Science.gov

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.

  2. Mechanism of bacterial pyrite oxidation.

    PubMed

    Silverman, M P

    1967-10-01

    The oxidation by Ferrobacillus ferrooxidans of untreated pyrite (FeS(2)) 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 O(2); recovery of ferric and ferrous ions was in excellent agreement with the reaction Fe(2)(SO(4))(3) + FeS(2) = 3FeSO(4) + 2S, but the elemental sulfur produced was negligible. Neither H(2)S nor S(2)O(3) (2-) 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.

  3. 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)].

  4. 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.

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

    SciTech Connect

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

    1999-02-01

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

  6. 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.

  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.

  8. Adenine oxidation by pyrite-generated hydroxyl radicals.

    PubMed

    Cohn, Corey A; Fisher, Shawn C; Brownawell, Bruce J; Schoonen, Martin Aa

    2010-04-26

    Cellular exposure to particulate matter with concomitant formation of reactive oxygen species (ROS) and oxidization of biomolecules may lead to negative health outcomes. Evaluating the particle-induced formation of ROS and the oxidation products from reaction of ROS with biomolecules is useful for gaining a mechanistic understanding of particle-induced oxidative stress. Aqueous suspensions of pyrite particles have been shown to form hydroxyl radicals and degrade nucleic acids. Reactions between pyrite-induced hydroxyl radicals and nucleic acid bases, however, remain to be determined. Here, we compared the oxidation of adenine by Fenton-generated (i.e., ferrous iron and hydrogen peroxide) hydroxyl radicals to adenine oxidation by hydroxyl radicals generated in pyrite aqueous suspensions. Results show that adenine oxidizes in the presence of pyrite (without the addition of hydrogen peroxide) and that the rate of oxidation is dependent on the pyrite loading. Adenine oxidation was prevented by addition of either catalase or ethanol to the pyrite/adenine suspensions, which implies that hydrogen peroxide and hydroxyl radicals are causing the adenine oxidation. The adenine oxidation products, 8-oxoadenine and 2-hydroxyadenine, were the same whether hydroxyl radicals were generated by Fenton or pyrite-initiated reactions. Although nucleic acid bases are unlikely to be directly exposed to pyrite particles, the formation of ROS in the vicinity of cells may lead to oxidative stress.

  9. 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.

  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. 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

  12. 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

  13. 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.

  14. 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.

  15. Aqueous pyrite oxidation by dissolved oxygen and by ferric iron

    USGS Publications Warehouse

    Moses, Carl O.; Nordstrom, D Kirk; Herman, Janet S.; Mills, Aaron L.

    1987-01-01

    Rates of aqueous, abiotic pyrite oxidation were measured in oxygen-saturated and anaerobic Fe(III)-saturated solutions with initial pH from 2 to 9. These studies included analyses of sulfite, thiosulfate, polythionates and sulfate and procedures for cleaning oxidation products from pyrite surfaces were evaluated. Pyrite oxidation in oxygen-saturated solutions produced (1) rates that were only slightly dependent on initial pH, (2) linear increases in sulfoxy anions and (3) thiosulfate and polythionates at pH > 3.9. Intermediate sulfoxy anions were observed only at high stirring rates. In anaerobic Fe(III)-saturated solutions, no intermediates were observed except traces of sulfite at pH 9. The faster rate of oxidation in Fe(III)-saturated solutions supports a reaction mechanism in which Fe(III) is the direct oxidant of pyrite in both aerobic and anaerobic systems. The proposal of this mechanism is also supported by theoretical considerations regarding the low probability of a direct reaction between paramagnetic molecular oxygen and diamagnetic pyrite. Results from a study of sphalerite oxidation support the hypothesis that thiosulfate is a key intermediate in sulfate production, regardless of the bonding structure of the sulfide mineral.

  16. [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.

  17. Studies of incipient oxidation of coal-pyrite for improved pyrite rejection. Third quarterly technical progress report, April 1, 1993--June 30, 1993

    SciTech Connect

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

    1993-11-01

    The initial stages of pyrite oxidation are being studied to develop methods to control pyrite surface chemistry and foster pyrite rejection in coal flotation circuits. A major objective of this work is to study incipient oxidation, which is accomplished by fracturing pyrite electrodes in an electrochemical cell. It has been shown that by holding the potential at various values during fracture and measuring the current passed at fracture, pyrite oxidation or reduction can be precisely controlled. The oxidation and reduction products on pyrite following fracture are being studied by a combination of voltammetry, photocurrent, and impedance spectroscopy techniques. During this report period, major effort was devoted to characterizing the surfaces by impedance spectroscopy.

  18. 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.

  19. Trace metal pyritization variability in response to mangrove soil aerobic and anaerobic oxidation processes.

    PubMed

    Machado, W; Borrelli, N L; Ferreira, T O; Marques, A G B; Osterrieth, M; Guizan, C

    2014-02-15

    The degree of iron pyritization (DOP) and degree of trace metal pyritization (DTMP) were evaluated in mangrove soil profiles from an estuarine area located in Rio de Janeiro (SE Brazil). The soil pH was negatively correlated with redox potential (Eh) and positively correlated with DOP and DTMP of some elements (Mn, Cu and Pb), suggesting that pyrite oxidation generated acidity and can affect the importance of pyrite as a trace metal-binding phase, mainly in response to spatial variability in tidal flooding. Besides these aerobic oxidation effects, results from a sequential extraction analyses of reactive phases evidenced that Mn oxidized phase consumption in reaction with pyrite can be also important to determine the pyritization of trace elements. Cumulative effects of these aerobic and anaerobic oxidation processes were evidenced as factors affecting the capacity of mangrove soils to act as a sink for trace metals through pyritization processes.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. Rates and potential mechanism of anaerobic nitrate-dependent microbial pyrite oxidation.

    PubMed

    Bosch, Julian; Meckenstock, Rainer U

    2012-12-01

    Pyrite (FeS2) is a major iron- and sulfur-containing mineral phase in the environment. Oxidation of pyrite by aerobic micro-organisms has been well investigated. However, the reactivity of pyrite under anoxic conditions is still an open question. In the present paper, we summarize field and laboratory data on this chemolithotrophic respiration process with nitrate as terminal electron acceptor. Geochemical and stable isotope field data indicate that this process is occurring. Laboratory studies are more ambiguous, but recent positive results provide evidence that anaerobic microbial pyrite oxidation can, in fact, occur with nitrate as electron acceptor.

  5. Anaerobic, nitrate-dependent oxidation of pyrite nanoparticles by Thiobacillus denitrificans.

    PubMed

    Bosch, Julian; Lee, Keun-Young; Jordan, Guntram; Kim, Kyoung-Woong; Meckenstock, Rainer U

    2012-02-21

    Pyrite is a key mineral in the global biogeochemical cycles of sulfur and iron, yet its anaerobic microbial oxidation has eluded geochemists and microbiologists for decades. Recent reports indicated that anaerobic oxidation of pyrite is occurring, but the mechanism remains unclear. Here, we provide evidence for the capability of Thiobacillus denitrificans to anaerobically oxidize a putatively nanosized pyrite particle fraction with nitrate as electron acceptor. Nanosized pyrite was readily oxidized to ferric iron and sulfate with a rate of 10.1 μM h(-1). The mass balance of pyrite oxidation and nitrate reduction revealed a closed recovery of the electrons. This substantiates a further "missing lithotrophy" in the global cycles of sulfur and iron and emphasizes the high reactivity of nanominerals in the environment.

  6. Studies of incipient oxidation of coal-pyrite for improved pyrite rejection. Technical Progress report, January 1, 1993--March 31, 1993

    SciTech Connect

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

    1993-06-01

    To foster the development of advanced coal cleaning technologies, the initial stages of pyrite oxidation are being studied. The voltammetry behavior of polished pyrite at moderate overpotentials is known to be dominated by iron oxides and hydroxides that are generated during the polishing process. The present work is being done on pyrite surfaces that are freshly fractured in an electrolyte solution. The creation of fresh surfaces by in situ fracture allows studies of the initial oxidation of pyrite itself, without complications from overlayers of iron oxides and hydroxides produced by polishing. Chronoamperometry immediately after fracture and subsequent cyclic voltammetry is being used to elucidate the initial oxidation reaction that produces hydrophobic sulfur species on pyrite.

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

    SciTech Connect

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

    1994-12-31

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

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

    PubMed

    Kong, Linghao; Hu, Xingyun; He, Mengchang

    2015-03-17

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

  9. [Characterization of oxidation on pyrite by in situ attenuated total reflection-Fourier transform infrared spectroscopy].

    PubMed

    Zhang, Ping; Chen, Yong-Heng; Liu, Juan; Wang, Chun-Lin

    2008-11-01

    Pyrite is one of common natural minerals in the environment, which is easily oxidated and is the main source of acidity mine drainage (AMD). The study on the oxidation of pyrite is helpful to comprehend the mechanism of its pollution. In the present paper, the oxidation of pyrite under the condition of air and water was respectively investigated by the attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR) through the designing experiment on the formation of carbon dioxide by the reaction of carbonate in pyrite with sulfuric acid formed by the oxidation of pyrite. The CO2 measurement by in situ ATR indicated that the oxidation rate of pyrite both in the air and in water both reduced by time and the latter reduced more obviously than the former, which indicates that the oxidation rate of pyrite in water is slower than that in the air. In the ATR measurement, the double absorption peaks at 2 350 cm(-1) that indicates CO2 have high selectivity, and permits the in situ analysis.

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

    NASA Astrophysics Data System (ADS)

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

    2010-09-01

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

  11. Studies of incipient oxidation of pyrite for improved rejection. Seventh quarterly technical progress report, April 1, 1994--June 30, 1994

    SciTech Connect

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

    1994-10-01

    The major objectives of this work are (i) to determine the Eh-pH conditions under which pyrite is stable, (ii) to determine the mechanism of the initial stages of pyrite oxidation, and (iii) to determine if the semiconducting 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 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 pre-existing oxidation products on the surface. Electrochemical reduction and oxidation of these pre-existing products essentially mask the oxidation of pyrite itself. 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, electrochemical impedance spectroscopy (EIS) has been conducted on pyrite from different sources. In addition, EIS studies have been conducted on an electrode that was first fractured in situ and then polished.

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

    SciTech Connect

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

    1994-07-01

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

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

    SciTech Connect

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

    1996-03-01

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

  14. Manipulation of pyrite colonization and leaching by iron-oxidizing Acidithiobacillus species.

    PubMed

    Bellenberg, Sören; Barthen, Robert; Boretska, Mariia; Zhang, Ruiyong; Sand, Wolfgang; Vera, Mario

    2015-02-01

    In this study, the process of pyrite colonization and leaching by three iron-oxidizing Acidithiobacillus species was investigated by fluorescence microscopy, bacterial attachment, and leaching assays. Within the first 4-5 days, only the biofilm subpopulation was responsible for pyrite dissolution. Pyrite-grown cells, in contrast to iron-grown cells, were able to oxidize iron(II) ions or pyrite after 24 h iron starvation and incubation with 1 mM H₂O₂, indicating that these cells were adapted to the presence of enhanced levels of reactive oxygen species (ROS), which are generated on metal sulfide surfaces. Acidithiobacillus ferrivorans SS3 and Acidithiobacillus ferrooxidans R1 showed enhanced pyrite colonization and biofilm formation compared to A. ferrooxidans (T). A broad range of factors influencing the biofilm formation on pyrite were also identified, some of them were strain-specific. Cultivation at non-optimum growth temperatures or increased ionic strength led to a decreased colonization of pyrite. The presence of iron(III) ions increased pyrite colonization, especially when pyrite-grown cells were used, while the addition of 20 mM copper(II) ions resulted in reduced biofilm formation on pyrite. This observation correlated with a different extracellular polymeric substance (EPS) composition of copper-exposed cells. Interestingly, the addition of 1 mM sodium glucuronate in combination with iron(III) ions led to a 5-fold and 7-fold increased cell attachment after 1 and 8 days of incubation, respectively, in A. ferrooxidans (T). In addition, sodium glucuronate addition enhanced pyrite dissolution by 25%.

  15. 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

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

    SciTech Connect

    Doyle, F.M.

    1992-12-31

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

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

    PubMed

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

    2017-01-01

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

  18. 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.

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

    PubMed

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

    1992-06-01

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

  20. 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

  1. Solid-phase products of bacterial oxidation of arsenical pyrite.

    PubMed

    Carlson, L; Lindström, E B; Hallberg, K B; Tuovinen, O H

    1992-03-01

    Bacterial leaching of an As-containing pyrite concentrate produced acidic (pH < 1) leachates. During the leaching, the bacteria solubilized both As and Fe, and these two elements were distributed in solution-phase and solid-phase products. Jarosite and scorodite were the exclusive crystalline products in precipitate samples from the bacterial leaching of the sulfide concentrate.

  2. Citrate-enhanced release of arsenic during pyrite oxidation at circumneutral conditions.

    PubMed

    Zhang, Peng; Yao, Weiyu; Yuan, Songhu

    2017-02-01

    The release of arsenic (As) from the oxidation of As-rich pyrite is an important source of the high arsenic in groundwater. As a widespread low-molecular-weight organic acid, citrate plays an important role on the cycling of Fe(II)/Fe(III) through complexation in circumneutral subsurface environments, while the influence of citrate on the release of As from the oxidation of As-rich pyrite is poorly understood. In this study, As was loaded onto pyrite particles under anoxic conditions, and its release was investigated in the presence of 0-1 mM citrate at pH 7.4 under oxic conditions. As-loaded pyrite suspension was prepared by the equilibrium of 2.67 μM As(III) in 10 g/L pyrite under anoxic conditions with the decrease in dissolved As(III) concentration to 1 μM. The suspension was subsequently exposed to air for oxygenation. In the absence of citrate, the oxygenation decreased the partitioning of As in the solution because of the re-adsorption of aqueous As by the in situ generated Fe(III) oxyhydroxides. However, with the increase in citrate concentration from 0.1 to 1 mM, the As partitioned in the solution increased from 0.3 to 2.67 μM. In the presence of 1 mM citrate, the As(III) was almost completely oxidized to As(V) during the oxygenation. The mechanisms of citrate-enhanced release of As were mainly attributed to the ligand exchange of citrate with As for pyrite surface sites, the competitive adsorption of citrate with As on Fe(III) oxyhydroxides and pyrite, and the partitioning of As on the newly formed Fe(III) colloids. This finding presents an overlooked mechanism of the release of pyrite-associated As under oxic and circumneutral conditions.

  3. Microbial oxidation of pyrite coupled to nitrate reduction in anoxic groundwater sediment.

    PubMed

    Jørgensen, Christian Juncher; Jacobsen, Ole Stig; Elberling, Bo; Aamand, Jens

    2009-07-01

    Although many areas in Denmark are intensively agricultured, the discharge of nitrate from groundwater aquifers to surface water is often lower than expected. In this study it is experimentally demonstrated that anoxic nitrate reduction in sandy sediment containing pyrite is a microbially mediated denitrification process with pyrite as the primary electron donor. The process demonstrates a temperature dependency (Q10) of 1.8 and could be completely inhibited by addition of a bactericide (NaN3). Experimentally determined denitrification rates show that more than 50% of the observed nitrate reduction can be ascribed to pyrite oxidation. The apparent zero-order denitrification rate in anoxic pyrite containing sediment at groundwater temperature has been determined to be 2-3 micromol NO3- kg(-1) day(-1). The in situ groundwater chemistry at the boundary between the redoxcline and the anoxic zone reveals that between 65 and 80% of nitrate reduction in the lower part of the redoxcline is due to anoxic oxidation of pyrite by nitrate with resulting release of sulfate. It is concluded that microbes can control groundwater nitrate concentrations by denitrification using primarily pyrite as electron donor at the oxic-anoxic boundary in sandy aquifers thus determining the position and downward progression of the redox boundary between nitrate-containing and nitrate-free groundwater.

