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Sample records for accelerating pyrite oxidation

  1. 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

  2. Bacterial Oxidation of Pyritic Materials in Coal

    PubMed Central

    Silverman, Melvin P.; Rogoff, Martin H.; Wender, Irving

    1961-01-01

    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 CaCO3 from a calcite-containing sample. PMID:16349610

  3. Pyrite oxidation by thermophilic archaebacteria

    SciTech Connect

    Larsson, L.; Olsson, G.; Holst, O.; Karlsson, H.T. )

    1990-03-01

    Three species of thermophilic archaebacteria of the genera Sulfolobus (Sulfolobus acidocaldarius and S. solfataricus) and Acidianus (Acidianus brierleyi) were tested for their ability to oxidize pyrite and to grow autotropbically on pyrite, to explore their potential for use in coal desulfurization. Only A. brierleyi was able to oxidize and grow autotrophically on pyrite. Jarosite was formed during the pyrite oxidation, resulting in the precipitation of sulfate and iron. The medium composition affected the extent of jarosite formation.

  4. Mechanism of Bacterial Pyrite Oxidation

    PubMed Central

    Silverman, Melvin P.

    1967-01-01

    The oxidation by Ferrobacillus ferrooxidans of untreated pyrite (FeS2) as well as HCl-pretreated pyrite (from which most of the acid-soluble iron species were removed) was studied manometrically. Oxygen uptake was linear during bacterial oxidation of untreated pyrite, whereas with HCl-pretreated pyrite both a decrease in oxygen uptake at 2 hr and nonlinear oxygen consumption were observed. Ferric sulfate added to HCl-pretreated pyrite restored approximately two-thirds of the decrease in total bacterial oxygen uptake and caused oxygen uptake to revert to nearly linear kinetics. Ferric sulfate also oxidized pyrite in the absence of bacteria and O2; recovery of ferric and ferrous ions was in excellent agreement with the reaction Fe2(SO4)3 + FeS2 = 3FeSO4 + 2S, but the elemental sulfur produced was negligible. Neither H2S nor S2O32− was a product of the reaction. It is probable that two mechanisms of bacterial pyrite oxidation operate concurrently: the direct contact mechanism which requires physical contact between bacteria and pyrite particles for biological pyrite oxidation, and the indirect contact mechanism according to which the bacteria oxidize ferrous ions to the ferric state, thereby regenerating the ferric ions required for chemical oxidation of pyrite. PMID:6051342

  5. Potential role of bicarbonate during pyrite oxidation

    SciTech Connect

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

    1998-07-15

    The need to prevent the development of acid mine drainage (AMD) by oxidation of pyrite has triggered numerous investigations into the mechanisms of its oxidation. According to Frontier molecular orbital (FMO) theory, the surface-exposed sulfur atom of pyrite possesses an unshared electron pair which produces a slightly negatively charged pyrite surface that can attract cations such as Fe{sup 2+}. Because of surface electroneutrality and pH considerations, however, the pyrite surface Fe{sup 2+} coordinates OH. The authors proposed that this surface Fe{sup 2+} OH when in the presence of CO{sub 2} is converted to {minus}FeCO{sub 3} or {minus}FeHCO{sub 3}, depending on pH. In this study, using Fourier transform infrared spectroscopy (FT-IR) they demonstrated that such complexes form on the surface of pyrite and continue to persist even after a significant fraction of the surface Fe{sup 2+} was oxidized to Fe{sup 3+}. FT-IR spectra also showed the presence of two carbonyl absorption bands (1,682 and 1,653 cm{sup {minus}1}) on the surface of pyrite upon exposure to CO{sub 2} which suggested that pyrite surface carbon complexes existed in two different surface chemical environments, pointing out two potential mechanisms of pyrite surface-CO{sub 2} interactions. One potential mechanism involved formation of a pyrite surface-Fe(II)HCO{sub 3} complex, whereas a second potential mechanism involved formation of a pyrite surface-carboxylic acid group complex [{minus}Fe(II)SSCOOFe-(II)].

  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. 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

  8. 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.

  9. Interfacial electrochemistry of pyrite oxidation and flotation. 1: Effect of borate on pyrite surface oxidation

    SciTech Connect

    Wang, X.H.

    1996-03-25

    The interfacial chemistry of pyrite is of great industrial importance in complex sulfide ore flotation, coal desulfurization, acid mine drainage mitigation, and conversion of solar energy to electrical or chemical energy. Sodium tetraborate (Na{sub 2}B{sub 4}O{sub 7}) has been widely used as an electrolyte and pH buffer in studying the interfacial electrochemistry of sulfide minerals in relation to sulfide mineral flotation. In all the previous studies published so far, borate was regarded as an inert electrolyte/pH buffer, and its reactions with the sulfide minerals were completely overlooked. In this first part of this series papers, the complicating effects of borate on the interfacial electrochemistry of pyrite have been studied. In the borate solutions, the surface oxidation of pyrite is strongly enhanced. The first and rate-determining step of the reaction between borate and pyrite has been shown to be the following irreversible reaction: FeS{sub 2} + B(OH){sub 4}{sup {minus}} {yields} FeS{sub 2} {hor_ellipsis} [B(OH){sub 4}]{sub ads} + e. This reaction appears in the voltammogram as an anodic oxidation peak at potentials of more than 0.4 V lower than the commencement of pyrite oxidation in sodium perchlorate or nitrate electrolyte solutions. As the borate concentration increases, the peak current increases linearly, while the peak potential shifts positively at 240 mV per decade. On a rotating-disc electrode, the peak becomes a plateau. The limiting current density is a linear function of the square root of the rotation speed at relatively low rotation speeds. The Tafel slope is close to 240 mV per decade and is independent of the rotation speed and borate concentration. The results indicate that charge transfer coefficient is 0.25.

  10. 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.

  11. 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

  12. 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

  13. Corrosion and electrochemical oxidation of a pyrite by Thiobacillus ferrooxidans

    SciTech Connect

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

    1992-04-01

    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.

  14. 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.

  15. 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

  16. 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.

  17. 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.

  18. [Investigation on mechanism of pyrite oxidation in acidic solutions].

    PubMed

    Wang, Nan; Yi, Xiao-Yun; Dang, Zhi; Liu, Yun

    2012-11-01

    The mechanism of pyrite oxidation in acidic solutions was investigated by electrochemical analysis methods, such as open-circuit potential, cyclic voltammetry, Tafel polarization curve and anodic polarization curve, using a pyrite-carbon paste electrode as working electrode. The results showed that the oxidation process of pyrite in acidic solutions was via a two-step reaction: the first step was the dissolution of iron moiety and formation of a passivation film composed of elemental sulphur, metal-deficient sulfide and polysulfide; the second step was the further oxidation of these intermediate products to SO4(2-). The final reaction products of pyrite oxidation were Fe3+ and SO4(2-) in acidic solutions. In addition, the open-circuit potential and corrosion potential were positively shifted, the peak current and the corrosion current were increased with the increase in concentration of H2SO4 solutions. This indicated that increased acidity of the system was advantageous to the oxidation of pyrite. PMID:23323425

  19. Oxidative dissolution of pyrite surfaces by hexavalent chromium: Surface site saturation and surface renewal

    NASA Astrophysics Data System (ADS)

    Graham, Andrew M.; Bouwer, Edward J.

    2012-04-01

    In-situ reduction of toxic Cr(VI) to nontoxic Cr(III) represents an important natural attenuation process for Cr(VI)-impacted environments. This study investigates the stoichiometry and kinetics of Cr(VI) reduction by pyrite, a reduced iron-sulfur mineral ubiquitous in recent estuarine and marine sediments. Pyrite suspensions at surface loadings of 0.28-2.10 m2/L (typical of estuarine or marine sediments) were capable of completely reducing 7-120 μM Cr(VI) on the timescale of minutes to days, with the time to reaction completion decreasing with increasing pyrite loading, decreasing initial Cr(VI) concentration, and decreasing suspension pH. Analysis of metal species (Cr and Fe) and sulfur species in solution and at the mineral surface indicated that Cr(VI) oxidatively dissolved the pyrite surface, releasing ferrous iron and sulfate into solution as the reaction progressed. Surface disulfide groups were postulated as the Cr(VI)-reactive surface entity. Net production or consumption of aqueous Fe(II) was shown to depend upon the relative rates of proton-promoted Fe(II) release, Fe(II) release due to oxidative dissolution of pyrite in the presence of Cr(VI), and Fe(II) consumption due to homogeneous reaction with Cr(VI). Kinetics of Cr(VI) reduction by pyrite displayed a biphasic pattern, and the time to reaction completion increased dramatically with increasing initial Cr(VI) concentration. Rapid Cr(VI) removal occurred early in the reaction progress, attributable to Cr(VI) loss under an adsorption-limited regime. Slow, approximately zero-order, Cr(VI) removal occurred over the bulk of the time courses, and corresponded to Cr(VI) removal under surface site saturation conditions. Stoichiometric Cr(VI) reduction was able to proceed under surface site limited conditions owing to regeneration of reactive surface sites following desorption/dissolution of oxidized surface products, as demonstrated in repeat Cr(VI)-spiking experiments. The role of surface passivation was

  20. Comparative Mössbauer study of the oxidation of pyrite under different conditions

    NASA Astrophysics Data System (ADS)

    Gracia, M.; Gancedo, J. R.; Martínez-Alonso, A.; Tascón, J. M. D.

    1990-07-01

    Samples of pyrite-rich brown coal from As Pontes and Meirama coalfields (Spain) were oxidized either by air at atmospheric pressure or by a cool oxygen plasma generated by radiofrequency activation. Despite the very different nature and characteristics of the oxidizing media, in both cases the RT Mössbauer spectra were easily fitted to two doublets, whose parameters matched those of pyrite and jarosite (hydrated iron (III) sulphate). The extent of pyrite oxidation to jarosite was monitored by the relative spectral areas of pyrite and jarosite doublets. Both, air and plasma, oxidized pyrite to the same extent and in a similar way, in contrast to coal organic matter, which was scarcely modified by air but completely oxidized by the plasma at the same temperature (ca. 423 K). The incomplete oxidation of pyrite by plasma is attributed to the action of a thin calcium sulphate layer which hinders the access of activated oxygen to small pyrite crystals.

  1. 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.

  2. Kinetics of pyrite oxidation in sodium carbonate solutions

    SciTech Connect

    Ciminelli, V.S.T.; Osseo-Asare, K.

    1995-04-01

    The kinetics of pyrite oxidation in sodium carbonate solutions were investigated in a stirred vessel, under temperatures ranging from 50 C to 85 C, oxygen partial pressures from 0 to 1 atm, particle size fractions from {minus}150 + 106 to {minus}38 + 10 {mu}m ({minus}100 + 150 Mesh to {minus}400 Mesh + 10 {mu}m) and pH values of up to 12.5. The rate of the oxidation reaction is described by the following expression: {minus}dN/dt = SbkpO{sup 0.5}{sub 2} [OH{sup {minus}}]{sup 0.1} where N represents moles of pyrite, S is the surface area of the solid particles, b is a stoichiometric factor, k is an apparent rate constant, pO{sub 2} is the oxygen partial pressure, and [OH{sup {minus}}] is the hydroxyl ion concentration. The experimental data were fitted by a stochastic model for chemically controlled reactions, represented by the following fractional conversion (X) vs time (t) equation: (1 {minus} X){sup {minus}2/3} {minus} 1 = k{sub ST}t. The assumption behind this model, i.e., surface heterogeneity leading to preferential dissolution, is supported by the micrographs of reacted pyrite particles, showing pits created by localized dissolution beneath an oxide layer. In addition to the surface texture, the magnitude of the activation energy (60.0 kJ/mol or 14.6 {+-} 2.7 kcal/mol), the independence of rate on the stirring speed, the inverse relationship between the rate constant and the initial particle diameter, and the fractional reaction orders are also in agreement with a mechanism controlled by chemical reaction.

  3. Kinetics of pyrite oxidation in sodium carbonate solutions

    NASA Astrophysics Data System (ADS)

    Ciminelli, V. S. T.; Osseo-Asare, K.

    1995-04-01

    The kinetics of pyrite oxidation in sodium carbonate solutions were investigated in a stirred vessel, under temperatures ranging from 50 °C to 85 °C, oxygen partial pressures from 0 to 1 atm, particle size fractions from -150 + 106 to -38 + 10 µm (-100 + 150 Mesh to -400 Mesh + 10 µm) and pH values of up to 12.5. The rate of the oxidation reaction is described by the following expression: -dN/dt = SbkpO{2/0.5} [OH-]0.1 where N represents moles of pyrite, S is the surface area of the solid particles, b is a stoichiometric factor, k is an apparent rate constant, pO```2`` is the oxygen partial pressure, and [OH-] is the hydroxyl ion concentration. The experimental data were fitted by a stochastic model for chemically controlled reactions, represented by the following fractional conversion (X) vs time ( t) equation: (1-X)-2/3-1 = k STt The assumption behind this model, i.e., surface heterogeneity leading to preferential dissolution, is supported by the micrographs of reacted pyrite particles, showing pits created by localized dissolution beneath an oxide layer. In addition to the surface texture, the magnitude of the activation energy (60.9 kJ/mol or 14.6 ± 2.7 kcal/mol), the independence of rate on the stirring speed, the inverse relationship between the rate constant and the initial particle diameter, and the fractional reaction orders are also in agreement with a mechanism controlled by chemical reaction.

  4. 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.

  5. Bioleaching of pyrite by Thiobacillus ferrooxidans: fixed grains electrode to study superficial oxidized compounds

    NASA Astrophysics Data System (ADS)

    Toniazzo, Valérie; Lazaro, Isabelle; Humbert, Bernard; Mustin, Christian

    1999-04-01

    An electrode with fixed pyrite grains on a graphite and silicon paste has been used to study the electrochemical processes at the surface of powdered pyrite during bioleaching by Thiobacillus ferrooxidans. The study of an air-oxidized pyrite shows that the fixed grains electrode (FGE) is more sensitive than the classical Carbon Paste Electrode (CPE) already used by different authors to characterize various oxides and sulfurs. On the other hand, the concommitant Raman and electrochemical analysis of autoclaved pyrite shows that the cleaned mineral FeS 2 has no electrochemical reactivity, and points out that the electrochemical response of the oxidized mineral is exclusively due to the chemical compounds present at its surface. Therefore, the electrode acts as an efficient sensor for pyrite superficial oxidized phases, which are fundamental for the biooxidation process and is consequently very well adapted for the control of the oxidation state of pyrite powder during bioleaching by Thiobacillus ferrooxidans.

  6. 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.

  7. 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.

  8. 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.

  9. Kinetics of pyrite oxidation in sodium hydroxide solutions

    NASA Astrophysics Data System (ADS)

    Ciminelli, V. S. T.; Osseo-Asare, K.

    1995-08-01

    The kinetics of pyrite oxidation in sodium hydroxide solution were investigated in a stirred reactor, under temperatures ranging from 50 °C to 85 °C, oxygen partial pressures of up to 1 atm, particle size fractions from -150 + 106 to -38 + 10µm (-100 + 150 mesh to -400 mesh + 10 µ), and pH values of up to 12.5. The surface reaction is represented by the rate equation:- dN/dt = Sbk″pO0.5 2[oH- 0.25/(1 + k‴ pO2 0.5) where N represents moles of pyrite, S is the surface area of the solid particles, k″ and k″ are constants, b is a stoichiometric factor, pO2 is the oxygen partial pressure, and [OH-] is the hydroxyl ion concentration. The corresponding fractional conversion ( X) vs time behavior follows the shrinking particle model for chemical reaction control: 1 - (1 - X)1/3 = k ct The rate increases with the reciprocal of particle size and has an activation energy of 55.6 kJ/mol (13.6 kcal/mol). The relationship between reaction rate and oxygen partial pressure resembles a Langmuir-type equation and thus suggests that the reaction involves adsorption or desorption of oxygen at the interface. The square-root rate law may be due to the adsorption of a dissociated oxygen molecule. The observed apparent reaction order with respect to the hydroxyl ion concentration is a result of a complex combination of processes involving the oxidation and nydrolysis of iron, oxidation and hydrolysis of sulfur, and the oxygen reduction.

  10. Effects of phospholipid on pyrite oxidation in the presence of autotrophic and heterotrophic bacteria

    NASA Astrophysics Data System (ADS)

    Hao, Jun; Murphy, Riley; Lim, Eelin; Schoonen, Martin A. A.; Strongin, Daniel R.

    2009-07-01

    Pyrite oxidation occurring in solutions containing iron oxidizing autotrophic bacteria, Acidithiobacillus ferrooxidans ( A. ferrooxidans), and/or heterotrophic bacteria, Acidiphilium acidophilum ( A. acidophilum), has been investigated. Under the conditions used, the amount of pyrite oxidized in the presence of both species was similar to the amount oxidized in the presence of A. ferrooxidans alone over a period of 30 days. Pretreatment of pyrite with the phospholipid, [1,2-bis(10,12-tricosadiynoyl)- sn-glycero-3-phosphocholine (23:2 Diyne PC)], to form an adsorbed organic layer reduced the amount of pyrite oxidation in the absence of bacteria and in the presence of A. ferrooxidans. The addition of lipid to pyrite prior to its exposure to a mixed A. ferrooxidans/ A. acidophilum solution also showed initial oxidation suppression. However, after 4-5 days the effectiveness of the lipid in suppressing pyrite oxidation was lost and oxidation of the mineral proceeded at a rate that was similar to lipid-free pyrite in the presence of both microbial populations. If, however, lipid/pyrite was pretreated with UV radiation to induce cross-linking of the lipid tails (via polymerization of diacetylene groups in the tails), the lipid layer showed a strong suppression of pyrite oxidation for up to at least 30 days in the presence of both microbial populations. It was also shown with in situ atomic force microscopy (AFM) that the introduction of lipid to pyrite with colonized A. ferrooxidans led to the displacement of a fraction of surface bound bacteria. This lipid-induced displacement was confirmed by ex situ attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR).

  11. Rate Equations and Kinetic Parameters of the Reactions Involved in Pyrite Oxidation by Thiobacillus ferrooxidans.

    PubMed

    Lizama, H M; Suzuki, I

    1989-11-01

    Rate equations and kinetic parameters were obtained for various reactions involved in the bacterial oxidation of pyrite. The rate constants were 3.5 muM Fe per min per FeS(2) percent pulp density for the spontaneous pyrite dissolution, 10 muM Fe per min per mM Fe for the indirect leaching with Fe, 90 muM O(2) per min per mg of wet cells per ml for the Thiobacillus ferrooxidans oxidation of washed pyrite, and 250 muM O(2) per min per mg of wet cells per ml for the T. ferrooxidans oxidation of unwashed pyrite. The K(m) values for pyrite concentration were similar and were 1.9, 2.5, and 2.75% pulp density for indirect leaching, washed pyrite oxidation by T. ferrooxidans, and unwashed pyrite oxidation by T. ferrooxidans, respectively. The last reaction was competitively inhibited by increasing concentrations of cells, with a K(i) value of 0.13 mg of wet cells per ml. T. ferrooxidans cells also increased the rate of Fe production from Fe plus pyrite. PMID:16348054

  12. 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.

  13. 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.

  14. Pyrite oxidation by hexavalent chromium: investigation of the chemical processes by monitoring of aqueous metal species.

    PubMed

    Demoisson, Frédéric; Mullet, Martine; Humbert, Bernard

    2005-11-15

    Pyrite, an iron sulfide, occurs in many soils and sediments, making it an important natural reductant of toxic metal pollutants. This study investigated the processes leading to aqueous Cr(VI) reduction by pyrite in a closed thermostated (25 +/- 0.1 degrees C) system and under an argon atmosphere. Synthetic pyrite suspensions were reacted with a range of Cr(VI) solutions from 0 to 7 x 10(-4) M and at pH 2-8. Metal species concentrations were continuously monitored during a period lasting approximately 20 h. Preliminary experiments carried out in acidic media without Cr(VI) have shown that some pyrite dissolution occurred. Then, metal species concentration changes with time during pyrite oxidation by Cr(VI) solutions exhibited two distinct trends depending on the complete or incomplete Cr(VI) removal. As long as chromate existed in solution, the Cr-(Ill) to Fe(lIl) ratio was found to be an effective parameter to investigate the pyrite reaction stoichiometry with Cr(VI). Experimental values close to 2 suggest that sulfur compounds with oxidation states between 0 and 2 should be formed during pyrite oxidation by Cr(VI). If Cr(VI) was completely reduced from solution, then the pyrite oxidation by Fe(lll) ions took place to generate ferrous ions. PMID:16323772

  15. Pyrite oxidation in unsaturated aquifer sediments. Reaction stoichiometry and rate of oxidation.

    PubMed

    Andersen, M S; Larsen, F; Postma, D

    2001-10-15

    The oxidation of pyrite (FeS2) contained in unsaturated aquifer sediment was studied by sediment incubation in gas impermeable polymer laminate bags. Reaction progress was followed over a period of nearly 2 months by monitoring the gas composition within the laminate bag. The gas phase in the incubation bags became depleted in O2 and enriched in CO2 and N2 and was interpreted as due to pyrite oxidation in combination with calcite dissolution. Sediment incubation provides a new method to estimate low rates of pyrite oxidation in unsaturated zone aquifer sediments. Oxidation rates of up to 9.4 x 10(-10) mol FeS2/g x s are measured, and the rates are only weakly correlated with the sediment pyrite content. The reactivity of pyrite, including the inhibition by FeOOH layers formed on its surface, apparently has a major effect on the rate of oxidation. The code PHREEQC 2.0 was used to calculate the reaction stoichiometry and partitioning of gases between the solution and the gas phase. Pyrite oxidation with concurrent calcite dissolution was found to be consistent with the experimental data while organic carbon oxidation was not. The reaction involves changes in the total volume of the gas phase. The reaction scheme predicts the volume of O2 gas consumed to be larger than of CO2 produced. In addition the solubility of CO2 in water is about 30 times larger than of O2 causing a further decrease in total gas volume. The change in total gas volume therefore also depends on the gas/water volume ratio and the lower the ratio the more pronounced the loss of volume will be. Under field conditions the change in total volume may amount up to 20% in the absence of calcite and over 10% in the presence of calcite. Such changes in gas volume during the oxidation of pyrite are expected to result in pressure gradients causing advective transport of gaseous oxygen. PMID:11686369

  16. 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.

  17. 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.

  18. 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

  19. 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.

  20. Effects of Cinnabar on Pyrite Oxidation by Thiobacillus ferrooxidans and Cinnabar Mobilization by a Mercury-Resistant Strain

    PubMed Central

    Baldi, Franco; Olson, Gregory J.

    1987-01-01

    The effect of cinnabar on pyrite oxidation by mercury-sensitive and mercury-resistant strains of Thiobacillus ferrooxidans was investigated by using percolation columns. Mercury-resistant strains oxidized pyrite in pyrite-cinnabar mixtures (1 and 10%, wt/wt), whereas a mercury-sensitive strain did not. Elemental mercury was produced by the mercury-resistant strains growing in the pyrite-cinnabar mixtures in percolation columns and in flasks containing cinnabar only. Manometric experiments showed that cinnabar had little effect on oxygen uptake of mercury-sensitive or mercury-resistant cells growing on ferrous sulfate, pyrite, or pyrite-ferrous sulfate mixtures. In addition, shake flask leaching experiments showed that cinnabar had little effect on pyrite oxidation at 1% (wt/wt) but inhibited growth of mercury-sensitive and mercury-resistant strains at 10%. Mercury-resistant strains were unable to grow on cinnabar as an energy source. PMID:16347321

  1. 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.

  2. 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

  3. 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

  4. 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.

  5. The iron-coating role on the oxidation kinetics of a pyritic sludge doped with fly ash

    NASA Astrophysics Data System (ADS)

    Pérez-López, Rafael; Cama, Jordi; Nieto, José Miguel; Ayora, Carles

    2007-04-01

    The present study examines the processes that control the oxidation attenuation of a pyrite-rich sludge (72 wt% pyrite) from the Iberian Pyrite Belt by the buffer capacity of a fly ash from Los Barrios power station (S Spain), using saturated column experiments. In addition, in order to understand the behaviour of both materials inside these experiments, a fly-ash leaching test and flow-through experiments with pyritic sludge were carried out. The fly-ash leaching test showed that after leaching this material with a slightly acid solution (Millipore MQ water; pH 5.6) the pH raised up to 10.2 and that the metals released by the fly-ash dissolution did not increase significantly the metal concentrations in the output solutions. The flow-through experiments with the pyritic sludge were performed at pH 9, 22 °C and O 2 partial pressure of 0.21 atm, to calculate the dissolution rate of this residue simulating the fly-ash addition. In the experiments Fe bearing oxyhydroxides precipitated as the sludge dissolved. In two non-stirred experiments the iron precipitates formed Fe-coatings on the pyrite surfaces preventing the interaction between the oxidizing agents and the pyrite grains, halting pyrite oxidation (this process is known as pyrite microencapsulation), whereas in two stirred experiments, stirring hindered the iron precipitates to coat the pyrite grains. Thus, based on the release of S (aqueous sulphate) the steady-state pyritic sludge dissolution rate obtained was 9.0 ± 0.2 × -11 mol m -2 s -1. In the saturated column experiments, the sludge dissolution was examined at acidic and basic pH at 22 °C and oxygen-saturated atmosphere. In a saturated column experiment filled with the pyritic sludge, pyrite oxidation occurred favourably at pH approx. 3.7. As the leachates of the fly ash yielded high basic pH, in another saturated column, consisting of an initial thick layer of fly-ash material and a layer of pyritic sludge, the pyrite dissolution took place at p

  6. 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

  7. 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

  8. 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.

  9. 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.

  10. 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.

  11. Pyrite (FeS 2) oxidation: A sub-micron synchrotron investigation of the initial steps

    NASA Astrophysics Data System (ADS)

    Chandra, Anand P.; Gerson, Andrea R.

    2011-10-01

    Pyrite is an environmentally significant mineral being the major contributor to acid rock drainage. Synchrotron based SPEM (scanning photoelectron microscopy) and micro-XPS (X-ray photoelectron spectroscopy) have been used to characterise fresh and oxidised pyrite (FeS 2) with a view to understanding the initial oxidation steps that take place during natural weathering processes. Localised regions of the pyrite surface containing Fe species of reduced coordination have been found to play a critical role. Such sites not only initiate the oxidation process but also facilitate the formation of highly reactive hydroxyl radical species, which then lead the S oxidation process. Four different S species are found to be present on fresh fractured pyrite surfaces: S 22-(bulk) (4-fold coordination), S 22-(surface) (3-fold coordination), S 2- and S 0/S n2- (metal deficient sulfide and polysulfide respectively). These species were found to be heterogeneously distributed on the fractured pyrite surface. Both O 2 and H 2O gases are needed for effective oxidation of the pyrite surface. The process is initiated when O 2 dissociatively and H 2O molecularly adsorb onto the surface Fe sites where high dangling bond densities exist. H 2O may then dissociate to produce rad OH radicals. The adsorption of these species leads to the formation of Fe-oxy species prior to the formation of sulfoxy species. Evidence suggests that Fe-O bonds form prior to Fe-OH bonds. S oxidation occurs through interactions of rad OH radicals formed at the Fe sites, with formation of SO 42- occurring via S 2O 32-/SO 32- intermediates. The pyrite oxidation process is electrochemical in nature and was found to occur in patches, where site specific adsorption of O 2 and H 2O has occurred. Fe and S oxidation was found to occur within the same area of oxidation probably in atomic scale proximity. Furthermore, the O in SO 42- arises largely from H 2O; however, depending on the surface history, SO 42- formed early in

  12. 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.

  13. Soluble microbial products decrease pyrite oxidation by ferric iron at pH < 2.

    PubMed

    Yacob, Tesfayohanes; Pandey, Sachin; Silverstein, Joann; Rajaram, Harihar

    2013-08-01

    Research on microbial activity in acid mine drainage (AMD) has focused on transformations of iron and sulfur. However, carbon cycling, including formation of soluble microbial products (SMP) from cell growth and decay, is an important biogeochemical component of the AMD environment. Experiments were conducted to study the interaction of SMP with soluble ferric iron in acidic conditions, particularly the formation of complexes that inhibit its effectiveness as the primary oxidant of pyrite during AMD generation. The rate of pyrite oxidation by ferric iron in sterile suspensions at pH 1.8 was reduced by 87% in the presence of SMP produced from autoclaved cells at a ratio of 0.3 mg DOC per mg total soluble ferric iron. Inhibition of pyrite oxidation by SMP was shown to be comparable to, but weaker than, the effect of a chelating synthetic siderophore, DFAM. Two computational models incorporating SMP complexation were fitted to experimental results. Results suggest that bacterially produced organic matter can play a role in slowing pyrite oxidation. PMID:23777272

  14. 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.

