) of small grain of pyrite crystals (5 micro-meter in diameter). Such morphological nature is quite similar to these found in the modern marine sediments. Sulfur isotope compositions of individual framboids were determined using the Nd-YAG laser microprobe system at Tohoku University. Their isotopic compositions are ranging from 1 per mil to +2 per mil and slightly lighter than these of the contemporary hydrothermal sulfides. Two possibilities are considerable for the origin of framboids: (1) biogenic origin or (2) abiogenic origin. If (1) is the case, sulfate-reducing bacteria in subvent region was responsible for the formation of framboidal pyrite. Average sulfur isotope compositions of sulfate minerals are closed to +20 per mil in entire region. This suggest that the progressive introduction of sea water sulfate into the shallow hydrothermal system. Some sulfate minerals have lighter isotopic compositions (+17 to +19 per mil) than the sea water sulfate value. These lighter values indicate the mixing process between sea

  20. Liposomal Doxorubicin Increases Radiofrequency Ablation–induced Tumor Destruction by Increasing Cellular Oxidative and Nitrative Stress and Accelerating Apoptotic Pathways1

    PubMed Central

    Solazzo, Stephanie A.; Ahmed, Muneeb; Schor-Bardach, Rachel; Yang, Wei; Girnun, Geoffrey D.; Rahmanuddin, Syed; Levchenko, Tatyana; Signoretti, Sabina; Spitz, Douglas R.; Torchilin, Vladimir

    2010-01-01

    comparisons). Conclusion: Combining RF ablation with liposomal doxorubicin increases cell injury and apoptosis in the zone of increased coagulation by using a mechanism that involves oxidative and nitrative stress that leads to accelerated apoptosis. © RSNA, 2010 PMID:20160000

  1. The mechanism of bacterial action in the leaching of pyrite by Thiobacillus ferrooxidans. An electrochemical study

    SciTech Connect

    Holmes, P.R.; Fowler, T.A.; Crundwell, F.K.

    1999-08-01

    In many of the experiments reported in the literature on the leaching of pyrite by Thiobacillus ferrooxidans, the concentrations of ferric and ferrous ions in the presence of bacteria differ significantly from experiments conducted in their absence. In addition, these concentrations change throughout the course of the experiment. This makes it difficult to determine whether the presence of bacteria increases the rate of leaching above that for chemical leaching at the same solution conditions. The authors have designed an experimental apparatus to overcome this problem. This apparatus controls the redox potential in one compartment of an electrolytic cell by manipulating the current to the cell. In this manner, the concentrations of ferrous and ferric ions are maintained at their initial values for the duration of the experiment. Two types of experiments are reported in this paper. In the first, pyrite electrodes were exposed to solutions of the same bulk conditions in the presence and absence of bacteria, and their mixed potentials were determined. In the second, particulate pyrite was leached with and without bacteria to determine the effect that bacteria have on the rate of leaching. The mixed potential of bacterially dissolved pyrite decreases as microcolonies and biofilms form on the surface of pyrite electrode over a 14 day period. On the other hand, the mixed potential of chemically dissolved pyrite is constant over the same period. The results of the leaching experiments show that Thiobacillus ferrooxidans enhances the rate of leaching above that found in the absence of bacteria at the same conditions in solution. An electrochemical model of pyrite dissolution is derived that describes the mixed potential and the kinetics of pyrite leaching. This analysis indicates that the decrease in mixed potential and the increase in the leaching rate in the presence of bacteria are due to an increase in the pH at the surface.

  2. Structure of selenium incorporated in pyrite and mackinawite as determined by XAFS analyses

    NASA Astrophysics Data System (ADS)

    Diener, A.; Neumann, T.; Kramar, U.; Schild, D.

    2012-05-01

    Selenium has a toxic potential leading to diseases by ingestion and a radiotoxic potential as 79Se radionuclide if discharged from a high-level nuclear waste repository in deep geological formations into the biosphere. Selenium is often associated with sulfides, such as pyrite, the most important near-surface iron sulfide and constituent of host rocks and bentonite backfills considered for radioactive waste disposal. This study was aimed at investigating the incorporation of Se2- and Se4+ into pyrite and mackinawite to determine the relevance of iron sulfides to Se retention and the type of structural bonding. The syntheses of pyrite and mackinawite occurred via direct precipitation in batches and also produced coatings on natural pyrite in mixed-flow reactor experiments (MFR) under anoxic conditions at Se concentrations in the solutions of up to 10- 3 mol/L. Mineralogical analyses by SEM and XRD reveal the formation of pyrite and mackinawite phases. The average Se2- uptake in pyrite in batch experiments amounts to 98.6%. In MFR syntheses, it reaches 99.5%, both suggesting a high potential for retention. XAFS results indicate a substitution of sulfur by selenide during instantaneous precipitation in highly supersaturated solutions only. In selenide-doted mackinawite S2- was substituted by Se2-, resulting in a mackinawite-type compound. S- is substituted by Se- in selenide-doted pyrite, yielding a FeSSe compound as a slightly distorted pyrite structure. Under slighter supersaturated conditions, XAFS results indicate an incorporation of Se2- and Se4+ predominantly as Se0. This study shows that a substitution of S by Se in iron sulfides is probable only for highly supersaturated solutions under acidic and anoxic conditions. Under closer equilibrium conditions, Se0 is expected to be the most stable species.

  3. Sulfur diagenesis in everglades peat and origin of pyrite in coal

    USGS Publications Warehouse

    Altschuler, Z.S.; Schnepfe, M.M.; Silber, C.C.; Simon, F.O.

    1983-01-01

    The pattern of sulfur transformation in peat across the Everglades basin indicates that pyrite formation in organic-rich swamps depends on the use of organic oxysulfur compounds in dissimilatory respiration by sulfur-reducing bacteria. This paragenesis explains the primary distribution of sulfur compounds in low-sulfur coals and possibly in most coals and many organic-rich soils and sediments. It also accounts for the occurrence of framboidal pyrite bound in fossil tissue in coal and sediments.

  4. Low temperature anaerobic bacterial diagenesis of ferrous monosulfide to pyrite

    NASA Astrophysics Data System (ADS)

    Donald, Ravin; Southam, Gordon

    1999-07-01

    In vitro enrichment cultures of dissimilatory sulfate-reducing bacteria precipitated FeS and catalyzed its transformation into FeS 2 at ambient temperature and pressure under anaerobic conditions. When compared to purely abiotic processes, the bacterially mediated transformation was shown to be more efficient in transforming FeS into FeS 2. This occurred due to the large, reactive surface area available for bacterially catalyzed diagenesis, where the biogenic FeS precursor was immobilized as a thin film (˜25 nm thick) on the μm-scale bacteria. The bacteria also contained the source(s) of sulfur for diagenesis to occur. Using a radiolabeled organic-sulfur tracer study, sulfur was released during cell autolysis and was immobilized at the bacterial cell surface forming FeS 2. The formation of FeS 2 occurred on both the inner and outer surfaces of the cell envelope and represented the first step of bacterial mineral diagenesis. Pyrite crystals, having linear dimensions of ˜1 μm, grew outward from the bacterial cell surfaces. These minerals were several orders of magnitude larger in volume than those originating abiotically.

  5. Preliminary Analysis of Pyrite Reactivity Under Venusian Temperature and Atmosphere

    NASA Technical Reports Server (NTRS)

    Radoman-Shaw, B. G.; Harvey, R. P.; Jacobson, N. S.; Costa, G. C. C.

    2015-01-01

    Measurements of Venus surface chemistry suggest a basaltic composition with a predominantly CO2 atmosphere. In order to understand the reactivity of certain possible mineral species on the surface, previous simulation chambers conduct experiments at 1 atmosphere with a simplified CO2 atmosphere. Following this procedure, pyrite (FeS2) samples are used to estimate the reactivity of sulfide minerals under a Venusian atmosphere and climate. Sulfurous gas species have been identified and quantified in the Venusian atmosphere, and sulfurous gas and mineral species are known to be created through volcanism, which is suggested to still occur on the surface of Venus. This experimentation is necessary to constrain reactions that could occur between the surface and atmosphere of Venus to understand terrestrial geology in a thick and hot greenhouse atmosphere. Quantifying this reaction can lead to approximations necessary for further experimentation in more complex environments such as those in the GEER chamber at Glenn Research Center that can simulate pressure along with temperature and a more inclusive and representative Venusian atmosphere.

  6. Pyritic shale integration into waste rock management, Mt. Whaleback

    SciTech Connect

    O'Kane, M.; Porterfield, D.; Weir, A.

    1999-07-01

    BHP Iron Ore operates the Mt. Whaleback mine in a semi-arid climate adjacent to Newman, Western Australia, approximately 1,200 km north-northeast of Perth, Western Australia. More than 2 billion tones of waste rock were excavated and deposited on the surface during the past 30 years. Ultimately, approximately 4 billion tonnes will be deposited in waste rock dumps constructed near the open pit. Management of the potentially acid forming pyritic shale is based on the application of state-of-the-art conceptual and numerically modeling tools, and operational considerations. The potentially acid forming material is encapsulated within barren run-of-mine material. A moisture storage and release cover system is employed to control water infiltration on the sloping and horizontal waste rock surfaces. This paper will first summarize the overall environmental management plan at Mt. Whaleback. The rationale for differentiating waste rock types is presented. A summary of the design of the moisture storage and release cover system is offered. Finally, performance of field trials are summarized.

  7. Effects of Particle Filters and Accelerated Engine Replacement on Heavy-Duty Diesel Vehicle Emissions of Black Carbon, Nitrogen Oxides, and Ultrafine Particles

    NASA Astrophysics Data System (ADS)

    Kirchstetter, T.; Preble, C.; Dallmann, T. R.; DeMartini, S. J.; Tang, N. W.; Kreisberg, N. M.; Hering, S. V.; Harley, R. A.