  4. Experimental oxidative dissolution of sphalerite in the Aznalcollar sludge and other pyritic matrices.

    PubMed

    Hita, Raúl; Torrent, José; Bigham, Jerry M

    2006-01-01

    After the collapse on 25 Apr. 1998 of the Aznalcóllar mine tailings dike in southwestern Spain, 45 km2 of the Guadiamar valley were covered by a pyritic sludge containing up to 2% sphalerite (ZnS). Later, the sludge was mechanically removed and calcium carbonate was plowed into the soil to immobilize heavy metals. By June 2001 more than 60% of the sulfides in the residual sludge had oxidized and soil Zn contents reached locally phytotoxic levels. Therefore, the oxidative dissolution of sphalerite in the sludge and other pyritic samples was examined. Flow-through oxidation experiments showed that: (i) about 5 and 17% of the sludge Fe and Zn were in soluble form, respectively, because the sludge sample had been partly oxidized in the field; (ii) the oxidation rates of the residual pyrite and sphalerite were similar; (iii) the overall sulfide oxidation rate was relatively unaffected by the addition of calcite; and (iv) poorly crystalline Fe (hydr)oxides containing Zn in occluded form and Zn (hydroxi)carbonates were formed in the presence of calcite. The rate of oxidation of reference sphalerite greatly increased when it was incorporated in the sludge or in a reference pyrite matrix. This enhancement was due to galvanic interaction because pyrite oxidation was depressed in the presence of sphalerite. Oxidation by Fe3+ ions was less important because the oxidation rates of native sphalerite were not greater at low than at high pH. The fast oxidation rate of sphalerite in the Aznalcóllar sludge indicates a need for quick adoption of remediation measures in similar accidents elsewhere. The use of calcite amendments has little influence on the oxidation rate but does result in the accumulation of Zn in relatively insoluble forms.

  5. Modeling of pyrite oxidation in saturated and unsaturated subsurface flow systems

    SciTech Connect

    Xu, Tianfu; White, Stephen P.; Pruess, Karsten; Brimhall, George H.

    2000-02-10

    Pyrite oxidation (FeS2) causes acidification and mobilization of metals. Mathematical modeling of pyrite oxidation in variably saturated reactive flow systems is challenging because (1) it occurs through a complex interplay of multi-phase flow and transport processes, and (2) aqueous concentrations of key species vary over tens orders of magnitude in different redox conditions. Here we present a general multi-phase 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. Both codes are used to simulate a fully and a variably-saturated pyrite oxidation problem with simple 1-D flow and reaction conditions. Results from both codes indicates that the effects of oxygen partial pressure reduction due to reactions on the fluid flow is not significant under ambient conditions. However, it must be noted that when fluid flow and chemical reactions are strongly coupled, such as when boiling takes place in geothermal reservoirs, this could be essential. The fully simultaneous approach has a complete process description. The sequential iteration approach is found to be more efficient computationally. The oxygen gas diffusion process plays a dominant role in the chemical evolution for pyrite oxidation in unsaturated conditions. An example in 2-D fractured rock is presented to demonstrate pyrite oxidation under complex flow and geochemical conditions. This example shows that pyrite oxidation exerts strong influence on hydrogeochemical evolution in variably saturated flow systems. The alteration of primary rock minerals and the development of secondary mineral assemblages predicted are consistent with field observations. This example serves as a prototype for oxidative weathering processes with broad significance for geoscientific, engineering, and environmental applications.

  6. Progressive Oxidation of Pyrite in Five Bituminous Coal Samples: An As XANES and 57Fe Mossbauer Spectroscopic Study

    SciTech Connect

    Kolker,A.; Huggins, F.

    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 O{sub 2} atmosphere; (3) room atmosphere (relative humidity {approx}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 {sup 57}Fe Mossbauer spectroscopy, respectively. Arsenic XANES spectroscopy shows progressive oxidation of pyritic As to arsenate, with wetted samples showing the most rapid oxidation. {sup 57}Fe Mossbauer spectroscopy also shows a much greater proportion of Fe{sup 3+} forms (jarosite, Fe{sup 3+} sulfate, FeOOH) for samples stored under wet conditions, but much less

  7. 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

  8. 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

  9. 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.

  10. 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.

  11. 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.

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

    NASA Astrophysics Data System (ADS)

    Gartman, Amy

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

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

    SciTech Connect

    Herrera, Miguel Nicolas

    1994-01-01

    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.

  14. The influence of pyrite grain size on the final oxygen isotope difference between sulphate and water in aerobic pyrite oxidation experiments.

    PubMed

    Heidel, Claudia; Tichomirowa, Marion; Junghans, Manuela

    2009-12-01

    Oxidation experiments with different pyrite grain sizes (63-100, 100-140, 140-180 microm) were carried out to investigate the oxygen and sulphur isotope composition of sulphate produced under aerobic acid conditions, which may help to understand oxidation mechanisms and to interpret data from natural sites. Long-term experiments with grain size 63-100 microm showed that constant delta (18)O(SO4) values were not achieved before 100 days. The final oxygen isotope difference between water and sulphate indicates that a small proportion of molecular oxygen is incorporated into sulphate even in the later course of the oxidation due to sulphite oxidation by molecular oxygen. However, most of the sulphate oxygen derives from water. Similar delta (18)O(SO4) values from experiments with grain sizes 63-100, 100-140, and 140-180 microm indicate similar oxidation mechanisms for all three grain sizes. These results differed from previous results of identical experiments with grain size<63 microm, where higher delta (18)O(SO4) values were obtained. We propose that the greater proportion of molecular oxygen in sulphate from oxidised fine-grained pyrite is caused by an intensified adsorption of molecular oxygen on sulphur sites of ultrafine pyrite particles. Hence, the formation of sulphate from the (initial) reaction on sulphur sites of pyrite and from sulphite oxidation should be more dominant if ultrafine material is present. The delta (34)S(SO4) values (2.0-2.7) obtained from experiments with the coarser grain sizes agreed with the delta (34)S value of pyrite (2.4), whereas sulphur isotopes of sulphate obtained from previous experiments with fine-grained pyrite showed an initial (32)S enrichment compared with pyrite. Due to the lack of delta (34)S(SO4) values from the beginning of the experiments with coarser grain sizes, it remains speculative that sulphur isotopes indicate at least initial differences in oxidation mechanisms between fine and coarser pyrite grain sizes.

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

    PubMed

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

    2013-08-06

    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.

  16. 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.

  17. 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.

  18. 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

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

    NASA Astrophysics Data System (ADS)

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

    2009-11-01

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

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. Pyrite oxidation in the presence of hematite and alumina: I. Batch leaching experiments and kinetic modeling calculations.

    PubMed

    Tabelin, Carlito Baltazar; Veerawattananun, Suchol; Ito, Mayumi; Hiroyoshi, Naoki; Igarashi, Toshifumi

    2017-02-15

    Pyrite is one of the most common and geochemically important sulfide minerals in nature because of its role in the redox recycling of iron (Fe). It is also the primary cause of acid mine drainage (AMD) that is considered as a serious and widespread problem facing the mining and mineral processing industries. In the environment, pyrite oxidation occurs in the presence of ubiquitous metal oxides, but the roles that they play in this process remain largely unknown. This study evaluates the effects of hematite (α-Fe2O3) and alumina (α-Al2O3) on pyrite oxidation by batch-reactor type experiments, surface-sensitive characterization of the oxidation layer and thermodynamic/kinetic modeling calculations. In the presence of hematite, dissolved sulfur (S) concentration dramatically decreased independent of the pH, and the formation of intermediate sulfoxy anionic species on the surface of pyrite was retarded. These results indicate that hematite minimized the overall extent of pyrite oxidation, but the kinetic model could not explain how this suppression occurred. In contrast, pyrite oxidation was enhanced in the alumina suspension as suggested by the higher dissolved S concentration and stronger infrared (IR) absorption bands of surface-bound oxidation products. Based on the kinetic model, alumina enhanced the oxidative dissolution of pyrite because of its strong acid buffering capacity, which increased the suspension pH. The higher pH values increased the oxidation of Fe(2+) to Fe(3+) by dissolved O2 (DO) that enhanced the overall oxidative dissolution kinetics of pyrite.

  7. Investigation of pyrite oxidation by hexavalent chromium: solution species and surface chemistry.

    PubMed

    Demoisson, Frédéric; Mullet, Martine; Humbert, Bernard

    2007-12-15

    Pyrite oxidation processes by aqueous Cr(VI) were investigated at 25 degrees C under an argon atmosphere. Synthetic pyrite suspensions (6 g L(-1)) were reacted for 20 h with a range of Cr(VI) solutions from 0 to 700 microM and at pH 2-12. The main objective of this work was to investigate the reaction mechanisms by emphasizing the role of sulfur species. Aqueous chemical processes were well illustrated in acidic media where significant amounts of sulfate and iron species were determined. Sulfate anions are the final stable sulfur species involved in the reaction pathway. Experiments showing complete Cr(VI) removal from solution displayed ratios [S(VI)]/[Fe](tot)<2, probably due to a deficit in aqueous sulfur species. Experiments showing incomplete Cr(VI) removal displayed ratios [Cr(VI)](removed)/[S(VI)] close to 1.5. This ratio was found to be consistent with the formation of thiosulfate (S(2)O(2-)(3)). Thiosulfate ions disproportionated into elemental sulfur S(0) and tetrathionate ions (S(4)O(2-)(6)) that were finally oxidized to sulfate anions under acidic conditions. The distribution of the oxidation state of sulfur atoms at the pyrite surface determined by XPS was additional evidence for the multistep sulfur oxidation process. The presence of elemental sulfur in the S(2p) spectra correlated well with the disproportion of thiosulfate under acidic conditions.

  8. 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.

  9. Studies of incipient oxidation of pyrite for improved rejection. Technical progress report for the fourth quarter, July 1, 1993--September 30, 1993

    SciTech Connect

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

    1993-10-01

    One major objective of this work is to determine the Eh-pH conditions under which pyrite is stable and then to determine the mechanism of the initial stages of pyrite oxidation. 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. In the previous quarterly report, pyrite oxidation in pH 9.2 buffer solution was discussed. During this report period, the initial stages of pyrite oxidation in pH 4.6 buffer solution were studied, and the results compared with those in pH 9.2 solution. The effect of anodic and cathodic potential limits on the subsequent photocurrent and voltammetry behavior of freshly-fractured pyrite electrodes was also determined.

  10. 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.

  11. 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.

  12. 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.

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

    SciTech Connect

    Doyle, F.M.

    1995-02-28

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

  14. 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.

  15. Lactate oxidation in pyrite suspension: a Fenton-like process in situ generating H2O2.

    PubMed

    Wang, Wei; Qu, Youpeng; Yang, Bin; Liu, Xiaoyang; Su, Wenhui

    2012-01-01

    Pyrite is a common mineral at many mining sites. In this study, the mineral pyrite was studied as a Fenton-like reagent for environmental concerns. We selected lactate as a model target molecule to evaluate the Fenton-like catalytic efficiency of pyrite upon organic oxidation. A complete set of control experiments in both aerobic and anaerobic atmospheres unequivocally established that the pyrite in aqueous solution could spontaneously in situ generate (·)OH and H(2)O(2), serving as a Fenton-like reagent to catalyze the oxidation of lactate to pyruvate with no need for additional H(2)O(2). We called it the pyrite-only Fenton-like (PF) reagent. Monitoring concentration changes of lactate and pyruvate with the time indicated that the pyrite mediated the favorable pyruvate formation at pH 4.5, 60 °C, under air atmosphere. The PF reaction could be stimulated by visible light illumination. Under the optimum conditions, up to 50% of lactate was degraded within 10d. The results suggest that pyrite and its Fenton-like processes may be potentially practical in wastewater treatment.

  16. 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.

  17. 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.

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

    SciTech Connect

    Doyle, F.M.

    1992-01-28

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

  19. 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

    2015-07-07

    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.

  20. 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.

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

    USGS Publications Warehouse

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

    2011-01-01

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

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

    USGS Publications Warehouse

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

    2007-01-01

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

  3. [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).

  4. 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.

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

    SciTech Connect

    Doyle, F.M.

    1993-04-01

    During the tenth 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. Electrokinetic tests were done on Upper Freeport and Pittsburgh coal pyrite. In addition, surface area measurements were done on Upper Freeport and Upper Clarion coals.

  6. 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.

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

    PubMed

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

    2012-03-14

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

  8. Interaction of Oxygen and Water with the (100) Surface of Pyrite: Mechanism of Sulfur Oxidation.

    PubMed

    Sit, Patrick H-L; Cohen, Morrel H; Selloni, Annabella

    2012-09-06

    We present a density-functional study of the adsorption and reactions of oxygen and water with the (100) surface of pyrite. We find that dissociative adsorption is energetically favorable for oxygen, forming ferryl-oxo, Fe(4+)═O(2-), species. These transform easily to ferric-hydroxy, Fe(3+)-OH(-), in the presence of coadsorbed water, and the latter fully covers the surface under room conditions. A mechanism for surface oxidation is identified, which involves successive reactions with molecular oxygen and water, and leads to the complete oxidation of a surface sulfur to SO4(2-). The crucial recurring process is the surface O(2-) and OH(-) species acting as proton acceptors for incoming water molecules. Using a recently proposed method, we examine the oxidation state changes of the surface ions and the electron flow during the adsorption and oxidation processes. The oxidation mechanism is consistent with isotopic labeling experiments, suggesting that the oxygens in SO4(2-) from gas-phase oxidation are derived from water.

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

    SciTech Connect

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

    1994-12-31

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

  10. 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.

  11. Pyrite oxidation in the presence of hematite and alumina: II. Effects on the cathodic and anodic half-cell reactions.

    PubMed

    Tabelin, Carlito Baltazar; Veerawattananun, Suchol; Ito, Mayumi; Hiroyoshi, Naoki; Igarashi, Toshifumi

    2017-03-01

    The oxidative dissolution of pyrite is an important process in the redox recycling of iron (Fe) and is well-known for its role in the formation of acid mine drainage (AMD), which is considered as the most serious and widespread problem after the closure of mines and mineral processing operations. Because this process requires the movement of electrons, common metal oxides in nature that have either semiconducting (e.g., hematite) or insulating (e.g., alumina) properties may have strong effects on it. In this study, changes in the electrochemical behavior of pyrite in the presence of hematite and alumina were investigated. Results showed that the formation of surface-bound species directly influenced the anodic and cathodic half-cell reactions as well as the transfer of electrons between these sites. Pyrite pretreated in the air became anodically more reactive than that pretreated in oxygenated water, but the type of oxidizing media had little effect on the cathodic half-cell reaction. The presence of hematite and alumina during pretreatment also had strong effects on the electrochemical properties of pyrite. Chronoamperometry measurements suggest that hematite and alumina enhanced the anodic half-cell reaction but suppressed the cathodic half-cell reaction of pyrite oxidation. Increased anodic half-cell reaction in the presence of hematite could be attributed to electron "bridging" and catalytic effects of this mineral. In contrast, the effects of alumina on the anodic half-cell reaction were indirect and could be explained by the formation of Fe(3+)-oxyhydroxide surface species during pretreatment. Suppression of the cathodic half-cell reaction by both minerals was attributed to their "protective" effect on cathodic sites. Our results also point to the cathodic half-cell reaction as the rate determining-step of the overall oxidative dissolution process.