  15. 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.

  16. Rising groundwater tables in partly oxidized pyrite bearing dump-sediments: Column study and modelling approach

    NASA Astrophysics Data System (ADS)

    Kohfahl, Claus; Pekdeger, Asaf

    2006-12-01

    SummaryThis paper reports the hydrogeochemical modelling of reactions that take place during the uptake of weathering products by a rising watertable into a partly oxidized pyrite bearing sediment. The anoxic material used for the column, which is 2 m long, was taken from a core while drilling into a pyrite bearing sediment with an average pyrite content of 0.04 wt%. After packing the column it was drained and maintained in an unsaturated state over a period of 107 days to allow oxygen supply and pyrite weathering. During this period oxygen breakthrough curves were measured. After 108 days the column was flooded with distilled anoxic water from the bottom to the top with an average water table rise of 5 cm per day. The chemical composition of the pore water in the saturated zone as well as the water saturation and the oxygen contents have been monitored over the profile of the column. The compositions of the water samples at different depths of the column were modelled with PHREEQC, defining a one-dimensional reactive transport model regarding the mixing process between the incoming flooding water and the residual pore water of the drained period. Kinetic relations were implemented to account for source terms of acids and acid generating components released during the drained period. This study showed that the evolution of the rising water table can be characterized by almost immediate uptake of gypsum and by kinetically controlled dissolution of pyrite weathering products in combination with mixing processes and dispersion.

  17. 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

  18. 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.

  19. Biogeochemical processes governing natural pyrite oxidation and release of acid metalliferous drainage.

    PubMed

    Chen, Ya-ting; Li, Jin-tian; Chen, Lin-xing; Hua, Zheng-shuang; Huang, Li-nan; Liu, Jun; Xu, Bi-bo; Liao, Bin; Shu, Wen-sheng

    2014-05-20

    The oxidative dissolution of sulfide minerals (principally pyrite) is responsible for the majority of acid metalliferous drainage from mine sites, which represents a significant environmental problem worldwide. Understanding the complex biogeochemical processes governing natural pyrite oxidation is critical not only for solving this problem but also for understanding the industrial bioleaching of sulfide minerals. To this end, we conducted a simulated experiment of natural pyrite oxidative dissolution. Pyrosequencing analysis of the microbial community revealed a distinct succession across three stages. At the early stage, a newly proposed genus, Tumebacillus (which can use sodium thiosulfate and sulfite as the sole electron donors), dominated the microbial community. At the midstage, Alicyclobacillus (the fifth most abundant genus at the early stage) became the most dominant genus, whereas Tumebacillus was still ranked as the second most abundant. At the final stage, the microbial community was dominated by Ferroplasma (the tenth most abundant genus at the early stage). Our geochemical and mineralogical analyses indicated that exchangeable heavy metals increased as the oxidation progressed and that some secondary sulfate minerals (including jarosite and magnesiocopiapite) were formed at the final stage of the oxidation sequence. Additionally, we propose a comprehensive model of biogeochemical processes governing the oxidation of sulfide minerals. PMID:24730689

  20. 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.

  1. 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.

  2. 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.

  3. Oxidation of coal and coal pyrite mechanisms and influence on surface characteristics. Final report

    SciTech Connect

    Doyle, F.M.

    1996-01-26

    Coal oxidation has been studies extensively in previous work. However, there is still no general agreement concerning the mechanisms of oxidation. Moreover, the oxidation behavior of coal and mineral matter have generally been regarded as separate processed. There is appreciable evidence that organic and inorganic oxidation process are actually coupled, consequently the changes in their surface properties induced by oxidation are difficult to predict. This makes the effectively of coal cleaning processes highly sensitive to the extent of weathering and oxidation that the coal has experienced. The objective of this research was to investigate the oxidation behavior of coal and coal pyrite, and to correlate the intrinsic physical and chemical properties of these minerals, along with changes resulting from oxidation, with these surface properties that would influence the behavior in physical cleaning processes.

  4. 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.

  5. 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.

  6. 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.

  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. 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

  10. 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

  11. 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.

  12. 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.

  13. 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. PMID:26938493

  14. 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

  15. 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

  16. Oxidation of sulphide minerals--I: determination of ferrous and ferric iron in samples of pyrrhotite, pyrite and chalcopyrite.

    PubMed

    Steger, H F

    1977-04-01

    A method has been developed for determining small amounts of both ferrous and ferric iron in oxidized samples of pyrrhotite, pyrite and chalcopyrite. The oxidized iron is selectively dissolved in 10M phosphoric acid under reflux and can be determined with the accuracy generally accepted in chemical phase analysis. PMID:18962075

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

    PubMed

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

    2013-10-01

    The microbial ecology of the pyrite-pyrolusite bioleaching system and its interaction with ore has not been well-described. A 16S rRNA gene clone library was created to evaluate changes in the microbial community at different stages of the pyrite-pyrolusite bioleaching process in a shaken flask. The results revealed that the bacterial community was disturbed after 5 days of the reaction. Phylogenetic analysis of 16S rRNA sequences demonstrated that the predominant microorganisms were members of a genus of sulfur-oxidizing bacteria, Thiomonas sp., that subsequently remained dominant during the bioleaching process. Compared with iron-oxidizing bacteria, sulfur-oxidizing bacteria were more favorable to the pyrite-pyrolusite bioleaching system. Decreased pH due to microbial acid production was an important condition for bioleaching efficiency. Iron-oxidizing bacteria competed for pyrite reduction power with Mn(IV) in pyrolusite under specific conditions. These results extend our knowledge of microbial dynamics during pyrite-pyrolusite bioleaching, which is a key issue to improve commercial applications. PMID:23673133

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

    SciTech Connect

    Doyle, F.M.

    1995-05-31

    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. Work during the nineteenth quarter has concluded studies of the surface functional groups produced on coal by severe thermal and chemical oxidation, and on investigating the partition of metal ions between such strongly oxidized coal samples and aqueous solutions. This partitioning behavior was being followed to obtain further information on the chemistry of the coal surfaces after different oxidation treatments. Adsorption isotherms for the uptake of Cd{sup 2+} on coal oxidized by different methods were obtained, and these and the Cu{sup 2+} adsorption isotherms reported in the last report have been scrutinized, and interpreted more exhaustively. The apparent discrepancies noted in the last report for the analysis of surface functional groups have been investigated further. The adsorption behavior has been related to the surface chemistry of Upper Freeport coal oxidized by different methods.

  19. [Thermoacidophilic micirobial community oxidizing the gold-bearing flotation concentrate of a pyrite-arsenopyrite ore].

    PubMed

    Paniushkina, A E; Tsaplina, I A; Grigor'eva, N V; Kondrat'eva, T F

    2014-01-01

    An aboriginal community of thermophilic acidophilic chemolithotrophic microorganisms (ACM) was isolated from a sample of pyrite gold-bearing flotation concentrateat 45-47 degrees C and pH 1.8-2.0. Compared to an experimental thermoacidophilic microbial consortium formed in the course of cultivation in parallel bioreactors, it had lower rates of iron leaching and oxidation, while its rate of sulfur oxidation was higher. A new thermophilic acidophilic microbial community was obtained by mutual enrichment with the micioorganisms from thie experimental and aboriginal communities during oxidation of sulfide ore flotation concentrate at 47 degrees C. The dominant bacteria of this new ACM community were Acidithiobacillus caldus strains (the most active sulfur oxidizers) and Sulfobacillus thermotolerans strains (active oxidizers of both iron and sulfur), while iron-oxidizing archaea of the family Ferroplasmaceae and heterotrophic bacteria Alicyclobacillus tolerans were the minor components. The new ACM community showed promise for leaching/oxidation of sulfides from flotation concentrates at high pulp density (S:L = 1:4). PMID:25844467

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

    NASA Astrophysics Data System (ADS)

    Balci, Nurgul; Shanks, Wayne C.; Mayer, Bernhard; Mandernack, Kevin W.

    2007-08-01

    To better understand reaction pathways of pyrite oxidation and biogeochemical controls on δ 18O and δ 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 O 2 as an oxidizing agent and under anaerobic conditions by using dissolved Fe(III) aq as an oxidant with varying δ 18O H 2O 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 δ 34S SO 4 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 (O 2) 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 O 2 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 (ε18O-HO) of ˜3.5‰ was determined for the anaerobic (biological and abiotic) experiments. This measured ε18OO value was then

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

    USGS Publications Warehouse

    Balci, N.; Shanks, Wayne C., III; 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. Morphology and formation mechanism of pyrite induced by the anaerobic oxidation of methane from the continental slope of the NE South China Sea

    NASA Astrophysics Data System (ADS)

    Zhang, Mei; Konishi, Hiromi; Xu, Huifang; Sun, Xiaoming; Lu, Hongfeng; Wu, Daidai; Wu, Nengyou

    2014-10-01

    In order to understand the response of authigenic pyrite to gas hydrate geo-systems, pyrite tubes or rods at the sulfate-methane transition (SMT) zone of core GC10 from the northern continental slope of the South China Sea (SCS) were investigated. In situ X-ray diffraction (XRD) results show that the pyrite tube consists of pyrite micro-crystals with trace amount of graphite in the inner tube. Scanning electron microscope (SEM) observations of pyrite tubes indicate various aggregations in the form of framboidal, euhedral, and colloidal pyrite microcrystals. Typical framboidal pyrite is considered as packing of octahedral microcrystals. Interestingly, many framboids in the tubes consist of round or irregular microcrystals and have an outer crust that consists of secondary pyrite. The size of the framboids in the inner wall of the tube is larger than that in the middle wall or foraminifer-filled pyrite. High-resolution transmission electron microscopic (HRTEM) images show marcasite lamellae defects in the spherulitic pyrite crystals, which reveal different solution conditions during the pyrite precipitation. Nano-foil-like graphitic carbon was observed to be closely associated with the pyrite spherules. The occurrence of both marcasite layers and nano-foil-like graphitic carbon suggest that the migration of methane from deep sediment. It is suggested that the formation of pyrite serves as a catalyst during the reaction from methane to elemental carbon under the anaerobic oxidation of methane. Meanwhile, this reaction results in local acidification of the solution inside the pyrite tubes, which favors marcasite lamellae growth on the host pyrite substrate.

  3. Oxidation of coal and coal pyrite mechanisms and influence on surface characteristics. [Quarterly] technical progress report, April--June 1993

    SciTech Connect

    Doyle, F.M.

    1993-06-30

    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 eleventh quarter, dry thermal oxidation tests were done on coal samples from the Pennsylvania State Coal Bank. As-received and oxidized coal samples were studied by ion-exchange methods to determine the carboxylate and phenolic group concentrations. Film flotation tests were done to characterize the flotability of as-received and oxidized coals. In addition, electrokinetic tests were done on different coals, to obtain information pertinent to the selection of flotation reagents. DRIFT analysis was done to characterize the structure of coals.

  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. 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

  6. 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

  7. Inhibition of pyrite oxidation by surface coating agents: Batch and field studies

    NASA Astrophysics Data System (ADS)

    Choi, Jaeyoung; Do Gee, Eun; Yun, Hyun-Shik; Ram Lee, Woo; Park, Young-Tae

    2013-04-01

    The potential of several surface coating agents to inhibit the oxidation of metal sulfide minerals from Young-Dong coal mine and the Il-Gwang gold mine was examined by conducting laboratory scale batch experiments and field tests. Powdered pyrite as a standard sulfide mineral and rock samples from two mine outcrops were mixed with six coating agents (KH2PO4, MgO and KMnO4 as chemical agents, and apatite, cement and manganite as mineral agents) and incubated with oxidizing agents (H2O2 or NaClO). For the observed time period (8 days), Young-Dong coal mine samples exhibited the least sulfate (SO42-) production in the presence of KMnO4 (16%) or cement (4%) while, for Il-Gwang mine samples, the least SO42- production was observed in presence of KH2PO4 (8%) or cement (2%) compared to control. Field-scale pilot tests at the Il-Gwang site also showed that addition of KH2PO4 decreased SO42- production from 200 to 13 mg L-1 and it also reduced Cu and Mn from 8 and 3 mg L-1, respectively to <0.05 mg L-1 (below ICP-OES detection limits). The experimental results suggested that the use of surface coating agents is a promising alternative for sulfide oxidation inhibition at acid mine drainage sites.

  8. 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.

  9. 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.''

  10. 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.

  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. Simulation of pyrite oxidation in fresh mine tailings under near-neutral conditions.

    PubMed

    Alakangas, Lena; Lundberg, Angela; Nason, Peter

    2012-08-01

    Sulphidic residual products from ore processing may produce acid rock drainage, when exposed to oxygen and water. Predictions of the magnitude of ARD and sulphide oxidation rates are of great importance in mine planning because they can be used to minimize or eliminate ARD and the associated economic and environmental costs. To address the lack of field data of sulphide oxidation rate in fresh sulphide-rich tailings under near-neutral conditions, determination and simulation of the rate was performed in pilot-scale at Kristineberg, northern Sweden. The quality of the drainage water was monitored, along with oxygen and carbon dioxide concentrations. The chemical composition of the solid tailings was also determined. The field data were compared to predictions from simulations of pyrite oxidation using a 1-D numerical model. The simulations' estimates of the amount of Fe and S released over a seven year period (52 kg and 178 kg, respectively) were in reasonably good agreement with those obtained by analysing the tailings (34 kg and 155 kg, respectively). The discrepancy is probably due to the formation of secondary precipitates such as iron hydroxides and gypsum; which are not accounted for in the model. The observed mass transport of Fe and S (0.05 and 1.0 kg per year, respectively) was much lower than expected on the basis of the simulations and the core data. Neutralization reactions involving carbonates in the tailings result in a near-neutral pH at all depths except at the oxidation front (pH < 5), indicating that the dissolution of carbonates was too slow for the acid to be neutralized, which instead neutralized deeper down in the tailings. This was also indicated by the reduced abundance of solid Ca at greater depths and the high levels of carbon dioxide both of which are consistent with the dissolution of carbonates. It could be concluded that the near-neutral pH in the tailings has no decreasing effect on the rate of sulphide oxidation, but does reduce the

  13. Oxidation state of gold and arsenic in gold-bearing arsenian pyrite

    SciTech Connect

    Simon, G.; Huang, H.; Penner-Hahn, J.E.; Kesler, S.E.; Kao, L.S.

    1999-07-01

    XANES measurements on gold-bearing arsenian pyrite from the Twin Creeks Carlin-type gold deposits show that gold is present as both Au{sup 0} and Au{sup 1+} and arsenic is present as As{sup 1{minus}}. Au{sup 0} is attributed to sub-micrometer size inclusions of free gold, whereas Au{sup 1+} is attributed to gold in the lattice of the arsenian pyrite. STEM observations suggest that As{sup 1{minus}} is probably concentrated in angstrom-scale, randomly distributed layers with a marcasite or arsenopyrite structure. Ionic gold (Au{sup 1+}) could be concentrated in these layers as well, and is present in both twofold- and fourfold-coordinated forms, with fourfold-coordinated Au{sup 1+} more abundant. Twofold-coordinated Au{sup 1+} is similar to gold in Au{sub 2}S in which it is linearly coordinated to two sulfur atoms. The nature of fourfold-coordinated Au{sup 1+} is not well understood, although it might be present as an Au-As-S compound where gold is bonded in fourfold coordination to sulfur and arsenic atoms, or in vacancy positions on a cation site in the arsenian pyrite. Au{sup 1+} was probably incorporated into arsenian pyrite by adsorption onto pyrite surfaces during crystal growth. The most likely compound in the case of twofold-coordinated Au{sup 1+} was probably a tri-atomic surface complex such as S{sub pyrite}-Au{sup 1+}-S{sub bi-sulfide}H or Au{sup 1+}-S-Au{sup 1+}. The correlation between gold and arsenic might be related to the role of arsenic in enhancing the adsorption of gold complexes of this type on pyrite surfaces, possibly through semiconductor effects.

  14. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2008-12-01

    The triple isotopes of oxygen (Δ17O' = δ17O'-0.528 × δ18O' using logarithmic deltas) can trace the oxygen sources of sulfate produced during sulfide oxidation, an important biogeochemical process on Earth's surface and possibly also on Mars [1]. δ18OSO4 compositions are determined by the isotopic selectivity of the mechanism(s) responsible for their changes, and the δ18O value of the reactants (O2 vs. H2O). The relative proportional importance and contribution of each of those sources and mechanisms, as well as their associated isotopic fractionations, are not well understood. We are investigating the use of Δ 17O as a quantitative and qualitative tracer for the different processes and oxygen sources involved in sulfate production. Δ17O signatures are distinct fingerprints of these reservoirs, independent of fractionation factors that can be ambiguous. We conducted controlled abiotic and biotic (Acidithiobacillus ferrooxidans, A.f.) laboratory experiments in which water was spiked with 18O, allowing us to quantify the sources of sulfate oxygen and therefore the processes attending sulfate formation. Results of this Δ17O tracer study show that A.f. microbes initiate pyrite S-oxidation within hours of exposure, and that sulfate is produced from ~90% atmospheric oxygen. This initial lag-phase (< 3 days) is characterized by subtle and multiple changes in oxygen source and contribution that is likely due to the adjustment of the microbial metabolism from S to Fe2+-oxidation. A more detailed understanding of the microbial mechanisms and behavior in the initial lag-phase will aid in the understanding of the ecological conditions required for microbial populations to establish and survive. An exponential phase of growth, facilitated by microbial Fe2+-oxidation, follows. The source of sulfate rapidly switches to abiotic sulfide oxidation during exponential growth and the source of oxygen switches from atmospheric O2 to nearly ~100% water. Pending acquisition of

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

    NASA Astrophysics Data System (ADS)

    Ma, Yingqun; Lin, Chuxia

    2013-06-01

    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.

  17. 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

  18. 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

  19. 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.

  20. 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.

  1. 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.

  2. Mechanistic aspects of pyrite oxidation in an oxidizing gaseous environment: an in situ HATR-IR isotope study.

    PubMed

    Usher, Courtney R; Paul, Kristian W; Narayansamy, Jayakumar; Kubicki, James D; Sparks, Donald L; Schoonen, Martin A A; Strongin, Daniel R

    2005-10-01

    The reaction of FeS2 (pyrite) with gaseous H2O, O2, and H2O/O2 was investigated using horizontal attenuated total reflection Fourier transform infrared spectroscopy (HATR-FTIR). Spectra were interpreted with the aid of hybrid molecular orbital/density functional theory calculations of sulfate-iron hydroxide clusters. Reaction of pyrite in gaseous H2O led primarily to the formation of iron hydroxide on pyrite. Exposure of the pyrite to gaseous O2 after exposure to H2O vapor led to the formation of sulfur oxyanions that included SO42-. Isotopic labeling experiments showed that after this exposure sequence the oxygen in the sulfate product was primarily derived from the H2O reactant. If, however, pyrite was exposed to gaseous O2 prior to pure H2O vapor, both SO42- and iron oxyhydroxide became significant products. Isotopic rabeling experiments using the O2-then-H2O sequence showed that the oxygen in the SO42- product was derived from both H2O and O2. The results indicate that H2O and O2 exhibit a competitive adsorption on pyrite, with H2O blocking surface sites for O2 adsorption. The extent of oxygen incorporation from either the H2O or the O2 component into the surface-bound sulfur oxyanion product appears to be a strong function of the relative concentration ratio of the reactant H2O and O2. PMID:16245830

  3. 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.

  4. The mobilization of toxic trace elements due to pyrite oxidation at the mega-nourishment The Sand Motor, the Netherlands

    NASA Astrophysics Data System (ADS)

    Pit, I.; Doodeman, L.; Van Heteren, S.; van Bruggen, M.; Griffioen, J.

    2014-12-01

    Pilot project "The Sand Motor" is a 21.5 million m3 nourishment of sandy sediment situated along the coast of the Netherlands close to The Hague (figure 1). It was constructed in 2011 and initially spans the shore over a 2.4 km stretch and extends up to 1 km offshore creating a hook-shaped peninsula. Due to wind, waves and currents the Sand Motor will gradually change in shape and eventually be fully incorporated into the dunes and beach. This concept is expected to be more environmentally friendly compared to traditional beach and shoreface nourishments. The aim of this project is to understand how oxidation changed the geochemistry of the sediment applied and to address possible toxic element mobilization. The sediment was taken 10 km out of shore from the sea floor, which was at a depth of 20 m. Grab samples of the upper 25 cm seabed analyzed for geochemical mapping of Southern North Sea sediments, show locally high contents of sulfur, iron and trace elements like arsenic indicating presence of pyrite with impurities. Sediment was removed to a maximum depth of 6 m below sea floor, reaching different geological layers including bog iron ore layers. Different degrees of pyrite oxidation are expected with depth at the Sand Motor. First, minimum oxidation when sediment was deposited from the ship directly by opening the bottom floor, which is now present under water at the deepest part of the nourishment. Second, limited oxidation when sediment was applied from the ship under high pressure through the air, and settled below sea level. Last, maximum oxidation when the same method was used but the sediment remains located in a surface layer having a maximum height of 4 m above sea level. At the Sand Motor, samples were taken of surface water, pore water and sediment from the surface to a depth of 10 m, the bottom of the nourishment. Analyses show that pyrite oxidation has occurred above sea level and mobilization of arsenic is present up to a maximum concentration of

  5. 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.

  6. Oxidation of coal and coal pyrite mechanisms and influence on surface characteristics. Technical progress report, May 31, 1995

    SciTech Connect

    Doyle, F.M.

    1995-12-31

    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. Work during the nineteenth quarter has concluded studies of the surface functional groups produced on coal by severe thermal and chemical oxidation, and on investigating the partition of metal ions between such strongly oxidized coal samples and aqueous solutions. This partitioning behavior was being followed to obtain further information on the chemistry of the coal surfaces after different oxidation treatments. Adsorption isotherms for the uptake of Cd{sup 2+} on coal oxidized by different methods were obtained, and these and the Cu{sup 2+} adsorption isotherms reported in the last report have been scrutinized, and interpreted more exhaustively. The apparent discrepancies noted in the last report for the analysis of surface functional groups have been investigated further. The adsorption behavior has been related to the surface chemistry of Upper Freeport coal oxidized by different methods.

  7. Different isotope and chemical patterns of pyrite oxidation related to lag and exponential growth phases of Acidithiobacillus ferrooxidans reveal a microbial growth strategy

    NASA Astrophysics Data System (ADS)

    Brunner, Benjamin; Yu, Jae-Young; Mielke, Randall E.; MacAskill, John A.; Madzunkov, Stojan; McGenity, Terry J.; Coleman, Max

    2008-06-01

    The solution chemistry during the initial (slow increase of dissolved iron and sulfate) and main stage (rapid increase of dissolved iron and sulfate) of pyrite leaching by Acidithiobacillus ferrooxidans (Af) at a starting pH of 2.05 shows significant differences. During the initial stage, ferrous iron (Fe2+) is the dominant iron species in solution and the molar ratio of produced sulfate (SO42-) and total iron (Fetot) is 1.1, thus does not reflect the stoichiometry of pyrite (FeS2). During the main stage, ferric iron (Fe3+) is the dominant iron species in solution and the SO42-:Fetot ratio is with 1.9, close to the stoichiometry of FeS2. Another difference between initial and main stage is an initial trend to slightly higher pH values followed by a drop during the main stage to pH 1.84. These observations raise the question if there are different modes of bioleaching of pyrite, and if there are, what those modes imply in terms of leaching mechanisms. Different oxygen and sulfur isotope trends of sulfate during the initial and main stages of pyrite oxidation confirm that there are two pyrite bioleaching modes. The biochemical reactions during initial stage are best explained by the net reaction FeS2 + 3O2 ⇒ Fe2+ + SO42- + SO2(g). The degassing of sulfur dioxide (SO2) acts as sink for sulfur depleted in 34S compared to pyrite, and is the cause of the SO42-:Fetot ratio of 1.1 and the near constant pH. During the exponential phase, pyrite sulfur is almost quantitatively converted to sulfate, according to the net reaction FeS2 + 15/4O2 + 1/2H2O ⇒ Fe3+ + 2SO42- + H+. We hypothesize that the transition between the modes of bioleaching of pyrite is due to the impact of the accumulation of ferrous iron, which induces changes in the metabolic activity of Af and may act as an inhibitor for the oxidation of sulfur species. This transition defines a fundamental change in the growth strategy of Af. A mode, where bacteria gain energy by oxidation of elemental sulfur to

  8. 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.

  9. Oxidation of detrital pyrite as a cause for Marcasite Formation in marine lag deposits from the Devonian of the eastern US

    NASA Astrophysics Data System (ADS)

    Schieber, Juergen

    2007-06-01

    Late Devonian black shale successions in the eastern US contain numerous discontinuities that are characterized by lags containing variable amounts of quartz sand mixed with reworked pyritic and phosphatic debris. These lags can be partially cemented by iron sulfides with a radial fibrous to massive morphology. Examination of iron sulfide cements via electron backscatter diffraction (EBSD) shows that these cements can consist entirely or partially of marcasite. It is proposed here that oxidation and dissolution of reworked pyrite debris led to favorable conditions for intermittent rapid marcasite formation by forcing a substantial pH drop in the surface sediment and by raising dissolved iron concentrations in the pore waters.

  10. 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.

  11. [Optimization of bioleaching and oxidation of gold-bearing pyrite-arsnopyrite ore concentrate in batch mode].

    PubMed

    Grigor'eva, N V; Tsaplina, I A; Paniushkina, A E; Kondrat'eva, T F

    2014-01-01

    Biooxidation of refractory gold-bearing pyrite-arsenopyrite flotation concentrate was optimized and aburidance of predominant groups in the community ofthermophilic acidophilic chemolithotrophic microorganisms at various stages ofbioleaching was determined. The optimal parameters for growth and leaching/oxidation of the mineral components of the concentrate were pSH 1.4, 1.6-1.8; 47.5 degrees C; and the following salt concentrations in the liquid phase (g/L): K2HPO4.3H2O, 0.53; (NH4)2SO4, 1.6 and MgSO4.7H2O, 2.5 (or (NH4)2SO4, 1.23; ammophos, 0.41; KOH, 0.1) with 0.03% yeast extract. The optimal conditions resulted in high growth rate, high levels of iron andarsenic leaching, of Fe2+ and S(2-)/S0 oxidation, and predominance of Acidithiobacillus caldus, Sulfobacillus spp., and Ferroplasma spp. in the community. PMID:25844468

  12. 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.``

  13. 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.

  14. 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.

  15. 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

  16. 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

  17. 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.

  18. 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. PMID:21350923

  19. 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

  20. Use of O2 consumption and CO2 production in kinetic cells to delineate pyrite oxidation-carbonate buffering and microbial respiration in unsaturated media.

    PubMed

    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 O2 consumption and CO2 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 O2 consumption and CO2 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 CO2 production to O2 consumption rates were 0.5 for lake sediment, 0.7 for forest soil, and 0.2 for gneissic waste rock. The different O2/CO2 ratios suggested that O2-CO2 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 O2 consumption and CO2 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 O2 and CO2 gas in waste-rock piles constructed upon the dewatered lake sediments. PMID:12935950

  1. 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.

  2. 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

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. Control of pyrite surface chemistry in physical coal cleaning

    SciTech Connect

    Luttrell, G.H.; Yoon, R.H.; Ou, Z.S.

    1992-06-24

    The successful separation of pyrite from coal by flotation is dependent to a large extent upon the selectivity of the process, and the use of a pyrite depressant is one of the most important and cost-effective techniques for achieving this. This report evaluates the effects of three factors on the floatability of pyrite. These are (1) the superficial oxidation of pyrite, (2) the contamination of pyrite surfaces by carbonaceous matter, and (3) pulp redox potentials. XPS (x-ray photoelectron spectroscopy) and IR spectrometry have been used to identify surface reaction products. Microflotation, laboratory-scale conventional flotation and microbubble column flotation were used to quantify the effects of these factors. It was found that low (reducing) pulp potentials are effective depressants of pyrite (more so for fresh, unoxidized samples than for oxidized samples), whilst at the same time do not materially affect coal flotation.