    2013-12-01

    Diesel particle filters have become widely used in the United States since the introduction in 2007 of a more stringent exhaust particulate matter emission standard for new heavy-duty diesel vehicle engines. California has instituted additional regulations requiring retrofit or replacement of older in-use engines to accelerate emission reductions and air quality improvements. This presentation summarizes pollutant emission changes measured over several field campaigns at the Port of Oakland in the San Francisco Bay Area associated with diesel particulate filter use and accelerated modernization of the heavy-duty truck fleet. Pollutants in the exhaust plumes of hundreds of heavy-duty trucks en route to the Port were measured in 2009, 2010, 2011, and 2013. Ultrafine particle number, black carbon (BC), nitrogen oxides (NOx), and nitrogen dioxide (NO2) concentrations were measured at a frequency ≤ 1 Hz and normalized to measured carbon dioxide concentrations to quantify fuel-based emission factors (grams of pollutant emitted per kilogram of diesel consumed). The size distribution of particles in truck exhaust plumes was also measured at 1 Hz. In the two most recent campaigns, emissions were linked on a truck-by-truck basis to installed emission control equipment via the matching of transcribed license plates to a Port truck database. Accelerated replacement of older engines with newer engines and retrofit of trucks with diesel particle filters reduced fleet-average emissions of BC and NOx. Preliminary results from the two most recent field campaigns indicate that trucks without diesel particle filters emit 4 times more BC than filter-equipped trucks. Diesel particle filters increase emissions of NO2, however, and filter-equipped trucks have NO2/NOx ratios that are 4 to 7 times greater than trucks without filters. Preliminary findings related to particle size distribution indicate that (a) most trucks emitted particles characterized by a single mode of approximately

  8. Geomicrobiology of La Zarza-Perrunal Acid Mine Effluent (Iberian Pyritic Belt, Spain) ▿ †

    PubMed Central

    González-Toril, Elena; Aguilera, Ángeles; Souza-Egipsy, Virginia; López Pamo, Enrique; Sánchez España, Javier; Amils, Ricardo

    2011-01-01

    Effluent from La Zarza-Perrunal, a mine on the Iberian Pyrite Belt, was chosen to be geomicrobiologically characterized along a 1,200-m stream length. The pH at the origin was 3.1, which decreased to 1.9 at the final downstream sampling site. The total iron concentration showed variations along the effluent, resulting from (i) significant hydrolysis and precipitation of Fe(III) (especially along the first reach of the stream) and (ii) concentration induced by evaporation (mostly in the last reach). A dramatic increase in iron oxidation was observed along the course of the effluent [from Fe(III)/Fetotal = 0.11 in the origin to Fe(III)/Fetotal = 0.99 at the last sampling station]. A change in the O2 content along the effluent, from nearly anoxic at the origin to saturation with oxygen at the last sampling site, was also observed. Prokaryotic and eukaryotic diversity throughout the effluent was determined by microscopy and 16S rRNA gene cloning and sequencing. Sulfate-reducing bacteria (Desulfosporosinus and Syntrophobacter) were detected only near the origin. Some iron-reducing bacteria (Acidiphilium, Acidobacterium, and Acidosphaera) were found throughout the river. Iron-oxidizing microorganisms (Leptospirillum spp., Acidithiobacillus ferrooxidans, and Thermoplasmata) were increasingly detected downstream. Changes in eukaryotic diversity were also remarkable. Algae, especially Chlorella, were present at the origin, forming continuous, green, macroscopic biofilms, subsequently replaced further downstream by sporadic Zygnematales filaments. Taking into consideration the characteristics of this acidic extreme environment and the physiological properties and spatial distribution of the identified microorganisms, a geomicrobiological model of this ecosystem is advanced. PMID:21357431

  9. Nitric Oxide Deficiency Accelerates Chlorophyll Breakdown and Stability Loss of Thylakoid Membranes during Dark-Induced Leaf Senescence in Arabidopsis

    PubMed Central

    Liu, Fang; Guo, Fang-Qing

    2013-01-01

    Nitric oxide (NO) has been known to preserve the level of chlorophyll (Chl) during leaf senescence. However, the mechanism by which NO regulates Chl breakdown remains unknown. Here we report that NO negatively regulates the activities of Chl catabolic enzymes during dark-induced leaf senescence. The transcriptional levels of the major enzyme genes involving Chl breakdown pathway except for RED CHL CATABOLITE REDUCTASE (RCCR) were dramatically up-regulated during dark-induced Chl degradation in the leaves of Arabidopsis NO-deficient mutant nos1/noa1 that exhibited an early-senescence phenotype. The activity of pheide a oxygenase (PAO) was higher in the dark-induced senescent leaves of nos1/noa1 compared with wild type. Furthermore, the knockout of PAO in nos1/noa1 background led to pheide a accumulation in the double mutant pao1 nos1/noa1, which retained the level of Chl during dark-induced leaf senescence. The accumulated pheide a in darkened leaves of pao1 nos1/noa1 was likely to inhibit the senescence-activated transcriptional levels of Chl catabolic genes as a feed-back inhibitory effect. We also found that NO deficiency led to decrease in the stability of photosynthetic complexes in thylakoid membranes. Importantly, the accumulation of pheide a caused by PAO mutations in combination with NO deficiency had a synergistic effect on the stability loss of thylakoid membrane complexes in the double mutant pao1 nos1/noa1 during dark-induced leaf senescence. Taken together, our findings have demonstrated that NO is a novel negative regulator of Chl catabolic pathway and positively functions in maintaining the stability of thylakoid membranes during leaf senescence. PMID:23418559

  10. Nitric oxide deficiency accelerates chlorophyll breakdown and stability loss of thylakoid membranes during dark-induced leaf senescence in Arabidopsis.

    PubMed

    Liu, Fang; Guo, Fang-Qing

    2013-01-01

    Nitric oxide (NO) has been known to preserve the level of chlorophyll (Chl) during leaf senescence. However, the mechanism by which NO regulates Chl breakdown remains unknown. Here we report that NO negatively regulates the activities of Chl catabolic enzymes during dark-induced leaf senescence. The transcriptional levels of the major enzyme genes involving Chl breakdown pathway except for RED CHL CATABOLITE REDUCTASE (RCCR) were dramatically up-regulated during dark-induced Chl degradation in the leaves of Arabidopsis NO-deficient mutant nos1/noa1 that exhibited an early-senescence phenotype. The activity of pheide a oxygenase (PAO) was higher in the dark-induced senescent leaves of nos1/noa1 compared with wild type. Furthermore, the knockout of PAO in nos1/noa1 background led to pheide a accumulation in the double mutant pao1 nos1/noa1, which retained the level of Chl during dark-induced leaf senescence. The accumulated pheide a in darkened leaves of pao1 nos1/noa1 was likely to inhibit the senescence-activated transcriptional levels of Chl catabolic genes as a feed-back inhibitory effect. We also found that NO deficiency led to decrease in the stability of photosynthetic complexes in thylakoid membranes. Importantly, the accumulation of pheide a caused by PAO mutations in combination with NO deficiency had a synergistic effect on the stability loss of thylakoid membrane complexes in the double mutant pao1 nos1/noa1 during dark-induced leaf senescence. Taken together, our findings have demonstrated that NO is a novel negative regulator of Chl catabolic pathway and positively functions in maintaining the stability of thylakoid membranes during leaf senescence.

  11. Semiconductor electrochemistry of coal pyrite. Technical progress report, July--September 1993

    SciTech Connect

    Osseo-Asare, K.; Wei, D.

    1993-11-01

    Pyrite (FeS{sub 2}) synthesis was studied in aqueous solution at room temperature and atmospheric pressure using ferric chloride (FeCl{sub 3}) and sodium hydrosulfide (NaHS) as reactants, and sodium hexametaphosphate ((NaPO{sub 3}){sub 6}) as dispersant and crystal growth modifier (to control the particle size of pyrite). The effects of the reaction pH and the concentrations of the reactants and the dispersant on the product characteristics were studied. The pH of the reaction system determines the chemical constitution of the products. Elemental sulfur is produced at pH 2.4. As pH increases, the reaction product becomes a mixture of elemental sulfur plus pyrite at pH 2.9. In the pH range of 3.6 to 5.7, pyrite is formed with a pseudospherical shape and a size of 2 {mu}m. With further increase in pH, amorphous iron sulfides are obtained. Lowering the concentrations of the reactants decreases the particle size of pyrite in the earlier stages of the reaction. However the final particles have the same size irrespective of the initial concentrations of the reactants used in the study. Addition of the dispersant can change the properties of the products. The mechanism of the dispersant action is currently under investigation, in an effort to minimize particle aggregation and produce discrete nanosize pyrite particles.

  12. Semiconductor electrochemistry of coal pyrite. Quarterly technical progress report, July--September 1993

    SciTech Connect

    Osseo-Asare, K.; Wei, D.

    1993-12-31

    Pyrite (FeS{sub 2}) synthesis was studied in aqueous solution at room temperature and pressure using ferric chloride (FeCl{sub 3}) and sodium hydrosulfide (NaHS) as reactants, and sodium hexametaphosphate ((NaPO{sub 3}){sub 6}) as dispersant, which was added in the system to control the particle size of pyrite. The effects of the reaction pH and the concentrations of the reactants and the dispersant on the characterization of pyrite were studied. The pH of the reaction determines the products of the reaction. Elemental sulfur is produced at pH 2.4. As pH increases, the reaction product becomes a mixture of elemental sulfur plus pyrite at pH 2.9. In the pH range of 3.6 to 5.7, pyrite is formed with a spherical shape and a size of 2 {mu}m. Further increasing pH, the amorphous iron sulfides are obtained. lowering of the concentration of the reactant can decrease the particle size of pyrite only in the earlier stage of the reaction. The final particles have the same size for any initial concentration of the reactants used in the study. Addition of dispersant can change the properties of the products. The mechanism of the dispersant reaction is carrying out currently in this laboratory.

  13. Effect of thiamine hydrochloride on the redox reactions of iron at pyrite surface

    SciTech Connect

    Pesic, B.; Oliver, D.J.

    1990-01-01

    The present investigation is a part of our studies on the electro chemical aspects of pyrite bioleaching involving Thiobacillus ferrooxidans. Previously (1,2) we have examined the effect of T. ferrooxidans and their metabolic products on the redox reactions of Fe[sup 2+]/Fe[sup 3+] couple at the pyrite surface. Results obtained suggest that beyond 1. 5 days during their growth in a batch fermenter, the bacteria and their metabolic products completely cover the pyrite surface and shut down all electron transfer across the electrode-solution interface. In addition, it has been observed that the bacteria serve as the nucleation site for jarosite formation, which is found detrimental to bioleaching. In the present work we have focussed on the effect of the presence of vitamins on the redox chemistry of iron. Our examination of the effect of the presence of thiamine hydrochloride in the redox behavior of Fe[sup 2+]/Fe[sup 3+] at the pyrite surface has revealed that thiamine hydrochloride does not undergo chemical interaction with ferrous or ferric iron. However, it may adsorb onto the pyrite surface causing polarization of the pyrite electrode.

  14. Research on genesis of pyrite near the Permian-Triassic boundary in meishan, Zhejiang, China

    USGS Publications Warehouse

    Jiang, Y.-F.; Tang, Y.-G.; Chou, C.-L.