  12. 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

  13. 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

  14. 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.

  15. A combined kinetic and diffusion model for pyrite oxidation in tailings: a change in controls with time

    NASA Astrophysics Data System (ADS)

    Elberling, , B.; Nicholson, R. V.; Scharer, J. M.

    1994-05-01

    Acidic drainage from the oxidation of mine tailing wastes is an important environmental problem. The purpose of this paper is to develop a model (1) to simulate the rate of oxidation of pyrite over time, (2) to verify the importance of chemical kinetic control and diffusion control on the oxidation rate with time and, (3) to evaluate the sensitivity of the model to critical parameters of the tailings, such as grain size, pyrite content and the effective diffusion coefficient. The source code comprises four main modules including parameter allocation (kinetics, transport), sulphide oxidation (shrinking particle), oxygen transport and pyrite mass balance. The results show that high oxidation rates are observed in the initial time after tailings deposition. During this initial period of high rates, an apparent shift occurs from kinetic to diffusional control over a period of time that depends on the composition and properties of the tailings. Based on the simulation results, it is evident that the overall rate of oxidation after a few years will be controlled dominantly by the diffusion of oxygen rather than by biological or non-biological kinetics in the tailings.

  16. 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.''

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

    SciTech Connect

    Frost, J.K.

    1995-12-31

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

  18. 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.

  19. 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.

  20. Hydrochemical and stable isotope indicators of pyrite oxidation in carbonate-rich environment; the Hamersley Basin, Western Australia

    NASA Astrophysics Data System (ADS)

    Dogramaci, Shawan; McLean, Laura; Skrzypek, Grzegorz

    2017-02-01

    Sulphur (S) is a commonly occurring element in most aquifers, primarily in oxidised (sulphates) and reduced (sulphides) forms. Sulphides often constitute a risk to groundwater quality due to acid rock drainage, especially in catchments that are subject to mining excavations or groundwater injection. However, in semi-arid regions detection of the acid rock drainage risk can be challenging and traditional methods based on observations of increasing SO4 concentrations or SO4/Cl ratios in surface and groundwater, are not necessarily applicable. In addition, decreasing pH, usually accompanying pyrite oxidation, can be masked by the high pH-neutralisation capacity of carbonate and silicate minerals. Analysis of 73 surface and groundwater samples from different water bodies and aquifers located in the Hamersley Basin, Western Australia found that most of the samples are characterised by neutral pH but there was also a large spatial variability in the dissolved sulphate (SO4) concentrations that ranged from 1 mg/L to 15,000 mg/L. Not surprisingly, groundwater in aquifers that contained pyrite had high sulphate concentrations (>1000 mg/L). This was associated with low δ34SSO4 values (+1.2‰ to +4.6‰) and was consistent with the values obtained from aquifer matrix pyritic rock samples (-1.9‰ to +4.4‰). It was also found that the SO4 concentrations and acidity levels were not only dependent on δ34SSO4 values and existence of pyrite but also on the presence of carbonate minerals in the aquifer matrix. The groundwater in aquifers containing both pyrite and carbonate minerals had a neutral pH and was also saturated with respect to gypsum and had high magnesium concentrations of up to 2200 mg/L suggesting de-dolomitisation as the process buffering the acidity generated by pyrite oxidation. Based on the findings from this study, a classification scheme has been developed for identification of the acid rock drainage contribution to groundwater that encompasses a myriad of

  1. Oxidation of coal and coal pyrite mechanisms and influence on surface characteristics. Technical progress report, December 1, 1993--May 31, 1994

    SciTech Connect

    Doyle, F.M.

    1994-08-01

    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 term of the bulk and surface chemistry, the microstructure, and the semiconductor properties of the pyrite. During the fourteenth and fifteenth quarters, flotation tests were done on Upper Freeport coal from the Troutvill {number_sign}2 Mine, Clearfield County, Pennsylvania and on coal samples from the Pennsylvania State Coal Bank. The influence of electrode potential on the surface properties of coal pyrite was tested using contact angle measurements on polarized Pittsburgh coal pyrite electrode.

  2. Oxidation of coal and coal pyrite mechanisms and influence on surface characteristics. Quarterly technical progress report, December 1, 1993--May 31, 1994

    SciTech Connect

    Doyle, F.M.

    1996-01-01

    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 term of the bulk and surface chemistry, the microstructure, and the semiconductor properties of the pyrite. During the fourteenth and fifteenth quarters, flotation tests were done on Upper Freeport coal from the Troutville No. 2 Mine, Clearfield County, Pennsylvania and on coal samples from the Pennsylvania State Coal Bank. The influence of electrode potential on the surface properties of coal pyrite was tested using contact angle measurements on polarized Pittsburgh coal pyrite electrode.

  3. 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.

  4. 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.

  5. Analysis of the surface proteins of Acidithiobacillus ferrooxidans strain SP5/1 and the new, pyrite-oxidizing Acidithiobacillus isolate HV2/2, and their possible involvement in pyrite oxidation.

    PubMed

    Klingl, Andreas; Moissl-Eichinger, Christine; Wanner, Gerhard; Zweck, Josef; Huber, Harald; Thomm, Michael; Rachel, Reinhard

    2011-12-01

    Two strains of rod-shaped, pyrite-oxidizing acidithiobacilli, their cell envelope structure and their interaction with pyrite were investigated in this study. Cells of both strains, Acidithiobacillus ferrooxidans strain SP5/1 and the moderately thermophilic Acidithiobacillus sp. strain HV2/2, were similar in size, with slight variations in length and diameter. Two kinds of cell appendages were observed: flagella and pili. Besides a typical Gram-negative cell architecture with inner and outer membrane, enclosing a periplasm, both strains were covered by a hitherto undescribed, regularly arranged 2-D protein crystal with p2-symmetry. In A. ferrooxidans, this protein forms a stripe-like structure on the surface. A similar surface pattern with almost identical lattice vectors was also seen on the cells of strain HV2/2. For the surface layer of both bacteria, a direct contact to pyrite crystals was observed in ultrathin sections, indicating that the S-layer is involved in maintaining this contact site. Observations on an S-layer-deficient strain show, however, that cell adhesion does not strictly depend on the presence of the S-layer and that this surface protein has an influence on cell shape. Furthermore, the presented data suggest the ability of the S-layer protein to complex Fe3+ ions, suggesting a role in the physiology of the microorganisms.

  6. 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

  7. 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

  8. 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

  9. 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.

  10. Soil pollution by oxidation of tailings from toxic spill of a pyrite mine.

    PubMed

    Simón, M; Martín, F; Ortiz, I; García, I; Fernández, J; Fernández, E; Dorronsoro, C; Aguilar, J

    2001-11-12

    On the 25th April 1998, toxic water and tailings from a pyrite mine of Aznalcóllar (southern Spain) spilled into the Agrio and Guadiamar River Basin affecting some 40 km2. In five sectors throughout the basin, we monitored the physical and chemical properties of the tailings as well as the degree of pollution in the soils on four different sampling dates: 5 May, 20 May, 4 June and 22 July 1998. The characteristics of the tailings deposited on the soils are shown to be related to distance from the spill. The oxidation rate of the tailings and the solubilization of the pollutant elements were more pronounced in the middle and lower sectors of the basin, where the particle size was finer, the sulfur content higher and the bulk density less. The increases in water-soluble sulfates, Zn. Cd and Cu were very rapid (the highest values being reached 25 days after the spill) and intense (reaching 45% of the total Cu, 65% of the total Zn and Cd). Meanwhile, the increases in water-soluble As, Bi, Sb, Pb and Tl were far lower (ranging between 0.002% of the total Tl and 2.5% of the total As) and less rapid in the case of As, Bi and Pb (the highest values for these elements being reached 40 days after the spill). These soluble elements infiltrated the soils with the rainwater, swiftly augmenting the soil pollution. Twenty-five days after the spill, when the rainfall ranged between 45 and 63 mm, the first 10-cm of the soils in the middle and lower sectors of the basin exceeded the maximum concentration permitted for agricultural soils in Zn, Cu and Tl. At 40 days after the spill, when the rainfall ranged between 60 and 89 mm, all the soils reached or exceeded the maximum permitted concentrations for As and Tl. Nevertheless, the pollutants tended to concentrate in the first 10 cm of the soils without seriously contaminating either the subsoil or the groundwaters. Consequently, a rapid removal of the tailings and the ploughing of the first 25-30 cm of the soils would be urgent

  11. 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.

  12. 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.

  13. 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.

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

    PubMed

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

    2015-10-30

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

  15. 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.

  16. Oxidation of coal and coal pyrite mechanisms and influence on surface characteristics. Technical progress report, March 31, 1993

    SciTech Connect

    Doyle, F.M.

    1993-04-01

    During the tenth 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. Electrokinetic tests were done on Upper Freeport and Pittsburgh coal pyrite. In addition, surface area measurements were done on Upper Freeport and Upper Clarion coals.

  17. 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.

  18. Enhanced pyrite rejection in coal flotation

    SciTech Connect

    Tao, D.P.; Lu, M.X.; Richardson, P.E.; Luttrell, G.H.; Adel, G.T.; Yoon, R.H.

    1994-12-31

    Difficulties in rejecting pyrite from coal by flotation primarily result from two mechanisms of particle recovery: attachment and middlings. Attachment of pyrite is the consequence of surface hydrophobicity induced by superficial oxidation; middlings that can float readily are caused by incomplete liberation of pyrite from coal. New flotation schemes have been developed to enhance pyrite rejection. They are referred to as Electrochemically-Enhanced Sulfur Rejection (EESR) and Polymer-Enhanced Sulfur Rejection (PESR) processes. In the EESR process, the formation of hydrophobic products is prevented by electrochemical techniques in which active metals are used as sacrificial anodes to cathodically protect pyrite from oxidation; in the PESR process, hydrophilic polymers is used to mask coal in middlings by specific adsorption on pyrite, and thus depress coal-pyrite middlings.

  19. Oxidation of Framboidal Pyrite as a Mobilization Mechanism During Aquifer Storage and Recovery in the Upper Floridan Aquifer, Southwest Florida

    NASA Astrophysics Data System (ADS)

    Price, R. E.; Pichler, T.

    2002-12-01

    During a recent study conducted at the University of South Florida, core samples were collected from 20 wells located in the southern half of the Southwest Florida Water Management District (SWFWMD), and analyzed to gain a better understanding of arsenic distribution and mineralogy throughout the Oligocene-aged Suwannee Limestone, Upper Floridan Aquifer. The Suwannee is the primary storage zone utilized to date for Aquifer Storage and Recovery (ASR), the process of capturing excess water during the rainy season and storing that water underground until needed. The SWFWMD recently determined that ASR is a critical component for its 20-year strategy to enhance water supply in southwest Florida where, as of January 2002, 26 facilities are in operation and 19 are permitted for construction. The Comprehensive Everglades Restoration Project (CERP) calls for over 330 ASR wells to store 1.7 billion gallons of water per day. This research was conducted because of the discovery of elevated arsenic (As) levels during recovery cycle testing of several ASR facilities throughout southwest Florida. Before any solution or mobilization mechanism can be suggested, the exact mineralogical association of the arsenic must be determined. Possible sources for the arsenic include: 1) sulfide minerals, 2) iron oxyhydroxide coatings, 3) organic material, and/or 4) phosphate nodules. Sampling was carried out with the purpose to sample each core at constant intervals and to collect samples at locations that may have a higher potential for the presence of arsenic, such as fractures, organic material, sulfide-rich zones and iron oxyhydroxide-rich zones. Detailed lithologic descriptions for each sample showed that framboidal pyrite was present, and in fact abundant, throughout the unit, while the iron oxides, organics, and phosphate nodules were uncommon. Total arsenic concentrations for each sample were determined by hydride generation-atomic fluorescence spectrometry (HG-AFS), which showed much

  20. [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.

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

    SciTech Connect

    V. P. Evangelou

    1997-04-14

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

  2. Kinetics of pyrite formation by the H 2S oxidation of iron (II) monosulfide in aqueous solutions between 25 and 125°C: The rate equation

    NASA Astrophysics Data System (ADS)

    Rickard, David

    1997-01-01

    A kinetic study of the reaction FeS+ H2S=FeS2+ H2 where FeS is precipitated FeS, H 2S (aq) is aqueous H 2S, FeS 2 is pyrite, and H 2(g) is hydrogen gas, shows that the rate between 25 and 125°C can be described by the equation dFeS2/dt = k(FeS) >(cH2S) where k the second order rate constant varies between 1.03 × 10 -4L mol -1 s -1 at 25°C and 3.20 × 10 -3 L mol -1 s -1 at 125°C. The rate constant shows a sigmoidal temperature dependence with an average Arrhenius activation energy of 35 kJ mol -1. The reaction is surprisingly fast at ambient temperatures with up to 50% reaction being completed within one day. The direct dependence of the rate on cH 2S (aq) means that the rate is pH dependent for any fixed total sulfide concentration. In typical sulfidic aquatic systems and sediments 9 × 10 -13 to 9 × 10 -8 mol FeS 2 per L sediment will be formed each day by this process. This is equivalent to approximately 3 × 10 -10 to 3 × 10 -5 mol FeS 2 per g sediment per year. At pH = 7, for the same total sulfide and FeS constraints, the rate of pyrite formation 1.5 × 10 -9 to 1.5 × 10 -4 mol FeS 2 per g sediment per year. In hydrothermal systems, such as deep ocean vents, the rate of pyrite formation by oxidation of FeS by H 2S at 125°C assuming a typical H 2S concentration of 1 mM is 3.2 × 10 -6 mol L -1 s -1 per mol FeS. A 1 million tonne pyrite deposit could form from a solution containing 1 mmol FeS and 1 mmol H 2S by this process in 1000 years at a flow rate of 0.3 Ls -1. The fluid would have a H 2 concentration of 3 × 10 -9 M. The process is by far the most rapid of the pyrite-forming reactions hitherto identified. Alternative pyrite-forming processes involving HS -, rather than H 2S, as the reaction requires an additional oxidising agent to maintain electron balance. These pathways may involve reactants such as polysulfides or intermediaries such as greigite, Fe 3S 4. In natural systems, therefore, the H 2S process will tend to be favored in strictly

  3. Synergistic effect of biogenic Fe(3+) coupled to S° oxidation on simultaneous bioleaching of Cu, Co, Zn and As from hazardous Pyrite Ash Waste.