  9. Arsenic speciation in pyrite and secondary weathering phases, Mother Lode gold district, Tuolumne County, California

    SciTech Connect

    Savage, K.S.; Tingle, Tracy N.; O'Day, Peggy A.; Waychunas, Glenn A.; Bird, Dennis K.

    2004-10-27

    Arsenian pyrite, formed during Cretaceous gold mineralization, is the primary source of As along the Melones fault zone in the southern Mother Lode Gold District of California. Mine tailings and associated weathering products from partially submerged inactive gold mines at Don Pedro Reservoir, on the Tuolumne River, contain approx. 20-1300 ppm As. The highest concentrations are in weathering crusts from the Clio mine and nearby outcrops which contain goethite or jarosite. As is concentrated up to 2150 ppm in the fine-grained (<63 mu-m) fraction of these Fe-rich weathering products. Individual pyrite grains in albite-chlorite schists of the Clio mine tailings contain an average of 1.2 wt. percent As. Pyrite grains are coarsely zoned, with local As concentrations ranging from approx. 0 to 5 wt. percent. Electron microprobe, transmission electron microscope, and extended X-ray absorption fine-structure spectroscopy (EXAFS) analyses indicate that As substitutes for S in pyrite and is not present as inclusions of arsenopyrite or other As-bearing phases. Comparison with simulated EXAFS spectra demonstrates that As atoms are locally clustered in the pyrite lattice and that the unit cell of arsenian pyrite is expanded by approx. 2.6 percent relative to pure pyrite. During weathering, clustered substitution of As into pyrite may be responsible for accelerating oxidation, hydrolysis, and dissolution of arsenian pyrite relative to pure pyrite in weathered tailings. Arsenic K-edge EXAFS analysis of the fine-grained Fe-rich weathering products are consistent with corner-sharing between As(V) tetrahedra and Fe(III)-octahedra. Determinations of nearest-neighbor distances and atomic identities, generated from least-squares fitting algorithms to spectral data, indicate that arsenate tetrahedra are sorbed on goethite mineral surfaces but substitute for SO4 in jarosite. Erosional transport of As-bearing goethite and jarosite to Don Pedro Reservoir increases the potential for As

  10. Arsenic speciation in pyrite and secondary weathering phases, Mother Lode gold district, Tuolumne County, California

    SciTech Connect

    Savage, K.S.; Tingle, Tracy N.; O'Day, Peggy A.; Waychunas, Glenn A.; Bird, Dennis K.

    2004-10-27

    Arsenian pyrite, formed during Cretaceous gold mineralization, is the primary source of As along the Melones fault zone in the southern Mother Lode Gold District of California. Mine tailings and associated weathering products from partially submerged inactive gold mines at Don Pedro Reservoir, on the Tuolumne River, contain approx. 20-1300 ppm As. The highest concentrations are in weathering crusts from the Clio mine and nearby outcrops which contain goethite or jarosite. As is concentrated up to 2150 ppm in the fine-grained (<63 mu-m) fraction of these Fe-rich weathering products. Individual pyrite grains in albite-chlorite schists of the Clio mine tailings contain an average of 1.2 wt. percent As. Pyrite grains are coarsely zoned, with local As concentrations ranging from approx. 0 to 5 wt. percent. Electron microprobe, transmission electron microscope, and extended X-ray absorption fine-structure spectroscopy (EXAFS) analyses indicate that As substitutes for S in pyrite and is not p resent as inclusions of arsenopyrite or other As-bearing phases. Comparison with simulated EXAFS spectra demonstrates that As atoms are locally clustered in the pyrite lattice and that the unit cell of arsenian pyrite is expanded by approx. 2.6 percent relative to pure pyrite. During weathering, clustered substitution of As into pyrite may be responsible for accelerating oxidation, hydrolysis, and dissolution of arsenian pyrite relative to pure pyrite in weathered tailings. Arsenic K-edge EXAFS analysis of the fine-grained Fe-rich weathering products are consistent with corner-sharing between As(V) tetrahedra and Fe(III)-octahedra. Determinations of nearest-neighbor distances and atomic identities, generated from least-squares fitting algorithms to spectral data, indicate that arsenate tetrahedra are sorbed on goethite mineral surfaces but substitute for SO4 in jarosite. Erosional transport of As-bearing goethite and jarosite to Don Pedro Reservoir increases the potential for As

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. RECLAMATION OF PYRITIC WASTE

    EPA Science Inventory

    The reclamation of land used for the disposal of pyritic mine waste utilizing sewage sludge as a soil conditioner has been studied in laboratory greenhouse studies and a full-scale demonstration project. Analysis of samples revealed that some of the mining waste had a pH as low a...

  19. 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.

  20. 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.

  1. 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

  2. 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

  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; 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

  4. Conductive iron oxides accelerate thermophilic methanogenesis from acetate and propionate.

    PubMed

    Yamada, Chihaya; Kato, Souichiro; Ueno, Yoshiyuki; Ishii, Masaharu; Igarashi, Yasuo

    2015-06-01

    Anaerobic digester is one of the attractive technologies for treatment of organic wastes and wastewater, while continuous development and improvements on their stable operation with efficient organic removal are required. Particles of conductive iron oxides (e.g., magnetite) are known to facilitate microbial interspecies electron transfer (termed as electric syntrophy). Electric syntrophy has been reported to enhance methanogenic degradation of organic acids by mesophilic communities in soil and anaerobic digester. Here we investigated the effects of supplementation of conductive iron oxides (magnetite) on thermophilic methanogenic microbial communities derived from a thermophilic anaerobic digester. Supplementation of magnetite accelerated methanogenesis from acetate and propionate under thermophilic conditions, while supplementation of ferrihydrite also accelerated methanogenesis from propionate. Microbial community analysis revealed that supplementation of magnetite drastically changed bacterial populations in the methanogenic acetate-degrading cultures, in which Tepidoanaerobacter sp. and Coprothermobacter sp. dominated. These results suggest that supplementation of magnetite induce electric syntrophy between organic acid-oxidizing bacteria and methanogenic archaea and accelerate methanogenesis even under thermophilic conditions. Findings from this study would provide a possibility for the achievement of stably operating thermophilic anaerobic digestion systems with high efficiency for removal of organics and generation of CH4. PMID:25488041

  5. Interference of Nitrite with Pyrite under Acidic Conditions: Implications for Studies of Chemolithotrophic Denitrification.

    PubMed

    Yan, Ruiwen; Kappler, Andreas; Peiffer, Stefan

    2015-10-01

    Chemolithotrophic denitrification coupled to pyrite oxidation is regarded a key process in the removal of nitrate in aquifers. A common product is nitrite, which is a strong oxidant under acidic conditions. Nitrite may thus interfere with Fe(II) during acidic extraction, a procedure typically used to quantify microbial pyrite oxidation, in overestimating Fe(III) production. We studied the reaction between pyrite (5-125 mM) and nitrite (40-2000 μM) at pH 0, 5.5, and 6.8 in the absence and presence of oxygen. Significant oxidation of pyrite was measured at pH 0 with a yield of 100 μM Fe(III) after 5 mM pyrite was incubated with 2000 μM nitrite for 24 h. Dissolved oxygen increased the rate at pH 0. No oxidation of pyrite was observed at pH 5.5 and 6.8. Our data imply a cyclic model for pyrite oxidation by Fe(III) on the basis of the oxidation of residual Fe(II) by NO and NO2. Interference by nitrite could be avoided if nitrite was removed from the pyrite suspensions through a washing procedure prior to acidic extraction. We conclude that such interferences should be considered in studies on microbially mediated pyrite oxidation with nitrate. PMID:26335043

  6. A Supramolecularly Activated Radical Cation for Accelerated Catalytic Oxidation.

    PubMed

    Jiao, Yang; Li, Wan-Lu; Xu, Jiang-Fei; Wang, Guangtong; Li, Jun; Wang, Zhiqiang; Zhang, Xi

    2016-07-25

    Tuning the activity of radicals is crucial for radical reactions and radical-based materials. Herein, we report a supramolecular strategy to accelerate the Fenton reaction through the construction of supramolecularly activated radical cations. As a proof of the concept, cucurbit[7]uril (CB[7]) was introduced, through host-guest interactions, onto each side of a derivative of 1,4-diketopyrrolo[3,4-c]pyrrole (DPP), a model dye for Fenton oxidation. The DPP radical cation, the key intermediate in the oxidation process, was activated by the electrostatically negative carbonyl groups of CB[7]. The activation induced a drastic decrease in the apparent activation energy and greatly increased the reaction rate. This facile supramolecular strategy is a promising method for promoting radical reactions. It may also open up a new route for the catalytic oxidation of organic pollutants for water purification and widen the realm of supramolecular catalysis. PMID:27273046

  7. 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.

  8. 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.

  9. 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

  10. 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

  11. Grain boundary oxidation and oxidation accelerated fatigue crack nucleation and propagation

    NASA Technical Reports Server (NTRS)

    Liu, H. W.; Oshida, Y.

    1986-01-01

    Fatigue life at elevated temperatures is often shortened by oxidation. Grain boundary oxidation penetrates deeper than the surface oxidation. Therefore, grain boundary oxide penetration could be the primary cause of accelerated fatigue crack nucleation and propagation, and the shortened fatigue life at elevated temperatures. Grain boundary oxidation kinetics was studied and its statistical scatter was analyzed by the Weibull's distribution function. The effects of grain boundary oxidation on shortened fatigue life was analyzed and discussed. A model of intermittent microruptures of the grain boundary oxide was proposed for the fatigue crack growth in the low frequency region. The proposed model is consistent with the observations that fatigue crack growth rate in the low frequency region with hold time at K sub max is inversely proportional to cyclic frequency and that crack growth is intergranular.

  12. Floatability of coal and pyrite

    SciTech Connect

    Le, H.V.

    1981-10-01

    Effect of surface-active agents on floatability of an Iowa coal and associated pyrite was studied with and without methyl isobutyl carbinol (MIBC). Effectiveness of chemical pretreatment for depressing pyrite was also investigated. In another phase of the research, the zeta potential of the same coal and pyrite was measured under the same conditions used in the flotation tests (in the absence of frother). In the absence of MIBC, the floatability of coal and pyrite was low and depended on pH. Max recovery of pyrite was obtained at a pH of 4.5. Addition of small amounts of sodium cyanide, ferric chloride, Na/sub 2/H/sub 2/EDTA, and ammonium thiocyanate reduced the floatability of pyrite somewhat over a wide range of pH. Addition of a small amount of MIBC increased the recovery of coal and pyrite with the increase in the recovery of coal being much greater than the increase in the recovery of pyrite. The floatability of coal and pyrite seemed to be affected more by pH than in the absence of MIBC. On the other hand, several potential pyrite depressants were found to be ineffective in the presence of MIBC. Chemical pretreatment reduced the floatability of pyrite markedly while not greatly affecting the floatability of coal. Measurement of the zeta potential of coal and pyrite suspensions in dilute aqueous solutions of various reagents provided an indication of adsorption phenomena. However, there appeared to be no consistent direct correlation between zeta potential and floatability.

  13. 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.

  14. 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

  15. Method of synthesizing pyrite nanocrystals

    DOEpatents

    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.

  16. 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.

  17. 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.

  18. 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.

  19. 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

  20. Acceleration of catalytic activity of calcium oxide for biodiesel production.

    PubMed

    Kawashima, Ayato; Matsubara, Koh; Honda, Katsuhisa

    2009-01-01

    This research was aimed at studying the acceleration of the catalytic activity of calcium oxide (CaO) for developing an effective heterogeneous catalyst for biodiesel production by the transesterification of plant oil with methanol. CaO was activated by pretreatment with methanol and was used for the transesterification reaction. The activation and transesterification reaction conditions were examined. The obtained optimal reaction conditions were 0.1-g CaO, 3.9-g methanol, 15-g rapeseed oil, and 1.5-h activation time at room temperature that provided methyl ester in approximately 90% yield within a reaction time of 3h at 60 degrees C. The activation mechanism was also investigated, and the proposed mechanism is as follows. By pretreatment with methanol, a small amount of CaO gets converted into Ca(OCH(3))(2) that acts as an initiating reagent for the transesterification reaction and produces glycerin as a by-product. Subsequently, a calcium-glycerin complex, formed due to the reaction of CaO with glycerin, functions as the main catalyst and accelerates the transesterification reaction. PMID:18684617

  1. Comparative Oxidative Stability of Fatty Acid Alkyl Esters by Accelerated Methods

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Several fatty acid alkyl esters were subjected to accelerated methods of oxidation, including EN 14112 (Rancimat method) and pressurized differential scanning calorimetry (PDSC). Structural trends elucidated from both methods that improved oxidative stability included decreasing the number of doubl...

  2. 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.

  3. The biological leaching of an auriferous pyrite ore

    NASA Astrophysics Data System (ADS)

    Riekkola-Vanhanen, Marja; Heimala, Seppo; Sivelä, Carita A.; Viguera, Felipe; Varjola, Irma; Niemelä, Seppo I.; Tuovinen, Olli H.

    1993-12-01

    The oxidation of an auriferous pyrite ore sample was evaluated in biological leaching experiments for subsequent gold recovery via cyanidation. In batch cultures, organisms derived from the mine site oxidized pyrite and ferrous iron at pH values as low as pH 0.6. The recovery of gold was variable in shake flask experiments. In stirred tank bioreactor leaching, gold recovery was proportional to the extent of iron dissolution by bioleaching. The leaching of arsenic from the sample was also directly proportional to iron dissolution.

  4. 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.

  5. 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.

  6. 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.

  7. 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. PMID:25804530

  8. Hydrogeologic and environmental impact of amjhore pyrite mines, India

    NASA Astrophysics Data System (ADS)

    Choubey, Vishnu D.; Rawat, Rajendra K.

    1991-01-01

    Drainage from active and inactive pyrite mines has produced chemical and physical pollution of both ground- and surface water in Amjhore region. In the present case, chemical pollution is caused by exposing pyrite minerals to oxidation or leaching, resulting in undesirable concentrations of dissolved materials. Pyrite mining suddenly exposed large quantities of sulfides to direct contact with oxygen, and oxidation proceeds rapidly, resulting in acidity and release of metal (Fe) and sulfates to the water system, eventually resulting in water pollution in the region. The magnitude and impact of the problem is just being recognized and, as the present and the future projected demand for clean water is of top priority, the present studies were undertaken. Mine drainage includes water flowing from the surface and underground mines and runoff or seepage from the pyrite mines. This article describes the various hydrologic factors that control acid water formation and its transport. The mine drainage is obviously a continuing source of pollution and, therefore, remedial measures mainly consisting of a double-stage limestone-lime treatment technique have been suggested. The present results will be used to develop an alternative and more effective abatement technology to mitigate acid production at the source, namely, the technique of revegetation of the soil cover applied to the waste mine dump material. Water quality change is discussed in detail, with emphasis on acidity formed from exposed pyrite material and on increase in dissolved solids. Preventive and treatment measures are recommended.

  9. Accelerated life ac conductivity measurements of CRT oxide cathodes

    NASA Astrophysics Data System (ADS)

    Hashim, A. A.; Barratt, D. S.; Hassan, A. K.; Nabok, A.

    2006-07-01

    The ac conductivity measurements have been carried out for the activated Ba/SrO cathode with additional 5% Ni powder for every 100 h acceleration life time at the temperature around 1125 K. The ac conductivity was studied as a function of temperature in the range 300-1200 K after conversion and activation of the cathode at 1200 K for 1 h in two cathodes face to face closed configuration. The experimental results prove that the hopping conductivity dominate in the temperature range 625-770 K through the traps of the WO 3 associate with activation energy Ea = 0.87 eV, whereas from 500-625 K it is most likely to be through the traps of the Al 2O 3 with activation energy of Ea = 1.05 eV. The hopping conductivity at the low temperature range 300-500 K is based on Ni powder link with some Ba contaminants in the oxide layer stricture which indicates very low activation energy Ea = 0.06 eV.

  10. 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.

  11. Analysis of iron- and sulfur-oxidizing bacteria in a treatment plant of acid rock drainage from a Japanese pyrite mine by use of ribulose-1, 5-bisphosphate carboxylase/oxygenase large-subunit gene.

    PubMed

    Kamimura, Kazuo; Okabayashi, Ai; Kikumoto, Mei; Manchur, Mohammed Abul; Wakai, Satoshi; Kanao, Tadayoshi

    2010-03-01

    Iron- and sulfur-oxidizing bacteria in a treatment plant of acid rock drainage (ARD) from a pyrite mine in Yanahara, Okayama prefecture, Japan, were analyzed using the gene (cbbL) encoding the large subunit of ribulose-1, 5-bisphosphate carboxylase/oxygenase (RubisCO). Analyses of partial sequences of cbbL genes from Acidithiobacillus ferrooxidans, Acidithiobacillus thiooxidans and Acidithiobacillus caldus strains revealed the diversity in their cbbL gene sequences. In contrast to the presence of two copies of form I cbbL genes (cbbL1 and cbbL2) in A. ferrooxidans genome, A. thiooxidans and A. caldus had a single copy of form I cbbL gene in their genomes. A phylogenetic analysis based on deduced amino acid sequences from cbbL genes detected in the ARD treatment plant and their close relatives revealed that 89% of the total clones were affiliated with A. ferrooxidans. Clones loosely affiliated with the cbbL from A. thiooxidans NB1-3 or Thiobacillus denitrificans was also detected in the treatment plant. cbbL gene sequences of iron- or sulfur-oxidizing bacteria isolated from the ARD and the ARD treatment plant were not detected in the cbbL libraries from the treatment plant, suggesting the low frequencies of isolates in the samples. PMID:20159572

  12. 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.

  13. 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.

  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. 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.

  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. 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...

  18. 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...

  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, 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...

  1. 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.

  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. Control of pyrite surface chemistry in physical coal cleaning. Fifth quarterly progress report, September 1, 1990--November 30, 1990

    SciTech Connect

    Luttrell, G.H.; Yoon, R.H.; Ou, Z.S.

    1992-06-24

    The successful separation of pyrite from coal by flotation is dependent to a large extent upon the selectivity of the process, and the use of a pyrite depressant is one of the most important and cost-effective techniques for achieving this. This report evaluates the effects of three factors on the floatability of pyrite. These are (1) the superficial oxidation of pyrite, (2) the contamination of pyrite surfaces by carbonaceous matter, and (3) pulp redox potentials. XPS (x-ray photoelectron spectroscopy) and IR spectrometry have been used to identify surface reaction products. Microflotation, laboratory-scale conventional flotation and microbubble column flotation were used to quantify the effects of these factors. It was found that low (reducing) pulp potentials are effective depressants of pyrite (more so for fresh, unoxidized samples than for oxidized samples), whilst at the same time do not materially affect coal flotation.

  5. [Periodic bioleaching of refractory gold-bearing pyrite ore].

    PubMed

    Vardanian, N S; Nagdalian, S Z

    2009-01-01

    The main characteristics of a periodic bioleaching of the refractory gold-bearing pyrite ore from the Tandzut deposit (Armenia) with the help of moderate thermophilic bacterium Sulfobacillus thermosulfidooxi-dans subsp. asporogenes and original thermotolerant strains Leptospirillum spp. were studied. The optimal pH for oxidizing the ore by S. thermosulfidooxidans subsp. asporogenes was 1.8; the pulp density providing maximal iron leaching rate was 10%. The intensity of oxidation processes decreased at higher ore concentrations. When using S. thermosulfidooxidans subsp. asporogenes, the largest amount of iron passed into the solution at the initial oxidant (Fe3+) concentration of 1.3 g/l. Cocultivation of S. thermosulfidooxidans subsp. asporogenes and Leptospirillum spp. increased the degree of pyrite ore leaching to 98.4% vs. 34.1% in the case of the former bacterium alone. PMID:19764614

  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. 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.

  8. Pyrite formation and the measurement of sulfate reduction in salt marsh sediments

    SciTech Connect

    Howarth, R.W.; Merkel, S.

    1984-05-01

    A new method was used to study the formation of pyrite plus elemental sulfur during /sup 35/SO/sub 4//sup 2 -/ reduction experiments in salt marsh sediments: the reduction with chromium(II) of pyrite and elemental sulfur to hydrogen sulfide. It is both more specific and more sensitive than the previous method, the oxidation of pyrite and elemental sulfur to sulfate by aqua regia, which measures the formation of refractory organic sulfur compounds as well as pyrite and elemental sulfur. A direct comparison of the two methods in salt marsh sediments in Georgia and in Massachusetts showed that they compare very well. The chromium(II) reduction method, combined with the authors' previous results, conclusively shows that pyrite is the major product of /sup 35/SO/sub 4//sup 2 -/ reduction measurements in these sediments. The agreement between the two methods indicates that the formation of /sup 35/S-labeled, refractory organic matter is a minor process if it occurs at all. The authors' results suggest that both the aqua regia oxidation method and the chromium(II) reduction method, if used with care, are suitable for measuring incorporation of /sup 35/S into pyrite and elemental sulfur during /sup 35/SO/sub 4//sup 2 -/ reduction measurements in salt marsh sediments. Failure to explicitly measure the formation of /sup 35/S-labeled pyrite can result in the rate of sulfate reduction being underestimated by 2-fold to 10-fold or more.

  9. Pyrite-driven reactive oxygen species formation in simulated lung fluid: implications for coal workers' pneumoconiosis.

    PubMed

    Harrington, Andrea D; Hylton, Shavonne; Schoonen, Martin A A

    2012-08-01

    The origin of coal worker's pneumoconiosis (CWP) has been long debated. A recent epidemiological study shows a correlation between what is essentially the concentration of pyrite within coal and the prevalence of CWP in miners. Hydrogen peroxide and hydroxyl radical, both reactive oxygen species (ROS), form as byproducts of pyrite oxidative dissolution in air-saturated water. Motivated by the possible importance of ROS in the pathogenesis of CWP, we conducted an experimental study to evaluate if ROS form as byproducts in the oxidative dissolution of pyrite in simulated lung fluid (SLF) under biologically applicable conditions and to determine the persistence of pyrite in SLF. While the rate of pyrite oxidative dissolution in SLF is suppressed by 51% when compared to that in air-saturated water, the initial amount of hydrogen peroxide formed as a byproduct in SLF is nearly doubled. Hydroxyl radical is also formed in the experiments with SLF, but at lower concentrations than in the experiments with water. The formation of these ROS indicates that the reaction mechanism for pyrite oxidative dissolution in SLF is no different from that in water. The elevated hydrogen peroxide concentration in SLF suggests that the decomposition, via the Fenton mechanism to hydroxyl radical or with Fe(III) to form water and molecular oxygen, is initially inhibited by the presence of SLF components. On the basis of the oxidative dissolution rate of pyrite measured in this paper, it is calculated that a respirable two micron pyrite particle will take over 3 years to dissolve completely. PMID:21989857

  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. PMID:20028047

  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. 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.

  14. 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.

  15. 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.

  16. Selective redox degradation of chlorinated aliphatic compounds by Fenton reaction in pyrite suspension.

    PubMed

    Che, Hyeongsu; Lee, Woojin

    2011-02-01

    Selective redox degradation of chlorinated aliphatics by Fenton reaction in pyrite suspension was investigated in a closed system. Carbon tetrachloride (CT) was used as a representative target of perchlorinated alkanes and trichloroethylene (TCE) was used as one of highly chlorinated alkenes. Degradation of CT in Fenton reaction was significantly enhanced by pyrite used as an iron source instead of soluble Fe. Pyrite Fenton showed 93% of CT removal in 140 min, while Fenton reaction with soluble Fe(II) showed 52% and that with Fe(III) 15%. Addition of 2-propanol to the pyrite Fenton system significantly inhibited degradation of TCE (99% to 44% of TCE removal), while degradation of CT was slightly improved by the 2-propanol addition (80-91% of CT removal). The result suggests that, unlike oxidative degradation of TCE by hydroxyl radical in pyrite Fenton system, an oxidation by the hydroxyl radical is not a main degradation mechanism for the degradation of CT in pyrite Fenton system but a reductive dechlorination by superoxide can rather be the one for the CT degradation. The degradation kinetics of CT in the pyrite Fenton system was decelerated (0.13-0.03 min(-1)), as initial suspension pH decreased from 3 to 2. The formation of superoxide during the CT degradation in the pyrite Fenton system was observed by electron spin resonance spectroscopy. The formation at initial pH 3 was greater than that at initial pH 2, which supported that superoxide was a main reductant for degradation of CT in the pyrite Fenton system. PMID:21186044

  17. 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.

  18. 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

  19. Increased LDL susceptibility to oxidation accelerates future carotid artery atherosclerosis

    PubMed Central

    2012-01-01

    Background We analyzed the causal relationship between LDL susceptibility to oxidation and the development of new carotid artery atherosclerosis over a period of 5 years. We previously described the determinants related to a risk of cardiovascular changes determined in a Japanese population participating in the Niigata Study, which is an ongoing epidemiological investigation of the prevention of cardiovascular diseases. Methods We selected 394 individuals (169 males and 225 females) who underwent a second carotid artery ultrasonographic examination in 2001 - 2002 for the present study. The susceptibility of LDL to oxidation was determined as the photometric absorbance and electrophoretic mobility of samples that had been collected in 1996 - 1997. The measurements were compared with ultrasonographic findings obtained in 2001 - 2002. Results The multivariate-adjusted model showed that age (odds ratio (OR), 1.034; 95% confidence interval (95%CI), 1.010 - 1.059), HbA1c (OR, 1.477; 95%CI, 0.980 - 2.225), and photometric O/N (OR, 2.012; 95%CI, 1.000 - 4.051) were significant variables that could independently predict the risk of new carotid artery atherosclerosis. Conclusion The susceptibility of LDL to oxidation was a significant parameter that could predict new carotid artery atherosclerosis over a 5-year period, and higher susceptibility was associated with a higher incidence of new carotid artery atherosclerosis. PMID:22230558

  20. 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

  1. Accelerated Aging during Chronic Oxidative Stress: A Role for PARP-1

    PubMed Central

    Boesten, Daniëlle M. P. H. J.; de Vos-Houben, Joyce M. J.; Timmermans, Leen; den Hartog, Gertjan J. M.; Bast, Aalt; Hageman, Geja J.

    2013-01-01

    Oxidative stress plays a major role in the pathophysiology of chronic inflammatory disease and it has also been linked to accelerated telomere shortening. Telomeres are specialized structures at the ends of linear chromosomes that protect these ends from degradation and fusion. Telomeres shorten with each cell division eventually leading to cellular senescence. Research has shown that poly(ADP-ribose) polymerase-1 (PARP-1) and subtelomeric methylation play a role in telomere stability. We hypothesized that PARP-1 plays a role in accelerated aging in chronic inflammatory diseases due to its role as coactivator of NF-κb and AP-1. Therefore we evaluated the effect of chronic PARP-1 inhibition (by fisetin and minocycline) in human fibroblasts (HF) cultured under normal conditions and under conditions of chronic oxidative stress, induced by tert-butyl hydroperoxide (t-BHP). Results showed that PARP-1 inhibition under normal culturing conditions accelerated the rate of telomere shortening. However, under conditions of chronic oxidative stress, PARP-1 inhibition did not show accelerated telomere shortening. We also observed a strong correlation between telomere length and subtelomeric methylation status of HF cells. We conclude that chronic PARP-1 inhibition appears to be beneficial in conditions of chronic oxidative stress but may be detrimental under relatively normal conditions. PMID:24319532

  2. 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.

  3. 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.

  4. Reactions in pyrite framboids induced by electron beam heating in a HVEM

    SciTech Connect

    Harris, L.A.; Kenik, E.A.; Yust, C.S.