    2006-01-01

    The content and crystal forms of pyrite and sulfur isotope composition of pyrite sulfur as well as its vertical distribution near the Permian-Triassic (P/T) boundary in the Meishan section, Changxing county, Zhejiang province, China were studied using geological, petrological, mineralogical and geochemical methods (techniques). The result showed that the genesis of abundant pyrites in bed 24e2 at the uppermost part of the Changxing Formation in the Meishan section may be related to volcanic activity. In bed 24e2 of the Meishan section, pyrite has its highest content of 1.84% and the sulfur isotope composition has the highest ??34S value at + 2.2??? which is very similar to that of the average value of volcanic gas. There are some volcanic products such as ??-quartz, siliceous cylinders and siliceous spherules which coexisted with pyrites in beds 24e2 and 24f. It can be concluded that a large quantity of volcanic ash fell into the South China Sea and was incorporated into marine sediments during the formation of limestone at the uppermost part of the Changxing Formation. The volcanic eruption with massive amounts of H2S and S02 gas at the end of the Permian period resulted in the enrichment of H2S in the South China Sea areas. The reaction of H2S with reactive iron minerals formed the mass of abundant pyrites.

  15. Enargite oxidation: A review

    NASA Astrophysics Data System (ADS)

    Lattanzi, Pierfranco; Da Pelo, Stefania; Musu, Elodia; Atzei, Davide; Elsener, Bernhard; Fantauzzi, Marzia; Rossi, Antonella

    2008-01-01

    Enargite, Cu 3AsS 4, is common in some deposit types, e.g. porphyry systems and high sulphidation epithermal deposits. It is of environmental concern as a potential source of arsenic. In this communication, we review the current knowledge of enargite oxidation, based on the existing literature and our own original data. Explicit descriptions of enargite oxidation in natural environments are scarce. The most common oxidized alteration mineral of enargite is probably scorodite, FeAsO 4.2H 2O, with iron provided most likely by pyrite, a phase almost ubiquitously associated with enargite. Other secondary minerals after enargite include arsenates such as chenevixite, Cu 2Fe 2(AsO 4) 2(OH) 4.H 2O, and ceruleite, Cu 2Al 7(AsO 4) 4.11.5H 2O, and sulphates such as brochantite, Cu 4(SO 4)(OH) 6, and posnjakite, Cu 4(SO 4)(OH) 6·H 2O. Detailed studies of enargite field alteration at Furtei, Sardinia, suggest that most alteration occurs through dissolution, as testified by the appearance of etch pits at the surface of enargite crystals. However, apparent replacement by scorodite and cuprian melanterite was observed. Bulk oxidation of enargite in air is a very slow process. However, X-ray photoelectron spectroscopy (XPS) reveals subtle surface changes. From synchrotron-based XPS it was suggested that surface As atoms react very fast, presumably by forming bonds with oxygen. Conventional XPS shows the formation, on aged samples, of a nanometer-size alteration layer with an appreciably distinct composition with respect to the bulk. Mechanical activation considerably increases enargite reactivity. In laboratory experiments at acidic to neutral pH, enargite oxidation/dissolution is slow, although it is accelerated by the presence of ferric iron and/or bacteria such as Acidithiobacillus ferrooxidans and Sulfolobus BC. In the presence of sulphuric acid and ferric iron, the reaction involves dissolution of Cu and formation of native sulphur, subsequently partly oxidized to sulphate

  16. An unusual occurrence of arsenic-bearing pyrite in the Upper Freeport coal bed, West-Central Pennsylvania

    USGS Publications Warehouse

    Ruppert, L.F.; Minkin, J.A.; McGee, J.J.; Cecil, C.B.

    1992-01-01

    Scanning electron microscopy and electron microprobe analysis were used to identify a rare type of As-bearing pyrite in selected specific gravity separates from the Pennsylvanian age Upper Freeport coal bed, west-central Pennsylvania. Arsenic was detected mainly in cell-wall replacement pyrite where concentrations ranged from nondetectable to 1.9 wt %. Although the majority of arsenic-bearing pyrite in the Upper Freeport coal bed is concentrated in massive and late diagenetic pyrite morphologies, the rarer As-bearing cell-replacement pyrite was observed in both light and heavy gravity separates from the three coal facies examined. Arsenic was occasionally detected in cell-filling replacement pyrite, but this As appears to be an artifact produced by signals from underlying and/or adjacent As-bearing cell-wall replacement pyrite. It is postulated that some plants of the Upper Freeport paleoswamp may have biomethylated As, which later could have been converted to dimethylarsine or other volatile organoarsenic compounds by either biologically or chemically driven processes. Once liberated, the arsenic may have been incorporated into pyrite during pyritization of the cell walls. The As incorporation occurred early, before significant compaction of the peat, because the pyritized cell walls are not compacted.

  17. Pyrite multiple-sulfur isotope evidence for rapid expansion and contraction of the early Paleoproterozoic seawater sulfate reservoir

    NASA Astrophysics Data System (ADS)

    Scott, Clint; Wing, Boswell A.; Bekker, Andrey; Planavsky, Noah J.; Medvedev, Pavel; Bates, Steven M.; Yun, Misuk; Lyons, Timothy W.

    2014-03-01

    Earth's oxygenation is often described in terms of two unidirectional steps at the beginning and end of the Proterozoic Eon, separated by a long-lived intermediate redox state. Recent work defines a more complicated path to oxygenation, exemplified by an apparent drop in oxidation state following the early Paleoproterozoic Lomagundi carbon isotope excursion. The timing of this proposed drop in oxidation state is not well constrained, and it is not clear how it relates to redox conditions during the remainder of the Proterozoic. Here we present a study of pyrite multiple-sulfur isotopes, supported by Fe speciation and organic carbon isotopes, from early Paleoproterozoic black shales. We find evidence for the rapid expansion of the seawater sulfate reservoir during the Great Oxidation Event at ca. 2.3 Ga followed by a subsequent contraction in the size of the seawater sulfate reservoir at ca. 2.05 Ga. This scenario is consistent with the emerging view of a rise and fall in surface oxidation state during the early Paleoproterozoic. Comparison of our new data to other records of the seawater sulfate reservoir suggests that the elevated sulfate concentrations that characterize the early Paleoproterozoic did not return until the late Neoproterozoic.

  18. Modelling the behaviour of oxide fuels containing minor actinides with urania, thoria and zirconia matrices in an accelerator-driven system

    NASA Astrophysics Data System (ADS)

    Sobolev, V.; Lemehov, S.; Messaoudi, N.; Van Uffelen, P.; Aı̈t Abderrahim, H.

    2003-06-01

    The Belgian Nuclear Research Centre, SCK • CEN, is currently working on the pre-design of the multipurpose accelerator-driven system (ADS) MYRRHA. A demonstration of the possibility of transmutation of minor actinides and long-lived fission products with a realistic design of experimental fuel targets and prognosis of their behaviour under typical ADS conditions is an important task in the MYRRHA project. In the present article, the irradiation behaviour of three different oxide fuel mixtures, containing americium and plutonium - (Am,Pu,U)O 2- x with urania matrix, (Am,Pu,Th)O 2- x with thoria matrix and (Am,Y,Pu,Zr)O 2- x with inert zirconia matrix stabilised by yttria - were simulated with the new fuel performance code MACROS, which is under development and testing at the SCK • CEN. All the fuel rods were considered to be of the same design and sizes: annular fuel pellets, helium bounded with the stainless steel cladding, and a large gas plenum. The liquid lead-bismuth eutectic was used as coolant. Typical irradiation conditions of the hottest fuel assembly of the MYRRHA subcritical core were pre-calculated with the MCNPX code and used in the following calculations as the input data. The results of prediction of the thermo-mechanical behaviour of the designed rods with the considered fuels during three irradiation cycles of 90 EFPD are presented and discussed.

  19. Future accelerators (?)

    SciTech Connect

    John Womersley

    2003-08-21

    I describe the future accelerator facilities that are currently foreseen for electroweak scale physics, neutrino physics, and nuclear structure. I will explore the physics justification for these machines, and suggest how the case for future accelerators can be made.

  20. A comparison of iron extraction methods for the determination of degree of pyritisation and the recognition of iron-limited pyrite formation

    NASA Technical Reports Server (NTRS)

    Raiswell, R.; Canfield, D. E.; Berner, R. A.

    1994-01-01

    Measurements of degree of pyritisation require an estimate of sediment iron which is capable of reaction with dissolved sulphide to form pyrite, either directly or indirectly via iron monosulphide precursors. Three dissolution techniques (buffered dithionite, cold 1 M HCl, boiling 12 M HCl) were examined for their capacity to extract iron from a variety of iron minerals, and iron-bearing sediments, as a function of different extraction times and different grain sizes. All the iron oxides studied are quantitatively extracted by dithionite and boiling HCl (but not by cold HCl). Both HCl techniques extract more iron from silicates than does dithionite but probably about the same amounts as are potentially capable of sulphidation. Modern sediment studies indicate that most sedimentary pyrite is formed rapidly from iron oxides, with smaller amounts formed more slowly from iron silicates (if sufficient geologic time is available). It is therefore recommended that the degree of pyritisation be defined with respect to the dithionite-extractable (mainly iron oxide) pool and/or the boiling HCl-extractable pool (which includes some silicate iron) for the recognition of iron-limited pyritisation.

  1. First-principles electronic structure and relative stability of pyrite and marcasite: Implications for photovoltaic performance

    NASA Astrophysics Data System (ADS)

    Sun, Ruoshi; Chan, M. K. Y.; Ceder, G.

    2011-06-01

    Despite the many advantages (e.g., suitable band gap, exceptional optical absorptivity, earth abundance) of pyrite as a photovoltaic material, its low open-circuit voltage (OCV) has remained the biggest challenge preventing its use in practical devices. Two of the most widely accepted reasons for the cause of the low OCV are (i) Fermi level pinning due to intrinsic surface states that appear as gap states, and (ii) the presence of the metastable polymorph, marcasite. In this paper, we investigate these claims, via density-functional theory, by examining the electronic structure, bulk, surface, and interfacial energies of pyrite and marcasite. Regardless of whether the Hubbard U correction is applied, the intrinsic {100} surface states are found to be of dz2 character, as expected from ligand field theory. However, they are not gap states but rather located at the conduction-band edge. Thus, ligand field splitting at the symmetry-broken surface cannot be the sole cause of the low OCV. We also investigate epitaxial growth of marcasite on pyrite. Based on the surface, interfacial, and strain energies of pyrite and marcasite, we find from our model that only one layer of epitaxial growth of marcasite is thermodynamically favorable. Within all methods used (LDA, GGA-PBE, GGA-PBE+U, GGA-AM05, GGA-AM05+U, HSE06, and Δ-sol), the marcasite band gap is not less than the pyrite band gap, and is even larger than the experimental marcasite gap. Moreover, gap states are not observed at the pyrite-marcasite interface. We conclude that intrinsic surface states or the presence of marcasite are unlikely to undermine the photovoltaic performance of pyrite.

  2. The Gruta de las Maravillas (Aracena, South-West Iberia): Setting and origin of a cave in marbles from dissolution of pyrite

    NASA Astrophysics Data System (ADS)

    Martínez-Moreno, F. J.; Pedrera, A.; Galindo-Zaldívar, J.; López-Chicano, M.; Azor, A.; Martín-Rosales, W.; Ruano, P.; Calaforra, J. M.; Hódar-Pérez, A.