    PubMed

    Panda, Sandeep; Akcil, Ata; Mishra, Srabani; Erust, Ceren

    2017-03-05

    Pyrite ash, a waste by-product formed during roasting of pyrite ores, is a good source of valuable metals. The waste is associated with several environmental issues due to its dumping in sea and/or land filling. Although several other management practices are available for its utilization, the waste still awaits and calls for an eco-friendly biotechnological application for metal recovery. In the present study, chemolithotrophic meso-acidophilic iron and sulphur oxidisers were evaluated for the first time towards simultaneous mutli-metal recovery from pyrite ash. XRD and XRF analysis indicated higher amount of Hematite (Fe2O3) in the sample. ICP-OES analysis indicated concentrations of Cu>Zn>Co>As that were considered for bioleaching. Optimization studies indicated Cu - 95%, Co - 97%, Zn - 78% and As - 60% recovery within 8days at 10% pulp density, pH - 1.75, 10% (v/v) inoculum and 9g/L Fe(2+). The productivity of the bioleaching system was found to be Cu - 1696ppm/d (12% dissolution/d), Co - 338ppm/d (12.2% dissolution/d), Zn k 576ppm/d (9.8% dissolution/d) and As - 75ppm/d (7.5% dissolution/d). Synergistic actions for Fe(2+) - S° oxidation by iron and sulphur oxidisers were identified as the key drivers for enhanced metal dissolution from pyrite ash sample.

  4. 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.``

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

    PubMed

    Márquez-García, Belén; Córdoba, Francisco

    2009-11-01

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

  6. Measurements of the effective diffusion coefficient of dissolved oxygen and oxidation rate of pyrite by dissolved oxygen in compacted sodium bentonite

    SciTech Connect

    Manaka, Mitsuo; Kawasaki, Manabu; Honda, Akira

    2000-05-01

    The redox condition of the near field is expected to affect the performance of engineered barrier systems. In particular, the oxygen initially existing in the pore spaces of compacted bentonites strongly affects the redox condition of the near field. To assess the influence of the oxygen, research was done to assess its transport parameters in the compacted bentonite and consumption process. To understand the diffusion of dissolved oxygen (DO) in compacted bentonite and to predict the effect of the DO, the measurements of the effective diffusion coefficient of DO in compacted sodium bentonite were made by electro-chemistry. As a result, the following relationship between the dry density of compacted sodium bentonite and the effective diffusion coefficient of DO in compacted sodium bentonite was derived: D{sub e} = 3.0 {+-} 0.5 {times} 10{sup {minus}9} exp({minus}3.7 {+-} 0.2 {times} 10{sup -3}p), where D{sub e} is the effective diffusion coefficient (m{sup 2}s{sup -1}) of DO in compacted sodium bentonite and p is the dry density (kg m{sup -3})of compacted sodium bentonite. The oxygen concentration in the bentonite is expected to be controlled by the oxidation of pyrite as an impurity in the bentonite. To investigate this idea, the rates of pyrite oxidation by DO in compacted sodium bentonite were estimated from the experimental data in pyrite-bentonite systems using the obtained effective diffusion coefficient of DO. The results show that the average of the rate constants of pyrite oxidation by DO in compacted sodium bentonite was 1.16 {+-} 0.35 {times} 10{sup {minus}8}m s{sup {minus}1}, whereas the rate constant in a carbonate-buffered solution (pH = 9.24) was 1.46 {+-} 0.09 {times}10{sup {minus}9}m s{sup {minus}1}.

  7. An investigation of pyrite depression in coal flotation by electrochemical pyrite surface control

    SciTech Connect

    Zhu Hong; Ou Zeshen; Shi Xiuping; Shen Yanchun

    1995-12-31

    This paper introduces a new potential method of pyrite depression in the flotation of high sulfur coal based on the electrochemical pyrite surface control. Experimental date show that the natural hydrophobicity of pyrite depends on the oxidation-reduction potential of the pulp. The mechanism and products of electrochemical reaction on the pyrite surface are also discussed under various conditions. The pyrite flotation is generally suppressed under low pulp potentials. Therefore, the sulfur removal in the flotation of high sulfur coal could be improved by the pulp redox potential control, while the coal flotation is materially not affected.

  8. 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.

  9. 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.

  10. Semiconductor electrochemistry of particulate pyrite: Mechanisms and products of dissolution

    SciTech Connect

    Wei, D.; Osseo-Asare, K.

    1997-02-01

    Pyrite dissolution in acidic solution was found to occur via 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 observed to be of negligible magnitude in acetonitrile solution compared with that in aqueous solution, which indicated that direct reaction of the 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 products of pyrite in acidic aqueous solution included elemental sulfur which was detected by x-ray diffraction.

  11. Control of pyrite surface chemistry in physical coal cleaning

    SciTech Connect

    Luttrell, G.H.; Yoon, R.H.; Lagno, M.L.

    1991-01-01

    The removal of pyrite from coal by flotation or any other surface- based separation process is often hampered by the apparent hydrophobicity of the mineral. Microflotation tests and induction time measurements conducted under different conditions showed that the hydrophobicity of coal pyrite is due to superficial oxidation of the mineral surface. X-ray photoelectron spectroscopy (XPS) analysis of the oxidized pyrite samples suggests that the sulfur-rich surfaces formed during oxidation may be responsible for the hydrophobicity of both coal pyrite and mineral pyrite. Based on these findings, an oxidation mechanism is proposed in which metal polysulfides and iron oxides-hydroxides are produced. The floatability of both coal pyrite and mineral pyrite can be correlated with the atomic ration between these hydrophobic and hydrophilic species that are formed on the surface. 14 refs., 7 figs., 1 tab.

  12. 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

  13. 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

  14. The Effective Diffusion Coefficient of Dissolved Oxygen and Oxidation Rate of Pyrite by Dissolved Oxygen in Compacted Purified and Crude Sodium Bentonites in Carbonate Buffered Solution

    SciTech Connect

    Manaka, Mitsuo

    2003-09-15

    Immediately after the geological disposal of high-level radioactive waste, the oxygen initially existing in the repository is expected to strongly affect the redox condition of the near field. The oxygen dissolves in the groundwater, is transported by diffusion through it, and is consumed by the oxidation of pyrite as an impurity in bentonite. To assess the influence of the oxygen, this study was conducted to estimate the diffusion of dissolved oxygen (DO) and the rate of pyrite oxidation by DO in compacted purified and crude sodium bentonites (SBs) in more detail than the Manaka et al. study. The effective diffusion coefficient (De) of DO in the compacted purified SB was measured in low ionic strength solution (carbonate buffered solution with pH {approx} 9) using the electrochemical method. The empirical equation between De value of DO and dry density (0.5 x 10{sup 3}-1.8 x 10{sup 3} kg m{sup -3}) of purified SB was obtained as follows:De{sub DO}{sup Kunipia-F} = 8.2 {+-} 1.5 x 10{sup -10}x exp(-2.6 {+-} 0.2 x10{sup -3}{rho},where De{sub DO}{sup Kunipia-F} is the De of DO in compacted purified SB (Kunipia F) (m{sup 2} s{sup -1}) and {rho} is the dry density of the SB (kg m{sup -3}).On the other hand, the De value of DO in the compacted crude SB was estimated using the relationship between De values of tritiated water in compacted purified and crude SBs. The empirical equation between the De value of DO and dry density (0.5 x 10{sup 3}-1.8 x 10{sup 3} kg m{sup -3}) of crude SB was derived as follows:De{sub DO}{sup Kunigel-V1} = 2.04 x 10{sup -9} exp(-2.6 x 10{sup -3}{rho}),where De{sub DO}{sup Kunigel-V1} is the De of DO in compacted crude SB (Kunigel V1) (m{sup 2} s{sup -1}) and {rho} is the dry density of the SB (kg m{sup -3}).The rates of pyrite oxidation by DO were estimated from the experimental data in pyrite-purified SB systems using the obtained De values of DO. The relation between rate constant (k') of pyrite oxidation by DO and dry density ({rho}) of

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

    PubMed

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

    2011-12-01

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

  16. Triple-oxygen-isotope determination of molecular oxygen incorporation in sulfate produced during abiotic pyrite oxidation (pH = 2-11)

    NASA Astrophysics Data System (ADS)

    Kohl, Issaku; Bao, Huiming

    2011-04-01

    Aqueous oxidation of sulfide minerals to sulfate is an integral part of the global sulfur and oxygen cycles. The current model for pyrite oxidation emphasizes the role of Fe 2+-Fe 3+ electron shuttling and repeated nucleophilic attack by water molecules on sulfur. Previous δ 18O-labeled experiments show that a variable fraction (0-60%) of the oxygen in product sulfate is derived from dissolved O 2, the other potential oxidant. This indicates that nucleophilic attack cannot continue all the way to sulfate and that a sulfoxyanion of intermediate oxidation state is released into solution. The observed variability in O 2% may be due to the presence of competing oxidation pathways, variable experimental conditions (e.g. abiotic, biotic, or changing pH value), or uncertainties related to the multiple experiments needed to effectively use the δ 18O label to differentiate sulfate-oxygen sources. To examine the role of O 2 and Fe 3+ in determining the final incorporation of O 2 oxygen in sulfate produced during pyrite oxidation, we designed a set of aerated, abiotic, pH-buffered (pH = 2, 7, 9, 10, and 11), and triple-oxygen-isotope labeled solutions with and without Fe 3+ addition. While abiotic and pH-buffered conditions help to eliminate variables, triple oxygen isotope labeling and Fe 3+ addition help to determine the oxygen sources in sulfate and examine the role of Fe 2+-Fe 3+ electron shuttling during sulfide oxidation, respectively. Our results show that sulfate concentration increased linearly with time and the maximum concentration was achieved at pH 11. At pH 2, 7, and 9, sulfate production was slow but increased by 4× with the addition of Fe 3+. Significant amounts of sulfite and thiosulfate were detected in pH ⩾ 9 reactors, while concentrations were low or undetectable at pH 2 and 7. The triple oxygen isotope data show that at pH ⩾ 9, product sulfate contained 21-24% air O 2 signal, similar to pH 2 with Fe 3+ addition. Sulfate from the pH 2 reactor

  17. A geochemical transport model for redox-controlled movement of mineral fronts in groundwater flow systems: A case of nitrate removal by oxidation of pyrite

    USGS Publications Warehouse

    Engesgaard, Peter; Kipp, Kenneth L.

    1992-01-01

    A one-dimensional prototype geochemical transport model was developed in order to handle simultaneous precipitation-dissolution and oxidation-reduction reactions governed by chemical equilibria. Total aqueous component concentrations are the primary dependent variables, and a sequential iterative approach is used for the calculation. The model was verified by analytical and numerical comparisons and is able to simulate sharp mineral fronts. At a site in Denmark, denitrification has been observed by oxidation of pyrite. Simulation of nitrate movement at this site showed a redox front movement rate of 0.58 m yr−1, which agreed with calculations of others. It appears that the sequential iterative approach is the most practical for extension to multidimensional simulation and for handling large numbers of components and reactions. However, slow convergence may limit the size of redox systems that can be handled.

  18. Accelerated evaporation of water on graphene oxide.

    PubMed

    Wan, Rongzheng; Shi, Guosheng

    2017-03-15

    Using molecular dynamics simulations, we show that the evaporation of nanoscale volumes of water on patterned graphene oxide is faster than that on homogeneous graphene oxide. The evaporation rate of water is insensitive to variation in the oxidation degree of the oxidized regions, so long as the water film is only distributed on the oxidized regions. The evaporation rate drops when the water film spreads onto the unoxidized regions. Further analysis showed that varying the oxidation degree observably changed the interaction between the outmost water molecules and the solid surface, but the total interaction for the outmost water molecules only changed a very limited amount due to the correspondingly regulated water-water interaction when the water film is only distributed on the oxidized regions. When the oxidation degree is too low and some unoxidized regions are also covered by the water film, the thickness of the water film decreases, which extends the lifetime of the hydrogen bonds for the outmost water molecules and lowers the evaporation rate of the water. The insensitivity of water evaporation to the oxidation degree indicates that we only need to control the scale of the unoxidized and oxidized regions for graphene oxide to regulate the evaporation of nanoscale volumes of water.

  19. 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

  20. Control of pyrite surface chemistry in physical coal cleaning

    SciTech Connect

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

    1992-06-24

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

  1. 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.

  2. 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

  3. 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

  4. 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.

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

    SciTech Connect

    Wang, Xiang-Huai.

    1991-01-01

    The objective of this project is to conduct extensive studies on the 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. Metal-accelerated oxidation in plant cell death

    SciTech Connect

    Czuba, M. )

    1993-05-01

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

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

    SciTech Connect

    Jiang, Chengliang

    1993-01-01

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

  12. 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.

  13. 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.

  14. Accelerating Quinoline Biodegradation and Oxidation with Endogenous Electron Donors.

    PubMed

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

    2015-10-06

    Quinoline, a recalcitrant heterocyclic compound, is biodegraded by a series of reactions that begin with mono-oxygenations, which require an intracellular electron donor. Photolysis of quinoline can generate readily biodegradable products, such as oxalate, whose bio-oxidation can generate endogenous electron donors that ought to accelerate quinoline biodegradation and, ultimately, mineralization. To test this hypothesis, we compared three protocols for the biodegradation of quinoline: direct biodegradation (B), biodegradation after photolysis of 1 h (P1h+B) or 2 h (P2h+B), and biodegradation by adding oxalate commensurate to the amount generated from photolysis of 1 h (O1+B) or 2 h (O2+B). The experimental results show that P1h+B and P2h+B accelerated quinoline biodegradation by 19% and 50%, respectively, compared to B. Protocols O1+B and O2+B also gave 19% and 50% increases, respectively. During quinoline biodegradation, its first intermediate, 2-hydroxyquinoline, accumulated gradually in parallel to quinoline loss but declined once quinoline was depleted. Mono-oxygenation of 2-hydroxyquinoline competed with mono-oxygenation of quinoline, but the inhibition was relieved when extra electrons donors were added from oxalate, whether formed by UV photolysis or added exogenously. Rapid oxalate oxidation stimulated both mono-oxygenations, which accelerated the overall quinoline oxidation that provided the bulk of the electron donor.

  15. Role of the carbonate impurities on the surface state of pyrite and arsenopyrite under treatment by high power electromagnetic pulses (HPEMP): oxidation of 50-100 μm size particles

    NASA Astrophysics Data System (ADS)

    Filippova, I.; Chanturiya, V.; Filippov, L.; Ryazantseva, M.; Bunin, I.

    2013-03-01

    Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) and Transmission Electron Microscopy (TEM) have shown the variation of surface phase compositions of carbonate bearing pyrite and arsenopyrite as a result of the combined action of chemical oxidation and thermal processes after the treatment by high power electromagnetic pulses (HPEMP). The monitoring of the surface phase composition allowed to determine the correlation between the treatment conditions, the surface phase composition, and the flotation yield. Thus, HPEMP treatment may be regarded as a tool controlling the surface composition and the sorption ability of flotation collector onto minerals surface, and therefore, allowing to control the hydrophobic-hydrophilic surface balance. It was confirmed in this study that the flotation of pyrite with xanthate as a result of the influence HPEMP may vary depending on the presence of impurities such as calcite.

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

    NASA Astrophysics Data System (ADS)

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

    1996-04-01

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

  17. 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.