    1981-01-01

    Pyrite is a common mineral constituent in most bituminous coals. In addition to being a source of sulfur pollution, pyrite is also thought to act as an internal catalyst in coal liquefaction processes. Since much of the pyrite in coal is in the form of submicron to micron size crystals, their location and identity may be obtained by means of electron microscopy in conjunction with electron microprobe analysis (EMA). Transmission and scanning electron microscopy (TEM and SEM) are generally nondestructive techniques; however, in recent studies reactions have been observed to occur in several pyrite framboids on exposure to the focussed electron beam of a high voltage electron microscope (HVEM). The reaction resulted in the formation of a rim surrounding the reactive pyrite crystals as well as conversion of some pyrite to pyrrhotite (Fe/sub 1-x/S). On further examination of these specimens it was found that only some framboids were reactive whereas others remained inert. Detailed TEM, SEM, and EMA studies of the coal revealed the presence of iron sulfate hydrate minerals, especially szomolnokite (FeSO/sub 4/.H/sub 2/O) associated with some pyrite framboids. In addition to the iron sulfates, the electron diffraction patterns contained ring patterns that could be indexed as magnetite, Fe/sub 3/O/sub 4/. These data suggest that at least one possible cause for the reactivity of pyrite framboids is the oxidation of the iron disulfide phase. Other possibilities are related to the effect of specimen configuration on local heating in the electron beam and the specific iron disulfide mineral that is present in the framboid (pyrite or marcasite).

  5. Surface reactivity of pyrite and related sulfides

    NASA Astrophysics Data System (ADS)

    Murphy, Riley; Strongin, Daniel R.

    2009-01-01

    Pyrite, FeS 2, commonly referred to as "Fool's gold" is the most common sulfide in the Earth's surface region. Not only is the mineral ubiquitous, but the reactivity of pyrite is of central importance in a devastating environmental issue known as acid mine drainage (AMD) and in beneficial commercial processes such as mineral benefaction, which can range from the desulfurization of coal to the isolation of copper or gold ores. Pyrite has even been postulated to be a key constituent of a prebiotic iron-sulfur world existing at the high pressure and temperature conditions common to hydrothermal vents at the oceanic floor. The development of an atomic level picture of the structure and reactivity of pyrite is paramount to understanding the chemistry of this mineral in these wide-ranging environments. This contribution focuses on research carried out over the past three decades that has used modern surface science tools to understand the reactivity of pyrite surfaces. An understanding of the reactivity of the pyrite surfaces has benefited from studies using a wide range of experimental techniques that range from vacuum-based experiments utilizing electron and photon spectroscopies, and probe microscopy to in situ studies using infra-red spectroscopy. Synchrotron-based techniques that include photoelectron spectroscopy and X-ray absorption spectroscopy have played a large role in both these environments. These techniques have perhaps been the most useful in establishing the structure of the pristine pyrite surface. Related iron sulfides are also briefly introduced in this review including pyrrhotite (Fe xS 1- x) and the dimorph of pyrite, marcasite. The surface reactivity of these sulfides exhibit both similarities and differences to pyrite, and help to bring forward the unique activity of pyrite in both environmentally and technologically important conditions.

  6. A study on the toxic effects of chloride on the biooxidation efficiency of pyrite.

    PubMed

    Gahan, Chandra Sekhar; Sundkvist, Jan-Eric; Sandström, Ake

    2009-12-30

    Bioleaching operations in areas with limited chloride-free water and use of ashes and dust as neutralizing agents have motivated to study the chloride toxicity and tolerance level of the microorganisms. Biooxidation of pyrite using chloride containing waste ash compared with Ca(OH)(2)+NaCl as neutralizing agent was investigated to evaluate the causes of low pyrite oxidation. Both precipitation of jarosite as well as the toxic effect of chloride on the microorganisms were responsible for lower pyrite recoveries. Another study with sudden exposure of chloride during pyrite biooxidation, addition of 4 g/L was lethal for the microorganisms. Addition of 2g/L chloride resulted in precipitation of jarosite with slightly lower pyrite recovery whereas the addition of 3g/L chloride temporarily chocked the microorganisms but activity was regained after a short period of adaptation. Population dynamics study conducted on the experiment with 3g/L chloride surprisingly showed that Leptospirillum ferriphilum, which was dominating in the inoculum, completely disappeared from the culture already before chloride was added. Sulphobacillus sp. was responsible for iron oxidation in the experiment. Both Acidithiobacillus caldus and Sulphobacillus sp. were adaptive and robust in nature and their numbers were slightly affected after chloride addition. Therefore, it was concluded that the microbial species involved in the biooxidation of pyrite vary in population during the different stages of biooxidation. PMID:19720455

  7. 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.

  8. 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.

  9. Thermal stability and kinetics of decomposition of ammonium nitrate in the presence of pyrite.

    PubMed

    Gunawan, Richard; Zhang, Dongke

    2009-06-15

    The interaction between ammonium nitrate based industrial explosives and pyrite-rich minerals in mining operations can lead to the occurrence of spontaneous explosion of the explosives. In an effort to provide a scientific basis for safe applications of industrial explosives in reactive mining grounds containing pyrite, ammonium nitrate decomposition, with and without the presence of pyrite, was studied using a simultaneous Differential Scanning Calorimetry and Thermogravimetric Analyser (DSC-TGA) and a gas-sealed isothermal reactor, respectively. The activation energy and the pre-exponential factor of ammonium nitrate decomposition were determined to be 102.6 kJ mol(-1) and 4.55 x 10(7)s(-1) without the presence of pyrite and 101.8 kJ mol(-1) and 2.57 x 10(9)s(-1) with the presence of pyrite. The kinetics of ammonium nitrate decomposition was then used to calculate the critical temperatures for ammonium nitrate decomposition with and without the presence of pyrite, based on the Frank-Kamenetskii model of thermal explosion. It was shown that the presence of pyrite reduces the temperature for, and accelerates the rate of, decomposition of ammonium nitrate. It was further shown that pyrite can significantly reduce the critical temperature of ammonium nitrate decomposition, causing undesired premature detonation of the explosives. The critical temperature also decreases with increasing diameter of the blast holes charged with the explosive. The concept of using the critical temperature as indication of the thermal stability of the explosives to evaluate the risk of spontaneous explosion was verified in the gas-sealed isothermal reactor experiments. PMID:19056177

  10. Obesity-induced oxidative stress, accelerated functional decline with age and increased mortality in mice

    PubMed Central

    Zhang, Yiqiang; Fischer, Kathleen E.; Soto, Vanessa; Liu, Yuhong; Sosnowska, Danuta; Richardson, Arlan; Salmon, Adam B.

    2015-01-01

    Obesity is a serious chronic disease that increases the risk of numerous co-morbidities including metabolic syndrome, cardiovascular disease and cancer as well as increases risk of mortality leading some to suggest this represents accelerated aging. Obesity is associated with significant increases in oxidative stress in vivo and, despite the well-explored relationship between oxidative stress and aging, the role this plays in the increased mortality of obese subjects remains an unanswered question. Here, we addressed this by undertaking a comprehensive, longitudinal study of a group of high fat-fed obese mice and assessed both their changes in oxidative stress and in their performance in physiological assays known to decline with aging. In female C57BL/6J mice fed a high-fat diet starting in adulthood, mortality was significantly increased in high fat-fed mice as was oxidative damage in vivo. High fat-feeding significantly accelerated the decline in performance in several assays, including activity, gait, and rotarod. However, we also found that obesity had little effect on other markers and actually improved performance in grip strength, a marker of muscular function. Together, this first comprehensive assessment of longitudinal functional changes in high fat-fed mice suggests that obesity may induce segmental acceleration of some of the aging process. PMID:25558793

  11. 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.

  12. 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.

  13. 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.

  14. 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

  15. Degradation of off-gas toluene in continuous pyrite Fenton system.

    PubMed

    Choi, Kyunghoon; Bae, Sungjun; Lee, Woojin

    2014-09-15

    Degradation of off-gas toluene from a toluene reservoir and a soil vapor extraction (SVE) process was investigated in a continuous pyrite Fenton system. The removal of off-gas toluene from the toluene reservoir was >95% by 8h in the pyrite Fenton system, while it was ∼97 % by 3h in classic Fenton system and then rapidly decreased to initial level by 8h. Continuous consumption of low Fe(II) concentration dissolved from pyrite surface (0.05-0.11 mM) was observed in the pyrite Fenton system, which can lead to the effective and successful removal of the gas-phase toluene due to stable production of OH radical (OH). Inhibitor and spectroscopic test results showed that OH was a dominant radical that degraded gas-phase toluene during the reaction. Off-gas toluene from the SVE process was removed by 96% in the pyrite Fenton system, and remnant toluene from rebounding effect was treated by 99%. Main transformation products from toluene oxidation were benzoic acid (31.4%) and CO2 (38.8%) at 4h, while traces of benzyl alcohol (1.3%) and benzaldehyde (0.7%) were observed. Maximum operation time of continuous pyrite Fenton system was estimated to be 56-61 d and its optimal operation time achieving emission standard was 28.9 d. PMID:25125037

  16. Pyrite-enhanced degradation of chloramphenicol by low concentrations of H2O2.

    PubMed

    Wu, Deli; Liu, Yanxia; Zhang, Zhiyong; Ma, Luming; Zhang, Yalei

    2015-01-01

    A pyrite-catalyzed reaction was used to degrade chloramphenicol. Chloramphenicol could be almost 100% removed within 60 minutes when 1 mM H2O2 and 0.1 g/L pyrite were added at an initial pH=3. During oxidation, intermediates such as nitrobenzaldehyde and dichloroacetamide were identified by gas chromatography/mass spectrometry (GC/MS). The •OH was identified by electron spin-resonance spectroscopy. Pyrite was digested to determine elements by ICP (inductive coupled plasma emission spectrometer). To understand the reaction mechanism and the role of natural pyrite in these processes, techniques including scanning electron microscopy and energy dispersive spectrometry were employed to characterize the solid sample. The results explain that pyrite acts as a 'bond' between Fe3+ and H2O2, and this pathway continues to form •OH and inhibit the quenching reaction. Therefore, pyrite-catalyzed reactions would proceed even in low concentrations of H2O2. PMID:26177399

  17. Electrochemistry of thiobacillus ferrooxidans interactions with pyrite

    NASA Astrophysics Data System (ADS)

    Pesic, Batric; Kim, Inbeum

    1993-10-01

    A cyclic voltammetry technique was used to study the interactions of mineral-pyrite during bioleaching with the bacterium Thiobacillus (T.) ferrooxidans over its entire growth cycle. Invariably, the pyrite surface drastically changed its properties on the second day of bacterial rowth (bioleaching). After 2 days, the cyclic voltammograms (CVs) were insensitive to convective diffusion produced by stirring. The product layer was examined by scanning electron microscopy (SEM), X-ray diffraction, and chemical analysis. The SEM study revealed an extremely high density of bacteria on the pyrite surface. The high density of bacteria, along with the solid reaction products formed on the pyrite surface, created conditions for crack/pore diffusion, explaining why the CVs became insensitive to convective diffusion (stirring) in solution. X-ray diffraction study confirmed jarosite as a product layer. A mechanism is proposed by which T. ferrooxidans cells serve as nucleation sites for jarosite formation.

  18. Electrochemistry of Thiobacillus ferrooxidans interactions with pyrite

    SciTech Connect

    Pesic, B. . Coll. of Mines and Earth Resources); Kim, I. )

    1993-10-01

    A cyclic voltammetry technique was used to study the interactions of mineral-pyrite during bioleaching with the bacterium Thiobacillus (T.) ferrooxidans over its entire growth cycle. Invariably, the pyrite surface drastically changed its properties on the second day of bacterial growth (bioleaching). After 2 days, the cyclic voltammograms (CVs) were insensitive to convective diffusion produced by stirring. The product layer was examined by scanning electron microscopy (SEM), X-ray diffraction, and chemical analysis. The SEM study revealed an extremely high density of bacteria on the pyrite surface. The high density of bacteria, along with the solid reaction products formed on the pyrite surface, created conditions for crack/pore diffusion, explaining why the CVs became insensitive to convective diffusion (stirring) in solution. X-ray diffraction study confirmed jarosite as a product layer. A mechanism is proposed by which T. ferrooxidans cells serve as nucleation sites for jarosite formation.

  19. Electrochemistry of Thiobacillus ferrooxidans reactions with pyrite

    SciTech Connect

    Pesic, B.

    1991-01-01

    The interactions of mineral-pyrite with T. ferrooxidans were studied by using a cyclic voltametry technique. The interactions with bacteria were examined during the entire growth stage of bacterial (fermentation). The pyrite surface invariably drastically changed its properties at the second day of fermentation. Beyond two days of fermentation, the cyclic voltamograms were insensitive to convective diffusion produced by stirring. The product layer was examined by SEM, X-ray diffraction and chemical analysis. The SEM study revealed that bacteria populated the pyrite surface at an extremely high density levels. The high density of bacteria, and the solid reaction products formed on the pyrite surface created conditions for pore diffusion which explained why the CVs became insensitive to convective diffusion in solution (stirring). The X-ray diffraction study confirmed jarosite as a product layer. A mechanism of T. ferrooxidans cells serving as nucleation sites for jarosite formation is proposed. 16 refs., 8 figs., 2 tabs.

  20. 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.

  1. Electrochemistry of Thiobacillus ferrooxidans reactions with pyrite

    SciTech Connect

    Pesic, B.

    1992-01-01

    The objective of this project is to provide the fundamental information on the mechanisms of bacterial leaching of pyrite. The knowledge of how bacterial leaching of pyrite functions is essential for design and development of a technology for coal cleaning with bacteria. The features of major electrochemical techniques will be examined to find out if any of them can provide a diagnostic information on the mechanisms of related reactions.

  2. 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

  3. 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.

  4. Pyrite Recrystallization Experiments With Circulating Hydrothermal Solution

    NASA Astrophysics Data System (ADS)

    Isobe, H.; Abe, A.; Tanaka, K.

    2007-12-01

    Pyrite is one of the most common sulfide minerals found in hydrothermal deposits and sea-floor sediments from hydrothermal fumaroles. Hydrothermal fluid flow plays an important role in crystallization of sulfide minerals. In this study, we tried to reproduce pyrite crystallization with one-way flowing hydrothermal fluid. We designed a circuit circulating hydrothermal fluid by thermal convection. A rectangular circuit (42.6 cm by 17.3 cm) of SUS316 pressure tubes with 5 mm in inner diameter was used as a reaction vessel. In the circuit, pyrite dissolves to acidic fluid in upstream region. Then, pyrite will crystallize again in downstream region as temperature decreases. The rectangular plane was held to be 20 degrees inclination to generate thermal convection. One of the long sides of the rectangular was heated by an electric furnace. Starting materials were put in a tube to be heated. Upper half, approximately 20 cm, of the tube was filled with quartz sand. Next quarter was filled with equivalent mass mixture of quartz sand and powdered pyrite crystals. The lowest quarter was filled with mixture of quartz sand, pyrite, anhydrite and sulfur, those mass are equivalent. The solution was a mixture of 0.5mol/l HCl and 3.0mol/l NaCl. Maximum temperature was controlled to approximately 350°C at the center of the heated tube. Experimental durations were up to 9 days. Fluid pressure increased to approximately 6 MPa as heating. After the experiments, the run products were fixed with resin in a sample tube, and vertical sections were observed by SEM. In the run products, pyrite dissolved at the lower part of the starting material. In the upper half of the sample tube, pyrite crystals precipitated on quartz surface. Crystallization density depends on temperature gradient of the fluid. Predominant morphology of the pyrite crystals consists (100) plains. Tiny framboidal aggregates and crystals with (210) plains also occur. In the run products of longer than 3 days run durations

  5. 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

    2016-03-26

    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

  6. 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

  7. 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.

  8. 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

  9. Biofilm formation, communication and interactions of leaching bacteria during colonization of pyrite and sulfur surfaces.

    PubMed

    Bellenberg, Sören; Díaz, Mauricio; Noël, Nanni; Sand, Wolfgang; Poetsch, Ansgar; Guiliani, Nicolas; Vera, Mario

    2014-11-01

    Bioleaching of metal sulfides is an interfacial process where biofilm formation is considered to be important in the initial steps of this process. Among the factors regulating biofilm formation, molecular cell-to-cell communication such as quorum sensing is involved. A functional LuxIR-type I quorum sensing system is present in Acidithiobacillus ferrooxidans. However, cell-to-cell communication among different species of acidophilic mineral-oxidizing bacteria has not been studied in detail. These aspects were the scope of this study with emphasis on the effects exerted by the external addition of mixtures of synthetic N-acyl-homoserine-lactones on pure and binary cultures. Results revealed that some mixtures had inhibitory effects on pyrite leaching. Some of them correlated with changes in biofilm formation patterns on pyrite coupons. We also provide evidence that A. thiooxidans and Acidiferrobacter spp. produce N-acyl-homoserine-lactones. In addition, the observation that A. thiooxidans cells attached more readily to pyrite pre-colonized by living iron-oxidizing acidophiles than to heat-inactivated or biofilm-free pyrite grains suggests that other interactions also occur. Our experiments show that pre-cultivation conditions influence A. ferrooxidans attachment to pre-colonized pyrite surfaces. The understanding of cell-to-cell communication may consequently be used to develop attempts to influence biomining/bioremediation processes. PMID:25172572

  10. Searching for Biosignatures in Pyrite Framboids

    NASA Astrophysics Data System (ADS)

    Popa, R.; Schelble, R. T.; Douglas, S.; Nealson, K. H.

    2004-12-01

    Framboids are submillimeter raspberry-like structures with 10-109 microcrystallites, often composed of pyrite (FeS2). The origin and mechanisms of formation of framboids are poorly understood. Framboid morphology can be obtained in abiotic simulations, but are also very common in the presence of microbial communities. Although some microbial communities are rich in framboids, the role that microbes potentially play in the formation of framboids, and the impact of microorganisms on framboid characteristics remains unclear. The purpose of this study was to use morphological and geochemical differences between abiotic pyrite framboids, and pyrite framboids formed in microbial mats to determine whether framboids can be used as a biosignature in the study of ancient sediments. By manipulating the experimental conditions we tried to understand more about the conditions conducive to pyrite framboid formation, and whether there was a microbial role in the genesis of sedimentary deposits containing framboids. We studied synthetic produced (abiotic) framboids with framboids formed within microbial mats and with framboids found in geological deposits. Size distribution, microtexture, composition, isotopic composition, and mineralogy of pyrite framboids was compared. Images were obtained using environmental scanning electron microscopy and the microtextures were analyzed using shape-analysis tools providing information about the overall size distribution of framboids, number of microcrystallites per unit volume, and size distribution of microcrystallites. Synthetic framboids were made in the laboratory, and framboids from microbial mats were collected from the Mangalia (Romania) subsurface sulfidic system. Neoproterozoic (750-600 Ma) manganese carbonate deposits containing fossilized pyrite framboids were collected from a mine (Hunan Province, China). Our results show that the framboids from microbial mats have a distinct size distribution, different number of crystallites

  11. 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

  12. DFT study on the galvanic interaction between pyrite (100) and galena (100) surfaces

    NASA Astrophysics Data System (ADS)

    Ke, Baolin; Li, Yuqiong; Chen, Jianhua; Zhao, Cuihua; Chen, Ye

    2016-03-01

    The galvanic interaction between pyrite and galena surface has been investigated using density functional theory (DFT) method. The calculated results show that galvanic interactions between pyrite and galena surface are decreased with the increase of contact distance. The galvanic interactions still occurs even the distance larger than the sum of two atoms radius (≈2.8 Å), and the limit distance of galvanic interaction between galena and pyrite surface is about 10 Å, which is consistent with the quantum tunneling effect. Through Mulliken charge population calculation, it is found that electrons transfer from galena to pyrite. For galena surface, Pb 6s and 6p states lose electrons and S 3p state loses a small amount of electrons, which causes the electron loss of galena. For pyrite surface, Fe 4p state obtains large numbers of electrons, resulting in the decrease of positive charge of Fe atom. However, the 3p state of S atom loses a small numbers of electrons. The reactivity of mineral surface has also been studied by calculating the frontier orbitals of minerals. Results suggest that the highest occupied molecular orbital (HOMO) coefficients of galena are increased whereas those of pyrite are decreased with the enhancing galvanic interaction, indicating that the oxidation of galena surface would be enhanced due to the galvanic interaction. The Fukui indices and dual descriptor values of surface atoms suggest that the nucleophilicity of the galena surface increases, meanwhile, the electrophilicity of pyrite surface increases with the decrease of the contact distance. In addition, the density of states (DOS) of atoms results show that the activity of electrons in Pb 6s and 6p orbitals enhances while the activity of electrons in Fe 3d orbitals weaken due to the galvanic contact between minerals.

  13. 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. PMID:22613465

  14. 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.

  15. 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

  16. Electrochemistry of Thiobacillus ferroxidans reactions with pyrite

    SciTech Connect

    Pesic, B.; Oliver, D.J.

    1990-01-01

    The objective of this project is to provide the fundamental information on the mechanisms of bacterial leaching of pyrite. The knowledge of how bacterial leaching of pyrite functions is essential for design and development of a technology for coal cleaning with bacteria. The features of major electrochemical techniques will be examined to find out if any of them can provide a diagnostic information on the mechanisms of related reactions. This quarter the activity of T. ferrooxidans with duration of fermentation was examined. It was found that there were three distinct stages of fermentation. 1 fig.

  17. 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

  18. In situ characterization of natural pyrite bioleaching using electrochemical noise technique

    NASA Astrophysics Data System (ADS)

    Chen, Guo-bao; Yang, Hong-ying; Li, Hai-jun

    2016-02-01

    An in situ characterization technique called electrochemical noise (ECN) was used to investigate the bioleaching of natural pyrite. ECN experiments were conducted in four active systems (sulfuric acid, ferric-ion, 9k culture medium, and bioleaching solutions). The ECN data were analyzed in both the time and frequency domains. Spectral noise impedance spectra obtained from power spectral density (PSD) plots for different systems were compared. A reaction mechanism was also proposed on the basis of the experimental data analysis. The bioleaching system exhibits the lowest noise resistance of 0.101 MΩ. The bioleaching of natural pyrite is considered to be a bio-battery reaction, which distinguishes it from chemical oxidation reactions in ferric-ion and culture-medium (9k) solutions. The corrosion of pyrite becomes more severe over time after the long-term testing of bioleaching.

  19. Quantification of the production of hydrogen peroxide H2O2 during accelerated wine oxidation.

    PubMed

    Héritier, Julien; Bach, Benoît; Schönenberger, Patrik; Gaillard, Vanessa; Ducruet, Julien; Segura, Jean-Manuel

    2016-11-15

    Understanding how wines react towards oxidation is of primary importance. Here, a novel approach was developed based on the quantitative determination of the key intermediate H2O2 produced during accelerated oxidation by ambient oxygen. The assay makes use of the conversion of the non-fluorescent Amplex Red substrate into a fluorescent product in presence of H2O2. The total production of H2O2 during 30min was quantified with low within-day and between-day variabilities. Polymerized pigments, but not total polyphenols, played a major role in the determination of H2O2 levels, which were lower in white wines than red wines. H2O2 amounts also increased with temperature and the addition of metal ions, but did not depend on the concentration of many other wine constituents such as SO2. H2O2 levels did not correlate with anti-oxidant properties. We believe that this novel methodology might be generically used to decipher the oxidation mechanisms in wines and food products. PMID:27283717

  20. 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

  1. 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

  2. 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.

  3. Electrochemistry of Thiobacillus ferrooxidans reactions with pyrite

    SciTech Connect

    Pesic, B.

    1990-01-01

    The present investigation is a part of our studies on the electrochemical aspects of pyrite bioleaching involving Thiobacillus ferrooxidans. Previously 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 focused on the effect of the presence of vitamins on the redox chemistry of iron. To date, we have examined the effect of the presence of thiamine pyrophosphate in the redox behavior of Fe{sup 2+}/Fe{sup 3+} at the pyrite surface. The results are described herein.

  4. Electrochemistry of Thiobacillus ferrooxidans reactions with pyrite

    SciTech Connect

    Pesic, B.

    1990-01-01

    The present investigation is a part of our studies on the electrochemical aspects of pyrite bioleaching involving Thiobacillus ferrooxidans. Previously 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 focused on the effect of the presence of vitamins on the redox chemistry of iron. To date, we have examined the effect of the presence of thiamine hydrochloride in the redox behavior of Fe{sup 2+}/Fe{sup 3+} at the pyrite surface. The results are described herein.

  5. Increased Oxidative and Nitrative Stress Accelerates Aging of the Retinal Vasculature in the Diabetic Retina

    PubMed Central

    Lamoke, Folami; Shaw, Sean; Yuan, Jianghe; Ananth, Sudha; Duncan, Michael; Martin, Pamela; Bartoli, Manuela

    2015-01-01

    Hyperglycemia-induced retinal oxidative and nitrative stress can accelerate vascular cell aging, which may lead to vascular dysfunction as seen in diabetes. There is no information on whether this may contribute to the progression of diabetic retinopathy (DR). In this study, we have assessed the occurrence of senescence-associated markers in retinas of streptozotocin-induced diabetic rats at 8 and 12 weeks of hyperglycemia as compared to normoglycemic aging (12 and 14 months) and adult (4.5 months) rat retinas. We have found that in the diabetic retinas there was an up-regulation of senescence-associated markers SA-β-Gal, p16INK4a and miR34a, which correlated with decreased expression of SIRT1, a target of miR34a. Expression of senescence-associated factors primarily found in retinal microvasculature of diabetic rats exceeded levels measured in adult and aging rat retinas. In aging rats, retinal expression of senescence associated-factors was mainly localized at the level of the retinal pigmented epithelium and only minimally in the retinal microvasculature. The expression of oxidative/nitrative stress markers such as 4-hydroxynonenal and nitrotyrosine was more pronounced in the retinal vasculature of diabetic rats as compared to normoglycemic aging and adult rat retinas. Treatments of STZ-rats with the anti-nitrating drug FeTPPS (10mg/Kg/day) significantly reduced the appearance of senescence markers in the retinal microvasculature. Our results demonstrate that hyperglycemia accelerates retinal microvascular cell aging whereas physiological aging affects primarily cells of the retinal pigmented epithelium. In conclusion, hyperglycemia-induced retinal vessel dysfunction and DR progression involve vascular cell senescence due to increased oxidative/nitrative stress. PMID:26466127

  6. 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.

  7. 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.

  8. Antioxidative properties of Murraya koenigii leaf extracts in accelerated oxidation and deep-frying studies.

    PubMed

    Nor, Fatihanim Mohd; Suhaila, Mohamed; Aini, Idris Nor; Razali, Ismail

    2009-01-01

    Murraya koenigii leaf extract antioxidant potentials were evaluated in palm olein using accelerated oxidation storage and deep-frying studies at 180 degrees C for up to 40 h. The extracts (0.2%) retarded oil oxidation and deterioration significantly (P<0.05), slightly less effectively than 0.02% butylated hydroxytoluene in tests such as the peroxide value, anisidine value, iodine value, free fatty acid, Oxidative Stability Index, and polar and polymer compound content. Sensory evaluation on French fries indicated that the extract was useful in improving colour, flavour and overall acceptability and the quality of the fried product. All samples were more acceptable by panellists, especially after the 40th hour frying, compared with those similarly fried in the control oils and the oil containing butylated hydroxytoluene. M. koenigii leaf extract, had a polyphenol content of 109.5+/-0.3 mg gallic acid equivalents/g extract, and contain a heat-stable antioxidant that could be a natural alternative to synthetic antioxidants for the industry. PMID:19488917

  9. Adsorption of trace elements on pyrite surfaces in sulfidic mine tailings from Kristineberg (Sweden) a few years after remediation.

    PubMed

    Müller, Barbara; Axelsson, Mikael D; Ohlander, Björn

    2002-10-21

    Laser ablation inductively coupled plasma mass spectrometry (LA ICP-MS) has been used to determine the elemental composition of the surface and interior layers of pyrite grains from the mine tailings from Kristineberg (northern Sweden) in order to determine concentration gradients between these two layers. The pyrite grains were collected from oxidized and unoxidized zones within the tailings. The aim of this study was to assess the role of pyrite surfaces as sites for the attenuation of solutes from the mine-tailings porewater. The normalized intensities of Cu, Zn, Ag, Sb, Ce, Pb and Bi are highest at the surface of each grain (within the surface layer drilled by the LA) and decrease towards the interior. The surface adsorption of Cu, Zn and Pb is more pronounced within the unoxidized than within the oxidized zone of the tailings. Copper exhibits a distinct concentration peak at the surface of the pyrite grains below the pre-remediation oxidation front. Silver, Sb, Bi, As and Au are preferably adsorbed within the uppermost layer of the oxidized zone in the tailings, where the pH is as high as 6.2. The conversion of intensity signals of the elements to concentration values in ppm was accomplished using an external calibration against an in-house pyrite standard. PMID:12449325

  10. 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.