    2016-01-01

    The Gruta de las Maravillas cave is located at the WNW side of the Cerro del Castillo hill in Aracena (Huelva, SW Spain). The cavity is hosted within marbles included in a strip of high-grade metamorphic rocks belonging to the so-called Aracena Massif in the southernmost Ossa-Morena Zone. The hill is made up of granodiorites, marbles, quartzites, and gneisses, with the foliation trending N110°E and dipping roughly 60-80° towards NE. The marbles appear highly deformed in ductile conditions, with isoclinal folds of different sizes, boudins, porphyroblasts with sigmoidal morphology, and left-lateral S-C shear fabrics. Close to the granodiorite contact, the marbles include a thin band of disseminated and massive pyrite, partially transformed to Fe-oxides. Analysis of the brittle deformation and the associated paleostresses indicates a NE-SW oriented maximum compression, probably related to the latest Variscan collisional tectonics (300 Ma; Late Carboniferous). The Gruta de las Maravillas is divided into three main levels (located at ~ 650, ~ 665 and ~ 685 m a.s.l.), the dissolution having progressed from top to bottom in different stages of stability of the water table. The initial dissolution phases were probably favoured by the presence of pyrite in the host rock, which, in turn, would have caused acidification of the circulating water. Favouring this hypothesis, a thin layer of Fe-oxides, locally including gypsum, covers some parts of the cave walls. The morphology and structure of the cavity result from interaction between the general NNE dipping foliation with sub-perpendicular joints, the pyrite-bearing band in the host marbles, and the descending water table.

  3. [Dependence of the genotypic characteristics of Acidithiobacillus ferrooxidans on the physical, chemical, and electrophysical properties of pyrites].

    PubMed

    Tupikina, O V; Kondrat'eva, T F; Karavaĭko, G I

    2005-01-01

    This study focused on the effect of physical, chemical, and electrophysical properties of two pyrites, pyrite 1, which had hole-type (p-type) conductivity, and pyrite 2, with electron-type (n-type) conductivity, on the genotypic characteristics of Acidithiobacillus ferrooxidans strains TFV-1 and TFBk, which were isolated from different substrates. After the adaptation of the strains to the pyrites at a pulp density of 1%, pulsed-field electrophoresis revealed changes in the chromosomal DNA of strain TFV-1 adapted to pyrite 1 and strain TFBk adapted to either of the pyrite types. In pyrite-adapted strain TFBk, the plasmid composition was the same as after growth on a medium containing ferrous iron, whereas, in strain TFV-1, changes in plasmid sizes or both in plasmid sizes and plasmid number occurred. After an increase in the density of the pyrite 2 pulp from 1 to 10%, the plasmid number increased from three to four, and, after an increase in the density of the pyrite 1 pulp from 1 to 7%, the plasmid number increased from two to six. PMID:16315978

  4. [Dependence of the genotypic characteristics of Acidithiobacillus ferrooxidans on the physical, chemical, and electrophysical properties of pyrites].

    PubMed

    Tupikina, O V; Kondrat'eva, T F; Karavaĭko, G I

    2005-01-01

    This study focused on the effect of physical, chemical, and electrophysical properties of two pyrites, pyrite 1, which had hole-type (p-type) conductivity, and pyrite 2, with electron-type (n-type) conductivity, on the genotypic characteristics of Acidithiobacillus ferrooxidans strains TFV-1 and TFBk, which were isolated from different substrates. After the adaptation of the strains to the pyrites at a pulp density of 1%, pulsed-field electrophoresis revealed changes in the chromosomal DNA of strain TFV-1 adapted to pyrite 1 and strain TFBk adapted to either of the pyrite types. In pyrite-adapted strain TFBk, the plasmid composition was the same as after growth on a medium containing ferrous iron, whereas, in strain TFV-1, changes in plasmid sizes or both in plasmid sizes and plasmid number occurred. After an increase in the density of the pyrite 2 pulp from 1 to 10%, the plasmid number increased from three to four, and, after an increase in the density of the pyrite 1 pulp from 1 to 7%, the plasmid number increased from two to six.

  5. Phosphate Sorption and Desorption on Pyrite in Primitive Aqueous Scenarios: Relevance of acidic → Alkaline Transitions

    NASA Astrophysics Data System (ADS)

    de Souza-Barros, Fernando; Braz-Levigard, Raphael; Ching-San, Yonder; Monte, Marisa M. B.; Bonapace, José A. P.; Montezano, Viviane; Vieyra, Adalberto

    2007-02-01

    Phosphate (P i) sorption assays onto pyrite in media simulating primeval aquatic scenarios affected by hydrothermal emissions, reveal that acidic conditions favour P i sorption whereas mild alkaline media as well as those simulating sulfur oxidation to SO2- 4 revert this capture process. Several mechanisms relevant to P i availability in prebiotic eras are implicated in the modulation of these processes. Those favouring sorption are: (a) hydrophobic coating of molecules, such as acetate that could be formed in the vicinity of hydrothermal vents; (b) water and Mg2+ bridging in the interface mineral-aqueous media; (c) surface charge neutralization by monovalent cations (Na+ and K+). The increase of both the medium pH and the SO2- 4 trapping by the mineral interface would provoke the release of sorbed P i due to charge polarization. Moreover it is shown that P i self-modulates its sorption, a mechanism that depends on the abundance of SO2- 4 in the interface. The relevance of the proposed mechanisms of P i capture, release and trapping arises from the need of abundant presence of this molecule for primitive phosphorylations, since similarly to contemporary aqueous media inorganic phosphate concentrations in primitive seas should have been low. It is proposed that the presence of sulphide minerals with high affinity to P i could have trapped this molecule in an efficient manner, allowing its concentration in specific niches. In these niches, the conditions studied in the present work would have been relevant for its availability in soluble form, specially in primitive insulated systems with pH gradients across the wall.

  6. Phosphate sorption and desorption on pyrite in primitive aqueous scenarios: relevance of acidic --> alkaline transitions.

    PubMed

    de Souza-Barros, Fernando; Braz-Levigard, Raphael; Ching-San, Yonder; Monte, Marisa M B; Bonapace, José A P; Montezano, Viviane; Vieyra, Adalberto

    2007-02-01

    Phosphate (P(i)) sorption assays onto pyrite in media simulating primeval aquatic scenarios affected by hydrothermal emissions, reveal that acidic conditions favour P(i) sorption whereas mild alkaline media--as well as those simulating sulfur oxidation to SO(2-) (4)--revert this capture process. Several mechanisms relevant to P(i) availability in prebiotic eras are implicated in the modulation of these processes. Those favouring sorption are: (a) hydrophobic coating of molecules, such as acetate that could be formed in the vicinity of hydrothermal vents; (b) water and Mg(2+) bridging in the interface mineral-aqueous media; (c) surface charge neutralization by monovalent cations (Na+ and K+). The increase of both the medium pH and the SO(2-) (4) trapping by the mineral interface would provoke the release of sorbed P(i) due to charge polarization. Moreover it is shown that P(i) self-modulates its sorption, a mechanism that depends on the abundance of SO(2-) (4) in the interface. The relevance of the proposed mechanisms of P(i) capture, release and trapping arises from the need of abundant presence of this molecule for primitive phosphorylations, since--similarly to contemporary aqueous media--inorganic phosphate concentrations in primitive seas should have been low. It is proposed that the presence of sulphide minerals with high affinity to P(i) could have trapped this molecule in an efficient manner, allowing its concentration in specific niches. In these niches, the conditions studied in the present work would have been relevant for its availability in soluble form, specially in primitive insulated systems with pH gradients across the wall.

  7. Magnetic pyrite cinder as an efficient heterogeneous ozonation catalyst and synergetic effect of deposited Ce.

    PubMed

    Wu, Deli; Liu, Ying; He, Hongping; Zhang, Yalei

    2016-07-01

    Heterogeneous catalytic ozonation was emerged to be a promising alternative in the mineralization of various persistent organic pollutants in recent decades. Magnetic pyrite cinder (PyC), which was employed as the catalyst in our investigation, was further deposited by Ce (Ce-PyC) to enhance its catalytic activity in the degradation of aqueous reactive black 5 (RB5). The results showed that additional 17.39%, 42.12% mineralization efficiency was obtained by O3/PyC, O3/Ce-PyC, respectively, in the degradation of RB5 compared to that of O3 alone under identical experimental condition. The reaction mechanism involved the enhanced mineralization of aqueous RB5 at the catalyst-solution interface via hydroxyl radicals produced by the reaction between O3 and catalyst surface. Besides surface hydroxyl, surface Ce(Ⅲ) was crucial for Ce-PyC in the enhanced generation of hydroxyl radicals. More surprisingly, it was found that both PyC and Ce-PyC could exert quite stable catalytic activity in a wide pH range from 3 to 10, which was supposed to be combined with inherently comprised various metal oxide, such as Fe2O3, Fe3O4, MnO2 and CuO. Ozone utilization evaluation demonstrated that PyC and Ce-PyC facilitated effective ozone decomposition, as ozone utilization efficiency (mgTOC/mgO3) of O3/PyC and O3/Ce-PyC increased 64.0%, 155.0%, respectively, compared to that of O3 alone. This investigation provided an effective alternative in the resource utilization of PyC, which was traditionally characterized as a waste material. PMID:27108370

  8. Magnetic pyrite cinder as an efficient heterogeneous ozonation catalyst and synergetic effect of deposited Ce.

    PubMed

    Wu, Deli; Liu, Ying; He, Hongping; Zhang, Yalei

    2016-07-01

    Heterogeneous catalytic ozonation was emerged to be a promising alternative in the mineralization of various persistent organic pollutants in recent decades. Magnetic pyrite cinder (PyC), which was employed as the catalyst in our investigation, was further deposited by Ce (Ce-PyC) to enhance its catalytic activity in the degradation of aqueous reactive black 5 (RB5). The results showed that additional 17.39%, 42.12% mineralization efficiency was obtained by O3/PyC, O3/Ce-PyC, respectively, in the degradation of RB5 compared to that of O3 alone under identical experimental condition. The reaction mechanism involved the enhanced mineralization of aqueous RB5 at the catalyst-solution interface via hydroxyl radicals produced by the reaction between O3 and catalyst surface. Besides surface hydroxyl, surface Ce(Ⅲ) was crucial for Ce-PyC in the enhanced generation of hydroxyl radicals. More surprisingly, it was found that both PyC and Ce-PyC could exert quite stable catalytic activity in a wide pH range from 3 to 10, which was supposed to be combined with inherently comprised various metal oxide, such as Fe2O3, Fe3O4, MnO2 and CuO. Ozone utilization evaluation demonstrated that PyC and Ce-PyC facilitated effective ozone decomposition, as ozone utilization efficiency (mgTOC/mgO3) of O3/PyC and O3/Ce-PyC increased 64.0%, 155.0%, respectively, compared to that of O3 alone. This investigation provided an effective alternative in the resource utilization of PyC, which was traditionally characterized as a waste material.