  18. Cerium oxide nanoparticles accelerate the decay of peroxynitrite (ONOO(-)).

    PubMed

    Dowding, Janet M; Seal, Sudipta; Self, William T

    2013-08-01

    Cerium oxide nanoparticles (CeO2 NPs) have been shown to possess a substantial oxygen storage capacity via the interchangeable surface reduction and oxidation of cerium atoms, cycling between the Ce(4+) and Ce(3+) redox states. It has been well established in many studies that depending on their reactivity and surface chemistry, CeO2 NPs can effectively convert both reactive oxygen species (superoxide, O2 (•-), and hydrogen peroxide) into more inert species and scavenge reactive nitrogen species (RNS)(nitric oxide, •NO), both in vitro and in vivo. Since much of damage attributed to •NO and O2 (•-) is actually the result of oxidation or nitration by peroxynitrite or its breakdown products and due to the multiple species that these nanoparticles target in vivo, it was logical to test their interaction with the highly reactive molecule peroxynitrite (ONOO(-)). Here, we report that CeO2 NPs significantly accelerated the decay of ONOO(-) by three independent methods. Additionally, our data suggest the ability of CeO2 NPs to interact with ONOO(-) is independent of the Ce(3+)/Ce(4+) ratio on the surface of the CeO2 NPs. The accelerated decay was not observed when reactions were carried out in an inert gas (argon), suggesting strongly that the decay of peroxynitrite is being accelerated due to a reaction of CeNPs with the carbonate radical anion. These results suggest that one of the protective effects of CeO2 NPs during RNS is likely due to reduction in peroxynitrite or its reactive breakdown products.

  19. Postprandial lipids accelerate and redirect nitric oxide consumption in plasma.

    PubMed

    Vrancken, Kurt; Schroeder, Hobe J; Longo, Lawrence D; Power, Gordon G; Blood, Arlin B

    2016-05-01

    Nitric oxide (NO) and O2 are both three-to four-fold more soluble in biological lipids than in aqueous solutions. Their higher concentration within plasma lipids accelerates NO autoxidation to an extent that may be of importance to overall NO bioactivity. This study was undertaken to test the hypothesis that increased plasma lipids after a high-fat meal appreciably accelerate NO metabolism and alter the byproducts formed. We found that plasma collected from subjects after consumption of a single high-fat meal had a higher capacity for NO consumption and consumed NO more rapidly compared to fasting plasma. This increased NO consumption showed a direct correlation with plasma triglyceride concentrations (p = 0.006). The accelerated NO consumption in postprandial plasma was reversed by removal of the lipids from the plasma, was mimicked by the addition of hydrophobic micelles to aqueous buffer, and could not be explained by the presence of either free hemoglobin or ceruloplasmin. The products of NO consumption were shifted in postprandial plasma, with 55% more nitrite (n = 12, p = 0.002) but 50% less SNO (n = 12, p = 0.03) production compared to matched fasted plasma. Modeling calculations indicated that NO autoxidation was accelerated by about 48-fold in the presence of plasma lipids. We conclude that postprandial triglyceride-rich lipoproteins exert a significant influence on NO metabolism in plasma.

  20. 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.

  1. 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.

  2. 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

  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.

  4. 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

  5. Control of pyrite surface chemistry in physical coal cleaning

    SciTech Connect

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

    1992-01-01

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

  6. Silane-based coatings on the pyrite for remediation of acid mine drainage.

    PubMed

    Diao, Zenghui; Shi, Taihong; Wang, Shizhong; Huang, Xiongfei; Zhang, Tao; Tang, Yetao; Zhang, Xiaying; Qiu, Rongliang

    2013-09-01

    Acid mine drainage (AMD) resulting from the oxidation of pyrite and other metal sulfides has caused significant environmental problems, including acidification of rivers and streams as well as leaching of toxic metals. With the goal of controlling AMD at the source, we evaluated the potential of tetraethylorthosilicate (TEOS) and n-propyltrimethoxysilane (NPS) coatings to suppress pyrite oxidation. The release of total Fe and SO4(-2) from uncoated and coated pyrite in the presence of a chemical oxidizing agent (H2O2) or iron-oxidizing bacteria (Acidithiobacillus ferrooxidans) was measured. Results showed that TEOS- and NPS-based coatings reduced chemical oxidation of pyrite by as much as 59 and 96% (based on Fe release), respectively, while biological oxidation of pyrite was reduced by 69 and 95%, respectively. These results were attributed to the formation of a dense network of Fe-O-Si and Si-O-Si bonds on the pyrite surface that limited permeation of oxygen, water, and bacteria. Compared with results for TEOS-coated pyrite, higher pH and lower concentrations of total Fe and SO4(-2) were observed for oxidation of NPS-coated pyrite, which was attributed to its crack-free morphology and the presence of hydrophobic groups on the NPS-based coating surface. The silane-based NPS coating was shown to be highly effective in suppressing pyrite oxidation, making it a promising alternative for remediation of AMD at its source.

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

    PubMed

    Yan, Ruiwen; Kappler, Andreas; Peiffer, Stefan

    2015-10-06

    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.

  8. 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

  9. 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.

  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. 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.

  12. 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.

  13. 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...

  14. 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.

  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. 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.

  17. 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.

  18. Electrochemical Investigation of Arsenic Redox Processes on Pyrite.

    PubMed

    Renock, Devon; Voorhis, James

    2017-04-04

    The specific Eh-pH conditions and mechanism(s) for the reduction of arsenite, As(III), by pyrite are incompletely understood. A fundamental question is what role the pyrite surface plays in the reduction process. We used electrochemical methods to evaluate the reduction of As(III) under controlled redox conditions. As(III) reduction to elemental As(0) occurs on the pyrite surface under suboxic-reducing conditions and is promoted at low pH. Remarkably, As(III) reduction on pyrite occurs at similar potentials to those for reduction on platinum metal, suggesting a similar mechanism and kinetics for these surfaces. The onset for As(III) reduction at pH ≤ 3.5 coincides with the potential for hydrogen electroadsorption on pyrite, E ≈ +0.1 V (versus RHE). Batch reactions show that As(III) is reduced on pyrite at the Eh-pH predicted by the electrochemical study. X-ray photoelectron spectroscopy reveals that, at pH ≤ 3.5, a significant fraction of the surface arsenic (30-60%) has an oxidation state consistent with As(0). Here, we propose a mechanism whereby atomic hydrogen that forms on ferric (hydr)oxide surface layers promotes As(III) reduction at low Eh and pH. Insights provided by this study will have implications for understanding the controls on dissolved As(III) concentrations in suboxic-anoxic environments.

  19. Degradation of trichloroethylene by Fenton reaction in pyrite suspension.

    PubMed

    Che, Hyeongsu; Bae, Sungjun; Lee, Woojin

    2011-01-30

    Degradation of trichloroethylene (TCE) by Fenton reaction in pyrite suspension was investigated in a closed batch system under various experimental conditions. TCE was oxidatively degraded by OH in the pyrite Fenton system and its degradation kinetics was significantly enhanced by the catalysis of pyrite to form OH by decomposing H(2)O(2). In contrast to an ordinary classic Fenton reaction showing a second-order kinetics, the oxidative degradation of TCE by the pyrite Fenton reaction was properly fitted by a pseudo-first-order rate law. Degradation kinetics of TCE in the pyrite Fenton reaction was significantly influenced by concentrations of pyrite and H(2)O(2) and initial suspension pH. Kinetic rate constant of TCE increased proportionally (0.0030 ± 0.0001-0.1910 ± 0.0078 min(-1)) as the pyrite concentration increased 0.21-12.82 g/L. TCE removal was more than 97%, once H(2)O(2) addition exceeded 125 mM at initial pH 3. The kinetic rate constant also increased (0.0160 ± 0.005-0.0516 ± 0.0029 min(-1)) as H(2)O(2) concentration increased 21-251 mM, however its increase showed a saturation pattern. The kinetic rate constant decreased (0.0516 ± 0.0029-0.0079 ± 0.0021 min(-1)) as initial suspension pH increased 3-11. We did not observe any significant effect of TCE concentration on the degradation kinetics of TCE in the pyrite Fenton reaction as TCE concentration increased.

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

    NASA Astrophysics Data System (ADS)

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

    1995-05-01

    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

  1. 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

  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. Degradation of Diclofenac by sonosynthesis of pyrite nanoparticles.

    PubMed

    Khabbaz, M; Entezari, M H

    2017-02-01

    The aim of this work is to evaluate the ability of synthesized pyrite nanoparticles (NPs) on the degradation of Diclofenac (DCF) as a model pharmaceutical pollutant. Pyrite NPs were synthesized by sonication with 20 kHz apparatus under optimum conditions. The effects of pyrite loading (0.02-0.20 g/L), DCF concentration (10-50 mg/L) and initial pH (2-10) on the degradation were investigated. The results revealed that the NPs have a great activity in the degradation of DCF with 25 mg/L concentration. A first-order kinetic model was found to match the experimental data. Complete degradation (100%) of DCF was achieved by pyrite within 3 min and 20 min in acidic and natural pH, respectively. To gain an understanding of the degradation mechanism and the role of pyrite, a UV-Vis spectrophotometer was employed to follow the DCF concentration. In addition, the Chemical Oxygen Demand (COD) and the amounts of ammonium and chloride ions verified complete degradation of DCF in both pH values. The results demonstrated that Fe(2+) ions were generated by the pyrite surface and the hydroxyl radical (OH) was formed by Fe(2+) ions through the Fenton reaction. Based on using radical scavengers in the degradation process, OH was mainly responsible for the fast degradation of DCF. COD measurements confirmed that DCF finally degraded to further oxidized forms (NH4(+), Cl(-)).

  4. 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.

  5. 46 CFR 148.225 - Calcined pyrites (pyritic ash, fly ash).

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 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 of calcined pyrites that are the residual ash of oil or coal fired power stations. (b) This section applies...

  6. 46 CFR 148.225 - Calcined pyrites (pyritic ash, fly ash).

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 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 of calcined pyrites that are the residual ash of oil or coal fired power stations. (b) This section applies...

  7. 46 CFR 148.225 - Calcined pyrites (pyritic ash, fly ash).

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 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 of calcined pyrites that are the residual ash of oil or coal fired power stations. (b) This section applies...

  8. 46 CFR 148.225 - Calcined pyrites (pyritic ash, fly ash).

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 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 of calcined pyrites that are the residual ash of oil or coal fired power stations. (b) This section applies...

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. Formation of As(II)-pyrite during experimental replacement of magnetite under hydrothermal conditions

    NASA Astrophysics Data System (ADS)

    Qian, Gujie; Brugger, Joël; Testemale, Denis; Skinner, William; Pring, Allan

    2013-01-01

    A 'new' type of arsenian pyrite was formed during experimental replacement of magnetite under hydrothermal conditions (T = 125 and 220 °C; Psat) and in the presence of S(-II) and various As-containing species. The amount of As in pyrite depended on the As-source, with sources containing cationic As (As(II), As(III) and As(V)) resulting in considerably higher amounts of As in the product arsenian pyrite than anionic sources. The highest As content was 23.83 ± 0.20 wt%, corresponding to a S:Fe:As molar ratio of 2:0.58:0.42. Electron probe micro-analyses revealed an inverse correlation between the Fe and As contents in the arsenian pyrite, indicating that As is substituting for Fe. Arsenic concentrations were highly inhomogeneous within the pyrite rim; in general, higher As contents were found within solid pyrite growing on the outer rim, compared to the highly porous and texturally complex pyrite found close to the reaction boundary. This likely reflects different uptake mechanisms for As during the pyrite nucleation and growth stages. X-ray Absorption Near Edge Structure (XANES) analyses showed that the As in the arsenian pyrite was predominantly in the form of As(II). Cross-sectional X-ray photoelectron spectroscopy (XPS) analysis of the arsenian pyrite confirmed the presence of As(II), but also showed evidence for more oxidized species (As(III) and As(V) oxides), as well as small amounts of polymeric As-As bonding. This indicates a large difference between As in the bulk (XANES measurements) and at the pyrite surface (XPS). Ab initio XANES calculations are consistent with As replacing Fe in pyrite in the form of As(II). Our experimental study suggests that the formal oxidation state of As in this type of arsenian pyrite is close to +2, and that in addition to fluid composition and oxidation state, the reaction path leading to pyrite formation plays a significant role in controlling the chemistry of arsenian pyrite.

  14. Spectroscopic study of cystine adsorption on pyrite surface: From vacuum to solution conditions

    NASA Astrophysics Data System (ADS)

    Sanchez-Arenillas, M.; Mateo-Marti, E.

    2015-09-01

    We characterized the adsorption of cystine molecules on pyrite surface via X-ray photoelectron spectroscopy. Anoxic conditions were simulated under ultra-high-vacuum conditions. In contrast, to simulate oxidation conditions, the molecules were adsorbed on pyrite surface from solution. A novel comparative analysis revealed remarkable differences with respect to molecular adsorption and surface chemistry induced by environmental conditions. Molecular adsorption under anoxic conditions was observed to be more favorable, concentrating a large number of molecules on the surface and two different chemical species. In contrast, the presence of oxygen induced an autocatalytic oxidation process on the pyrite surface, which facilitated water binding on pyrite surface and partially blocked molecular adsorption. Pyrite is a highly reactive surface and contains two crucial types of surface functional groups that drive molecular chemistry on the surface depending on the surrounding conditions. Therefore, the system explored in this study holds interesting implications for supporting catalyzed prebiotic chemistry reactions.

  15. Reactivity of surface chemical states on fractured pyrite

    NASA Astrophysics Data System (ADS)

    Schaufuß, Andrea G.; Nesbitt, H. Wayne; Kartio, Ilkka; Laajalehto, Kari; Bancroft, G. Michael; Szargan, Rüdiger

    1998-08-01

    Synchrotron-radiation-excited photoelectron spectroscopy was used to monitor sulfur chemical states on fractured pyrite surfaces reacted with atmospheric gases. The results demonstrate that there are at least three distinct states at the pyrite surface and each is oxidised at a very different rate in air. The two surface chemical states are more reactive than bulk sulfur, the most reactive surface sulfur component being S 2-. The second chemical state is identified as the surface atom of the first disulfide layer (S 2-2), and the least reactive species are sulfur atoms of disulfide groups beneath the surface layer (i.e., all sulfur atoms having bulk coordination). A model combining the interpretation of sulfur surface species after Nesbitt et al. (Am. Mineral. in press) and the proposed oxidation mechanism of Eggleston et al. (Am. Mineral. 81 (1996) 1036) was developed to explain the initial oxidation processes on pyrite surfaces, where air oxidation of pyrite commences with the oxidation of S 2- sites at the surface.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

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

    SciTech Connect

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

    1992-06-24

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

  1. 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.

  2. 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.

  3. 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.

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

    PubMed

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

    2013-05-01

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

  5. 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.

  6. 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

  7. 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.

  8. [Analysis of XPS in the removal of Se(IV) from groundwater with pyrite].