  11. 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.

  12. Reversible reactions between pyrite and pyrrhotite in SO2

    NASA Astrophysics Data System (ADS)

    Hausen, D. M.

    1991-04-01

    Differential thermal analysis (DTA) of iron sulfides in inert atmospheres containing varying amounts of SO2 indicates temperature-dependent reversible reactions between pyrite and pyrrhotite in the range from 350°C to 520°C. Hexagonal pyrrhotite (troilite) and sulfur dioxide interact above 350°C to form pyrite and magnetite. Pyrite decomposes endothermically to pyrrhotite and sulfur above 520°C in the same atmosphere. The sulfurization of hexagonal pyrrhotite to pyrite has been investigated kinetically by DTA and confirmed by x-ray diffraction and wet chemical analyses. The reversibility of this pyrrhotite-pyrite reaction in a sulfur dioxide atmosphere merits further metallurgical consideration.

  13. 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

  14. Uptake of uranium and trace elements in pyrite (FeS 2) suspensions

    NASA Astrophysics Data System (ADS)

    Descostes, M.; Schlegel, M. L.; Eglizaud, N.; Descamps, F.; Miserque, F.; Simoni, E.

    2010-03-01

    Pyrite dissolution and interaction with Fe (II), Co (II), Eu (III) and U (VI) have been studied under anoxic conditions by solution chemistry and spectroscopic techniques. Aqueous data show a maximal cation uptake above pH 5.5. Iron (II) uptake can explain the non-stoichiometric [S] aq/[Fe] aq ratios often observed during dissolution experiments. Protonation data corrected for pyrite dissolution resulted in a proton site density of 9 ± 3 sites nm -2. Concentration isotherms for Eu (III) and U (VI) sorption on pyrite indicate two different behaviours which can be related to the contrasted redox properties of these elements. For Eu (III), sorption can be explained by the existence of a unique site with a saturation concentration of 1.25 × 10 -6 mol g -1. In the U (VI) case, sorption seems to occur on two different sites with a total saturation concentration of 4.5 × 10 -8 mol g -1. At lower concentration, uranium reduction occurs, limiting the concentration of dissolved uranium to the solubility of UO 2(s). Scanning electron microscopy and micro-Raman spectrometry of U (VI)-sorbed pyrite indicate a heterogeneous distribution of U at the pyrite surface and a close association with oxidized S. X-ray photoelectron spectroscopy confirms the partial reduction of U and the formation of a hyperstoichiometric UO 2+x(s). Our results are consistent with a chemistry of the pyrite surface governed not by Fe (II)-bound hydroxyl groups, but by S groups which can either sorb cations and protons, or sorb and reduce redox-sensitive elements such as U (VI).

  15. 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.

  16. 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. PMID:25059331

  17. Accelerated testing of solid oxide fuel cell stacks for micro combined heat and power application

    NASA Astrophysics Data System (ADS)

    Hagen, Anke; Høgh, Jens Valdemar Thorvald; Barfod, Rasmus

    2015-12-01

    State-of-the-art (SoA) solid oxide fuel cell (SOFC) stacks are tested using profiles relevant for use in micro combined heat and power (CHP) units. Such applications are characterised by dynamic load profiles. In order to shorten the needed testing time and to investigate potential acceleration of degradation, the profiles are executed faster than required for real applications. Operation with fast load cycling, both using hydrogen and methane/steam as fuels, does not accelerate degradation compared to constant operation, which demonstrates the maturity of SoA stacks and enables transferring knowledge from testing at constant conditions to dynamic operation. 7.5 times more cycles than required for 80,000 h lifetime as micro CHP are achieved on one-cell-stack level. The results also suggest that degradation mechanisms that proceed on a longer time-scale, such as creep, might have a more dominating effect for long life-times than regular short time changes of operation. In order to address lifetime testing it is suggested to build a testing program consisting of defined modules that represent different application profiles, such as one module at constant conditions, followed by modules at one set of dynamic conditions etc.

  18. Nitric oxide-releasing nanoparticles accelerate wound healing by promoting fibroblast migration and collagen deposition.

    PubMed

    Han, George; Nguyen, Long N; Macherla, Chitralekha; Chi, Yuling; Friedman, Joel M; Nosanchuk, Joshua D; Martinez, Luis R

    2012-04-01

    Wound healing is a complex process that involves coordinated interactions between diverse immunological and biological systems. Long-term wounds remain a challenging clinical problem, affecting approximately 6 million patients per year, with a high economic impact. To exacerbate the problem, these wounds render the individual susceptible to life-threatening microbial infections. Because current therapeutic strategies have proved suboptimal, it is imperative to focus on new therapeutic approaches and the development of technologies for both short- and long-term wound management. In recent years, nitric oxide (NO) has emerged as a critical molecule in wound healing, with NO levels increasing rapidly after skin damage and gradually decreasing as the healing process progresses. In this study, we examined the effects of a novel NO-releasing nanoparticle technology on wound healing in mice. The results show that the NO nanoparticles (NO-np) significantly accelerated wound healing. NO-np modified leukocyte migration and increased tumor growth factor-β production in the wound area, which subsequently promoted angiogenesis to enhance the healing process. By using human dermal fibroblasts, we demonstrate that NO-np increased fibroblast migration and collagen deposition in wounded tissue. Together, these data show that NO-releasing nanoparticles have the ability to modulate and accelerate wound healing in a pleiotropic manner. PMID:22306734

  19. Accelerated evolutionary rate in sulfur-oxidizing endosymbiotic bacteria associated with the mode of symbiont transmission.

    PubMed

    Peek, A S; Vrijenhoek, R C; Gaut, B S

    1998-11-01

    The nearly neutral theory of molecular evolution predicts that the rate of nucleotide substitution should accelerate in small populations at sites under low selective constraint. We examined these predictions with respect to the relative population sizes for three bacterial life histories within chemolithoautotrophic sulfur-oxidizing bacteria: (1) free-living bacteria, (2) environmentally captured symbionts, and (3) maternally transmitted symbionts. Both relative rates of nucleotide substitution and relative ratios of loop, stem, and domain substitutions from 1,165 nt of the small-subunit 16S rDNA were consistent with expectations of the nearly neutral theory. Relative to free-living sulfur-oxidizing autotrophic bacteria, the maternally transmitted symbionts have faster substitution rates overall and also in low-constraint domains of 16S rDNA. Nucleotide substitition rates also differ between loop and stem positions. All of these findings are consistent with the predictions that these symbionts have relatively small effective population sizes. In contrast, the rates of nucleotide substitution in environmentally captured symbionts are slower, particularly in high-constraint domains, than in free-living bacteria. PMID:12572615

  20. 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

  1. 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

  2. Glutamate Cysteine Ligase Modifier Subunit (Gclm) Null Mice Have Increased Ovarian Oxidative Stress and Accelerated Age-Related Ovarian Failure.

    PubMed

    Lim, Jinhwan; Nakamura, Brooke N; Mohar, Isaac; Kavanagh, Terrance J; Luderer, Ulrike

    2015-09-01

    Glutathione (GSH) is the one of the most abundant intracellular antioxidants. Mice lacking the modifier subunit of glutamate cysteine ligase (Gclm), the rate-limiting enzyme in GSH synthesis, have decreased GSH. Our prior work showed that GSH plays antiapoptotic roles in ovarian follicles. We hypothesized that Gclm(-/-) mice have accelerated ovarian aging due to ovarian oxidative stress. We found significantly decreased ovarian GSH concentrations and oxidized GSH/oxidized glutathione redox potential in Gclm(-/-) vs Gclm(+/+) ovaries. Prepubertal Gclm(-/-) and Gclm(+/+) mice had similar numbers of ovarian follicles, and as expected, the total number of ovarian follicles declined with age in both genotypes. However, the rate of decline in follicles was significantly more rapid in Gclm(-/-) mice, and this was driven by accelerated declines in primordial follicles, which constitute the ovarian reserve. We found significantly increased 4-hydroxynonenal immunostaining (oxidative lipid damage marker) and significantly increased nitrotyrosine immunostaining (oxidative protein damage marker) in prepubertal and adult Gclm(-/-) ovaries compared with controls. The percentage of small ovarian follicles with increased granulosa cell proliferation was significantly higher in prepubertal and 2-month-old Gclm(-/-) vs Gclm(+/+) ovaries, indicating accelerated recruitment of primordial follicles into the growing pool. The percentages of growing follicles with apoptotic granulosa cells were increased in young adult ovaries. Our results demonstrate increased ovarian oxidative stress and oxidative damage in young Gclm(-/-) mice, associated with an accelerated decline in ovarian follicles that appears to be mediated by increased recruitment of follicles into the growing pool, followed by apoptosis at later stages of follicular development. PMID:26083875

  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. Bioleaching of cobalt and zinc from pyrite ore in relation to calcitic gangue content.

    PubMed

    Baldi, F; Bralia, A; Riccobono, F; Sabatini, G

    1991-05-01

    Bioleaching of a pyrite ore containing high concentrations of cobalt (0.1%) and zinc (0.065%) was affected by small amounts of calcitic gangue (from 0.01 to 1.01%). Results from an air-lift percolator and from Erlenmeyer flask experiments show that a small percentage of calcite raises the pH and arrests the growth of the acidophilic bacterium Thiobacillus ferrooxidans. In percolator experiments, when calcite is completely removed by the continuous addition of small quantities of acid, and the pH of the liquor becomes acid, the micro-organism begins to grow and to bio-oxidize the pyrite ore. The growth of T. ferrooxidans shows different lag phase spans (from 13 to 190 days) depending on carbonate dissolution. The metals Fe, Zn and Co are released into the leaching solution together at different rates after a lag-time which depends on calcite concentrations in pyrite gangue. Metal ratios in the mineral bulk are different from those in the liquor, Zn dissolving 5 times more readily than Co. Bioleaching rates for metal removal from pyrite are higher in percolator (for Fe, from 5 to 15 mg/l/h) than in flask experiments (from 0.5 to 2 mg/l/h), but the lag phases are shorter (from 2 to 65 days). The differences between the two systems are related to calcite dissolution and gypsum precipitation. PMID:24425016

  5. 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

  6. 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

  7. 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.

  8. 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.

  9. Drug loaded composite oxidized pectin and gelatin networks for accelerated wound healing.

    PubMed

    Tummalapalli, Mythili; Berthet, Morgane; Verrier, Bernard; Deopura, B L; Alam, M S; Gupta, Bhuvanesh

    2016-05-30

    Biocomposite interactive wound dressings have been designed and fabricated using oxidized pectin (OP), gelatin and nonwoven cotton fabric. Due to their inherent virtues of antimicrobial activity and cytocompatibility, these composite structures are capable of redirecting the healing cascade and influencing cell attachment and proliferation. A novel in situ reduction process has been followed to synthesize oxidized pectin-gelatin-nanosilver (OP-Gel-NS) flower like nanohydrocolloids. This encapsulation technology controls the diffusion and permeation of nanosilver into the surrounding biological tissues. Ciprofloxacin hydrochloride has also been incorporated into the OP-Gel matrix to produce OP-Gel-Cipro dressings. While OP-Gel-NS dressings exhibited 100% antimicrobial activity at extremely low loadings of 3.75μg/cm(2), OP-Gel-Cipro dressings were highly antimicrobial at 1% drug loading. While NIH3T3 mouse fibroblasts proliferated remarkably well when cultured with OP-Gel and OP-Gel-Cipro dressings, OP-Gel-NS hindered cell growth and Bactigras(®) induced complete lysis. Full thickness excisional wounds were created on C57BL/6J mice and the wound healing potential of the OP-Gel-NS dressings led to accelerated healing within 12days, while OP-Gel-Cipro dressings healed wounds at a rate similar to that of Bactigras(®). Histological examination revealed that OP-Gel-NS and OP-Gel-Cipro treatment led to organized collagen deposition, neovascularization and nuclei migration, unlike Bactigras(®). Therefore, the OP-Gel-NS and OP-Gel-Cipro biocomposite dressings exhibiting good hydrophilicity, sustained antimicrobial nature, promote cell growth and proliferation, and lead to rapid healing, can be considered viable candidates for effective management. PMID:27063849

  10. 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.

  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. CHEMICAL MAPPING OF ELEMENTAL SULFUR ON PYRITE AND ARSENOPYRITE SURFACES USING NEAR-INFRARED RAMAN IMAGING MICROSCOPY. (R826189)

    EPA Science Inventory

    Abstract

    Near-infrared Raman imaging microscopy (NIRIM) was used to produce chemical images of the distribution of elemental sulfur on oxidized pyrite and arsenopyrite surfaces. Analysis using Savitsky¯Golay filtering permits an unambiguous identificati...

  13. 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

  14. 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.

  15. An ESR Investigation of Synthetic Pyrite Crystals

    NASA Astrophysics Data System (ADS)

    Siebert, D.; Dahlem, J.; Fiechter, S.; Hartmann, A.

    1989-01-01

    Synthetic pyrite crystals doped with halogen (CI, Br) or manganese (Mn) were investigated by ESR at 78 K with an X-band spectrometer and a TE102 cavity with 100 kc field modulation. The crystals were preferably measured with the directions <100>, <110>, and <111> parallel to the static magnetic field HO. The ESR spectrum of Mn-doped crystals showed a sextet which can be explained by a spin-Hamiltonian for an electron spin S = 1/2 in interaction with the nuclear spin I = 5/2 of the Mn nucleus for axial symmetry. Due to the observed spin and due to the orientation of the paramagnetic centers the spectra were assigned to Mn2+ in the low spin state which resides on cation site in the FeS2, lattice. In halogen-doped crystals four pairs of lines can be interpreted by the interaction of the two isotopes of I = 3/2, 79Br, 81Br and 35Cl, 37Cl, respectively, with an electron spin S = 1/2. According to the observed symmetry of the ESR signals the paramagnetic centers can be explained as (S-X)2- radicals (X = CI, Br) which substitute for the (S2)2- dumb-bells of pyrite. All crystals evoked extremely narrow ESR lines, especially the halogen-doped crystals with linewidths down to 0.03 mT. Excellent agreement between measured and calculated spectra up to the finest details has been obtained.

  16. Electrochemistry of Thiobacillus ferrooxidans reactions with pyrite

    SciTech Connect

    Pesic, B.; Oliver, D.J.

    1990-01-01

    The objective of this project is to provide the fundamental information on the mechanisms of bacterial leaching of pyrite. The knowledge of how bacterial leaching of pyrite functions is essential for design and development of a technology for coal cleaning with bacteria. The features of major electrochemical techniques will be examined to find out if any of them can provide a diagnostic information on the mechanisms of related reactions. The research was focused on how to improve the chemical activity of bacteria. Two major approaches were undertaken. One was to provide more nutrient salts. It was anticipated that by providing higher amounts of nutrients the concentration and the activity of bacteria would increase. The other approach was to provide fresh environment to bacteria for the growth. Before the experiments it was decided to first examine their activity with time. However, there was no literature information available on this subject. The effect of the solution pH, was also studied. 4 refs., 8 figs.

  17. A thermodynamic study of pyrite and pyrrhotite

    USGS Publications Warehouse

    Toulmin, P., III; Barton, P.B., Jr.

    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.

  18. 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.

  19. 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

  20. 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

  1. 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

  2. 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

  3. Trace element transformations and partitioning during the roasting of pyrite ores in the sulfuric acid industry.

    PubMed

    Yang, Chunxia; Chen, Yongheng; Peng, Ping'an; Li, Chao; Chang, Xiangyang; Wu, Yingjuan

    2009-08-15

    Total concentrations combined with chemical partitioning of trace elements (Cd, Co, Cr, Mn, Ni, Pb, Tl, and Zn) in raw pyrite ore and solid roasting wastes were investigated in order to elucidate their transformations and partitioning during the roasting of raw pyrite ores in sulfuric acid production. In order to better understand the behavior of these elements during roasting, mineral transformations accompanying roasting were also investigated by using microscopy. Results indicated that the mode of occurrence of trace elements in raw pyrite ore and the thermostability of trace element-bearing species formed during roasting played major roles in the transformations of the selected trace elements. Silicate- and amorphous iron (hydr)oxide-bound elements (Cr and Pb) were stable and mainly retained in their original phases. However, acid-exchangeable and sulfide-bound elements tended to transform into other forms via different pathways: elements that tend to form low thermostable species (Cd, Pb and Tl) were significantly vaporized, whereas elements that tend to form high thermostable species (Co, Mn and Ni) mainly reacted with iron oxides or silicates, which then remained in the solid residues. The volatility of trace elements during the roasting has a significant effect on their subsequent partitioning in roasting wastes. Nonvolatile element (Co, Cr, Mn, and Ni) partitioning was determined by settling of the particulate in which they are bound, whereas the partitioning of (semi)volatile elements (Cd, Pb, Tl, and Zn) was controlled by the adsorption of their gaseous species on the particulate. PMID:19261379

  4. 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.

  5. 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

  6. A label-free colorimetric sensor for Pb2+ detection based on the acceleration of gold leaching by graphene oxide.

    PubMed

    Shi, Xinhao; Gu, Wei; Zhang, Cuiling; Zhao, Longyun; Peng, Weidong; Xian, Yuezhong

    2015-03-14

    In this work, we developed a novel, label-free, colorimetric sensor for Pb(2+) detection based on the acceleration of gold leaching by graphene oxide (GO) at room temperature. Gold nanoparticles (AuNPs) can be dissolved in a thiosulfate (S2O3(2-)) aqueous environment in the presence of oxygen; however, the leaching rate is very slow due to the high activation energy (27.99 kJ mol(-1)). In order to enhance the reaction rate, some accelerators should be added. In comparison with the traditional accelerators (metal ions or middle ligands), we found that GO could efficiently accelerate the gold leaching reaction. Kinetic data demonstrate that the dissolution rate of gold in the Pb(2+)-S2O3(2-)-GO system is 5 times faster than that without GO at room temperature. In addition, the effects of surface modification and the nanoparticle size on the etching of AuNPs were investigated. Based on the GO-accelerated concentration-dependent colour changes of AuNPs, a colorimetric sensor for Pb(2+) detection was developed with a linear range from 0.1 to 20 μM and the limit of detection (LOD) was evaluated to be 0.05 μM. This colorimetric assay is simple, low-cost, label-free, and has numerous potential applications in the field of environmental chemistry. PMID:25656247

  7. 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

  8. The coupled geochemistry of Au and As in pyrite from ore deposits and geothermal fields: monitoring fluid evolution and external forcing factors in hydrothermal systems

    NASA Astrophysics Data System (ADS)

    Reich, M.; Deditius, A.; Tardani, D.; Sanchez-Alfaro, P.

    2014-12-01

    Gold and arsenic incorporation into pyrite (FeS2) is strongly coupled in different types of ore deposits, including Carlin-type Au, porphyry Cu, epithermal Au, orogenic Au, volcanogenic massive sulphide (VMS) and iron-oxide Cu-Au (IOCG), among others. Despite significant advances in the last decades, the fundamental factors controlling Au and As partition in pyrite from hydrothermal systems formed under different tectonic settings and crustal levels remain poorly known. Furthermore, the complexity of pyrite microtextures and growth features suggest multi-stage growth that may be useful to monitor changes in fluid composition related to episodic pumping of fluids. Here we report a comprehensive database of EMPA, SIMS, LA-ICP-MS and micro-PIXE Au-As analyses that cover temperature conditions of pyrite formation from ~30ºC to ~600ºC. The global pyrite Au-As data form a wedge-shaped zone in compositional space, and show that the solid solubility limit of Au in arsenian pyrite is independent of the geochemical environment of pyrite formation and rather depends on its crystal-chemical properties and post-depositional alteration. Compilation of Au-As concentrations and formation temperatures for pyrite indicates that Au and As solubility is retrograde in this mineral, as Au and As contents decrease with increasing temperature from ~200-500ºC. Based on these results, we define one Au-As trend formed by pyrites from Carlin-type and orogenic Au deposits where compositions are largely controlled by fluid-rock-interactions and can be highly perturbed by changes of temperature or subsequent alteration. The second trend consists of pyrites from porphyry Cu, epithermal Au deposits and geothermal systems, which are characterized by compositions that preserve the Au/As signature of mineralizing magmatic-hydrothermal fluids. The well-developed oscillatory zoning in pyrite detected in these systems, where Cu-rich, Au-As-depleted growth zones alternate with Cu-poor, Au

  9. 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

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

    PubMed

    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

  11. 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

  12. Comparison of different chelating agents to enhance reductive Cr(VI) removal by pyrite treatment procedure.

    PubMed

    Kantar, Cetin; Ari, Cihan; Keskin, Selda

    2015-06-01

    New technologies involving in-situ chemical hexavalent chromium [Cr(VI)] reduction to trivalent chromium [Cr(III)] with natural Fe(II)-containing minerals can offer viable solutions to the treatment of wastewater and subsurface systems contaminated with Cr(VI). Here, the effects of five different chelating agents including citrate, EDTA, oxalate, tartrate and salicylate on reductive Cr(VI) removal from aqueous systems by pyrite were investigated in batch reactors. The Cr(VI) removal was highly dependent on the type of ligand used and chemical conditions (e.g., ligand concentration). While salicylate and EDTA had no or little effect on Cr(VI) removal, the ligands including citrate, tartrate and oxalate significantly enhanced Cr(VI) removal at pH < 7 relative to non-ligand systems. In general, the efficiency of organic ligands on Cr(VI) removal decreased in the order: citrate ≥ oxalate ≈ tartrate > EDTA > salicylate ≈ non-ligand system. Organic ligands enhanced Cr(VI) removal by 1) removing surface oxide layer via the formation of soluble Fe-Cr-ligand complexes, and 2) enhancing the reductive iron redox cycling for the regeneration of new surface sites. While citrate, oxalate and tartrate eliminated the formation of surface Cr (III)-Fe(III)-oxides, the surface phase Cr (III) species was observed in the presence of EDTA and salicylate indicating that Cr(III) complexed with EDTA and salicylate sorbed or precipitated onto pyrite surface, thereby blocking the access of CrO4(2-) to pyrite surface. The binding of Fe(III) with the disulfide reactive sites (≡Fe-S-S-Fe(III)) was essential for the regeneration of new surface sites through pyrite oxidation. Although Fe(III)-S species was detected at the pyrite surface in the presence of citrate, oxalate and tartrate, Fe(III) complexed with EDTA and salicylate did not strongly interact with the disulfide reactive sites due to the formation of non-sorbing Fe(III)-ligand complexes. The absence of surface Fe

  13. Multiple sulphur and iron isotope composition of detrital pyrite in Archaean sedimentary rocks: A new tool for provenance analysis

    NASA Astrophysics Data System (ADS)

    Hofmann, Axel; Bekker, Andrey; Rouxel, Olivier; Rumble, Doug; Master, Sharad

    2009-09-01

    Multiple S ( δ34S and δ33S) and Fe ( δ56Fe) isotope analyses of rounded pyrite grains from 3.1 to 2.6 Ga conglomerates of southern Africa indicate their detrital origin, which supports anoxic surface conditions in the Archaean. Rounded pyrites from Meso- to Neoarchaean gold and uranium-bearing strata of South Africa are derived from both crustal and sedimentary sources, the latter being characterised by non-mass dependent fractionation of S isotopes ( Δ33S as negative as - 1.35‰) and large range of Fe isotope values ( δ56Fe between - 1.1 and 1.2‰). Most sediment-sourced pyrite grains are likely derived from sulphide nodules in marine organic matter-rich shales, sedimentary exhalites and volcanogenic massive sulphide deposits. Some sedimentary pyrite grains may have been derived from in situ sulphidised Fe-oxides, prior to their incorporation into the conglomerates, as indicated by unusually high positive δ56Fe values. Sedimentary sulphides without significant non-mass dependent fractionation of S isotopes were also present in the source of some conglomerates. The abundance in these rocks of detrital pyrite unstable in the oxygenated atmosphere may suggest factors other than high pO 2 as the cause for the absence of significant non-mass dependent fractionation processes in the 3.2-2.7 Ga atmosphere. Rounded pyrites from the c. 2.6 Ga conglomerates of the Belingwe greenstone belt in Zimbabwe have strongly fractionated δ34S, Δ33S and δ56Fe values, the source of which can be traced back to black shale-hosted massive sulphides in the underlying strata. The study demonstrates the utility of combined multiple S and Fe isotope analyses for provenance reconstruction of Archaean sedimentary successions.

  14. Archaeal diversity and the extent of iron and manganese pyritization in sediments from a tropical mangrove creek (Cardoso Island, Brazil)

    NASA Astrophysics Data System (ADS)

    Otero, X. L.; Lucheta, A. R.; Ferreira, T. O.; Huerta-Díaz, M. A.; Lambais, M. R.

    2014-06-01

    Even though several studies on the geochemical processes occurring in mangrove soils and sediments have been performed, information on the diversity of Archaea and their functional roles in these ecosystems, especially in subsurface environments, is scarce. In this study, we have analyzed the depth distribution of Archaea and their possible relationships with the geochemical transformations of Fe and Mn in a sediment core from a tropical mangrove creek, using 16S rRNA gene profiling and sequential extraction of different forms of Fe and Mn. A significant shift in the archaeal community structure was observed in the lower layers (90-100 cm), coinciding with a clear decrease in total organic carbon (TOC) content and an increase in the percentage of sand. The comparison of the archaeal communities showed a dominance of methanogenic Euryarchaeota in the upper layers (0-20 cm), whereas Crenarchaeota was the most abundant taxon in the lower layers. The dominance of methanogenic Euryarchaeota in the upper layer of the sediment suggests the occurrence of methanogenesis in anoxic microenvironments. The concentrations of Fe-oxyhydroxides in the profile were very low, and showed positive correlation with the concentrations of pyrite and degrees of Fe and Mn pyritization. Additionally, a partial decoupling of pyrite formation from organic matter concentration was observed, suggesting excessive Fe pyritization. This overpyritization of Fe can be explained either by the anoxic oxidation of methane by sulfate and/or by detrital pyrite tidal transportation from the surrounding mangrove soils. The higher pyritization levels observed in deeper layers of the creek sediment were also in agreement with its Pleistocenic origin.

  15. 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.

  16. 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. PMID:21847529

  17. 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

  18. 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

  19. Enabling iron pyrite (FeS2) and related ternary pyrite compounds for high-performance solar energy applications

    NASA Astrophysics Data System (ADS)

    Caban Acevedo, Miguel

    The success of solar energy technologies depends not only on highly efficient solar-to-electrical energy conversion, charge storage or chemical fuel production, but also on dramatically reduced cost, to meet the future terawatt energy challenges we face. The enormous scale involved in the development of impactful solar energy technologies demand abundant and inexpensive materials, as well as energy-efficient and cost-effective processes. As a result, the investigation of semiconductor, catalyst and electrode materials made of earth-abundant and sustainable elements may prove to be of significant importance for the long-term adaptation of solar energy technologies on a larger scale. Among earth-abundant semiconductors, iron pyrite (cubic FeS2) has been considered the most promising solar energy absorber with the potential to achieve terawatt energy-scale deployment. Despite extensive synthetic progress and device efforts, the solar conversion efficiency of iron pyrite has remained below 3% since the 1990s, primarily due to a low open circuit voltage (V oc). The low photovoltage (Voc) of iron pyrite has puzzled scientists for decades and limited the development of cost-effective solar energy technologies based on this otherwise promising semiconductor. Here I report a comprehensive investigation of the syntheses and properties of iron pyrite materials, which reveals that the Voc of iron pyrite is limited by the ionization of a high density of intrinsic bulk defect states despite high density surface states and strong surface Fermi level pinning. Contrary to popular belief, bulk defects most-likely caused by intrinsic sulfur vacancies in iron pyrite must be controlled in order to enable this earth-abundant semiconductor for cost-effective and sustainable solar energy conversion. Lastly, the investigation of iron pyrite presented here lead to the discovery of ternary pyrite-type cobalt phosphosulfide (CoPS) as a highly-efficient earth-abundant catalyst material for

  20. 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

  1. Pyritization of trace metals in anoxic marine sediments

    NASA Astrophysics Data System (ADS)

    Huerta-Diaz, Miguel A.; Morse, John W.