  9. A chemical, morphological, and electrochemical (XPS, SEM/EDX, CV, and EIS) analysis of electrochemically modified electrode surfaces of natural chalcopyrite (CuFeS2) and pyrite (FeS2) in alkaline solutions.

    PubMed

    Velásquez, Pablo; Leinen, Dietmar; Pascual, José; Ramos-Barrado, José Ramón; Grez, Paula; Gómez, Humberto; Schrebler, Ricardo; Del Río, Rodrigo; Córdova, Ricardo

    2005-03-24

    Electrodic surfaces of natural chalcopyrite and natural pyrite minerals (El Teniente mine, Chile) have been studied by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy including microanalysis (SEM/EDX). For comparison, fractured and polished mineral surfaces were also studied by XPS. In both electrodes, the formation of Fe(III) species containing oxygen were detected and Cu(II) species containing oxygen were additionally detected for chalcopyrite at advanced oxidation states. The presence of Cu(II) species containing oxygen was not detected by XPS for the initial oxidation states of the chalcopyrite. For pyrite, the present results do not allow confirmation of the presence of polysulfurs such as have been previously proposed. In both minerals, the measurements of SEM and EDX show relevant alterations in the respective surfaces when different potential values were applied. The chalcopyrite surface shows the formation of protrusions with a high concentration of oxygen. The pyrite surface shows a layer of modified material with high oxygen content. The modifications detected by XPS, SEM, and EDX allowed the explanation of the complexity of the equivalent circuit used to simulate the experimental EIS data. At high oxidation states, both minerals showed a pseudoinductive loop in the equivalent circuit, which was due to the active electrodissolution of the minerals which takes place through a surface film previously formed. PMID:16863157

  10. A chemical, morphological, and electrochemical (XPS, SEM/EDX, CV, and EIS) analysis of electrochemically modified electrode surfaces of natural chalcopyrite (CuFeS2) and pyrite (FeS2) in alkaline solutions.

    PubMed

    Velásquez, Pablo; Leinen, Dietmar; Pascual, José; Ramos-Barrado, José Ramón; Grez, Paula; Gómez, Humberto; Schrebler, Ricardo; Del Río, Rodrigo; Córdova, Ricardo

    2005-03-24

    Electrodic surfaces of natural chalcopyrite and natural pyrite minerals (El Teniente mine, Chile) have been studied by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy including microanalysis (SEM/EDX). For comparison, fractured and polished mineral surfaces were also studied by XPS. In both electrodes, the formation of Fe(III) species containing oxygen were detected and Cu(II) species containing oxygen were additionally detected for chalcopyrite at advanced oxidation states. The presence of Cu(II) species containing oxygen was not detected by XPS for the initial oxidation states of the chalcopyrite. For pyrite, the present results do not allow confirmation of the presence of polysulfurs such as have been previously proposed. In both minerals, the measurements of SEM and EDX show relevant alterations in the respective surfaces when different potential values were applied. The chalcopyrite surface shows the formation of protrusions with a high concentration of oxygen. The pyrite surface shows a layer of modified material with high oxygen content. The modifications detected by XPS, SEM, and EDX allowed the explanation of the complexity of the equivalent circuit used to simulate the experimental EIS data. At high oxidation states, both minerals showed a pseudoinductive loop in the equivalent circuit, which was due to the active electrodissolution of the minerals which takes place through a surface film previously formed.

  11. Petrography, geochemistry and geochronology of granite hosted rhyodacites associated with a disseminated pyrite mineralization (Arnolz, Southern Bohemian Massif, Austria)

    NASA Astrophysics Data System (ADS)

    Göd, Richard; Kurzweil, Johannes; Klötzli, Urs

    2016-09-01

    The study focuses on a subvolcanic rhyodacite dyke intruding a fine grained biotite granite and paragneisses of the South Bohemian Massif, part of the Variscan Orogenic Belt in Central Europe. The subvertical dyke strikes NNE, displays a thickness of about 30 m and has been traced by boulder mapping for approximately 7 km. The rhyodacites have been affected by two hydrothermal fluids. An older one of oxidizing condition giving rise to a reddish to brownish type of rock (Type I) and a younger fluid of reducing condition causing a greenish variety (Type II). The hydrothermal alteration is associated with the formation of the clay minerals chlorite, sericite, kaolinite and smectite and a disseminated pyrite mineralization. Bulk chemistries of the rhyodacites emphasize the hydrothermal alterations to be isochemical with the exception of sulphur enriched up to a maximum of 0.6 wt%. Trace element composition of the rhyodacites points to a barren geochemical environment in terms of base and precious elements. Sulphur isotope investigations of pyrites from the rhyodacites and the hosting granites respectively yield d34S data ranging from +0.07 to -2.22 ‰, emphasizing a magmatic origin of the sulphur. Geochronological investigations yield in situ U/Pb zircon ages of 312 ± 4 Ma for the biotite granite and of 292 ± 4 Ma for the rhyodacitic dykes indicating a time gap of ≈ 20 Ma between these two intrusive events. A contemporaneous but geochemically specialized granitic intrusion associated with NW striking "felsitic" dykes occurs about 10 to 20 km to the NW of Arnolz. However, the rhyodacites around Arnolz differ significantly from these felsitic dykes in their geochemistry and alteration phenomena which points to a different magmatic source. This coincides with a change in the orientation of the dykes from a NW direction controlling the geochemically specialized intrusions in the NW to a dominating NNE direction mirrored by the studied rhyodacites at Arnolz.

  12. Arsenic-bearing pyrite and marcasite in the Fire Clay coal bed, Middle Pennsylvanian Breathitt Formation, eastern Kentucky

    USGS Publications Warehouse

    Ruppert, L.F.; Hower, J.C.; Eble, C.F.

    2005-01-01

    Arsenic concentrations determined on 11 lithotype samples from the Middle Pennsylvanian Breathitt Group Fire Clay coal bed, Leslie County, KY, range from 1 to 418 ppm (whole coal basis). The 11 lithotype samples, which vary in thickness from 4 to 18 cm, were sampled from a continuous 1.38 m channel sample, and were selected based on megascopic appearance (vitrain-rich versus attrital-rich). A lithotype that contains 418 ppm As is located near the top of the coal bed and is composed of 10.5 cm of bright clarain bands containing fusain that, within short distances, grade laterally into Fe sulfide bands. To determine the mode of occurrence of As in this lithotype, the coal was examined with scanning electron microscopy and analyzed by energy dispersive X-ray fluorescence. Massive, framboidal, cell filling, cell-wall replacement, and radiating forms of Fe sulfide were observed in the high As lithotype; many of the radiating Fe sulfide forms, and one of the cell-wall replacements contained As. Examination of the grains with optical light microscopy shows that the majority of radiating morphologies are pyrite, the remainder are marcasite. Selected Fe sulfide grains were also analyzed by electron microprobe microscopy. Arsenic concentrations within individual grains range from 0.0 wt.% to approximately 3.5 wt.%. On the basis of morphology, these Fe sulfides are presumed to be of syngenetic origin and would probably be removed from the coal during physical coal cleaning, thus eliminating a potential source of As from the coal combustion process. However, because the grains are radiating and have high surface area, dissolution and release of As could occur if the pyrite is oxidized in refuse ponds.

  13. Pyrite surface characterization and control for advanced fine coal desulfurization technologies. Seventh quarterly technical progress report, March 1, 1992--May 31, 1992

    SciTech Connect

    Wang, Xiang-Huai; Leonard, J.W.; Parekh, B.K.; Jiang, Chengliang; Raichur, A.M.

    1992-07-14

    The objective of this project is to conduct extensive studies on the surface reactivity and surface hydrophobicity of coal-pyrites using various surface characterization techniques and to correlate the alteration of the coal-pyrite surface with the efficiency of pyrite rejection in coal flotation. The flotation characteristics of coal-pyrites under various conditions was studied and compared with ore-pyrite and coal to determine the causes of pyrite rejection difficulties in coal flotation. Both the native and induced floatabilities of pyrites were investigated. It was found that both coal- and ore-pyrites, ff prepared by dry-grinding, show little or no floatability in the absence of any chemical reagents. After ultrasonic pretreatment, ore-pyrite floats effectively in the acidic to neutral pH range. Kentucky No. 9 coal-pyrite (KYPY) shows significant flotation in the pH range 7--10. With ethyl xanthate as collector, ore-pyrite floats well up to pH = 10; while coal-pyrite reveals no flotation above pH = 6. For the first time, the effect of coal collector on the floatability of coal-pyrite has been studied. It was shown that in the presence of fuel oil--a widely used collector for promoting coal flotation, coal-pyrite, particularly for the fine sizes, shows good flotation below pH = 11, whereas ore-pyrite has no or little floatability. These studies demonstrate that one of the main causes of the coal-pyrite flotation in coal separation is the oil-induced floatability due to adsorption/attachment of oil droplets on the coal-pyrite surfaces, the ``native`` or ``self-induced`` floatability of pyrite is no as profound as the oil-induced flotation.

  14. A demonstration of an affinity between pyrite and organic matter in a hydrothermal setting

    PubMed Central

    2011-01-01

    One of the key-principles of the iron-sulphur world theory is to bring organic molecules close enough to interact with each other, using the surface of pyrite as a substrate in a hydrothermal setting. The present paper explores the relationship of pyrite and organic matter in a hydrothermal setting from the geological record; in hydrothermal calcite veins from Carboniferous limestones in central Ireland. Here, the organic matter is accumulated as coatings around, and through, pyrite grains. Most of the pyrite grains are euhedral-subhedral crystals, ranging in size from ca 0.1-0.5 mm in diameter, and they are scattered throughout the matrix of the vein calcite. The organic matter was deposited from a hydrothermal fluid at a temperature of at least 200°C, and gives a Raman signature of disordered carbon. This study points to an example from a hydrothermal setting in the geological record, demonstrating that pyrite can have a high potential for the concentration and accumulation of organic materials. PMID:21299877

  15. [Limestone and pyrite-limestone constructed wetlands for treating river water].