    PubMed

    Liu, Hong-fang; Qian, Tian-wei; Zhang, Min-gang

    2015-02-01

    Selenium (Se) is an elementary trace nutrient element for human but there is a very narrow range between deficit and toxic levels. Furthermore, excessive intake of Selenium is harmful for human. The product species of selenite which was removal by pyrite particles was studied in the present research In the experiments, the pyrite particles were prepared by the wet ball mill method, and surface analyses of pyrite before and after contact with Se(IV) were conducted using X-ray photoelectron spectroscopy (XPS). Besides, the prepared pyrite samples were also characterized using both X-ray diffraction (XRD) and scanning electron microscope (SEM). X-ray diffraction analysis indicated that the purity of the prepared pyrite particles was above 97%, and the characteristic diffraction peaks of the particles well matched with that of FeS2 crystalline. Scanning electron microscope determination showed the shape of the particles was approximate ball and the size was range from 80 to 180 nm. And thus the pyrite particles prepared by the wet ball mill method had less particle size, larger specific surface area and higher reactive ability. The batch experiments exhibited the pyrite particles were able to remove 95% of Se(IV) (20 mg x L(-1)) from water within 12 hours. And the kinetic tests indicated reaction process between pyrite and Se(IV) fits a pseudo-first order kinetic model, which gives a pseudo-first order rate constant(kobs) of 0.26 h(-1). XPS analyses were using the XPSPEAK program which has a Gaussian Lorentzian function. The results clearly displays that Se(IV) prefer to react with the surface-bound S2(2-) rather than reacted with the surface-bound Fe2+ of pyrite particles. From XPS graph, it can be seen that the binding energy of sulfur element and iron element composed of pyrite shifted to the left a little, which means expensive state of sulfur element and iron element appeared on the pyrite surface. Analysis of the oxidation state of Se on the surface of pyrite

  9. 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.

  10. 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.

  11. 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.

  12. Synchrotron Spectroscopic Studies of the Reaction of Cleaved Pyrite ( {FeS2}) Surfaces with Cr(VI) Solutions

    NASA Astrophysics Data System (ADS)

    Doyle, C. S.; Kendelewicz, T.; Bostick, B. C.; Brown, G. E.

    2002-12-01

    Pyrite is one of the most common sulfide ores, and the separation of valuable sulfide minerals from it has been an area of considerable interest for a long time. This extraction has led to a large quantity of pyrite waste, typically remaining in mine tailings piles which can interact with oxygen and surface water. The oxidation of pyrite under these conditions leads to the commonly known environmental problem of acid mine drainage, with acidification of surface waters, and the release of potentially toxic metals remaining within the pyrite matrix. A microscopic understanding of this oxidation process is extremely important and has been the aim of a number of studies. We apply the methods of synchrotron based surface science to this problem, utilizing surface sensitive photoemission and X-ray absorption spectroscopy to study the surface species present on the pyrite surface at the initial stages of oxidation. We have reacted pyrite surfaces with solutions containing chromate. Chromium exists in solution in two principal valence states, trivalent Cr(III) and hexavalent Cr(VI). Hexavalent chromium is itself considered an environmental problem due to its high toxicity and solubility, and thus mobility, whilst trivalent chromium is much less toxic and relatively insoluble. Hexavalent chromate is a strong oxidizing agent, and will react rapidly with the pyrite surface allowing the identification of oxidized iron and sulfur surface species. The possibility of using pyrite as a means of reducing chromate, and at the same time using chromate to passivate the pyrite surface to further oxidation through the buildup of a non-reactive iron-chromium (oxy)hydroxide layer will be investigated. The work was performed on rods cut from a natural pyrite single crystal from the Logroño region of Spain. The rods were then fractured over a reaction vessel, producing a fresh (100) surface for each experiment. The pyrite surfaces were reacted with 50 μM Cr(VI) solutions for 5 minutes at

  13. 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

  14. 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.

  15. Iron Isotope Investigation of Sedimentary Pyrite Associated With Coal Mine Discharges (AMD)

    NASA Astrophysics Data System (ADS)

    Wolfe, A. L.; Stewart, B.; Capo, R.

    2005-12-01

    Water-rock interactions in abandoned coal mines results in the dissolution of pyrite and associated generation of acidic water with relatively high concentrations of iron and other metals. Analysis of changes that occur during dissolution of pyrite could improve our understanding of the movement of iron species within contaminated mine outflows, elucidate reaction mechanisms and processes that occur in solid-liquid systems and provide insight into the biogeochemistry of iron. We have begun an iron isotope investigation of pyrite extracted from coal seams and adjacent stratigraphic units, along with associated mine discharges, located in western Pennsylvania. We expect to find variations in iron isotope compositions of pyrite collected from different coal beds and adjacent stratigraphic units due to the variety of conditions under which pyrite can form (e.g, freshwater, brackish or marine; biotic or abiotic),. Pyrite deposited under marine conditions is mediated by sulfate-reducing bacteria and formation proceeds through the dissolution and reduction of lithogenic Fe oxides and Fe silicates to Fe (II). Most of the reactive iron is scavenged to form pyrite, minimizing Fe isotope fractionation; such processes are unlikely to produce pyrite with δ56Fe < -0.5 ‰ (Rouxel et al., 2005, Science 307: 1088). In contrast, in areas where high concentrations of Fe(II) accumulate under anoxic conditions and low sulfide concentrations (e.g., lacustrine or brackish water), large δ56Fe values may occur because of partial Fe(II) oxidation, Fe(II) reduction, and distillation processes during mineral precipitation (Rouxel et al., 2005). Preliminary iron isotope measurements of sedimentary pyrite in this study yield a range in δ56Fe of ~3.5‰. Additional analyses will be used to quantify and source-track the dissolution of pyrite within abandoned mine drainage systems. The iron in the outflows could potentially be used as a "fingerprint" to identify the most abundant and

  16. Protein footprinting by pyrite shrink-wrap laminate.

    PubMed

    Leser, Micheal; Pegan, Jonathan; El Makkaoui, Mohammed; Schlatterer, Joerg C; Khine, Michelle; Law, Matt; Brenowitz, Michael

    2015-04-07

    The structure of macromolecules and their complexes dictate their biological function. In "footprinting", the solvent accessibility of the residues that constitute proteins, DNA and RNA can be determined from their reactivity to an exogenous reagent such as the hydroxyl radical (·OH). While ·OH generation for protein footprinting is achieved by radiolysis, photolysis and electrochemistry, we present a simpler solution. A thin film of pyrite (cubic FeS2) nanocrystals deposited onto a shape memory polymer (commodity shrink-wrap film) generates sufficient ·OH via Fenton chemistry for oxidative footprinting analysis of proteins. We demonstrate that varying either time or H2O2 concentration yields the required ·OH dose-oxidation response relationship. A simple and scalable sample handling protocol is enabled by thermoforming the "pyrite shrink-wrap laminate" into a standard microtiter plate format. The low cost and malleability of the laminate facilitates its integration into high throughput screening and microfluidic devices.

  17. 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.

  18. Accelerated aging in schizophrenia patients: the potential role of oxidative stress.

    PubMed

    Okusaga, Olaoluwa O

    2014-08-01

    Several lines of evidence suggest that schizophrenia, a severe mental illness characterized by delusions, hallucinations and thought disorder is associated with accelerated aging. The free radical (oxidative stress) theory of aging assumes that aging occurs as a result of damage to cell constituents and connective tissues by free radicals arising from oxygen-associated reactions. Schizophrenia has been associated with oxidative stress and chronic inflammation, both of which also appear to reciprocally induce each other in a positive feedback manner. The buildup of damaged macromolecules due to increased oxidative stress and failure of protein repair and maintenance systems is an indicator of aging both at the cellular and organismal level. When compared with age-matched healthy controls, schizophrenia patients have higher levels of markers of oxidative cellular damage such as protein carbonyls, products of lipid peroxidation and DNA hydroxylation. Potential confounders such as antipsychotic medication, smoking, socio-economic status and unhealthy lifestyle make it impossible to solely attribute the earlier onset of aging-related changes or oxidative stress to having a diagnosis of schizophrenia. Regardless of whether oxidative stress can be attributed solely to a diagnosis of schizophrenia or whether it is due to other factors associated with schizophrenia, the available evidence is in support of increased oxidative stress-induced cellular damage of macromolecules which may play a role in the phenomenon of accelerated aging presumed to be associated with schizophrenia.

  19. Accelerated Aging in Schizophrenia Patients: The Potential Role of Oxidative Stress

    PubMed Central

    Okusaga, Olaoluwa O

    2014-01-01

    Several lines of evidence suggest that schizophrenia, a severe mental illness characterized by delusions, hallucinations and thought disorder is associated with accelerated aging. The free radical (oxidative stress) theory of aging assumes that aging occurs as a result of damage to cell constituents and connective tissues by free radicals arising from oxygen-associated reactions. Schizophrenia has been associated with oxidative stress and chronic inflammation, both of which also appear to reciprocally induce each other in a positive feedback manner. The buildup of damaged macromolecules due to increased oxidative stress and failure of protein repair and maintenance systems is an indicator of aging both at the cellular and organismal level. When compared with age-matched healthy controls, schizophrenia patients have higher levels of markers of oxidative cellular damage such as protein carbonyls, products of lipid peroxidation and DNA hydroxylation. Potential confounders such as antipsychotic medication, smoking, socio-economic status and unhealthy lifestyle make it impossible to solely attribute the earlier onset of aging-related changes or oxidative stress to having a diagnosis of schizophrenia. Regardless of whether oxidative stress can be attributed solely to a diagnosis of schizophrenia or whether it is due to other factors associated with schizophrenia, the available evidence is in support of increased oxidative stress-induced cellular damage of macromolecules which may play a role in the phenomenon of accelerated aging presumed to be associated with schizophrenia. PMID:25110609

  20. 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.

  1. 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

  2. Sulfide-Driven Arsenic Mobilization from Arsenopyrite and Black Shale Pyrite

    SciTech Connect

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

    2008-01-01

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

  3. 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

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

    SciTech Connect

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

    1992-12-31

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

  5. 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

  6. 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

  7. 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.

  8. 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.

  9. Hypercholesterolemia Induces Oxidant Stress That Accelerates the Ageing of Hematopoietic Stem Cells

    PubMed Central

    Tie, Guodong; Messina, Katharine E.; Yan, Jinglian; Messina, Julia A.; Messina, Louis M.

    2014-01-01

    Background Clinical studies suggest that hypercholesterolemia may cause ageing in hematopoietic stem cells (HSCs) because ageing‐associated alterations were found in peripheral blood cells and their bone marrow residing precursors in patients with advanced atherosclerosis. We hypothesized that hypercholesterolemia induces oxidant stress in hematopoietic stems cells that accelerates their ageing. Methods and Results Here we show that HSCs from ApoE−/− mice, as well as HSCs from C57Bl/6 mice fed a high cholesterol diet (HCD) accumulated oxLDL and had greater ROS levels. In accordance, the expression pattern of the genes involved in ROS metabolism changed significantly in HSCs from ApoE−/− mice. Hypercholesterolemia caused a significant reduction in phenotypically defined long‐term HSC compartment, telomere length, and repopulation capacity of KTLS cells, indicating accelerated ageing in these cells. Gene array analysis suggested abnormal cell cycle status, and the key cell cycle regulators including p19ARF, p27Kip1 and p21Waf1 were upregulated in KTLS cells from hypercholesterolemic mice. These effects were p38‐dependent and reversed in vivo by treatment of hypercholesterolemic mice with antioxidant N‐acetylcysteine. The oxidant stress also caused aberrant expression of Notch1 that caused loss of quiescence and proliferation leading to the expansion of KTLS compartment in hypercholesterolemic mice. Conclusion Taken together, we provide evidence that hypercholesterolemia can cause oxidant stress that accelerates the ageing and impairs the reconstitution capacity of HSCs. PMID:24470519

  10. Air stable, photosensitive, phase pure iron pyrite nanocrystal thin films for photovoltaic application.

    PubMed

    Bi, Yu; Yuan, Yongbo; Exstrom, Christopher L; Darveau, Scott A; Huang, Jinsong

    2011-11-09

    Iron pyrite (FeS(2)) is a naturally abundant and nontoxic photovoltaic material that can potentially make devices as efficient as silicon-based ones; however existing iron pyrite photovoltaic devices contain thermodynamically unstable FeS(2) film surfaces that lead to low open circuit voltages. We report the rational synthesis of phase pure, highly crystalline cubic FeS(2) nanocrystals (NCs) using a trioctylphosphine oxide (TOPO) assisted hot-injection method. The synthesized pyrite NC films have excellent air stability over one year. In contrast, obvious surface decomposition was observed on the surface of FeS(2) NCs synthesized without TOPO. A high carrier mobility of 80 cm(2)/(V s) and a strong photoconductivity were observed for the first time for pyrite films at room temperature. Our results indicate that TOPO passivates both iron and sulfur atoms on FeS(2) NC surfaces, efficiently inhibiting surface decomposition.

  11. XPS and XAS studies of copper(II) sorbed onto a synthetic pyrite surface.

    PubMed

    Naveau, Aude; Monteil-Rivera, Fanny; Guillon, Emmanuel; Dumonceau, Jacques

    2006-11-01

    Compounds containing copper are likely candidates to delay iodide migration in environmental media through the formation of sparingly soluble phases. Preliminary experiments showed that iodide was neither sorbed onto chalcopyrite nor by a binary system pyrite/copper(II), although significant amounts of copper were present at the pyrite surface. In the present study, spectroscopic studies (XPS, XANES and EXAFS) were thus performed to determine the nature of sorbed copper species. Although introduced as Cu(II), copper was mainly present at the oxidation state (I) on the pyrite surface suggesting a heterogeneous reduction process. Moreover, copper appeared tetrahedrally coordinated to two sulfur and two oxygen atoms onto the pyrite surface, a chemical environment, which seemingly stabilized the metal and made it unreactive towards iodide.

  12. 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.

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

    PubMed

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

    2014-06-01

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

  14. 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.

  15. 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.

  16. Confining a bi-enzyme inside the nanochannels of a porous aluminum oxide membrane for accelerating the enzymatic reactions.

    PubMed

    Shangguan, Li; Wei, Yuanqing; Liu, Xu; Yu, Jiachao; Liu, Songqin

    2017-02-28

    An artificial metabolon with high conversion efficiency was constructed by confining a bi-enzyme into porous aluminum oxide nanochannels, which accelerated enzymatic reactions by minimizing the diffusion loss of intermediate species.

  17. The uremic toxin methylguanidine increases the oxidative metabolism and accelerates the apoptosis of canine neutrophils.

    PubMed

    Bosco, A M; Almeida, B F M; Pereira, P P; Dos Santos, D B; Neto, Á J S; Ferreira, W L; Ciarlini, P C

    2017-03-01

    We investigated the hypothesis that the increased concentration of plasma methylguanidine (MG) increases oxidative metabolism and accelerates apoptosis of neutrophils from dogs with chronic kidney disease (CKD). To achieve this, the levels of MG were quantified in healthy (n=16) and uremic dogs with CKD stage 4 of according to the guidelines of the International Renal Interest Society (IRIS, 2015) (n=16) using high performance liquid chromatography (HPLC). To evaluate the isolated effect of MG on neutrophil oxidative metabolism and apoptosis, neutrophils isolated from 12 healthy dogs were incubated with the highest concentration of plasma MG (0.005g/L) observed in dogs with CKD. Neutrophil oxidative metabolism was assessed by flow cytometry, using the probes hydroethidine for superoxide production and 2',7'-dichlorofluorescein diacetate for hydrogen peroxide production, with or without phorbol myristate acetate (PMA) stimulus. Neutrophil apoptosis and viability were also evaluated in flow cytometer using the Annexin V-PE system, with or without the apoptosis-inducing effect of camptothecin. Uremic dogs presented higher concentrations of MG (p<0.0001), increased oxidative stress and primed neutrophils with higher apoptosis rate. The neutrophil abnormalities observed in vivo were also reproduced in vitro, using cells isolated from healthy dogs and incubated with MG. We obtained strong evidence that in dogs with CKD, increased MG levels contributed to oxidative stress and potentially compromised the non-specific immune response by altering the oxidative metabolism and viability of canine neutrophils.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

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

    PubMed

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

    2016-02-04

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

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

    PubMed

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

    2016-01-01

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

  9. 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

  10. 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.