    1992-07-01

    The pyritization of reactive trace elements in different anoxic marine sediments was investigated to determine the importance of factors such as ∑H 2S, reactive-Fe, pyrite content and salinity in controlling this process. The areas studied included anoxic-sulfidic sediments (Baffin Bay, a hypersaline coastal lagoon from Texas and Green Canyon, a hemipelagic oil seepage area), anoxic-nonsulfidic sediments with high sedimentation rates (Atchafalaya Bay-Mississippi Delta system), hemipelagic anoxic-nonsulfidic sediments with low sedimentation rates (Gulf of Mexico shelf and slope and Orca Basin, an euxinic hypersaline basin) and organic-rich marsh sediments (Atchafalaya Bay). Results indicate that the degree of trace metal pyritization (DTMP) of all trace metals, except Cd, increased with increasing degree of pyritization (DOP), irrespective of the type of sedimentary environment involved. However, for As, Hg and Mo, the DTMP/DOP values were generally above the 1:1 ratio line, whereas the transition metals Co, Cu, Mn and Ni displayed a close to linear increase in DTMP with DOP and moderate incorporation into pyrite. Chromium and the class B metals Pb and Zn were also gradually incorporated into the pyrite phase but without reaching the DTMP levels exhibited by the transition metals. Cadmium was not incorporated to a significant extent. These results are consistent with the chemical attributes of these different classes of trace elements. Availability of dissolved trace metals and organic matter content are apparently important factors controlling the incorporation of Co, Cr, Cu and Ni into pyrite in anoxicsulfidic (Fe-poor and H 2S-rich) environments.

  2. Aluminum ions accelerated the oxidative stress of copper-mediated melanin formation

    NASA Astrophysics Data System (ADS)

    Di, Junwei; Bi, Shuping

    2003-11-01

    A comparison between the effects of aluminum and cupric ions on the dopachrome (DC) conversion and the cooperation effect of the both ions in the DOPA oxidation to melanin pathway has been studied by UV-Vis spectrophotometric method. Both aluminum and cupric ions catalyze the DC conversion reaction, which is an important step in the melanin synthesis pathway. However, cupric ions catalyze the conversion of DC to yield 5,6-dihydroxyindole-2-carboxylic acid (DHICA) but the product of DC conversion catalyzed by aluminum is 5,6-dihydroxyindole (DHI). DOPA oxidation catalyzed by aluminum and cupric ions is studied in the presence of hydrogen peroxide. The results from our experiments provide evidence that aluminum can markedly increase the oxidative stress of copper-mediated the melanin formation and influence the properties of the melanin by means of changing the ratio of DHICA/DHI in the acidic environment (pH 5.5).

  3. 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

  4. 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.

  5. 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

  6. Arsenic Incorporation Into Authigenic Pyrite, Bengal Basin Sediment, Bangladesh

    SciTech Connect

    Lowers, H.A.; Breit, G.N.; Foster, A.L.; Whitney, J.; Yount, J.; Uddin, Md.N.; Muneem, Ad.A.; /Geological Survey, Denver /Geological Survey, Menlo Park

    2007-07-10

    Sediment from two deep boreholes ({approx}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.

  7. 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.

  8. 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.

  9. 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.

  10. Brazilian coal mining residues and sulphide oxidation by Fenton's reaction: an accelerated weathering procedure to evaluate possible environmental impact.

    PubMed

    Silva, L F O; Querol, X; da Boit, K M; Fdez-Ortiz de Vallejuelo, S; Madariaga, J M

    2011-02-15

    Fenton's reaction is proposed as an accelerated weathering test for sulphides associated with Brazilian Coal Mining Residues (CMR), that are exposed to oxygen and water during the mining of coal. TEM and SEM/EDX were used to evaluate the nature, occurrence and distribution of minerals in remaining coals and other lithological units, before and after applying the test. Oxidation of CMRs was examined by analyzing soluble sulphur (sulphate) and dissolved metals by ICP-MS or ICP OES. As dissolved sulphate increases, dissolved Zn, Cd, Cu and Co concentrations increase, leading to undetectable amounts in the remaining solid phases; dissolved Ni and Mn also increase with the mobilized sulphur, but the remainder in the solids is the most important fraction; Fe and Pb are not mobilized due to precipitation as jarosite or hematite in the case of Fe or as sulphate in the case of Pb. Agreement between the observed results and the predictions by geochemical modelling is discussed. PMID:21145167

  11. 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.

  12. Comparison of methods to determine degree of pyritization

    NASA Astrophysics Data System (ADS)

    Leventhal, Joel; Taylor, Cliff

    1990-09-01

    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.

  13. 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

  14. Fine pyrite removal from coal using a placer ore jig

    SciTech Connect

    Thomson, R.S.; Aplan, F.F.

    1995-10-01

    A placer ore jig, typically used to recover fine gold, tin and diamonds from alluvial ores, has been modified to remove fine pyrite from minus 6.4 mm ({minus}1/4 inch) coal. In parallel tests, it proved to be far superior to two conventional coal jigs, the Baum and the Baum-feldspar, in removing fine pyrite from coal. The Pan-Am placer jig was found to remove essentially all of the +28 mesh pyrite and from 99% to 90%, decreasingly, in the 28 to 200 mesh range. This jig also showed a superior performance to the Baum-Type jigs in removing fine coal from its associated refuse. The superiority of the Pan-Am placer jig is related to the strong emphasis given on the suction stroke and, hence, on consolidation trickling, whereas the Baum jigs principally emphasize the pulsion stroke during jigging.

  15. Thermally Accelerated Oxidative Degradation of Quercetin Using Continuous Flow Kinetic Electrospray-Ion Trap-Time of Flight Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Barnes, Jeremy S.; Foss, Frank W.; Schug, Kevin A.

    2013-10-01

    Thermally accelerated oxidative degradation of aqueous quercetin at pH 5.9 and 7.4 was kinetically measured using an in-house built online continuous flow device made of concentric capillary tubes, modified to fit to the inlet of an electrospray ionization-ion trap-time-of-flight-mass spectrometer (ESI-IT-TOF-MS). Time-resolved mass spectral measurements ranging from 2 to 21 min were performed in the negative mode to track intermediate degradation products and to evaluate the degradation rate of the deprotonated quercetin ion, [Q-H]-. Upon heating solutions in the presence of dissolved oxygen, degradation of [Q-H]- was observed and was accelerated by an increase in pH and temperature. Regardless of the condition, the same degradation pathways were observed. Degradation mechanisms and structures were determined using higher order tandem mass spectrometry (up to MS3) and high mass accuracy. The observed degradation mechanisms included oxidation, hydroxylation, and ring-cleavage by nucleophilic attack. A chalcan-trione structure formed by C-ring opening after hydroxylation at C2 was believed to be a precursor for other degradation products, formed by hydroxylation at the C2, C3, and C4 carbons from attack by nucleophilic species. This resulted in A-type and B-type ions after cross-ring cleavage of the C-ring. Based on time of appearance and signal intensity, nucleophilic attack at C3 was the preferred degradation pathway, which generated 2,4,6-trihydroxymandelate and 2,4,6-trihydroxyphenylglyoxylate ions. Overall, 23 quercetin-related ions were observed.

  16. 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

  17. 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

  18. Analytical interfacial studies of double carbonate thermionic oxide cathodes over accelerated operational life

    NASA Astrophysics Data System (ADS)

    Barber, D. K.; Jenkins, S. N.; Whiting, M. J.; Baker, M. A.

    2005-09-01

    Interfacial interactions between the nickel cap and emissive oxide in double carbonate thermionic oxide cathodes have been studied as a function of operational lifetime by SEM, AES, EDX and TEM. The surface of the interface region has been studied by stripping away the oxide from the cap. In cross-section, the interface has been examined by (a) preparing 10° taper cross-sections and (b) cutting FIB sections. Cracks are observed to develop in the bulk Ni and become more pronounced as a function of operational lifetime. Cracks are found both at grain boundaries and close to the surface, parallel to the interface. It is proposed that the cracks develop from voids, formed as a result of the high diffusivity of Mg and Al in the Ni matrix. EDX shows the presence of Al, Mg, Ba, Sr and O within the cracks and it is proposed that MgO and (Ba, Sr)Al 2O 4 are two major reaction products. A thin (skin) layer containing Al, Ba, Sr and O forms at the Ni cap/emissive layer interface, attributed primarily to (Ba, Sr)Al 2O 4 formation.

  19. 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. PMID:25827267

  20. 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

  1. Shock-induced modification of a coal-derived pyrite. [Effects on liquefaction conversions

    SciTech Connect

    Morosin, B.; Stohl, F.V.; Graham, R.A.; Richards, P.; Granoff, B.; Williamson, D.L.

    1983-09-01

    Objectives were to characterize the effects of high-pressure shock-wave loadings on a coal-derived pyrite and to determine the effect of the increased defect concentration of the pyrite on coal liquefaction. The materials used were Robena pyrite with about 30 wt. % of phases other than FeS/sub 2/ and a sample of cleaned Robena pyrite which only contained pyrite and marcasite. The defect concentration in these materials was altered by the use of high-pressure shock-wave loadings with peak pressures of 10 to 15 GPa and peak temperatures of 600 to 900/sup 0/K. Both shocked materials showed broadened high 2THETA lines in the pyrite x-ray pattern which were caused by strain-induced lattice defects. The shocked uncleaned pyrite showed the presence of two additional phases, Fe/sub 3/C and pyrrhotite. The shocked cleaned pyrite showed the possible formation of smythite (Fe/sub 9/S/sub 11/) and pyrrhotite. Catalytic activity tests of the shocked cleaned pyrite were carried out in tubing reactors with West Virginia Blacksville No. 2 coal and SRC-II heavy distillate at 425/sup 0/C. The toluene and THF conversions from the runs with the shocked cleaned pyrite were similar to those obtained from the unshocked cleaned pyrite. This suggests that pyrite may not be the active phase which yields improvements in coal liquefaction or that the defects in pyrite are lost under coal-liquefaction conditions.

  2. Temporal variations of mineral character of acid-producing pyritic coastal sediments, Southeast Queensland, Australia.

    PubMed

    Preda, Micaela; Cox, Malcolm E

    2004-06-29

    The lower Pimpama River catchment possesses many features of morphology, geology and landuse, typical for Southeast Queensland. Pimpama River and its main tributary Hotham Creek meander over a coastal plain which developed during the last several thousand years as a result of sea level fluctuations and changing fluvial and estuarine regimes which provided ideal conditions for the formation of sedimentary pyrite. A complex mixture of natural and human factors triggers and controls the oxidation and hydrolysis of this pyrite. The consequent production of sulfuric acid and leaching of metals from the pyrite-rich sediments represent main environmental issues of this coastal setting. This study aimed to determine the lithological character of the coastal unconsolidated sediments, and identify changes produced by acidity over a long period of time in a natural system and over a short period of time in a laboratory system. The mineral composition of the estuarine sediments of the coastal plain reflects the lithology of their source, the geological basement, and also the enhanced weathering rate due to acid production. The primary minerals present in the sediments consist of quartz and feldspars (primarily albite, K-feldspars to a lesser extent and minor anorthite) the product of physical weathering of bedrock material, mainly sandstone. Kaolinite is the dominant clay mineral and represents the product of intense leaching of feldspars promoted by acid conditions. Kaolinite is fairly ordered in structure in fresh and weathered bedrock and it becomes disordered in the estuarine sediments. Illite is mainly present in bedrock-related samples and the highest amounts are associated with muscovite. In the tidal sediments, illite is present to a lesser extent and is not found in the lower estuary. The distribution of mixed layers of smectite-illite is highly variable and their deposition is mainly controlled by the hydrodynamic conditions of the environment. Only low energy tidal

  3. 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

  4. DSC evaluation of extra virgin olive oil stability under accelerated oxidative test: effect of fatty acid composition and phenol contents.

    PubMed

    Cerretani, Lorenzo; Bendini, Alessandra; Rinaldi, Massimiliano; Paciulli, Maria; Vecchio, Stefano; Chiavaro, Emma

    2012-01-01

    Three extra virgin olive oils having different fatty acid compositions and total phenol contents were submitted to an accelerated storage test at 60°C for up to 21 weeks. Their oxidative status, evaluated by peroxide values and total phenolic content, was related to differential scanning calorimetry cooling profiles and thermal properties. Changes in crystallization profiles were consistent starting from 12 weeks for the two oil samples (B and C) that had a higher content of linoleic acid and medium/low amounts of phenols, respectively, whereas they became detectable at the end of the test for the remaining oil (sample A). Decrease of crystallization enthalpy and shift of transition towards lower temperature were also evident at 4 weeks of storage for samples B and C, whereas the same changes in the transition profile were noticeable at 12 weeks for sample A. Differential scanning calorimetry appears to be suitable for the discrimination of oxidative status of extra virgin olive oils with widely different fatty acid composition. PMID:22687775

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

    PubMed

    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 TiO2 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 TiO2 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. PMID:24746987

  6. 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

  7. 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

  8. 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

  9. 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. PMID:27132830

  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. 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.

  12. 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.

  13. Translucent tissue defect in potato (Solanum tuberosum L.) tubers is associated with oxidative stress accompanying an accelerated aging phenotype.

    PubMed

    Zommick, Daniel H; Kumar, G N Mohan; Knowles, Lisa O; Knowles, N Richard

    2013-12-01

    Translucent tissue defect (TTD) is an undesirable postharvest disorder of potato tubers characterized by the development of random pockets of semi-transparent tissue containing high concentrations of reducing sugars. Translucent areas turn dark during frying due to the Maillard reaction. The newly released cultivar, Premier Russet, is highly resistant to low temperature sweetening, but susceptible to TTD. Symptoms appeared as early as 170 days after harvest and worsened with time in storage (4-9 °C, 95 % RH). In addition to higher concentrations of glucose, fructose and sucrose, TTD resulted in lower dry matter, higher specific activities of starch phosphorylase and glc-6-phosphate dehydrogenase, higher protease activity, loss of protein, and increased concentrations of free amino acids (esp. asparagine and glutamine). The mechanism of TTD is unknown; however, the disorder has similarities with the irreversible senescent sweetening that occurs in tubers during long-term storage, where much of the decline in quality is a consequence of progressive increases in oxidative stress with advancing age. The respiration rate of non-TTD 'Premier Russet' tubers was inherently higher (ca. 40 %) than that of 'Russet Burbank' tubers (a non-TTD cultivar). Moreover, translucent tissue from 'Premier Russet' tubers had a 1.9-fold higher respiration rate than the average of non-translucent tissue and tissue from non-TTD tubers. Peroxidation of membrane lipids during TTD development resulted in increased levels of malondialdehyde and likely contributed to a measurable increase in membrane permeability. Superoxide dismutase and catalase activities and the ratio of oxidized to total glutathione were substantially higher in translucent tissue. TTD tubers also contained twofold less ascorbate than non-TTD tubers. TTD appears to be a consequence of oxidative stress associated with accelerated aging of 'Premier Russet' tubers. PMID:24037414

  14. Oxidized low-density lipoprotein accelerates the destabilization of extracellular-superoxide dismutase mRNA during foam cell formation.

    PubMed

    Makino, Junya; Nii, Miyuki; Kamiya, Tetsuro; Hara, Hirokazu; Adachi, Tetsuo

    2015-06-01

    Extracellular-superoxide dismutase (EC-SOD) is one of the main anti-oxidative enzymes that protect cells against the damaging effects of superoxide. In the present study, we investigated the regulation of EC-SOD expression during the oxidized low density lipoprotein (oxLDL)-induced foam cell formation of THP-1-derived macrophages. The uptake of oxLDL into THP-1-derived macrophages was increased and EC-SOD expression was decreased in a time-dependent manner by oxLDL. Furthermore, EC-SOD suppression by oxLDL was mediated by the binding to scavenger receptors, especially CD36, from the results with siRNA experience. EC-SOD expression is known to be regulated by histone acetylation and binding of the transcription factor Sp1/3 to the EC-SOD promoter region in human cell lines. However, oxLDL did not affect these processes. On the other hand, the stability of EC-SOD mRNA was decreased by oxLDL. Moreover, oxLDL promoted destabilization of ectopically expressed mRNA from EC-SOD or chimeric Cu,Zn-SOD gene with the sequence corresponding to 3'UTR of EC-SOD mRNA, whereas oxLDL had no effect on ectopic mRNA produced from EC-SOD gene lacking the sequence. These results suggested that oxLDL decreased the expression of EC-SOD, which, in turn, accelerated the destabilization of EC-SOD mRNA, leading to weaker protection against oxidative stress and atherosclerosis. PMID:25906743

  15. Shear stress–induced unfolding of VWF accelerates oxidation of key methionine residues in the A1A2A3 region

    PubMed Central

    Chen, Junmei; Gallagher, Ryan; Zheng, Ying; Chung, Dominic W.

    2011-01-01

    VWF is required for platelet adhesion to sites of vessel injury, a process vital for both hemostasis and thrombosis. Enhanced VWF secretion and oxidative stress are both hallmarks of inflammation. We recently showed that the neutrophil oxidant hypochlorous acid (HOCl) inhibits VWF proteolysis by ADAMTS13 by oxidizing VWF methionine 1606 (M1606) in the A2 domain. M1606 was readily oxidized in a substrate peptide, but required urea in multimeric plasma VWF. In the present study, we examined whether shear stress enhances VWF oxidation. With an HOCl-generating system containing myeloperoxidase (MPO) and H2O2, we found that shear stress accelerated M1606 oxidation, with 56% becoming oxidized within 1 hour. Seven other methionine residues in the VWF A1A2A3 region (containing the sites for platelet and collagen binding and ADAMTS13 cleavage) were variably oxidized, one completely. Oxidized methionines accumulated preferentially in the largest VWF multimers. HOCl-oxidized VWF was hyperfunctional, agglutinating platelets at ristocetin concentrations that induced minimal agglutination using unoxidized VWF and binding more of the nanobody AU/VWFa-11, which detects a gain-of-function conformation of the A1 domain. These findings suggest that neutrophil oxidants will both render newly secreted VWF uncleavable and alter the largest plasma VWF forms such that they become hyperfunctional and resistant to proteolysis by ADAMTS13. PMID:21917758

  16. 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

  17. Effects of pyrite and bornite on bioleaching of two different types of chalcopyrite in the presence of Leptospirillum ferriphilum.

    PubMed

    Zhao, Hongbo; Wang, Jun; Gan, Xiaowen; Zheng, Xihua; Tao, Lang; Hu, Minghao; Li, Yini; Qin, Wenqing; Qiu, Guanzhou

    2015-10-01

    The effects of pyrite and bornite on bioleaching of two different chalcopyrite samples by Leptospirillum ferriphilum were studied for the first time. Results showed that bioleaching behaviors of the two chalcopyrite samples were extremely different. Bornite decreased the redox potential (ORP) and maintained it at an appropriate range (380-480 mV vs. Ag/AgCl) to promote chalcopyrite (A) dissolution, but caused the redox potential out of the optimum range and inhibited chalcopyrite (B) dissolution. Large amount of pyrite decreased the redox potential and maintained it at an optimum range to promote chalcopyrite (A) dissolution, while increased the redox potential and kept it at appropriate range for a longer period of time to enhance the dissolution rate of chalcopyrite (B). Chalcopyrite (B) had significantly higher values of conductivity and oxidation-reduction rate when compared with those of chalcopyrite (A). The work is potentially useful in interpreting the inconsistence of the researches of chalcopyrite hydrometallurgy. PMID:26183922

  18. 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

  19. Curcumin mitigates accelerated aging after irradiation in Drosophila by reducing oxidative stress.

    PubMed

    Seong, Ki Moon; Yu, Mira; Lee, Kyu-Sun; 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

  20. 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...

  1. 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.

  2. 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.

  3. 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.

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

    PubMed

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

    2015-05-01

    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 oxidised 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 <50mg/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 labelled standards for quantitative characterisation of processing-induced volatile generation across related foodstuffs, and verify the origin of specific volatiles from parent n-3 fatty acids. PMID:25529686

  5. 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.

  6. 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.

  7. 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.

  8. Increasing the band gap of iron pyrite by alloying with oxygen

    NASA Astrophysics Data System (ADS)

    Law, Matthew; Hu, Jun; Zhang, Yanning; Wu, Ruqian

    2013-03-01

    Systematic density functional theory studies and model analyses have been used to show that the band gap of iron pyrite (FeS2) can be increased from ~ 1.0 to 1.2 -1.3 eV by replacing ~ 10% of the sulfur atoms with oxygen atoms (i.e., ~ 10% OS impurities). OS formation is exothermic, and the oxygen atoms tend to avoid O-O dimerization, which favors the structural stability of homogeneous FeS2-xOx alloys and frustrates phase separation into FeS2 and iron oxides. With an ideal band gap, absence of OSinduced gap states, high optical absorptivity, and low electron effective mass, FeS2-xOx alloys are promising for the development of pyrite-based heterojunction solar cells that feature large photovoltages and high device efficiencies. Acknowledgement: We thank the NSF SOLAR Program (Award CHE-1035218) and the UCI School of Physical Sciences Center for Solar Energy for support of this work. Calculations were performed on parallel computers at NERSC and at NSF supercomputer centers.

  9. Viability of pyrite pulled metabolism in the ‘iron-sulfur world’ theory: Quantum chemical assessment

    NASA Astrophysics Data System (ADS)

    Michalkova, Andrea; Kholod, Yana; Kosenkov, Dmytro; Gorb, Leonid; Leszczynski, Jerzy

    2011-04-01

    The viability of pyrite-pulled metabolism in the 'iron-sulfur world' theory was assessed using a simple model of iron-nickel sulfide (Fe-Ni-S) surface and data obtained from quantum chemical calculations. We have investigated how the individual reactions in the carbon fixation cycle (carboxylic acids formation) on an Fe-Ni-S surface could have operated to produce carboxylic acids from carbon oxide and water. The proposed model cycle reveals how the individual reactions might have functioned and provides the thermodynamics of each step of the proposed pathway. The feasibility of individual reactions, as well the whole cycle was considered. The reaction of acetic acid production from CH 3SH and CO on an Fe-Ni sulfide surface was revealed to be endergonic with a few partial steps having positive Gibbs free energy. On the other hand, the pyrite formation was found to be slightly exergonic. The significance of the catalytic activity of transition metal sulfides in generation of acetic acid was shown. The Gibbs free energy values indicate that the acetic acid synthesis is unfavorable to proceed on the studied Fe-Ni-S model under simulated conditions. The importance of these results in terms of a primordial chemistry on iron-nickel sulfide surfaces is discussed.

  10. 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

  11. High-Temperature Oxidation of Cr-Mo Steels and Its Relevance to Accelerated Rupture Testing and Life Assessment of In-Service Components

    NASA Astrophysics Data System (ADS)

    Singh Raman, R. K.; Al-Mazrouee, A.

    2007-08-01

    Use of accelerated creep rupture testing to assess the remaining life of components operating at elevated temperatures, such as pipes and tubes, is a common practice. At high temperatures, oxide growth can affect the creep results by diameter reduction and thus can increase the stress. However, the nature of oxide layer and hence oxidation behavior can be affected by minor changes in alloying composition of steels. This article presents the study of oxide-scale growth and specimen diameter reduction kinetics during oxidation of two Cr-Mo steels used in the manufacture of boiler tubing. Oxidation tests were carried out on 1.25Cr-0.5Mo and 2.25Cr-1Mo steels at 600 °C and 700 °C for times up to 1000 hours, using cylindrical specimens (similar to those used for creep testing). At 600 °C, the oxidation resistance of 2.25Cr-1Mo steel was superior to 1.25Cr-0.5Mo steel. However, the oxidation resistance of the two steels at 700 °C was similar in spite of the difference in their Cr contents. Multilayer oxide scales of oxides with various compositions were observed to have formed over the two steels. The similarity in oxidation kinetics of the two steels at 700 °C (in spite of differences in Cr contents) is ascribed to their Si contents and the predominant role of Si in oxidation at this temperature. The article also discusses implications of the variation in the oxidation kinetics to the stress enhancement in creep specimens due to scaling losses, and possible inaccuracies in creep data, as a result of minor variations in alloying composition.

  12. Enhancement of Fenton oxidation for removing organic matter from hypersaline solution by accelerating ferric system with hydroxylamine hydrochloride and benzoquinone.

    PubMed

    Peng, Siwei; Zhang, Weijun; He, Jie; Yang, Xiaofang; Wang, Dongsheng; Zeng, Guisheng

    2016-03-01

    Fenton oxidation is generally inhibited in the presence of a high concentration of chloride ions. This study investigated the feasibility of using benzoquinone (BQ) and hydroxylamine hydrochloride (HA) as Fenton enhancers for the removal of glycerin from saline water under ambient temperature by accelerating the ferric system. It was found that organics removal was not obviously affected by chloride ions of low concentration (less than 0.1mol/L), while the mineralization rate was strongly inhibited in the presence of a large amount of chloride ions. In addition, ferric hydrolysis-precipitation was significantly alleviated in the presence of HA and BQ, and HA was more effective in reducing ferric ions into ferrous ions than HA, while the H2O2 decomposition rate was higher in the BQ-Fenton system. Electron spin resonance analysis revealed that OH production was reduced in high salinity conditions, while it was enhanced after the addition of HA and BQ (especially HA). This study provided a possible solution to control and alleviate the inhibitory effect of chloride ions on the Fenton process for organics removal. PMID:26969046

  13. Comparisons of pyrite variability from selected western Kentucky and western Pennsylvania coals

    SciTech Connect

    Frankie, K.A.; Hower, J.C.

    1983-03-01

    Pyrite (and marcasite) variation in the lower Kittanning coal of western Pennsylvania has been petrographically characterized using three parameters of size (categories rather than absolute size), morphology (framboidal, euhedral, dendritic, massive, and cleat), and microlithotype (organic) association. The purpose of this study is to evaluate what influence paleo-environments have on the nature of variation of pyrite in coal. Comparison of coals has been done using the percentages of pyrite in the microlithotypes vitrite and clarite. In the lower Kittanning coal, framboidal pyrite is generally less abundant and dendritic pyrite was not observed at all. Euhedral pyrite exhibited no clear variation between the two environments. Massive pyrite was more abundant in the set of samples from the mine with the highest average pyritic sulfur but otherwise exhibited no variation. In contrast, a larger percentage of pyrite in the western Kentucky coals examined is framboidal and dendritic. Mines examined in the Moorman syncline of western Kentucky do have a framboidal pyrite percentage comparable to the lower Kittanning samples, but the percentage of dendritic pyrite (particularly in the Western Kentucky No. 9 coal) is significantly higher for the western Kentucky coals. Bulk petrography of the coals is similar with all having greater than 80% total vitrinite. The association of the pyritic sulfur does, however, change significantly between the various coals studied and particularly between the coals of western Kentucky and among the marine lower Kittanning samples and the fresh water lower Kittanning samples. Among the pyrite in the fresh water coals, massive (perhaps epigenetic) pyrite dominates the associations.

  14. 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

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. First-principles study of thermoelectric properties of pyrite

    NASA Astrophysics Data System (ADS)

    Xia, Yi; Zhou, Fei; Ozolins, Vidvuds

    2014-03-01

    Due to its natural abundance, moderate band gap and good light absorption properties, pyrite (FeS2) is being considered for use in nanocrystalline solar cells. High-quality n-type samples show high electron mobility, but their adoption in solar cells is hampered by low open circuit voltages. Here, using density-functional theory (DFT), we study charge and thermal transport properties of FeS2. Using the Debye-Callaway model, we obtain lattice thermal conductivity in good agreement with experimental data, suggesting that significant reduction of lattice thermal conductivity would be needed for thermoelectric applications. In addition, we find that holes in p-type pyrite form localized small polaron states, which naturally explains low hole mobilities observed experimentally.