    PubMed

    Zhang, Jing; Li, Rui-hua; Li, Jie; Hu, Jun-song; Sun, Qian-qian

    2013-09-01

    Polluted river water was treated with limestone and pyrite-limestone subsurface horizontal constructed wetlands. The aims were to know the performance of two wetlands on removal of common pollutants, especially nitrogen and phosphorus, and analyze the actions of these minerals. The relationship between hydraulic retention time and purification performance of two constructed wetlands was studied. The optimal hydraulic retention time for pollutant removal was about 3 d, The average removal efficiency of COD, TN and TP were 51%, 70% and 95%, respectively. With same influent and hydraulic loading, the average removal efficiency of COD, NH4+ -N, TN and TP were 53.93%, 82.13%, 66%, 50.9%, and 51.66%, 77.43%, 72.06%, 97.35% for limestone and pyrite-limestone constructed wetlands, respectively. There were few differences between limestone and pyrite-limestone wetlands on COD removal, but the nitrogen and phosphorus removal of pyrite-limestone constructed wetland was higher than that of limestone constructed wetland. The phosphorus removal of pyrite-limestone wetland was more efficiency and stable, not affected by temperature.

  16. History of water-column anoxia in the Black Sea indicated by pyrite framboid size distributions

    USGS Publications Warehouse

    Wilkin, R.T.; Arthur, M.A.; Dean, W.E.

    1997-01-01

    A detailed study of size distributions of framboidal pyrite in Holocene Black Sea sediments establishes the timing of a change from deposition under an oxic water column to deposition under an anoxic and sulfidic water column. In the most recent carbonate-rich sediments (Unit I) and in the organic carbon-rich sapropel (Unit II), framboid size distributions are remarkably uniform (mean diameter= 5 ??m); over 95% of the framboids in Unit I and Unit II are < 7 ??m in diameter. These properties of framboidal pyrite are consistent with framboid nucleation and growth within an anoxic and sulfidic water column, followed by transport to the sediment-water interface, cessation of pyrite growth due to the exhaustion of reactive iron, and subsequent burial. In contrast, the organic carbon-poor sediments of lacustrine Unit III contain pyrite framboids that are generally much larger in size (mean diameter = 10 ??m). In Unit III, over 95% of the framboids are < 25 ??m in diameter, 40% of framboids are between 7 ??m and 25 ??m, and framboids up to 50 ??m in diameter are present. This distribution of sizes suggests framboid nucleation and growth within anoxic sediment porewaters. These new data on size distributions of framboidal pyrite confirm that the development of water-column anoxia in the Black Sea coincided with the initiation of deposition of laminated Unit II sapropels.

  17. Development of a Co-deposition method for Deposition of Low-Contamination Pyrite Thin Films

    NASA Astrophysics Data System (ADS)

    Walimbe, Aditya

    Pyrite is a 0.95 eV bandgap semiconductor which is purported to have great potential in widespread, low--cost photovoltaic cells. A thorough material selection process was used in the design of a pyrite sequential vapor deposition chamber aimed at reducing and possibly eliminating contamination during thin film growth. The design process focused on identifying materials that do not produce volatile components when exposed to high temperatures and high sulfur pressures. Once the materials were identified and design was completed, the ultra--high vacuum growth system was constructed and tested. Pyrite thin films were deposited using the upgraded sequential vapor deposition chamber by varying the substrate temperature from 250°C to 420°C during deposition, keeping sulfur pressure constant at 1 Torr. Secondary Ion Mass Spectrometry (SIMS) results showed that all contaminants in the films were reduced in concentration by orders of magnitude from those grown with the previous system. Characterization techniques of Rutherford Back--scattering Spectrometry (RBS), X--Ray Diffraction (XRD), Raman Spectroscopy, Optical Profilometry and UV/Vis/Near--IR Spectroscopy were performed on the deposited thin films. The results indicate that stoichiometric ratio of S:Fe, structural--quality (epitaxy), optical roughness and percentage of pyrite in the deposited thin films improve with increase in deposition temperature. A Tauc plot of the optical measurements indicates that the pyrite thin films have a bandgap of 0.94 eV.

  18. Trace element mapping of pyrite from Archean gold deposits - A comparison between PIXE and EPMA

    NASA Astrophysics Data System (ADS)

    Agangi, A.; Przybyłowicz, W.; Hofmann, A.

    2015-04-01

    Chemical zoning of pyrites can record the evolution of mineralising fluids at widely varying P-T conditions ranging from diagenesis to medium-grade metamorphism. If preserved, zoning can reveal growth textures, brecciation and veining, resorption and recrystallisation events, thus shedding light on the processes that contributed to ore formation. Chemical zoning of sulfides is invisible in optical microscopy, but can be studied by chemical etching, high-contrast back-scattering electron images, and elemental imaging. In this study we compared micro-PIXE and WDS-EPMA elemental maps on the chemically zoned pyrites in mineralised vein-bearing samples from the Sheba and Fairview gold mines in the Barberton Greenstone Belt, South Africa. Elemental images show complex distribution of trace elements, suggesting multiple events of pyrite crystallisation and gold deposition. EPMA maps show fine-scale variations reflecting growth and recrystallisation textures marked, in particular, by variations of As, Ni, and Co. In PIXE maps, gold occurs both as finely-distributed and discrete inclusions, suggesting incorporation in the pyrite structure as solid solution, and deposition as electrum inclusions, respectively. Micro-PIXE and EPMA provide complementary information, forming together a powerful tool to obtain information on chemical zoning of pyrites in ore deposits.

  19. Reduction of oxidative stress during recovery accelerates normalization of primary cilia length that is altered after ischemic injury in murine kidneys.

    PubMed

    Kim, Jee In; Kim, Jinu; Jang, Hee-Seong; Noh, Mi Ra; Lipschutz, Joshua H; Park, Kwon Moo

    2013-05-15

    The primary cilium is a microtubule-based nonmotile organelle that extends from the surface of cells, including renal tubular cells. Here, we investigated the alteration of primary cilium length during epithelial cell injury and repair, following ischemia/reperfusion (I/R) insult, and the role of reactive oxygen species in this alteration. Thirty minutes of bilateral renal ischemia induced severe renal tubular cell damage and an increase of plasma creatinine (PCr) concentration. Between 8 and 16 days following the ischemia, the increased PCr returned to normal range, although without complete histological restoration. Compared with the primary cilium length in normal kidney tubule cells, the length was shortened 4 h and 1 day following ischemia, increased over normal 8 days after ischemia, and then returned to near normal 16 days following ischemia. In the urine of I/R-subjected mice, acetylated tubulin was detected. The cilium length of proliferating cells was shorter than that in nonproliferating cells. Mature cells had shorter cilia than differentiating cells. Treatment with Mn(III) tetrakis(1-methyl-4-pyridyl) porphyrin (MnTMPyP), an antioxidant, during the recovery of damaged kidneys accelerated normalization of cilia length concomitant with a decrease of oxidative stress and morphological recovery in the kidney. In the Madin-Darby canine kidney (MDCK) cells, H(2)O(2) treatment caused released ciliary fragment into medium, and MnTMPyP inhibited the deciliation. The ERK inhibitor U0126 inhibited elongation of cilia in normal and MDCK cells recovering from H(2)O(2) stress. Taken together, our results suggest that primary cilia length reflects cell proliferation and the length of primary cilium is regulated, at least, in part, by reactive oxygen species through ERK.

  20. Iron isotope compositions and origins of pyrites from the Turee Creek Group, Western Australia: the contribution of high-resolution femtosecond Laser Ablation -MC-ICP-MS

    NASA Astrophysics Data System (ADS)

    d'Abzac, F.; Beard, B. L.; Williford, K. H.; Valley, J. W.; Van Kranendonk, M. J.; Johnson, C.

    2013-12-01

    The Paleoproterozoic Great Oxidation Event (GOE) records a transition from an anoxic environment to a O2-bearing atmosphere, but its timing and duration remain unclear. High-spatial-resolution S isotope analyses by SIMS have shown that pyrite grains in the ~2.4Gy diamictites of the Meteorite Bore Member (MBM; Turee Creek Group, Western Australia), deposited during the GOE, contain evidence for a complex depositional and paragenetic history, including microbial sulfate reduction under low atmospheric O2 yet high seawater sulfate concentrations. The pyrites show various morphologies: euhedral, subhedral, anhedral, rounded, and zoned, where low- δ34S rounded cores may have high-δ34S euhedral/subhedral overgrowths [1]. New in-situ Fe isotope data by femtosecond laser ablation (fs-LA) analysis using Multi Collector ICP-MS on 118 pyrite grains within five rock samples previously analyzed for S isotopes documents δ56Fe values between -2.3‰ and +2.3‰. Transitional cherts at the base of the MBM record the highest δ56Fe values, >0.7‰. Within the upper mudstones/sandstones deposits, anhedral, rounded grains and zoned pyrite cores have a wide range of δ56Fe from -2.3‰ to +1.1‰ whereas euhedral grains and grains overgrowths have mainly positive δ56Fe values, up to +1.34‰, spread over narrower ranges in each sample (<1‰). Non-euhedral grains and rounded grain cores of likely detrital origin have highly scattered δ56Fe values, indicating a range of different sources. Although very low δ56Fe values suggest a source of biologically reduced Fe [2], they can be obtained by precipitation of FeS from low-δ56Fe seawater Fe2+ [3], or might reflect a kinetic signature during pyritization of FeS [4]. High-δ56Fe in pyrite overgrowths and authigenic grains likely reflects precipitation from a hydrothermal fluid (δ56Fe~0.0‰) at T>100°C [5, 6], in agreement with [1]. The δ34S gradient of highly negative to positive values from zoned pyrites cores to rims is well

  1. Oxidized and reduced mineral assemblages in greenstone belt rocks of the St. Ives gold camp, Western Australia: vectors to high-grade ore bodies in Archaean gold deposits?