  11. Endoplasmic Reticulum Oxidative Stress Triggers Tgf-Beta-Dependent Muscle Dysfunction by Accelerating Ascorbic Acid Turnover

    PubMed Central

    Pozzer, Diego; Favellato, Mariagrazia; Bolis, Marco; Invernizzi, Roberto William; Solagna, Francesca; Blaauw, Bert; Zito, Ester

    2017-01-01

    Endoplasmic reticulum (ER) and oxidative stress are two related phenomena that have important metabolic consequences. As many skeletal muscle diseases are triggered by oxidative stress, we explored the chain of events linking a hyperoxidized ER (which causes ER and oxidative stress) with skeletal muscle dysfunction. An unbiased exon expression array showed that the combined genetic modulation of the two master ER redox proteins, selenoprotein N (SEPN1) and endoplasmic oxidoreductin 1 (ERO1), led to an SEPN1-related myopathic phenotype due to excessive signalling of transforming growth factor (TGF)-beta. The increased TGF-beta activity in the genetic mutants was caused by accelerated turnover of the ER localized (anti-oxidant) ascorbic acid that affected collagen deposition in the extracellular matrix. In a mouse mutant of SEPN1, which is dependent on exogenous ascorbic acid, a limited intake of ascorbic acid revealed a myopathic phenotype as a consequence of an altered TGF-beta signalling. Indeed, systemic antagonism of TGF-beta re-established skeletal muscle function in SEPN1 mutant mice. In conclusion, this study sheds new light on the molecular mechanism of SEPN1-related myopathies and indicates that the TGF-beta/ERO1/ascorbic acid axis offers potential for their treatment. PMID:28106121

  12. 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

  13. 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.

  14. Nitric Oxide Is a Key Component in Inflammation-Accelerated Tumorigenesis

    PubMed Central

    Hussain, S. Perwez; He, Peijun; Subleski, Jeffery; Hofseth, Lorne J.; Trivers, Glenwood E.; Mechanic, Leah; Hofseth, Anne B.; Bernard, Mark; Schwank, Jonathan; Nguyen, Giang; Mathe, Ewy; Djurickovic, Draginja; Haines, Diana; Weiss, Jonathan; Back, Timothy; Gruys, Eilene; Laubach, Victor E.; Wiltrout, Robert H.; Harris, Curtis C.

    2008-01-01

    Nitric oxide (NO•), an important signaling molecule and a component of inflammatory response, is involved in tumorigenesis. However, the quantity of NO• and the cellular micro-environment influences the role of NO• in tumor development. We used a genetic strategy to test the hypothesis that an inflammatory microenvironment with an enhanced level of NO• accelerates spontaneous tumor development. C. parvum–induced inflammation and increased NO• synthase-2 (NOS2) expression coincided with accelerated spontaneous tumor development, mostly lymphomas, in p53−/−NOS2+/+ C57BL6 mice when compared with the controls (P = 0.001). However, p53−/−NOS2−/− mice did not show any difference in tumor latency between C. parvum–treated and control groups. In C. parvum–treated p53−/−NOS2+/+ mice, tumor development was preceded by a higher expression of NOS2 and phosphorylated Akt-Ser473 (pAkt-Ser473) in spleen, increased cell proliferation measured by Ki-67 IHC in spleen and thymus, and a lower apoptotic index and CD95-L expression in spleen and thymus. C. parvum–treated p53−/−NOS2+/+ mice showed an increase in the number of Foxp3(+) T-reg cells, dendritic cells (DC), as well as increased CD80+, CD86+, CD40+, and CD83+ on DC in the spleen. Regulatory T-cells (T-reg) and the maturation of DC may modulate tumorigenesis. An increase in the FoxP3(+)T-reg cells in C. parvum–treated p53−/−NOS2+/+ mice indicates a role of NO• in the regulation of T-reg cells that may contribute to a protumor shift of the immune environment favoring an accelerated tumor development. These data provide genetic and mechanistic evidence that an inflammatory microenvironment and an increased level of NO• can accelerate tumor development. PMID:18757428

  15. 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

  16. Short communication: Adverse effect of surface-active reagents on the bioleaching of pyrite and chalcopyrite by Thiobacillus ferrooxidans.

    PubMed

    Huerta, G; Escobar, B; Rubio, J; Badilla-Ohlbaum, R

    1995-09-01

    Oxidation of Fe(II) iron and bioleaching of pyrite and chalcopyrite by Thiobacillus ferrooxidans was adversely affected by isopropylxanthate, a flotation agent, and by LIX 984, a solvent-extraction agent, each at ≤ 1 g/l. The reagents/l were adsorbed on the bacterial surface, decreasing the bacteria's development and preventing biooxidation. Both reagents inhibited the bioleaching of pyrite and LIX 984 also inhibited the bioleaching of chalcopyrite.

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

    PubMed

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

    2015-11-01

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

  18. PDCD10 interacts with STK25 to accelerate cell apoptosis under oxidative stress.

    PubMed

    Zhang, Heyu; Ma, Xi; Deng, Xuan; Chen, Yiyu; Mo, Xiaoning; Zhang, Yingmei; Zhao, Hongshan; Ma, Dalong

    2012-06-01

    An apoptosis-related protein, cerebral cavernous malformation 3 (CCM3 or PDCD10), has recently been implicated in mutations associated with cerebral cavernous malformation. Herein, we show that PDCD10 interacts with serine/threonine kinase 25 (STK25), an oxidant stress response kinase related to sterile-20 (Ste20) that is activated by oxidative stress and induces apoptotic cell death. Functional investigations indicate that PDCD10 and STK25 protein are up-regulated by H2O2 stimulation, and that co-expression of the proteins accelerates cell apoptosis. The induction of small interfering PDCD10 (siPDCD10) or siSTK25 results in decreased endogenous PDCD10 and STK25 expression, which is accompanied by attenuated cell apoptosis. Interaction between PDCD10 and STK25 modulates ERK activity under oxidative stress. PDCD10 stabilizes STK25 protein through a proteasome-dependent pathway. Our findings suggest that PDCD10 might be a regulatory adaptor required for STK25 functions, which differ distinctly depending on the redox status of the cells that may be potentially related to tumor progression.

  19. 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.

  20. 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.

  1. Reduction of nitrite and nitrate to ammonium on pyrite.

    PubMed

    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 (NH(3)) 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 (FeS(2)) 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 NH(3) 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. NH(3) production from NO(2)(-) occurred at 70 and 120°C and from NO(3)(-) occurred only at 120°C.

  2. 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

  3. 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.

  4. Selective Accelerated Proliferation of Malignant Breast Cancer Cells on Planar Graphene Oxide Films.

    PubMed

    Kenry; Chaudhuri, Parthiv Kant; Loh, Kian Ping; Lim, Chwee Teck

    2016-03-22

    Graphene nanomaterials have been actively investigated for biomedical and biological applications, including that of cancer. Despite progress made, most of such studies are conducted on dispersed graphene nanosheets in solution. Consequently, the use of planar graphene films, especially in cancer research, has not been fully explored. Here, we investigate the cellular interactions between the graphene material films and breast cancer cell lines, specifically the effects these films have on cellular proliferation, spreading area, and cytotoxicity. We demonstrate that the graphene oxide (GO) film selectively accelerates the proliferation of both metastatic (MDA-MB-231) and nonmetastatic (MCF-7) breast cancer cells, but not that of noncancer breast epithelial cells (MCF-10A). Contrastingly, this accelerated proliferation is not observed with the use of graphene (G) film. Moreover, GO induces negligible cytotoxicity on these cells. We suggest that the observed phenomena originate from the synergistic effect resulted from the high loading capacity and conformational change of cellular attachment proteins on the GO film, and the high amount of oxygenated groups present in the material. We anticipate that our findings can further shed light on the graphene-cancer cellular interactions and provide better understanding for the future design and application of graphene-based nanomaterials in cancer research.

  5. 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.

  6. 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.

  7. Role of low molecular weight organic acids on pyrite dissolution in aqueous systems: implications for catalytic chromium (VI) treatment.

    PubMed

    Kantar, Cetin

    2016-01-01

    A systematic study combining batch experiments with spectroscopic analyses was carried out to better understand the effects of various organic acids on pyrite dissolution and subsequent Cr(VI) removal in aqueous systems. Our results suggest that organic acids had no effect on total Fe dissolution from pyrite relative to systems containing no acid. However, while nearly 100% of total Fe dissolved from pyrite was in Fe(II) form in the absence of ligands, the addition of organic acids led to significant oxidation of Fe(II) species to Fe(III). The degree and extent of Fe(II) oxidation increased in the order: tartrate < salicylate < oxalate ≈ citrate < EDTA. Except for salicylate (an aromatic compound), this stimulatory effect observed in Fe(II) oxidation was well correlated with the strength of Fe-ligand complexes. In systems containing Cr(VI), the amount of Fe dissolved increased significantly relative to non-Cr(VI) containing system, and the ligands enhanced the dissolution of surface oxidation products from pyrite. Overall, it is clear that the dissolution of pyrite with organic acids had very little effect on solution phase Cr(VI) removal, but significantly stimulated surface phase Cr(VI) reduction by removing surface oxidation products, and thus creating new surface sites for extended Cr(VI) removal.

  8. 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.

  9. 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

  10. Effect of pH on the removal of pyritic sulfur from coal by oxydesulfurization

    SciTech Connect

    Joshl, J.B.; Albal, R.S.; Ritz, H.J.; Shah, Y.T.

    1982-10-01

    The effect of pH on the removal of pyritic sulfur in air/water chemical coal cleaning was investigated. The pH was varied by adding sulfuric acid or sodium carbonate to a coal-water slurry. The effect of nearb neutral pH ( about7) was determined in a buffer solution of sodium dihydrogen phosphate and disodium hydrogen phosphate. Data were taken in the temperature range of 130 to 190/sup 0/C, oxygen partial pressure of 0.32 to 1.36 MPa, and reaction times up to 3600 s. The rate of pyrite oxidation was found to be minimum at the nearby neutral conditions. Under otherwise identical conditions, the rate of pyrite oxidation was greater in basic pH than in acidi pH. The enhancement in the rate of pyrite oxidation is explained on the basis of electrochemical reactions. Under nearly neutral conditions, the overall reaction is shown to be controlled by the surface reaction, whereas under acidic as well as basic conditions, diffusion of oxygen through the product ash layer as well as the surface chemical reaction seems to be important.

  11. Effect of pH on the removal of pyritic sulfur from coal by oxydesulfurization

    SciTech Connect

    Joshi, J.B.; Shah, Y.T.; Albal, R.S.

    1982-10-01

    The effect of pH on the removal of pyritic sulphur in air/water chemical coal cleaning was investigated. The pH was varied by adding sulphuric acid sodium carbonate to a coal-water slurry. The effect of nearly neutral pH (about 7) was determined in a buffer solution of sodium dihydrogen phosphate and disodium hydrogen phosphate. Data were taken in the temperature range of 130 to 190 C, oxygen partial pressure of 0.32 to 1.36 MPa, and reaction times up to 3600 s. The rate of pyrite oxidation was to be minimum at the nearly neutral conditions. Under otherwise identical conditions, the rate of pyrite oxidation was greater in basic pH than in acidic pH. The enhancement in the rate of pyrite oxidation is explained on the basis of electrochemical reactions. Under nearly neutral conditions, the overall reaction is shown to be controlled by the surface reaction, whereas under acidic as well as basic conditions, diffusion of oxygen through the product ash layer as well as the surface chemical reaction seems to be important.

  12. 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.

  13. Carbamylated low-density lipoprotein induces oxidative stress and accelerated senescence in human endothelial progenitor cells.

    PubMed

    Carracedo, Julia; Merino, Ana; Briceño, Carolina; Soriano, Sagrario; Buendía, Paula; Calleros, Laura; Rodriguez, Mariano; Martín-Malo, Alejandro; Aljama, Pedro; Ramírez, Rafael

    2011-04-01

    Carbamylated low-density lipoprotein (cLDL) plays a role in atherosclerosis. In this study we evaluate the effect of uremia on LDL carbamylation and the effect of cLDL and oxidized LDL (oxLDL; 200 μg/ml) on number, function, and genomic stability of endothelial progenitor cells (EPCs) obtained from healthy volunteers. cLDL was generated after incubation of native LDL (nLDL) with uremic serum from patients with chronic kidney disease (CKD) stages 2-4. Oxidative stress was measured by flow cytometry and fluorescent microscopy, mitochondrial depolarization by flow cytometry, senescence by β-galactosidase activity and telomere length, and DNA damage by phosphorylated histone H2AX (γH2AX). The percentage of cLDL by uremic serum was related to the severity of CKD. Compared with nLDL, cLDL induced an increase in oxidative stress (62±5 vs. 8±3%, P<0.001) and cells with mitochondrial depolarization (73±7 vs. 9±5%, P<0.001), and a decrease in EPC proliferation and angiogenesis. cLDL also induced accelerated senescence (73±16 vs. 12±9%, P<0.001), which was associated with a decrease in the expression of γH2AX (62±9 vs. 5±3%, P<0.001). The degree of injury induced by cLDL was comparable to that observed with oxLDL. This study supports the hypothesis that cLDL triggers genomic damage in EPCs, resulting in premature senescence. We can, therefore, hypothesize that EPCs injury by cLDL contributes to an increase in atherosclerotic disease in CKD.

  14. 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.

  15. Reactive oxygen species generated in the presence of fine pyrite particles and its implication in thermophilic mineral bioleaching.

    PubMed

    Jones, G C; van Hille, R P; Harrison, S T L

    2013-03-01

    In the tank bioleaching process, maximising solid loading and mineral availability, the latter through decreasing particle size, are key to maximising metal extraction. In this study, the effect of particle size distribution on bioleaching performance and microbial growth was studied through applying knowledge based on medical geology research to understand the adverse effects of suspended fine pyrite particles. Small-scale leaching studies, using pyrite concentrate fractions (106-75, 75-25, -25 μm fines), were used to confirm decreasing performance with decreasing particle size (D 50 <40 μm). Under equivalent experimental conditions, the generation of the reactive oxygen species (ROS), hydrogen peroxide and hydroxyl radicals from pyrite was illustrated. ROS generation measured from the different pyrite fractions was found to increase with increasing pyrite surface area loading (1.79-74.01 m(2) L(-1)) and Fe(2+) concentration (0.1-2.8 g L(-1)) in solution. The highest concentration of ROS was measured from the finest fraction of pyrite (0.85 mM) and from the largest concentration of Fe(2+) (0.78 mM). No ROS was detected from solutions containing only Fe(3+) under the same conditions tested. The potential of ROS to inhibit microbial performance under bioleaching conditions was demonstrated. Pyrite-free Sulfolobus metallicus cultures challenged with hydrogen peroxide (0.5-2.5 mM) showed significant decrease in both cell growth and Fe(2+) oxidation rates within the concentration range 1.5-2.5 mM. In combination, the results from this study suggest that conditions of large pyrite surface area loading, coupled with high concentrations of dissolved Fe(2+), can lead to the generation of ROS, resulting in oxidative stress of the microorganisms.