  1. Pyrite alteration and neoformed magnetic minerals in the fault zone of the Chi-Chi earthquake (Mw7.6, 1999): Evidence for frictional heating and co-seismic fluids

    NASA Astrophysics Data System (ADS)

    Chou, Yu-Min; Song, Sheng-Rong; Aubourg, Charles; Song, Yen-Fang; Boullier, Anne-Marie; Lee, Teh-Quei; Evans, Mark; Yeh, En-Chao; Chen, Yi-Ming

    2012-08-01

    During an earthquake, physical and chemical transformations lead to alteration and formation of minerals in the gouge layer. Altered and neoformed minerals can be used as tracers of some earthquake processes. In this study, we investigate pyrite and magnetic minerals within the host Chinshui siltstone and the 16-cm-thick gouge. This gouge hosts the principal slip zone of Chi-Chi earthquake (Mw7.6, 1999). In the Chinshui siltstone, pyrite framboids of various sizes and euhedral pyrite are observed. The magnetic mineral assemblage comprises stoichiometric magnetite, greigite, and fine-grained pyrrhotite. The pyrite content is generally reduced in the gouge compared to the wall rock. The magnetic mineral assemblage in the gouge consists of goethite, pyrrhotite, and partially oxidized magnetite. The pyrrhotite, goethite and some magnetite are neoformed. Pyrrhotite likely formed from high temperature decomposition of pyrite (>500°C) generated during co-seismic slip of repeated earthquakes. Goethite is inferred to have formed from hot aqueous co-seismic fluid (>350°C) in association with the 1999 Chi-Chi event. Elevated fluid temperatures can also explain the partial alteration of magnetite and the retrograde alteration of some pyrrhotite to pyrite. We suggest that characterization of neoformed magnetic minerals can provide important information for studying earthquake slip zones in sediment-derived fault gouge.

  2. 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

  3. 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

  4. Assessing metal transfer to vegetation and grazers on reclaimed pyritic Zn and Pb tailings.

    PubMed

    Callery, S; Courtney, R

    2015-12-01

    A study of the concentrations of zinc and lead in an engineered soil capping system overlying sulphide mine tailings was undertaken. Tailings geochemistry, soil cover and vegetation were monitored over a 4-year period, and a cattle grazing demonstration exercise was conducted over a 1-year period. Whilst the tailings had a relatively high pyrite content and demonstrated oxidation, a circum neutral pH was observed for the duration of the study period due to the high dolomitic content. No evidence of metal mobility into the soil cover and vegetation was observed over the monitoring period. Relatively high Zn herbage content is attributed to the glacial till component of the soil cover. Similarly, no evidence of metal transfer to grazing cattle was observed through blood and tissue analysis with Zn content not significantly different from control animals. Pb tissue content was below limit of detection. PMID:26282438

  5. 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.

  6. 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.

  7. Ultrafast band-gap oscillations in iron pyrite

    SciTech Connect

    Kolb, B; Kolpak, AM

    2013-12-20

    With its combination of favorable band gap, high absorption coefficient, material abundance, and low cost, iron pyrite, FeS2, has received a great deal of attention over the past decades as a promising material for photovoltaic applications such as solar cells and photoelectrochemical cells. Devices made from pyrite, however, exhibit open circuit voltages significantly lower than predicted, and despite a recent resurgence of interest in the material, there currently exists no widely accepted explanation for this disappointing behavior. In this paper, we show that phonons, which have been largely overlooked in previous efforts, may play a significant role. Using fully self-consistent GW calculations, we demonstrate that a phonon mode related to the oscillation of the sulfur-sulfur bond distance in the pyrite structure is strongly coupled to the energy of the conduction-band minimum, leading to an ultrafast (approximate to 100 fs) oscillation in the band gap. Depending on the coherency of the phonons, we predict that this effect can cause changes of up to +/- 0.3 eV relative to the accepted FeS2 band gap at room temperature. Harnessing this effect via temperature or irradiation with infrared light could open up numerous possibilities for novel devices such as ultrafast switches and adaptive solar absorbers.

  8. 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

  9. Rapid acceleration of ferrous iron/peroxymonosulfate oxidation of organic pollutants by promoting Fe(III)/Fe(II) cycle with hydroxylamine.

    PubMed

    Zou, Jing; Ma, Jun; Chen, Liwei; Li, Xuchun; Guan, Yinghong; Xie, Pengchao; Pan, Chao

    2013-10-15

    The reaction between ferrous iron (Fe(II)) with peroxymonosulfate (PMS) generates reactive oxidants capable of degrading refractory organic contaminants. However, the slow transformation from ferric iron (Fe(III)) back to Fe(II) limits its widespread application. Here, we added hydroxylamine (HA), a common reducing agent, into Fe(II)/PMS process to accelerate the transformation from Fe(III) to Fe(II). With benzoic acid (BA) as probe compound, the addition of HA into Fe(II)/PMS process accelerated the degradation of BA rapidly in the pH range of 2.0-6.0 by accelerating the key reactions, including the redox cycle of Fe(III)/Fe(II) and the generation of reactive oxidants. Both sulfate radicals and hydroxyl radicals were considered as the primary reactive oxidants for the degradation of BA in HA/Fe(II)/PMS process with the experiments of electron spin resonance and alcohols quenching. Moreover, HA was gradually degraded to N2, N2O, NO2 (−), and NO3 (−), while the environmentally friendly gas of N2 was considered as its major end product in the process. The present study might provide a promising idea based on Fe(II)/PMS process for the rapid degradation of refractory organic contaminants in water treatment. PMID:24033112

  10. An effective method of UV-oxidation of dissolved organic carbon in natural waters for radiocarbon analysis by accelerator mass spectrometry

    NASA Astrophysics Data System (ADS)

    Xue, Yuejun; Ge, Tiantian; Wang, Xuchen

    2015-12-01

    Radiocarbon (14C) measurement of dissolved organic carbon (DOC) is a very powerful tool to study the sources, transformation and cycling of carbon in the ocean. The technique, however, remains great challenges for complete and successful oxidation of sufficient DOC with low blanks for high precision carbon isotopic ratio analysis, largely due to the overwhelming proportion of salts and low DOC concentrations in the ocean. In this paper, we report an effective UV-Oxidation method for oxidizing DOC in natural waters for radiocarbon analysis by accelerator mass spectrometry (AMS). The UV-oxidation system and method show 95%±4% oxidation efficiency and high reproducibility for DOC in both river and seawater samples. The blanks associated with the method was also low (about 3 µg C) that is critical for 14C analysis. As a great advantage of the method, multiple water samples can be oxidized at the same time so it reduces the sample processing time substantially compared with other UV-oxidation method currently being used in other laboratories. We have used the system and method for 14C studies of DOC in rivers, estuaries, and oceanic environments and have received promise results.

  11. 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

  12. Vitamin E deficiency accelerates nitrate tolerance via a decrease in cardiac P450 expression and increased oxidative stress.

    PubMed

    Minamiyama, Yukiko; Takemura, Shigekazu; Hai, Seikan; Suehiro, Shigefumi; Okada, Shigeru

    2006-03-01

    accelerate nitrate tolerance via an increase in oxidative stress, the reduced bioconversion because of decreased P450 expression, and impairment of the NO/cGMP pathway in tolerant heart tissues. PMID:16520233

  13. 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.

  14. 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

  15. 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.

  16. 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.

  17. Reduction mechanisms of pyrite cinder-carbon composite pellets

    NASA Astrophysics Data System (ADS)

    Liu, Zheng-jian; Xing, Xiang-dong; Zhang, Jian-liang; Cao, Ming-ming; Jiao, Ke-xin; Ren, Shan

    2012-11-01

    The non-isothermal reduction mechanisms of pyrite cinder-carbon composite pellets were studied at laboratory scale under argon (Ar) atmosphere. The composite pellets as well as the specimens of separate layers containing pyrite cinder and coal were tested. The degree of reduction was measured by mass loss. The microstructures of the reduced composite pellets were characterized by scanning electron microscopy (SEM). It is found that the reduction processes of the composite pellets may be divided into four stages: reduction via CO and H2 from volatiles in coal at 673-973 K, reduction via H2 and C produced by cracking of hydrocarbon at 973-1123 K, direct reduction by carbon via gaseous intermediates at 1123-1323 K, and direct reduction by carbon at above 1323 K. Corresponding to the four stages, the apparent activation energies ( E) for the reduction of the composite pellets are 86.26, 78.54, 72.01, and 203.65 kJ·mol-1, respectively.

  18. 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.

  19. 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

  20. 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

  1. 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.

  2. 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

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

    SciTech Connect

    Onysko, S.J.; Kleinmann, R.L.P.; Erickson, P.M.

    1984-07-01

    Thiobacillus ferrooxidans promote indirect oxidation of pyrite through the catalysis of the oxidation of ferrous iron to ferric iron, which is an effective oxidant of pyrite. These bacteria also may catalyze direct oxidation of pyrite by oxygen. A number of organic compounds, under laboratory conditions, can apparently inhibit both the oxidation of ferrous iron to ferric iron by T. ferrooxidans and the weathering of pyritic material by mixed cultures of acid mine drainage microorganisms. In this study, benzoic acid, sorbic acid, and sodium lauryl sulfate at low concentrations (5 to 10 mg/liter) each effectively inhibited bacterial oxidation of ferrous iron in batch cultures of Thiobacillus ferrooxidans. The rate of chemical oxidation of ferrous iron in low-pH, sterile batch reactors was not substantially affected at the tested concentrations (5 to 50 mg/liter) of any of the compounds.

  4. Non-paragenesis of Authigenic Sulfide Minerals: Mackinawite and Greigite are Not Precursors of Sedimentary Pyrite

    NASA Astrophysics Data System (ADS)

    Morse, J. W.; Rickard, D.

    2004-12-01

    Sedimentary sulfide minerals have traditionally been "operationally" divided into pyrite and acid volatile sulfide (AVS) minerals. AVS minerals have generally, with very scant direct evidence, been held to be comprised of mackinawite (tetragonal FeS) and greigite (cubic Fe3S4). They are also often referred to in the literature generically as FeS or iron monosulfides. Based largely on experimental studies at elevated temperatures over almost a third of a century and their metastability relative to pyrite, it has become almost dogma among sedimentary geochemists that mackinawite and or griegite are necessary precursors for pyrite formation in sediments. Being precursors to pyrite necessarily implies that they must be formed before pyrite and the normal paragenesis is supposed to be mackinawite to greigite to pyrite. The implication is that in their absence no authigenic sedimentary pyrite can be produced. This is not supported by many observations of pyrite formation in sediments where, during early diagenesis, abundant pyrite is commonly produced in the absence of any detectable AVS. Reactions for pyrite formation such as FeS(s) + S0(s) = FeS2(s) or FeS(s) + H2S = FeS2(s) + H2S, for example, represent the net mass balances and do not describe the process. More recently, two reaction mechanisms for pyrite formation, the "polysulfide" and "H2S" pathways, have gained wide acceptance. The reaction mechanisms involve dissolved species.If present at all, mackinawite and greigite contribute to pyrite formation via their dissolution which provides reactive components to solution. However, these dissolved components do not necessarily require mackinawite or greigite as their source. For the polysulfide pathway for pyrite formation the net reaction is better expressed as Fe2+ + S2-n = FeS2(s) + S2-n-2 and for the H2S pathway the reaction is FeS(aq) + H2S = FeS2(s) + H2S. FeS(aq) represents aqueous FeS clusters that are true solution components formed by the reaction between

  5. 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.

  6. 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., II

    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.

  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. 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

  10. 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

  11. Proteomic identification of less oxidized brain proteins in aged senescence-accelerated mice following administration of antisense oligonucleotide directed at the Abeta region of amyloid precursor protein.

    PubMed

    Poon, H Fai; Farr, Susan A; Banks, William A; Pierce, William M; Klein, Jon B; Morley, John E; Butterfield, D Allan

    2005-07-29

    Amyloid beta-peptide (Abeta) is the major constituent of senile plaques, a pathological hallmark of Alzheimer's disease (AD) brain. It is generally accepted that Abeta plays a central role in the pathophysiology of AD. Abeta is released from cells under entirely normal cellular conditions during the internalization and endosomal processing of amyloid precursor protein (APP). However, accumulation of Abeta can induce neurotoxicity. Our previous reports showed that decreasing the production of Abeta by giving an intracerebroventricular injection of a 42-mer phosphorothiolated antisense oligonucleotide (AO) directed at the Abeta region of the APP gene reduces lipid peroxidation and protein oxidation and improves cognitive deficits in aged senescence-accelerated mice prone 8 (SAMP8) mice. In order to investigate how Abeta level reduction improves learning and memory performance of SAMP8 mice through reduction of oxidative stress in brains, we used proteomics to identify the proteins that are less oxidized in 12-month-old SAMP8 mice brains treated with AO against the Abeta region of APP (12 mA) compared to that of the age-control SAMP8 mice. We found that the specific protein carbonyl levels of aldoase 3 (Aldo3), coronin 1a (Coro1a) and peroxiredoxin 2 (Prdx2) are significantly decreased in the brains of 12 mA SAMP8 mice compared to the age-controlled SAMP8 treated with random AO (12 mR). We also found that the expression level of alpha-ATP synthase (Atp5a1) was significantly decreased, whereas the expression of profilin 2 (Pro-2) was significantly increased in brains from 12 mA SAMP8 mice. Our results suggest that decreasing Abeta levels in aged brain in aged accelerated mice may contribute to the mechanism of restoring the learning and memory improvement in aged SAMP8 mice and may provide insight into the role of Abeta in the memory and cognitive deficits in AD. PMID:15932783

  12. 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. PMID:24793112

  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. PMID:15673196

  14. Pyrite forms in recent peats and carbonates from the Florida Everglades

    SciTech Connect

    Brown, K.E.; Cohen, A.D. . Dept. of Geological Sciences)

    1994-03-01

    The modern sediments of the Everglades area of southern Florida demonstrate a variety of conditions for the syngenetic formation of pyrite. These conditions relate to the overall stratigraphy of the area, which is a transgressive sequence in which fresh water peats and carbonates are overlain by brackish and marine peats and marine carbonates. The pyrite observed in microtome thin sections of these sediments occurs in three general forms: framboidal aggregates, minute euhedral crystals (<2 micrometers) often in clusters, and solitary euhedral crystals (>2 micrometers, but not larger than 20 micrometers). The relative percentages and forms of pyrite vary in occurrence within any individual depth interval depending upon parameters such as the ratio of organic to inorganic constituents, the proximity to marine water, and the types of organic constituents present (i.e. roots, leaves, fungi, algae, etc.). The relationships between pyrite forms and the various organic and inorganic constituents demonstrate the importance of microenvironments to the formation of pyrite. Overall, the relative percentages of pyrite present do not show a direct correlation with depth, with the exception of the general scarcity of pyrite in the top 12 inches of the sediment, which likely represent a redox boundary in the sediment.

  15. A study on the structural behavior of reduced pyrite ash pellets by XRD and XRF analysis.

    PubMed

    Tugrul, Nurcan; Derun, Emek Moroydor; Piskin, Mehmet Burçin; Ekerim, Ahmet

    2009-05-01

    In Turkey, pyrite ash is created as waste from the roasting of pyrite ores in the production of sulfuric acid. These processes generate great amounts of pyrite ash waste that creates serious environmental pollution due to the release of acids and toxic substances. Pyrite ash waste can be used in the iron production industry as a raw material because of its high Fe(2)O(3) concentration. The aim of this study was to investigate the reduction behaviour of pyrite ash pellets. The pyrite ashes were reduced to obtain the iron contained in pellets. Pyrite ashes samples were pelletized dried at 105 degrees C for 24 h and sintered at 1200 degrees C for 30 min. then reduced in a pressure of 4 atm. under argon gas. The mineralogical transformations that occurred during reduction were analysed by X-ray diffraction and X-ray fluorescence. The X-ray diffraction and X-ray fluorescence measurements of these samples showed that Fe(3)O(4) was successfully reduced to a metallic iron phase in a laboratory-scale electric arc furnace. PMID:19443647

  16. Nickeliferous pyrite tracks pervasive hydrothermal alteration in Martian regolith breccia: A study in NWA 7533

    NASA Astrophysics Data System (ADS)

    Lorand, Jean-Pierre; Hewins, Roger H.; Remusat, Laurent; Zanda, Brigitte; Pont, Sylvain; Leroux, Hugues; Marinova, Maya; Jacob, Damien; Humayun, Munir; Nemchin, Alexander; Grange, Marion; Kennedy, Allen; Göpel, Christa

    2015-11-01

    Martian regolith breccia NWA 7533 (and the seven paired samples) is unique among Martian meteorites in showing accessory pyrite (up to 1% by weight). Pyrite is a late mineral, crystallized after the final assembly of the breccia. It is present in all of the lithologies, i.e., the fine-grained matrix (ICM), clast-laden impact melt rocks (CLIMR), melt spherules, microbasalts, lithic clasts, and mineral clasts, all lacking magmatic sulfides due to degassing. Pyrite crystals show combinations of cubes, truncated cubes, and octahedra. Polycrystalline clusters can reach 200 μm in maximum dimensions. Regardless of their shape, pyrite crystals display evidence of very weak shock metamorphism such as planar features, fracture networks, and disruption into subgrains. The late fracture systems acted as preferential pathways for partial replacement of pyrite by iron oxyhydroxides interpreted as resulting from hot desert terrestrial alteration. The distribution and shape of pyrite crystals argue for growth at moderate to low growth rate from just-saturated near neutral (6 < pH<10), H2S-HS-rich fluids at minimum log fO2 of >FMQ + 2 log units. It is inferred from the maximum Ni contents (4.5 wt%) that pyrite started crystallizing at 400-500 °C, during or shortly after a short-duration, relatively low temperature, thermal event that lithified and sintered the regolith breccias, 1.4 Ga ago as deduced from disturbance in several isotope systematics.

  17. 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.

  18. Grain-scale iron isotopic distribution of pyrite from Precambrian shallow marine carbonate revealed by a femtosecond laser ablation multicollector ICP-MS technique: Possible proxy for the redox state of ancient seawater

    NASA Astrophysics Data System (ADS)

    Nishizawa, Manabu; Yamamoto, Hiroki; Ueno, Yuichiro; Tsuruoka, Subaru; Shibuya, Takazo; Sawaki, Yusuke; Yamamoto, Shinji; Kon, Yoshiaki; Kitajima, Kouki; Komiya, Tsuyoshi; Maruyama, Shigenori; Hirata, Takafumi

    2010-05-01

    .) suggest partial Fe(II) oxidation in the 2.7-Ga shallow sea, i.e., pyritization of 56Fe-enriched ferric oxyhydroxide (Type 1) and 56Fe depleted Fe 2+aq in seawater (Type 2). Type 2 pyrite was probably not produced by microbial iron redox cycling during diagenesis because this scenario requires a higher abundance of pyrite with δ 56Fe of 0‰ than of -1.8‰. Consequently, the degree of Fe(II) oxidation in the 2.7-Ga shallow sea can be estimated by a Fe 2+aq steady-state model. The model calculation shows that half the Fe 2+aq influx was oxidized in the seawater. This implies that O 2 produced by photosynthesis would have been completely consumed by oxidation of the Fe 2+aq influx. Grain-scale iron isotopic distribution of pyrite could be a useful index for reconstructing the redox state of the Archean shallow sea.

  19. 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

  20. 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.

  1. Electron paramagnetic resonance, optical absorption and Raman spectral studies on a pyrite/chalcopyrite mineral

    NASA Astrophysics Data System (ADS)

    Udayabhaskar Reddy, G.; Seshamaheswaramma, K.; Nakamura, Yoshinobu; Lakshmi Reddy, S.; Frost, Ray L.; Endo, Tamio

    2012-10-01

    Pyrite and chalcopyrite mineral samples from Mangampet barite mine, Kadapa, Andhra Pradesh, India are used in the present study. XRD data indicate that the pyrite mineral has a face centered cubic lattice structure with lattice constant 5.4179 Å. Also it possesses an average particle size of 91.9 nm. An EPR study on the powdered samples confirms the presence of iron in pyrite and iron and Mn(II) in chalcopyrite. The optical absorption spectrum of chalcopyrite indicates presence of copper which is in a distorted octahedral environment. NIR results confirm the presence of water fundamentals and Raman spectrum reveals the presence of water and sulfate ions.

  2. 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.

  3. Rate of pyrite bioleaching by Thiobacillus ferrooxidans: Results of an interlaboratory comparison

    SciTech Connect

    Olson, G.J. )

    1991-03-01

    Ten laboratories participated in an interlaboratory comparison of determination of bioleaching rates of a pyrite reference material. A standardized procedure and a single strain of Thiobacillus ferroxidans were used in this study. The mean rate of bioleaching of the pyrite reference material was 12.4 mg of Fe per liter per h, with a coefficient of variation (percent relative standard deviation) of 32% as determined by eight laboratories. These results show the precision among laboratories of the determination of rates of pyrite bioleaching when a standard test procedure and reference material are used.

  4. Linear Accelerators

    NASA Astrophysics Data System (ADS)

    Sidorin, Anatoly

    2010-01-01

    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.

  5. 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.

  6. Microwave accelerated synthesis of zinc oxide nanoplates and their enhanced photocatalytic activity under UV and solar illuminations

    NASA Astrophysics Data System (ADS)

    Anas, S.; Rahul, S.; Babitha, K. B.; Mangalaraja, R. V.; Ananthakumar, S.

    2015-11-01

    Photoactive zinc based nanoplates were developed through a rapid microwave synthesis. A low temperature thermolysis reaction in a surfactant medium was initially performed for producing microwave active zinc based polar precursors. Using these precursors, the zinc oxide nanopowder having platelet morphologies were prepared. The nanoplatelets exhibited random growth with non-polar (1 0 1) surface as the major growth plane. The structural and functional features of the resultant zinc oxide samples were monitored using XRD, FTIR, TEM and PL. The photocatalytic activities of the samples were investigated through the standard photoreduction kinetics using the methylene blue dye. The catalytic efficiencies of the samples were checked both under UV and sunlight. A comparative study was also performed with the standard TiO2 sample. The analyses revealed that the microwave derived zinc oxide have higher catalytic efficiency, than the standard titania samples, both under UV and sunlight illuminations. The unique nature of the zinc oxide non-polar surfaces can be attributed due to the presence of more active two dimensional open surfaces and the higher content of oxygen defect concentrations.

  7. Iron Pyrite/Titanium Dioxide Photoanode for Extended Near Infrared Light Harvesting in a Photoelectrochemical Cell.

    PubMed

    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. 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

  9. 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.

  10. Iron Pyrite/Titanium Dioxide Photoanode for Extended Near Infrared Light Harvesting in a Photoelectrochemical Cell

    NASA Astrophysics Data System (ADS)

    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

    2016-02-01

    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.

  11. The energetics and kinetics of uranyl reduction on pyrite, hematite, and magnetite surfaces: A powder microelectrode study

    NASA Astrophysics Data System (ADS)

    Renock, Devon; Mueller, Megan; Yuan, Ke; Ewing, Rodney C.; Becker, Udo

    2013-10-01

    There are many studies describing the influence of parameters such as pH, pCO2, and complexing ligands on the sorption of the aqueous uranyl species onto mineral surfaces. However, few of these studies describe the reduction reaction mechanisms and the factors that influence the rate of reduction, despite the fact that the oxidation state of uranium is the most important factor controlling the mobility of uranium. In this study, the energetics and kinetics of the U(VI) reduction half-reaction on pyrite, hematite, and magnetite were investigated by electrochemical methods using a powder microelectrode (PME) as the working electrode. Anodic and cathodic peaks corresponding to the 1 e- redox couple, U(VI)/U(V), were identified in cyclic voltammograms of pyrite, hematite, and magnetite at pH 4.5. A second oxidation peak, corresponding to the oxidation of U(IV), was identified and provides evidence for the formation of reduced uranium phase(s) on the mineral surfaces. In addition, uranium-containing precipitates were identified on pyrite surfaces after polarization in a PME. This study identifies the disproportionation of U(V) species on the surface as a possible rate-limiting step in the two-step U(VI) reduction mechanism: (1) charge transfer to form U(V) followed by, (2) a disproportionation reaction that forms U(IV) and U(VI). The Tafel slope (i.e., the derivative of the electrode potential with respect to log [current]) was used to evaluate electrochemical mechanisms. High Tafel slopes (>220 mV/(log unit of current) on all minerals evaluated) suggest that uranyl reduction is mediated by insulating (hydr)oxide layers that are present on the semiconducting mineral surfaces. The onset potential for uranyl reduction was determined for pyrite (>+0.1 V vs. Ag/AgCl), and hematite and magnetite (between-0.02 and-0.1 V vs. Ag/AgCl). The onset potential values establish a baseline kinetic parameter that can be used to evaluate how solution conditions (e.g., dissolved

  12. Aqueous Cr(VI) reduction by pyrite: Speciation and characterisation of the solid phases by X-ray photoelectron, Raman and X-ray absorption spectroscopies

    NASA Astrophysics Data System (ADS)

    Mullet, Martine; Demoisson, Frédéric; Humbert, Bernard; Michot, Laurent J.; Vantelon, Delphine

    2007-07-01

    Optical microscopy, confocal Raman micro-spectrometry, X-ray photoelectron micro-spectroscopy (XPS) and synchrotron based micro-X-ray fluorescence (XRF), micro-X-ray absorption near edge spectroscopy (XANES) and micro-extended X-ray absorption fine structure (EXAFS) were used to investigate the reduction of aqueous Cr(VI) by pyrite. Special emphasis was placed on the characterisation of the solid phase formed during the reaction process. Cr(III) and Fe(III) species were identified by XPS analyses in addition to non-oxidised pyrite. Optical microscopy images and the corresponding Raman spectra reveal a strong heterogeneity of the samples with three different types of zones. (i) Reflective areas with Eg and Ag Raman wavenumbers relative to non-oxidised pyrite are the most frequently observed. (ii) Orange areas that display a drift of the Eg and Ag pyrite vibration modes of -3 and -6 cm -1, respectively. Such areas are only observed in the presence of Cr(VI) but are not specifically due to this oxidant. (iii) Bluish areas with vibration modes relative to a corundum-like structure that can be assigned to a solid solution Fe 2- xCr xO 3, x varying between 0.2 and 1.5. The heterogeneity in the spatial distribution of chromium observed by optical microscopy and associated Raman microspectroscopy is confirmed by μ-XRF. In agreement with both solution and XPS analyses, these spectroscopies clearly confirm that chromium is in the trivalent state. XANES spectra in the iron K-edge pre-edge region obtained in rich chromium areas reveal the presence of ferric ion thus revealing a systematic association between Cr(III) and Fe(III). In agreement with Raman analyses, Cr K-edge EXAFS can be interpreted as corresponding to Cr atoms involved in a substituted-type hematite structure Fe 2- xCr xO 3.

  13. 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

  14. {sup 233}U breeding measurements in a thorium-oxide blanket assembly using A (d,t) accelerator neutron source

    SciTech Connect

    Anand, R.P.; Basu, T.K.; Ramakrishna, D.V.S.

    1997-05-01

    Uranium-233 breeding studies are carried out in a compact thorium-oxide cylindrical blanket assembly surrounded by a thick polypropylene reflector in a fusion neutron environment. The assembly consists of 11 rings of thorium-oxide rods stacked in a hexagonal geometry with a central through channel for the 14-MeV (d,t) neutron source. A total of 120 thorium-oxide probes are inserted inside the rods in different axial and radial locations in the assembly, which is then subjected to 14-MeV neutron irradiation for 25 h. Protactinium-233 gamma activity produced in the probes because of neutron captures in the thorium is measured using a high-efficiency, high-purity germanium detector. The measured {sup 233}U production rates are fitted to obtain axial and radial distributions for different rings. These distributions are used to obtain the total {sup 233}U breeding in the whole assembly. The integral measured values are found to be in good agreement with the calculated values obtained employing the MCNP Monte Carlo code using the BMCCS2 cross-section library. 8 refs., 4 figs., 5 tabs.

  15. Accelerated aging of 28 Gb s-1 850 nm vertical-cavity surface-emitting laser with multiple thick oxide apertures

    NASA Astrophysics Data System (ADS)

    Kropp, J. R.; Steinle, G.; Schäfer, G.; Shchukin, V. A.; Ledentsov, N. N.; Turkiewicz, J. P.; Zoldak, M.

    2015-04-01

    850 nm vertical-cavity surface-emitting lasers with multiple thick oxide apertures suitable for temperature-insensitive error free transmission at 28 Gb s-1 are subjected to accelerated aging at high current densities and chip temperatures. The devices withstand a 20% power change test at a high current density (18 kA c{{m}-2}) at an ambient temperature of 120 {}^\\circ C for 2500 h. At 90-95 {}^\\circ C at this current density no degradation was observed up to 5000 h. We performed the studies at further elevated current densities and temperatures and define the acceleration factor as AF={{({{J}stress}/{{J}use})}8}exp [(1.3 eV/{{k}B})(1/{{T}use}-1/{{T}stress})]. The extrapolated lifetime for 20% power drop is estimated as 20 thousand years at 300 K at current density of 18 kA c{{m}-2} which is sufficient for 28 Gb s-1 error-free temperature-insensitive data transmission.