    NASA Astrophysics Data System (ADS)

    Neumayr, Peter; Walshe, John; Hagemann, Steffen; Petersen, Klaus; Roache, Anthony; Frikken, Peter; Horn, Leo; Halley, Scott

    2008-03-01

    Hydrothermal sulfide-oxide-gold mineral assemblages in gold deposits in the Archaean St. Ives gold camp in Western Australia indicate extremely variable redox conditions during hydrothermal alteration and gold mineralization in space and time. Reduced alteration assemblages (pyrrhotite-pyrite) occur in deposits in the southwest of the camp (e.g., Argo, Junction deposits) and moderately to strongly oxidized assemblages (magnetite-pyrite, hematite-pyrite) occur in deposits in the Central Corridor in the northeast (e.g., North Orchin, Revenge deposits). Reduced mineral assemblages flank the Central Corridor of oxidized deposits and, locally, cut across it along E-W trending faults. Oxidized mineral assemblages in the Central Corridor are focused on gravity lows which are interpreted to reflect abundant felsic porphyritic intrusions at about 1,000 m below present surface. Hydrothermal magnetite predates and is synchronous with early phases of gold-associated albite-carbonate-pyrite-biotite-chlorite hydrothermal alteration. Later-stage, gold-associated pyrite is in equilibrium with hematite. The spatial distribution and temporal sequence of iron sulfides and oxides with gold indicate the presence of at least two spatially restricted but broadly synchronous hydrothermal fluids with contrasting redox states. Sulfur isotope constraints support the argument that the different mineral assemblages reflect differences in redox conditions. The δ 34S values for pyrite for the St. Ives gold camp range between -8.4‰ and +5.1‰ with the negative values occurring in oxidized magnetite-rich domains and slightly negative or positive values occurring in reduced, pyrrhotitic domains. Preliminary spatial and paragenetic analysis of the distribution of iron sulfides and oxides in the St. Ives camp suggests that gold grades are highest where the redox state of the hydrothermal alteration assemblages switches from relatively reduced pyrrhotite-pyrite to relatively oxidized magnetite-pyrite

  2. Symmetry-defying iron pyrite (FeS₂) nanocrystals through oriented attachment.

    PubMed

    Gong, Maogang; Kirkeminde, Alec; Ren, Shenqiang

    2013-01-01

    Iron pyrite (fool's gold, FeS₂) is a promising earth abundant and environmentally benign semiconductor material that shows promise as a strong and broad absorber for photovoltaics and high energy density cathode material for batteries. However, controlling FeS₂ nanocrystal formation (composition, size, shape, stoichiometry, etc.) and defect mitigation still remains a challenge. These problems represent significant limitations in the ability to control electrical, optical and electrochemical properties to exploit pyrite's full potential for sustainable energy applications. Here, we report a symmetry-defying oriented attachment FeS₂ nanocrystal growth by examining the nanostructure evolution and recrystallization to uncover how the shape, size and defects of FeS₂ nanocrystals changes during growth. It is demonstrated that a well-controlled reaction temperature and annealing time results in polycrystal-to-monocrystal formation and defect annihilation, which correlates with the performance of photoresponse devices. This knowledge opens up a new tactic to address pyrite's known defect problems.

  3. MICROCHARACTERIZATION OF ARSENIC- AND SELENIUM-BEARING PYRITE IN UPPER FREEPORT COAL, INDIANA COUNTY, PENNSYLVANIA.

    USGS Publications Warehouse

    Minkin, J.A.; Finkelman, R.B.; Thompson, C.L.; Chao, E.C.T.; Ruppert, L.F.; Blank, H.; Cecil, C.B.

    1984-01-01

    Optical and scanning electron microscope as well as electron and proton microprobe techniques have been used in a detailed investigation of the modes of occurrence of arsenic and selenium in pyrite in Upper Freeport coal from the Homer City area, Indiana County, Pennsylvania. Polished blocks were prepared from columnar samples of the coal bed to represent particular zones continuously from top to bottom. Initial selection of zones to be studied was based on chemical analysis of bench-channel samples. Microprobe data indicate that the highest concentrations of arsenic (as great as 1. 5 wt. %) are apparently in solid solution in pyrite within a limited stratigraphic interval of the coal bed. Smaller amounts of arsenic and selenium (concentrations up to approximately 0. 1 and 0. 2 wt. % respectively) were detected at isolated points within pyrite grains in various strata of the coal bed.

  4. Micro-scale (1.5 microm) sulphur isotope analysis of contemporary and early Archean pyrite.

    PubMed

    Nishizawa, Manabu; Maruyama, Shigenori; Urabe, Tetsuro; Takahata, Naoto; Sano, Yuji

    2010-05-30

    We present a method for in situ sulphur (S) isotopic analysis of significantly small areas (1.5 microm in diameter) in pyrite using secondary ion mass spectrometry (NanoSIMS) to interpret microbial sulphur metabolism in the early earth. We evaluated the precision and accuracy of S isotopic ratios obtained by this method using hydrothermal pyrite samples with homogeneous S isotopic ratios. The internal precision of the delta(34)S value was 1.5 per thousand at the level of 1 sigma of standard error (named 1SE) for a single spot, while the external reproducibility was estimated to be 1.6 per thousand at the level of 1 sigma of standard deviation (named 1SD, n = 25). For each separate sample, the average delta(34)S value was comparable with that measured by a conventional method, and the accuracy was better than 2.3 per thousand. Consequently, the in situ method is sufficiently accurate and precise to detect the S isotopic variations of small sample of the pyrite (less than 20 microm) that occurs ubiquitously in ancient sedimentary rocks. This method was applied to measure the S isotopic distribution of pyrite within black chert fragments in early Archean sandstone. The pyrite had isotopic zoning with a (34)S-depleted core and (34)S-enriched rim, suggesting isotopic evolution of the source H(2)S from -15 to -5 per thousand. Production of H(2)S by microbial sulphate reduction (MSR) in a closed system provides a possible explanation for both the (34)S-depleted initial H(2)S and the progressive increase in the delta(34)S(H2S) value. Although more extensive data are necessary to strengthen the explanation for the origin of the MSR, the results show that the S isotopic distribution within pyrite crystals may be a key tracer for MSR activity in the early earth.

  5. Semiconductor electrochemistry of coal pyrite. Technical progress report, April--June 1993

    SciTech Connect

    Osseo-Asare, K.; Wei, D.

    1993-08-01

    Pyrite (FeS{sub 2}) and mackinawite (FeS) were synthesized successfully in aqueous solution at room temperature and atmospheric pressure. FeCl{sub 2} and FeCl{sub 3} were chosen as the sources of iron, and Na{sub 2}S, NaHS and Na{sub 2}S{sub 4} as the sources of sulfur. Pyrite was made from the reaction between Fe(III) and Na{sub 2}S or NaHS within a few days of aging. Mackinawite was made from the reaction between Fe(II) and Na{sub 2}S at pH 7.3 within 4 days. The reaction between Fe(II) and NaHS produced a mixture of mackinawite and pyrite at pH 4.0 within 4 days. Using Na{sub 2}S{sub 4} as the source of sulfur, no mackinawite was observed under the experimental conditions. A mixture of pyrite and elemental sulfur was obtained from the reaction between Fe(II) or Fe(III) and Na{sub 2}S{sub 4}. Particle size analysis by a transmission electron microscope (TEM) showed that pyrite formed from the reaction between Fe(III) and Na{sub 2}S or NaHS has an average diameter of 150 {mu}m. To reduce the particle size into nanosize range, pyrite is being made currently in our laboratory either in dispersed aqueous solution or in water-in-oil microemulsion.

  6. Micro-scale (1.5 microm) sulphur isotope analysis of contemporary and early Archean pyrite.

    PubMed

    Nishizawa, Manabu; Maruyama, Shigenori; Urabe, Tetsuro; Takahata, Naoto; Sano, Yuji

    2010-05-30

    We present a method for in situ sulphur (S) isotopic analysis of significantly small areas (1.5 microm in diameter) in pyrite using secondary ion mass spectrometry (NanoSIMS) to interpret microbial sulphur metabolism in the early earth. We evaluated the precision and accuracy of S isotopic ratios obtained by this method using hydrothermal pyrite samples with homogeneous S isotopic ratios. The internal precision of the delta(34)S value was 1.5 per thousand at the level of 1 sigma of standard error (named 1SE) for a single spot, while the external reproducibility was estimated to be 1.6 per thousand at the level of 1 sigma of standard deviation (named 1SD, n = 25). For each separate sample, the average delta(34)S value was comparable with that measured by a conventional method, and the accuracy was better than 2.3 per thousand. Consequently, the in situ method is sufficiently accurate and precise to detect the S isotopic variations of small sample of the pyrite (less than 20 microm) that occurs ubiquitously in ancient sedimentary rocks. This method was applied to measure the S isotopic distribution of pyrite within black chert fragments in early Archean sandstone. The pyrite had isotopic zoning with a (34)S-depleted core and (34)S-enriched rim, suggesting isotopic evolution of the source H(2)S from -15 to -5 per thousand. Production of H(2)S by microbial sulphate reduction (MSR) in a closed system provides a possible explanation for both the (34)S-depleted initial H(2)S and the progressive increase in the delta(34)S(H2S) value. Although more extensive data are necessary to strengthen the explanation for the origin of the MSR, the results show that the S isotopic distribution within pyrite crystals may be a key tracer for MSR activity in the early earth. PMID:20411578

  7. 3.4-Billion-year-old biogenic pyrites from Barberton, South Africa: sulfur isotope evidence.

    PubMed

    Ohmoto, H; Kakegawa, T; Lowe, D R

    1993-10-22

    Laser ablation mass spectroscopy analyses of sulfur isotopic compositions of microscopic-sized grains of pyrite that formed about 3.4 billion years ago in the Barberton Greenstone Belt, South Africa, show that the pyrite formed by bacterial reduction of seawater sulfate. These data imply that by about 3.4 billion years ago sulfate-reducing bacteria had become active, the oceans were rich in sulfate, and the atmosphere contained appreciable amounts (>10(-13) of the present atmospheric level) of free oxygen. PMID:11539502

  8. 3.4-Billion-year-old biogenic pyrites from Barberton, South Africa: sulfur isotope evidence

    NASA Technical Reports Server (NTRS)

    Ohmoto, H.; Kakegawa, T.; Lowe, D. R.

    1993-01-01

    Laser ablation mass spectroscopy analyses of sulfur isotopic compositions of microscopic-sized grains of pyrite that formed about 3.4 billion years ago in the Barberton Greenstone Belt, South Africa, show that the pyrite formed by bacterial reduction of seawater sulfate. These data imply that by about 3.4 billion years ago sulfate-reducing bacteria had become active, the oceans were rich in sulfate, and the atmosphere contained appreciable amounts (>>10(-13) of the present atmospheric level) of free oxygen.

  9. Authigenic kaolinite and associated pyrite in chalk of the Cretaceous Niobrara Formation, Eastern Colorado.

    USGS Publications Warehouse

    Pollastro, R.M.

    1981-01-01

    Cores from the Smoky Hill Chalk Member of the Cretaceous Niobrara Formation have several zones containing authigenic kaolinite as spherical, moldic, polycrystalline aggregates that occur within single or multichambered foraminiferal tests and are commonly associated with framboidal pyrite. Such kaolinite is inferred to result from volcanic ash deposited during chalk sedimentation. Shortly after burial, a colloidal aluminous gel or solution formed from the unstable ash and moved into organic-rich foraminiferal tests, where sulfate-reducing bacteria created a favorable microenvironment for the simultaneous crystallization of kaolinite and pyrite. -Author

  10. 3.4-Billion-Year-Old Biogenic Pyrites from Barberton, South Africa: Sulfur Isotope Evidence

    NASA Astrophysics Data System (ADS)

    Ohmoto, Hiroshi; Kakegawa, Takeshi; Lowe, Donald R.

    1993-10-01

    Laser ablation mass spectroscopy analyses of sulfur isotopic compositions of microscopic-sized grains of pyrite that formed about 3.4 billion years ago in the Barberton Greenstone Belt, South Africa, show that the pyrite formed by bacterial reduction of seawater sulfate. These data imply that by about 3.4 billion years ago sulfate-reducing bacteria had become active, the oceans were rich in sulfate, and the atmosphere contained appreciable amounts (> > 10-13 of the present atmospheric level) of free oxygen.

  11. Disseminated pyrite in a latite porphyry at Texan Mountain, Hudspeth County, Texas

    USGS Publications Warehouse

    Mullens, Thomas E.

    1973-01-01

    A pyrite-bearing latite porphyry that contains fragments of syenite and a quartz porphyry intruded into the Cretaceous Cox Sandstone are well exposed in a roadcut at Texan Mountain, Hudspeth County, Tex. The pyrite, which occurs along tiny fractures as well as disseminated, and the multiple episodes of intrusion, coupled with copper minerals in veins in the overlying Cox Sandstone, indicate a slight potential for porphyry-type copper or molybdenum deposits at depth.

  12. 3.4-Billion-year-old biogenic pyrites from Barberton, South Africa: sulfur isotope evidence.

    PubMed

    Ohmoto, H; Kakegawa, T; Lowe, D R

    1993-10-22

    Laser ablation mass spectroscopy analyses of sulfur isotopic compositions of microscopic-sized grains of pyrite that formed about 3.4 billion years ago in the Barberton Greenstone Belt, South Africa, show that the pyrite formed by bacterial reduction of seawater sulfate. These data imply that by about 3.4 billion years ago sulfate-reducing bacteria had become active, the oceans were rich in sulfate, and the atmosphere contained appreciable amounts (>10(-13) of the present atmospheric level) of free oxygen.

  13. Origins of Carbonaceous Matter, Hematite, and Pyrite in the 3.46Ga Marble Bar Chert/Jasper/Basalt Formation, Pilbara, Western Australia

    NASA Astrophysics Data System (ADS)

    Ohmoto, H.; Bevacqua, D. C.; Watanabe, Y.; Otake, T.

    2004-12-01

    The 3.46 Ga Marble Bar Chert/Jasper unit in the Pilbara district, W.A. was probably deposited in a deep (>500 m) ocean during the accumulation of a thick (>5 km) submarine basalt. Debate focuses on whether organic matter in pre-2.0 Ga cherts is a remnant of marine organisms or the product of abiotic synthesis in hydrothermal systems, whether the hematite crystals in jaspers were primary or products of modern oxidation of siderite and pyrite, and whether the pyrite crystals formed by sulfate-reducing bacteria, hydrothermal fluids, or atmospheric sulfur. At the drilling site, the Marble bar Chert/Jasper is over turned diping about 80 degrees. A continuous 264 m- long core, drilled at 50 degrees, was recovered. The major chert/jasper unit, comprising alternating beds (0.1 - 5 cm thick) of white/green/gray/black/red chert, is 105 m thick. The abundance of red jasper beds increases down hole, indicating that the hematite crystals were not produced by subaerial oxidation of ferrous minerals. Petrological, mineralogical, and geochemical investigations of the core samples, especially using an X-ray chemical microscope, have revealed that the dominant Fe-bearing minerals are siderite, magnetite, and hematite, in the green, gray-black, and red cherts, respectively. These Fe-bearing minerals and disseminated pyrite crystals (ubiquitous in all cherts) are typically very fine grained (less than 10 microns). The basalts (pillows and tuffs), which occur below, above, and interbedded with the chert/jasper unit, are in places heavily hematitized with various characteristics of submarine hydrothermal alteration, such as chloritization, silicification, pyritization, large variations in the contents of Fe, Mg, Ba, and depletions in Ca, Sr, and Na. Veinles containing quartz and pyrite are abundant in the chert/jaster beds and also in the heavily hematitized basalts. These data suggest the hematite, magnetie, siderite, pyrite and silica in the chert/jasper unit, basalt tuffs, and pillow

  14. Ionization of high-density deep donor defect states explains the low photovoltage of iron pyrite single crystals.

    PubMed

    Cabán-Acevedo, Miguel; Kaiser, Nicholas S; English, Caroline R; Liang, Dong; Thompson, Blaise J; Chen, Hong-En; Czech, Kyle J; Wright, John C; Hamers, Robert J; Jin, Song

    2014-12-10

    Iron pyrite (FeS2) is considered a promising earth-abundant semiconductor for solar energy conversion with the potential to achieve terawatt-scale deployment. However, despite extensive efforts and progress, the solar conversion efficiency of iron pyrite remains below 3%, primarily due to a low open circuit voltage (VOC). Here we report a comprehensive investigation on {100}-faceted n-type iron pyrite single crystals to understand its puzzling low VOC. We utilized electrical transport, optical spectroscopy, surface photovoltage, photoelectrochemical measurements in aqueous and acetonitrile electrolytes, UV and X-ray photoelectron spectroscopy, and Kelvin force microscopy to characterize the bulk and surface defect states and their influence on the semiconducting properties and solar conversion efficiency of iron pyrite single crystals. These insights were used to develop a circuit model analysis for the electrochemical impedance spectroscopy that allowed a complete characterization of the bulk and surface defect states and the construction of a detailed energy band diagram for iron pyrite crystals. A holistic evaluation revealed that the high-density of intrinsic surface states cannot satisfactorily explain the low photovoltage; instead, the ionization of high-density bulk deep donor states, likely resulting from bulk sulfur vacancies, creates a nonconstant charge distribution and a very narrow surface space charge region that limits the total barrier height, thus satisfactorily explaining the limited photovoltage and poor photoconversion efficiency of iron pyrite single crystals. These findings lead to suggestions to improve single crystal pyrite and nanocrystalline or polycrystalline pyrite films for successful solar applications.

  15. Marine origin of pyritic sulfur in the Lower Bakerstown coal bed, Castleman coal field, Maryland (U.S.A.)

    USGS Publications Warehouse

    Lyons, P.C.; Whelan, J.F.; Dulong, F.T.

    1989-01-01

    The amount, kind, distribution, and genesis of pyrite in the Lower Bakerstown coal bed in a 150 ?? 15 m area of the Bettinger mine, Castleman coal field, Maryland, were studied by various analytical techniques. The mined coal, which had a nonmarine roof rock, contained 1.4-2.8 wt.% total sulfur, generally much lower than the high-sulfur coal (> 3.0 wt.% total S) to the north, which is associated with marine roof rocks. Small-scale systematic and nonsystematic variations in total sulfur and pyrite distribution were found in the mined area. In the column sample, most of the pyrite was found in the upper 9 cm of the 69-cm-thick mined coal and occurred mainly as a pyrite lens containing cell fillings in seed-fern tissue (coal ball). As-bearing pyrite was detected by laser microprobe techniques in the cell walls of this tissue but not elsewhere in the column sample. This may indicate that the As was derived from decomposition of organic matter in the cell walls. The sulfur isotopic composition and distribution of pyrite in the coal are consistent with introduction of marine sulfate shortly after peat deposition, followed by bacterial reduction and pyrite precipitation. Epigenetic cleat pyrite in the coal is isotopically heavy, implying that later aqueous sulfate was 34S-enriched. ?? 1989.

  16. Automated microscopy methods for measuring pyritic sulfur content of coal and determining degree of liberation of pyrite in coal: Final report

    SciTech Connect

    Chaparro, L.F.

    1987-07-25

    The objective of this project is to develop an automated procedure, to be implemented in an IBAS image analyzer, to determine size, shape and degree of liberation of pyrite particles in a coal matrix. This procedure is to work in real time conditions and with minimal intervention from the operator. Our approach is to create from the original microscopic image a three level image with the following components: epoxy, coal macerals and pyrite to simplify the calculations. Enhancing the original image by histogram scaling and median filtering, we segment it and form the three level image. After the boundaries of the pyrite particles are defined, we mask the surroundings of the particle to estimate the degree of liberation. The percentage of epoxy included in the mask is defined as the degree of liberation of the particle. Size and shape factor values are simultaneously calculated for each of the analyzed particles. These particles are classified according to their maximum diameter, shape factor and degree of liberation by the program. 6 refs., 18 figs.

  17. Geochemical evidence for Se mobilization by the weathering of pyritic shale, San Joaquin Valley, California, U.S.A.

    USGS Publications Warehouse

    Presser, T.S.; Swain, W.C.

    1990-01-01

    Acidic (pH 4) seeps issue from the weathered Upper Cretaceous-Paleocene marine sedimentary shales of the Moreno Formation in the semi-arid Coast Ranges of California. The chemistry of the acidic solutions is believed to be evidence of current reactions ultimately yielding hydrous sodium and magnesium sulfate salts, e.g. mirabilite and bloedite, from the oxidation of primary pyrite. The selenate form of Se is concentrated in these soluble salts, which act as temporary geological sinks. Theoretically, the open lattice structures of these hydrous minerals could incorporate the selenate (SeO4-2) anion in the sulfate (SO4-2) space. When coupled with a semi-arid to arid climate, fractional crystallization and evaporative concentration can occur creating a sodium-sulfate fluid that exceeds the U.S. Environmental Protection Agency limit of 1000 ??g l-1 for a toxic Se waste. The oxidative alkaline conditions necessary to ensure the concentration of soluble selenate are provided in the accompanying marine sandstones of the Panoche and Lodo Formations and the eugeosynclinal Franciscan assemblage. Runoff and extensive mass wasting in the area reflect these processes and provide the mechanisms which transport Se to the farmlands of the west-central San Joaquin Valley. Subsurface drainage from these soils consequently transports Se to refuge areas in amounts elevated to cause a threat to wildlife. ?? 1990.

  18. Voltage regulation in linear induction accelerators

    DOEpatents

    Parsons, W.M.

    1992-12-29

    Improvement in voltage regulation in a linear induction accelerator wherein a varistor, such as a metal oxide varistor, is placed in parallel with the beam accelerating cavity and the magnetic core is disclosed. The non-linear properties of the varistor result in a more stable voltage across the beam accelerating cavity than with a conventional compensating resistance. 4 figs.

  19. Voltage regulation in linear induction accelerators

    DOEpatents

    Parsons, William M.

    1992-01-01

    Improvement in voltage regulation in a Linear Induction Accelerator wherein a varistor, such as a metal oxide varistor, is placed in parallel with the beam accelerating cavity and the magnetic core. The non-linear properties of the varistor result in a more stable voltage across the beam accelerating cavity than with a conventional compensating resistance.

  20. Wakefield accelerators

    SciTech Connect

    Simpson, J.D.

    1990-01-01

    The search for new methods to accelerate particle beams to high energy using high gradients has resulted in a number of candidate schemes. One of these, wakefield acceleration, has been the subject of considerable R D in recent years. This effort has resulted in successful proof of principle experiments and in increased understanding of many of the practical aspects of the technique. Some wakefield basics plus the status of existing and proposed experimental work is discussed, along with speculations on the future of wake field acceleration. 10 refs., 6 figs.