  16. 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

  17. 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

  18. 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.

  19. 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.

  20. 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.

  1. The Iberian Pyrite Belt: What Reflection Seismics Can Say

    NASA Astrophysics Data System (ADS)

    Kashubin, A.; Juhlin, C.; Carbonell, R.; Simancas, F.

    The south-western part of the Variscan Orogen has been well studied in the past by geological mapping and potential field methods. The recently acquired 300 km long IBERSEIS reflection seismic profile crosses three major units south-west of the Iberian massif and adds an additional dimension to our knowledge of the area. Ma- jor results from the IBERSEIS experiment are presented elsewhere, whereas here we present detailed reflection seismic images of the uppermost seconds of the most south- western part of the profile. This section of profile includes the Iberian Pyrite Belt that contains known sulfide ore bodies. In this part of the section there are number of NE dipping reflectors reaching the surface, hence pre-stack migration and careful DMO analysis are of great importance before relating seismic reflections to surface geology. Taking into account the crooked line acquisition geometry and proper handling of out-of-the-plane of the profile reflections improves the stack and gives additional geo- metrical information about the reflectors. Seismic tomography from first arrivals from the same data set provides velocity information in uppermost hundreds meters. Am- plitude analysis provides some information on impedance contrast. Combined with surface geology, these methods help to constrain the geometry of the reflectors and help characterize the source of the reflectivity.

  2. Comparison of amorphous Fe-S-O and crystalline FeS2 pyrite for photovoltaic application

    NASA Astrophysics Data System (ADS)

    Kawai, Shoichi; Kajima, Takahiro; Ichimura, Masaya

    2016-02-01

    Iron sulfide oxide thin films were deposited by electrochemical deposition and annealed with sulfur powder. The composition ratio of the as-deposited film is Fe:S:O = 1:1.5:0.4. X-ray diffraction (XRD) and Raman measurement results showed that the as-deposited film is amorphous. After the annealing at 400 °C with sulfur powder, oxygen content was significantly reduced, and crystallization of FeS2 pyrite was confirmed by XRD. Heterojunction cells were fabricated using both the as-deposited and annealed films with ZnO thin film as the partner, and rectification properties were confirmed for all the samples. However, the leakage current was increased and the forward current was decreased by the annealing. Thus, the as-deposited amorphous film seems to be more suited for photovoltaic application than the annealed ones.

  3. Sulfur diagenesis in Everglades peat and origin of pyrite in coal

    SciTech Connect

    Altschuler, Z.S.; Schnepfe, M.M.; Silber, C.C.; Simon, F.O.

    1983-07-15

    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. The Fe removal through mineralogical phase transformation of pyrite by physicochemical method

    NASA Astrophysics Data System (ADS)

    Kim, BongJu; Cho, Kanghee; Jo, JiYu; Bak, GeonYeong; Choi, NagChoul; Park*, Cheonyoung

    2015-04-01

    Gold is often associated with sulfide minerals (arsenopyrite, pyrite, chalcopyrite, pyrrhotite, galena) as ''invisible'' gold that is thought to consist either of submicrometer metallic particles or to be bound to sulfur in metal sulfide lattice. Pyrite is one of the major minerals accumulating gold in most ores, although a solubility of Au in nonarsenian pyrite is minor, and increased concentrations of gold are associated with arsenic content and iron deficiency. The objective of this study was to investigate the Fe removal through mineralogical phase transformation of pyrite by physical treatment (high frequency) and chemical leaching (ammonia solvent). The high frequency treatment experiment for the pyrite showed that (1) the pyrite phase was transformed pyrrhotite and magnetite, (2) mass loss of the sample by volatilization of included sulfur(S) in pyrite. The treated pyrite by high frequency was observed rim structure from photomicrograph result. Fe removal experiments for were performed under various conditions of high frequency exposure (10~60min), grain size (+140 mesh~-325mesh), sulfuric acid concentration (0.5~3.0M), ammonia sulfate concentration (1.7~6.8M), hydrogen peroxide concentration (0.5~3.0M). Increasing the high frequency exposure produced a positive effect on Fe removal in arsenopyrite. The highest percentage Fe removal of 95.53% was obtained under the following conditions by ammonia solvent: grain size = -325mesh, sulfuric acid concentration = 2.0M, ammonia sulfate concentration = 5.1M, hydrogen peroxide concentration = 1.0M. This subject is supported by Korea Ministry of Environment(MOE) as "Advanced Technology Program for Environmental Industry".

  5. 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.

  6. 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.

  7. Electrochemistry of Thiobacillus ferrooxidans reactions with pyrite. Technical progress report, September 1991--January 1992

    SciTech Connect

    Pesic, B.

    1992-04-01

    The objective of this project is to provide the fundamental information on the mechanisms of bacterial leaching of pyrite. The knowledge of how bacterial leaching of pyrite functions is essential for design and development of a technology for coal cleaning with bacteria. The features of major electrochemical techniques will be examined to find out if any of them can provide a diagnostic information on the mechanisms of related reactions.

  8. 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.

  9. 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

  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. 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

  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. Inhibition of U(VI) reduction by synthetic and natural pyrite.

    PubMed

    Yang, Zhuanwei; Kang, Mingliang; Ma, Bin; Xie, Jinglin; Chen, Fanrong; Charlet, Laurent; Liu, Chunli

    2014-09-16

    Reductive precipitation is an effective method of attenuating the mobility of uranium (U) in subsurface environments. The reduction of U(VI) by synthetic and naturally occurring pyrite was investigated at pH 3.0-9.5. In contrast to thermodynamic calculations that were used to predict UO2(s) precipitation, a mixed U(IV) and U(VI) product (e.g., U3O8/U4O9/U3O7) was only observed at pH 6.21-8.63 and 4.52-4.83 for synthetic and natural pyrite, respectively. Under acidic conditions, the reduction of UO2(2+) by surface-associated Fe(2+) may not be favored because the mineral surface is nearly neutral or not negative enough. At high pH, the sorption of negatively charged U(VI) species is not favored on the negatively charged mineral surface. Thus, the redox reaction is not favored. Trace elements generally contained within the natural pyrite structure can affect the reactivity of pyrite and lead to a different result between the natural and synthetic pyrite. Because UO2(s) is extremely redox-sensitive toward U(VI), the observed UO2+x(s) phase reduction product indicates a surface reaction that is largely controlled by reaction kinetics and pyrite surface chemistry. These factors may explain why most laboratory experiments have observed incomplete U(VI) reduction on Fe(II)-bearing minerals. PMID:25148405

  14. 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.

  15. 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.

  16. Atmospheric-Pressure Chemical Vapor Deposition of Iron Pyrite Thin Films

    SciTech Connect

    Berry, Nicholas; Cheng, Ming; Perkins, Craig L.; Limpinsel, Moritz; Hemminger, John C.; Law, Matt

    2012-10-23

    Iron pyrite (cubic FeS{sub 2}) is a promising candidate absorber material for earth-abundant thin-film solar cells. In this report, single-phase, large-grain, and uniform polycrystalline pyrite thin films are fabricated on glass and molybdenum-coated glass substrates by atmospheric-pressure chemical vapor deposition (AP-CVD) using the reaction of iron(III) acetylacetonate and tert-butyl disulfide in argon at 300 C, followed by sulfur annealing at 500--550 C to convert marcasite impurities to pyrite. The pyrite-marcasite phase composition depends strongly on the concentration of sodium in the growth substrate and the sulfur partial pressure during annealing. Phase and elemental composition of the films are characterized by X-ray diffraction, Raman spectroscopy, Auger electron spectroscopy, secondary ion mass spectrometry, Rutherford backscattering spectrometry, and X-ray photoelectron spectroscopy. The in-plane electrical properties are surprisingly insensitive to phase and elemental impurities, with all films showing p-type, thermally activated transport with a small activation energy ({approx}30 meV), a room- temperature resistivity of {approx}1 {Omega} cm, and low mobility. These ubiquitous electrical properties may result from robust surface effects. These CVD pyrite thin films are well suited to fundamental electrical studies and the fabrication of pyrite photovoltaic device stacks.

  17. 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.

  18. 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.

  19. PARTICLE ACCELERATOR

    DOEpatents

    Teng, L.C.

    1960-01-19

    ABS>A combination of two accelerators, a cyclotron and a ring-shaped accelerator which has a portion disposed tangentially to the cyclotron, is described. Means are provided to transfer particles from the cyclotron to the ring accelerator including a magnetic deflector within the cyclotron, a magnetic shield between the ring accelerator and the cyclotron, and a magnetic inflector within the ring accelerator.

  20. Age-dependent acceleration of ischemic injury in endothelial nitric oxide synthase-deficient mice: potential role of impaired VEGF receptor 2 expression.

    PubMed

    Qian, Hu Sheng; de Resende, Micheline Monterio; Beausejour, Christian; Huw, Ling-Yuh; Liu, Perry; Rubanyi, Gabor M; Kauser, Katalin

    2006-04-01

    Morbidity and mortality of peripheral arterial occlusive disease significantly increases with age, often exhibiting more severe disease pathology and decreased treatment effectiveness. Therapeutic angiogenesis with angiogenic growth factors may represent a valuable treatment option for the severely ill, older adult patient population. Aging is considered an independent cardiovascular risk factor, but pathomechanistically it is not well understood. Diminished endothelial nitric oxide (EDNO) production has been considered as a major contributor to the aging process. To investigate the effect of age on postischemic revascularization independent of changes in EDNO, we used endothelial nitric oxide synthase-deficient (ecNOS-KO) mice. We found an age-dependent acceleration in ischemic injury following unilateral femoral artery ligation in these animals compared to C57BL/J6 mice. Postischemic revascularization, quantified by measuring von Willebrand factor expression, was significantly impaired, suggesting that factors other than progressive EDNO deterioration are also involved in the age-dependent severe disease phenotype. Ischemia led to an increase in the expression of vascular endothelial growth factor receptor-2, KDR, in younger ecNOS-KO; however, this increase in KDR expression was absent in the older animals. Lack of increased KDR expression may provide a mechanistic explanation for the severe ischemic injury and perhaps can be used as a clinical marker to identify severe, vascular endothelial growth factor refractory patient population. PMID:16680073

  1. 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

  2. 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.

  3. 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

  4. 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

  5. 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

  6. 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

  7. Recrystallization Experiments of Pyrite From Circulating Hydrothermal Solution by Thermal Convection

    NASA Astrophysics Data System (ADS)

    Tanaka, K.; Isobe, H.

    2005-12-01

    Pyrite is one of the most common accessory minerals in many rocks and generally occurs in hydrothermal deposit. However, pyrite morphology and association with other sulfide minerals is not well known with respect to the solution condition, especially with the hydrothermal solution under circulation. In this study, recrystallization experiments of pyrite from circulating hydrothermal solution by thermal convection were carried out. A rectangular circuit (42.6 cm by 17.3 cm) of SUS316 pressure tubing with 5 mm in inner diameter was used as a reaction vessel. The volume of the circuit is approximately 24 ml. Long sides of the rectangular circuit were held to be 20 degrees inclination. One of the long sides was heated by an electric furnace. Solution in the circuit evaporates in the high temperature tubing and the vapor condenses in room temperature tubing. The solution backs to the bottom of the high temperature tubing. Thus, thermal convection of the solution produces circulation in the circuit. Starting material was filled in the high temperature tubing. The lower half was filled with mixture of 2 g of powdered natural pyrite and 4 g of quartz grains. The upper half was filled with quartz grains only. 9 ml of 5 mol/l NH4Cl solution was sealed in the circuit with the starting material. Temperature gradient of the sample was monitored by 6 thermocouples. Maximum temperature was controlled at 350°C. Experimental durations are 3, 5, 10 and 30 days. After the experiments, the run products are fixed with resin and cut every 2 cm. Thin sections of vertical cross-sections are made and observed by microscope and SEM. Tiny pyrite crystals occurred at the upper outside of the furnace, where temperature should be much lower than 200°C. In the lower half of the starting material, pyrite decomposed and pyrrhotite formed around pyrite grains. At higher temperature area, pyrite decomposition and pyrrhotite formation is remarkable. Circulating sulfur-bearing solution provided by

  8. 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.

  9. 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.

  10. 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

  11. [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

  12. Degradation of Acid Orange 7 in aqueous solution by dioxygen activation in a pyrite/H₂O/O₂ system.

    PubMed

    Hao, Feifei; Guo, Weilin; Lin, Xin; Leng, Yanqiu; Wang, Anqi; Yue, Xinxin; Yan, Liangguo

    2014-05-01

    Increasing attention has been paid to pyrite due to its ability to generate hydroxyl radicals in air-saturated solutions. In this study, the mineral pyrite was studied as a catalyst to activate molecular oxygen to degrade Acid Orange 7 (AO7) in aqueous solution. A complete set of control experiments were conducted to optimize the reaction conditions, including the dosage of pyrite, the AO7 concentration, as well as the initial pH value. The role of reactive oxygen species (ROS) generated by pyrite in the process was elucidated by free radical quenching reactions. Furthermore, the concentrations of Fe(II) and total Fe formed were also measured. The mechanism for the production of ROS in the pyrite/H2O/O2 system was that H2O2 was formed by hydrogen ion and superoxide anion (O2(·-)) which was produced by the reaction of pyrite activating O2 and then reacted with Fe(II) dissolved from pyrite to produce (·)OH through Fenton reaction. The findings suggest that pyrite/H2O/O2 system is potentially practical in pollution treatment. Moreover, the results provide a new insight into the understanding of the mechanism for degradation of organic pollutants by pyrite. PMID:24510532

  13. 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.

  14. 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

  15. 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

  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. 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

  18. The Pyrite Structure of PdS2 and PdSe2 Monolayers

    NASA Astrophysics Data System (ADS)

    Singh, Arunima K.; Hennig, Richard G.; National Institute of Standards; Technology Collaboration; University of Florida Collaboration

    There has been a rising interest in two-dimensional (2D) materials due to a range of extraordinary electronic, optical and mechanical properties which are different from their bulk counterparts. The structure, stability and electronic properties of 2D PdS2 and PdSe2 have been investigated in the past in the well-known hexagonal 1T and 2H structures. However, bulk PdS2 and PdSe2 are layered compounds with individual rhombohedral pyrite-type monolayers vertically stacked with van-der Waals forces. Using density functional theory simulations, and five different functionals, we compare the energetic stability of 2D PdS2 and PdSe2 pyrite structure with the 1T and 2H structures. We find that the PdS2 is most stable in the pyrite structure, whereas the PdSe2 is most stable in the 1T structure with the pyrite structure closely competing in energy. The fundamental band gap of these compounds as a function of the structure, number of layers, the stacking arrangement and in-layer strain has been investigated. The pyrite structures of PdS2 and PdSe2 are found to be semi-conducting with indirect band gaps, and effective masses comparable to that of monolayer MoS2; thus are potential candidates for nano-electronic applications.

  19. 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.

  20. 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.

  1. Surface Chemical Studies on Pyrite in the Presence of Polysaccharide-Based Flotation Depressants.

    PubMed

    Rath; Subramanian; Pradeep

    2000-09-01

    The interaction of dextrin and guar gum with pyrite has been investigated through adsorption, flotation, and electrokinetic measurements. The adsorption densities of the polysaccharides onto pyrite reveal a region of higher adsorption density in the pH range 7.5-11, with a maximum around pH 10 for both polymers. The isotherms exhibit Langmuirian behavior. The adsorption density of guar gum onto pyrite is higher than that of dextrin. Electrokinetic measurements indicate a decrease in the electrophoretic mobility values in proportion to the concentration of the polymer added. Co-precipitation tests confirm polymer-ferric species interaction in the bulk solution, especially in the pH range 5.5-8.5. The pH range for higher adsorption, significant co-precipitation, and appreciable depression of pyrite encompass each other. XPS and FTIR spectroscopic studies provide evidence in support of chemical interaction between hydroxylated pyrite and the hydroxyl groups of the polymeric depressants. Copyright 2000 Academic Press. PMID:10942544

  2. 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.

  3. 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.

  4. 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.

  5. Laser Combustion Analyses Of Pyrite Grains From Arghash Gold Prospect, Iran

    NASA Astrophysics Data System (ADS)

    Alirezaei, S.; Ashrafpour, E.; Ansdell, K. M.

    2009-05-01

    The Arghash gold prospect is located in the Sabzevar zone in northeastern Iran. The basement of the Sabzevar zone consists of Precambrian metamorphosed rocks covered by Paleozoic epicontinental sediments and Upper Cretaceous ophiolitic mélange. Tertiary magmatic rocks, with chemical compositions characteristic of continental arc magmas, overlie or crosscut the older rocks. The Arghash gold prospect includes five gold- bearing vein systems, hosted in Eocene-Oligocene, intermediate-felsic volcanic and intrusive rocks of volcanic rocks. Pyrite is the main sulfide mineral in the hypogene ore. Four generations of pyrite (Py-I-Py-IV) were identified through detailed microscopic observations and electron microprobe analyses. Py-I is euhedral to anhedral fine- to coarse-grained pyrite, which is disseminated in the vein quartz and locally is associated with minor chalcopyrite, marcasite, arsenopyrite and, native gold grains (<30 μm). This pyrite generation is characterized by low contents of As, Sb, and Au. Py-II is a framboidal pyrite which fills microfractures in quartz and calcite and is characterized by concentric arsenic-rich and arsenic-poor bands, the former also rich in gold (up to 963 ppm). Arsenian pyrite overgrowths (Py-III) form <10 μm thick rims on Py-I and contain 1.2-7.9 wt. percent As, up to 6000 ppm Ni, and up to 1980 ppm Au. Py-IV is a coarse-grained, anhedral, barren pyrite, forming veinlets <5mm thick in quartz. The trace elements in this pyrite were below detection limits. Sulfur isotope analyses were first carried out on bulk pyrite concentrates from auriferous vein materials and adjacent altered wall rocks. The δ34S values for ten pyrite concentrates vary from -4.3 to +21.8 per mil. The wide variations of δ34S values could be related to different generations of pyrite and the occurrence of more than one generation in the samples, and possibly different origins for sulfur in the hydrothermal system. To characterize the isotopic compositions of

  6. Theoretical study of the properties of PtN with pyrite and marcasite structures

    NASA Astrophysics Data System (ADS)

    Zhu, Y.; Fan, C. Z.; Zhang, X. Y.; Zhang, S. H.; Li, L. X.; Zhang, S. L.; Jin, H. Y.; Liu, R. P.

    2009-07-01

    Pyrite and marcasite structures are both potential structures of platinum nitride. The mechanical properties of these two structures are similar, so we further investigate the thermodynamic properties of platinum nitride under high pressure and high temperature by the quasi-harmonic Debye model, in which phonon effects are considered. In the paper the important thermodynamic parameters, Debye temperature and heat capacity, have been investigated. The results show that the melting point is higher and the interatomic force is stronger in the pyrite structure than in the marcasite and fluorite structures. In addition, the marcasite structure has a much higher value of CV at the same T and P, and the change in CV is much sharper than that of the pyrite structure at low temperatures. Moreover, we notice that pressure has less influence on CV.

  7. 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.

  8. Plasma accelerators

    SciTech Connect

    Ruth, R.D.; Chen, P.

    1986-03-01

    In this paper we discuss plasma accelerators which might provide high gradient accelerating fields suitable for TeV linear colliders. In particular we discuss two types of plasma accelerators which have been proposed, the Plasma Beat Wave Accelerator and the Plasma Wake Field Accelerator. We show that the electric fields in the plasma for both schemes are very similar, and thus the dynamics of the driven beams are very similar. The differences appear in the parameters associated with the driving beams. In particular to obtain a given accelerating gradient, the Plasma Wake Field Accelerator has a higher efficiency and a lower total energy for the driving beam. Finally, we show for the Plasma Wake Field Accelerator that one can accelerate high quality low emittance beams and, in principle, obtain efficiencies and energy spreads comparable to those obtained with conventional techniques.

  9. 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.

  10. 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

  11. 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

  12. 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.

  13. 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

  14. The Sulfur Isotope Composition of the Pyrite Burial Flux in the Modern Ocean

    NASA Astrophysics Data System (ADS)

    Turchyn, A. V.; Antler, G.; Byrne, D. J.; Sun, X.

    2014-12-01

    Microbial sulfate reduction followed by sulfide mineral burial, typically as pyrite, represents the largest removal pathway for sulfur from the exogenic sulfur reservoir. During microbial sulfate reduction, sulfur isotopes are partitioned such that the lighter 32S isotope is preferentially reduced; the magnitude of this partitioning has a large range (0 to 72‰), and therefore the average sulfur isotope composition of the global pyrite burial flux remains enigmatic. Recent work has mapped the global spatial distribution of microbial sulfate reduction rates in the modern ocean, which allows conclusions to be drawn concerning the conditions and controls on where sulfate respiration occurs (Bowles et al., 2014). The local rate of sulfate reduction in a particular sediment column can be calculated by the change in sulfate concentrations in pore fluids below the surface, which yields the net flux of sulfate into marine sediments. A flux of sulfate into the sediment is assumed to be due to diffusion along a concentration gradient set up by the consumption of sulfate at depth. We have calculated the deep-sea rates of microbial sulfate reduction using over 700 drilling sites and arrive at a similar estimate of the global modern rate of sulfate respiration. Rates of sulfate reduction are not, however, the same as the rates of pyrite burial, which is likely limited to the uppermost sediments where reactive iron may be available, or in the most nearshore environments where the terrestrial supply of iron is high and rates of sulfate reduction are orders of magnitude higher than those in the deep-sea. Sulfur isotope fractionation during microbial sulfate reduction is a function of several environmental factors, including the rate of sulfate reduction. We use a new compilation of the link between sulfate reduction rate and sulfur isotope fractionation with a model of pyrite burial in a range of modern marine sediments to derive an estimate of the global pyrite burial flux and

  15. 3. 4-billion-year-old biogenic pyrites from Barberton, South Africa: Sulfur isotope evidence

    SciTech Connect

    Ohmoto, H.; Kakegawa, T. ); Lowe, D.R. )

    1993-10-22

    Laser ablation mass spectroscopy analysis 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[sup [minus]13] of the present atmospheric level) of free oxygen.

  16. 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

  17. Postnatal exposure to chromium through mother’s milk accelerates follicular atresia in F1 offspring through increased oxidative stress and depletion of antioxidant enzymes

    PubMed Central

    Stanley, Jone A.; Sivakumar, Kirthiram K.; Nithy, Thamizh K.; Arosh, Joe A.; Hoyer, Patricia B.; Burghardt, Robert C.; Banu, Sakhila K.

    2013-01-01

    Hexavalent chromium, CrVI, is a heavy metal endocrine disruptor, known as a mutagen, teratogen, and a group A carcinogen. Environmental contamination with CrVI, including drinking water, has been increasing in more than 30 cities in the United States. CrVI is rapidly converted to CrIII intracellularly, and CrIII can cause DNA strand breaks and cancer or apoptosis through different mechanisms. Our previous study demonstrated that lactational exposure to chromium results in a delay or arrest in follicle development and a decrease in steroid hormone levels in F1 female rats, both of which are mitigated (partial inhibition) by vitamin C. The current study tested the hypothesis that lactational exposure to CrIII accelerates follicle atresia in F1 offspring by increasing reactive oxygen species (ROS) and decreasing cellular antioxidants. Results showed that lactational exposure to CrIII dose-dependently increased follicular atresia and decreased steroidogenesis in postnatal day 25, 45, and 65 rats. Vitamin C mitigated or inhibited the effects of CrIII at all doses. CrIII increased hydrogen peroxide and lipid hydroperoxide in plasma and ovary; decreased the antioxidant enzymes (AOXs) GPx1, GR, SOD, and catalase; and increased glutathione S-transferase in plasma and ovary. To understand the effects of CrVI on ROS and AOXs in granulosa (GC) and theca (TC) cell compartments in the ovary, ROS levels and mRNA expression of cytosolic and mitochondrial AOXs, such as SOD1, SOD2, catalase, GLRX1, GSTM1, GSTM2, GSTA4, GR, TXN1, TXN2, TXNRD2, and PRDX3, were studied in GCs and TCs and in a spontaneously immortalized granulosa cell line (SIGC). Overall, CrVI downregulated each of the AOXs; and vitamin C mitigated the effects of CrVI on these enzymes in GCs and SIGCs, but failed to mitigate CrVI effects on GSTM1, GSTM2, TXN1, and TXN2 in TCs. Thus, these data for the first time reveal that lactational exposure to CrIII accelerated follicular atresia and decreased steroidogenesis in F1

  18. 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.

  19. Evaluation of reverse coal-pyrite flotation for a proposed Ohio advanced coal-cleaning test facility

    SciTech Connect

    Miller, K.J.

    1989-07-01

    A laboratory test program was conducted at the Pittsburgh Energy Technology Center with precleaned and classified middlings samples of three high-sulfur Ohio coals. The test program was run to evaluate the possible application of the US Department of Energy's two-stage reverse coal-pyrite flotation process in a new coal-cleaning test facility to be built in Ohio by the Ohio Coal Development Office. Results showed that the pyritic sulfur content of all three of the prepared coal samples could be substantially lowered via the coal-pyrite flotation process. But with two of the three coals, the organic sulfur levels were so high that removal of all of the pyrite would have contributed little to total sulfur reduction. Thus, processes aimed at pyritic sulfur reduction alone (such as the reverse coal-pyrite flotation process) would have limited impact on total sulfur reduction with some Ohio coals. However, with other coals in which sulfur is predominantly in the form of pyrite and marcasite, the process would likely prove beneficial. Therefore, the inclusion of reverse coal-pyrite flotation circuitry in the new facility would be prudent, especially since the proposed advanced coal-cleaning test plant will contain other deep-cleaning circuitry to ensure maximum ash reduction to achieve the lowest possible SO/sub 2/ per Btu emission levels. 13 refs., 2 figs., 6 tabs.

  20. 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.

  1. AN INNOVATIVE INTEGRATED APPROACH TO MINIMIZING GYPSUM AND PYRITE WASTES BY CONVERSION TO MARKETABLE PRODUCTS

    SciTech Connect

    Daniel Tao

    2000-06-27

    The objective of this research program is to develop a novel integrated process to eliminate millions of tons of gypsum and pyrite wastes generated annually by the U.S. energy industries and reduce the emission of millions of tons of greenhouse gas carbon dioxide. This was accomplished by converting gypsum and pyrite wastes to marketable products such as lime, direct reduced iron (DRI), and sulfur products and obviating the need to calcine millions of tons of limestone for use in utility scrubbers. Specific objectives included: (1) Develop a novel, integrated process for utilizing two major wastes generated by mining and energy industries to produce lime for recycling and other marketable products. (2) Study individual chemical reactions involved in pyrite decomposition, DRI production, and Muller-Kuhne process for lime regeneration to determine optimum process variables such as temperature, time, and reactant composition. (3) Investigate techniques for effective concentration of pyrite from tailing waste and methods for effective separation of DRI from calcium sulfide.

  2. Reflectivity and microhardness of sulfide minerals as genetic information source (case study: pyrite and arsenopyrite)

    NASA Astrophysics Data System (ADS)

    Sinkina, E. A.; Korovkin, M. V.; Savinova, O. V.; Makarova, A. A.

    2016-03-01

    Reflectivity and microhardness of pyrite and arsenopyrite of black shale gold-ore deposits in Chertovo Koryto (Patom upland) were studied. It was found that sulfides of different generations are characterized by different values of above-mentioned parameters which is associated mechanical and isomorphic impurities.

  3. Pyrite-pyrrhotite intergrowths in calcite marble from Bistriški Vintgar, Slovenia

    NASA Astrophysics Data System (ADS)

    Zavašnik, J.

    2016-02-01

    Roman marble quarry in Bistrica gorge in southern Pohorje Mt. (north-eastern Slovenia) is situated in a 20 m thick lens of layered marble, at the contact zone between granodiorite and metamorphites. Grey and yellowish non-homogenous calcite marble is heavily included by mica, quartz, feldspars, zoisite, pyrite and amphiboles. In the present research, we have studied numerous pyrite (FeS2) crystals associated with yellowish-bronze non-stoichiometric pyrrhotite (Fe1-xS), not previously reported from this locality. SEM investigation revealed unusual sequence of crystallisation: primary skeletal pyrrhotite matrix