  16. 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.

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

    PubMed Central

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

    2015-01-01

    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

  18. 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.

  19. 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.

  20. 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

  1. 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.

  2. 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

  3. Degradation of anthraquinone dye reactive blue 4 in pyrite ash catalyzed Fenton reaction.

    PubMed

    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.

  4. Sorption of selenium(IV) and selenium(VI) onto synthetic pyrite (FeS2): spectroscopic and microscopic analyses.

    PubMed

    Han, Dong Suk; Batchelor, Bill; Abdel-Wahab, Ahmed

    2012-02-15

    Pyrite was hydrothermally synthesized and used to remove Se(IV) and Se(VI) selectively from solution. Surface analyses of pyrite before and after contact with Se(IV) and Se(VI) were conducted using X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and atomic force microscopy (AFM). All solid samples were acquired by allowing 3.1 mmol/L of Se(IV) or Se(VI) to react with 1 g/L of pyrite for 1, 15, or 30 days. The XPS spectra were fitted using the XPSPEAK program that applies a Gaussian Lorentzian function. The fitted spectra indicate that Se(IV) more strongly reacts with the surface-bound S than with the surface-bound Fe of pyrite. However, there is no apparent evidence of surface reaction with Se(VI). Specifically, fitted XPS spectra showed the presence of sulfide and tetrathionate on the surface, indicating that sulfur (S(2)(2-)) at the surface of pyrite can be both oxidized and reduced after contact with Se(IV). This occurs via surface disproportionation, possibly resulting in the formation of surface precipitates. Evidence for the formation of precipitates was seen in SEM and AFM images that showed rod-like particles and a phase image with higher voltage. In contrast, there were no important changes in the pyrite after contact with Se(VI) over a period of 30 days.

  5. 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

    2016-06-01

    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.

  6. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

  8. 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

  9. Trace Element Pattern of Authigenic Pyrite: A Promising Proxy for the Redox State of Depositional Environment

    NASA Astrophysics Data System (ADS)

    Stueben, D.; Berner, Z. A.; Puchelt, H.; Noeltner, T.

    2002-12-01

    Authigenic pyrite is formed in a wide range of depositional conditions, including not only typically euxinic conditions (when it can precipitate as syngenetic pyrite already in the water column), but also the anoxic part of normal marine sediments, below the water/sediment interface. We investigated the response in trace element composition of pyrite to such environmental differences in 49 pyrite separates prepared from the cores recovered by a 15.2 m deep drilling executed at Weilstetten, in SW of Germany. The drilling crossed a sedimentary sequence, encompassing the transition from normal marine sediments of the Lias Epsilon-I to the black shales of the Posidonienschiefer (Lower Toarcian, Lias Epsilon-II, and -III). The trace element composition of pyrite was analyzed by means of ICP-MS and the results were evaluated in a broader geochemical context, including the isotopic composition of S in Pyrite, the S-, Ccarbonate-, and Corganic- content of the host rocks, as well as their isotopic composition (C and O). Results document a sudden change in trace element pattern of the pyrites, simultaneously with changes in other geochemical parameters and proxies at the transition mentioned above. The evaluation of the data by means of factor analysis shows that high contents of Co, Ni and Cu coupled with very low δ34S values are indicative for early diagenetic pyrites formed in the low-redox environment of the sediment, which, however, was still open for sulfate supply, but in the same time also permitted a backwards diffusion and reoxidation of the not reacted H2S. The open system conditions coupled with the disproportionation of sulfur species with intermediate oxidation states led to a strong fractionation of the S isotopes. In contrast, pyrites from black shales are characterized by relatively high concentrations of As, Mo and Sb and high δ34S values. Together with other parameters (S/Corg ratios, δ13Corg values) the data suggest that such pyrites were formed under

  10. 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.

  11. Oxidative stress accelerates amyloid deposition and memory impairment in a double-transgenic mouse model of Alzheimer's disease.

    PubMed

    Kanamaru, Takuya; Kamimura, Naomi; Yokota, Takashi; Iuchi, Katsuya; Nishimaki, Kiyomi; Takami, Shinya; Akashiba, Hiroki; Shitaka, Yoshitsugu; Katsura, Ken-Ichiro; Kimura, Kazumi; Ohta, Shigeo

    2015-02-05

    Oxidative stress is known to play a prominent role in the onset and early stage progression of Alzheimer's disease (AD). For example, protein oxidation and lipid peroxidation levels are increased in patients with mild cognitive impairment. Here, we created a double-transgenic mouse model of AD to explore the pathological and behavioral effects of oxidative stress. Double transgenic (APP/DAL) mice were constructed by crossing Tg2576 (APP) mice, which express a mutant form of human amyloid precursor protein (APP), with DAL mice expressing a dominant-negative mutant of mitochondrial aldehyde dehydrogenase 2 (ALDH2), in which oxidative stress is enhanced. Y-maze and object recognition tests were performed at 3 and 6 months of age to evaluate learning and memory. The accumulation of amyloid plaques, deposition of phosphorylated-tau protein, and number of astrocytes in the brain were assessed histopathologically at 3, 6, 9, and 12-15 months of age. The life span of APP/DAL mice was significantly shorter than that of APP or DAL mice. In addition, they showed accelerated amyloid deposition, tau phosphorylation, and gliosis. Furthermore, these mice showed impaired performance on Y-maze and object recognition tests at 3 months of age. These data suggest that oxidative stress accelerates cognitive dysfunction and pathological insults in the brain. APP/DAL mice could be a useful model for exploring new approaches to AD treatment.

  12. 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.

  13. 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

  14. 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

  15. 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.

  16. Oxidation of Alloy 600 and Alloy 690: Experimentally Accelerated Study in Hydrogenated Supercritical Water

    NASA Astrophysics Data System (ADS)

    Moss, Tyler; Cao, Guoping; Was, Gary S.

    2017-02-01

    The objective of this study is to determine whether the oxidation of Alloys 600 and 690 in supercritical water occurs by the same mechanism in subcritical water. Coupons of Alloys 690 and 600 were exposed to hydrogenated subcritical and supercritical water from 633 K to 673 K (360 °C to 400 °C) and the oxidation behavior was observed. By all measures of oxide character and behavior, the oxidation process is the same above and below the supercritical line. Similar oxide morphologies, structures, and chemistries were observed for each alloy across the critical point, indicating that the oxidation mechanism is the same in both subcritical and supercritical water. Oxidation results in a multi-layer oxide structure composed of particles of NiO and NiFe2O4 formed by precipitation on the outer surface and a chromium-rich inner oxide layer formed by diffusion of oxygen to the metal-oxide interface. The inner oxide on Alloy 600 is less chromium rich than that observed on Alloy 690 and is accompanied by preferential oxidation of grain boundaries. The inner oxide on Alloy 690 initially forms by internal oxidation before a protective layer of chromium-rich MO is formed with Cr2O3 at the metal-oxide interface. Grain boundaries in Alloy 690 act as fast diffusion paths for chromium that forms a protective Cr2O3 layer at the surface, preventing grain boundary oxidation from occurring.

  17. Oxidation of Alloy 600 and Alloy 690: Experimentally Accelerated Study in Hydrogenated Supercritical Water

    NASA Astrophysics Data System (ADS)

    Moss, Tyler; Cao, Guoping; Was, Gary S.

    2017-04-01

    The objective of this study is to determine whether the oxidation of Alloys 600 and 690 in supercritical water occurs by the same mechanism in subcritical water. Coupons of Alloys 690 and 600 were exposed to hydrogenated subcritical and supercritical water from 633 K to 673 K (360 °C to 400 °C) and the oxidation behavior was observed. By all measures of oxide character and behavior, the oxidation process is the same above and below the supercritical line. Similar oxide morphologies, structures, and chemistries were observed for each alloy across the critical point, indicating that the oxidation mechanism is the same in both subcritical and supercritical water. Oxidation results in a multi-layer oxide structure composed of particles of NiO and NiFe2O4 formed by precipitation on the outer surface and a chromium-rich inner oxide layer formed by diffusion of oxygen to the metal-oxide interface. The inner oxide on Alloy 600 is less chromium rich than that observed on Alloy 690 and is accompanied by preferential oxidation of grain boundaries. The inner oxide on Alloy 690 initially forms by internal oxidation before a protective layer of chromium-rich MO is formed with Cr2O3 at the metal-oxide interface. Grain boundaries in Alloy 690 act as fast diffusion paths for chromium that forms a protective Cr2O3 layer at the surface, preventing grain boundary oxidation from occurring.

  18. Abiotic pyrite formation produces a large Fe isotope fractionation.

    PubMed

    Guilbaud, Romain; Butler, Ian B; Ellam, Rob M

    2011-06-24

    The iron isotope composition of sedimentary pyrite has been proposed as a potential proxy to trace microbial metabolism and the redox evolution of the oceans. We demonstrate that Fe isotope fractionation accompanies abiotic pyrite formation in the absence of Fe(II) redox change. Combined fractionation factors between Fe(II)(aq), mackinawite, and pyrite permit the generation of pyrite with Fe isotope signatures that nearly encapsulate the full range of sedimentary δ(56)Fe(pyrite) recorded in Archean to modern sediments. We propose that Archean negative Fe isotope excursions reflect partial Fe(II)(aq) utilization during abiotic pyrite formation rather than microbial dissimilatory Fe(III) reduction. Late Proterozoic to modern sediments may reflect greater Fe(II)(aq) utilization and variations in source composition.

  19. Assessing the impact of preload on pyrite-rich sediment and groundwater quality.

    PubMed

    Karikari-Yeboah, Ohene; Addai-Mensah, Jonas

    2017-02-01

    Pyrite-rich sediments would, invariably, undergo redox reactions which would lead to acidic aqueous environment containing solubilized toxic metal species. When such sediments are subjected to preload, a technique employed by geotechnical engineers to improve the load-bearing capacity of highly compressible formation, transient flow of pore water, accompanied by acidity transfer, would occur as a response. Despite the concomitant environmental and socio-economic significance, to date, there has been limited interdisciplinary research on the underpinning geotechnical engineering and geo-environmental science issues for pyrite-rich sediments under preload. In this study, we investigate the effect of pyrite-rich sediment pore water transfer under preload surcharge on the receiving environment and the impact on the groundwater speciation and quality. Sediment samples were obtained at close depth intervals from boreholes established within pristine areas and those subjected to the preload application. Soil and pore water samples were subjected to solid/solution speciation, moisture contents, soil pH and the Atterberg Limits' analyses using standard analytical techniques and methods. Standpipes were also installed in the boreholes for groundwater sampling and in situ monitoring of water quality parameters. It is shown that the imposition of preload surcharge over pyritic sediment created a reducing environment rich in SO4(2-), iron oxide minerals and organic matter. This reducing environment fostered organic carbon catabolism to generate excess pyrite and bicarbonate alkalinity, which would invariably impact adversely on soil quality and plant growth. These were accompanied by increase in pH, dissolved Al, Ca, Mg and K species beneath the surcharge.

  20. 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...

  1. 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

  2. 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.

  3. A thermodynamic study of pyrite and pyrrhotite

    USGS Publications Warehouse

    Toulmin, P.; Barton, P.B.

    1964-01-01

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

  4. 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.

  5. Arsenic Incorporation in Pyrite at Ambient Temperature at Both Tetrahedral S(-I) and Octahedral Fe(II) Sites: Evidence from EXAFS-DFT Analysis.

    PubMed

    Le Pape, Pierre; Blanchard, Marc; Brest, Jessica; Boulliard, Jean-Claude; Ikogou, Maya; Stetten, Lucie; Wang, Shuaitao; Landrot, Gautier; Morin, Guillaume

    2017-01-03

    Pyrite is a ubiquitous mineral in reducing environments and is well-known to incorporate trace elements such as Co, Ni, Se, Au, and commonly As. Indeed, As-bearing pyrite is observed in a wide variety of sedimentary environments, making it a major sink for this toxic metalloid. Based on the observation of natural hydrothermal pyrites, As(-I) is usually assigned to the occupation of tetrahedral S(-I) sites, with the same oxidation state as in arsenopyrite (FeAsS), although rare occurrences of As(III) and As(II) have been reported. However, the modes of As incorporation into pyrite during its crystallization under low-temperature diagenetic conditions have not yet been elucidated because arsenic acts as an inhibitor for pyrite nucleation at ambient temperature. Here, we provide evidence from X-ray absorption spectroscopy for As(II,III) incorporation into pyrite at octahedral Fe(II) sites and for As(-I) at tetrahedral S(-I) sites during crystallization at ambient temperature. Extended X-ray absorption fine structure (EXAFS) spectra of these As-bearing pyrites are explained by local structure models obtained using density functional theory (DFT), assuming incorporation of As at the Fe and S sites, as well as local clustering of arsenic. Such observations of As(-I) incorporation at ambient temperature can aid in the understanding of the early formation of authigenic arsenian pyrite in subsurface sediments. Moreover, evidence for substitution of As(II,III) for Fe in our synthetic samples raises questions about both the possible occurrence and the geochemical reactivity of such As-bearing pyrites in low-temperature subsurface environments.

  6. 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.

  7. 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.

  8. 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.

  9. Matrix composition and community structure analysis of a novel bacterial pyrite leaching community.

    PubMed

    Ziegler, Sibylle; Ackermann, Sonia; Majzlan, Juraj; Gescher, Johannes

    2009-09-01

    Here we describe a novel bacterial community that is embedded in a matrix of carbohydrates and bio/geochemical products of pyrite (FeS(2)) oxidation. This community grows in stalactite-like structures--snottites--on the ceiling of an abandoned pyrite mine at pH values of 2.2-2.6. The aqueous phase in the matrix contains 200 mM of sulfate and total iron concentrations of 60 mM. Micro-X-ray diffraction analysis showed that jarosite [(K,Na,H(3)O)Fe(3)(SO(4))(2)(OH)(6)] is the major mineral embedded in the snottites. X-ray absorption near-edge structure experiments revealed three different sulfur species. The major signal can be ascribed to sulfate, and the other two features may correspond to thiols and sulfoxides. Arabinose was detected as the major sugar component in the extracellular polymeric substance. Via restriction fragment length polymorphism analysis, a community was found that mainly consists of iron oxidizing Leptospirillum and Ferrovum species but also of bacteria that could be involved in dissimilatory sulfate and dissimilatory iron reduction. Each snottite can be regarded as a complex, self-contained consortium of bacterial species fuelled by the decomposition of pyrite.

  10. 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

  11. 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

  12. 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.

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

    PubMed Central

    Knoll, Andrew H.; Barghoorn, Elso S.

    1974-01-01

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

  14. An XPS study on the valence states of arsenic in arsenian pyrite: Implications for Au deposition mechanism of the Yang-shan Carlin-type gold deposit, western Qinling belt

    NASA Astrophysics Data System (ADS)

    Liang, Jin-long; Sun, Wei-dong; Li, Yi-liang; Zhu, San-yuan; Li, He; Liu, Yu-long; Zhai, Wei

    2013-01-01

    The enrichment of gold in arsenian pyrite is usually associated closely with the enrichment of arsenic in the mineral, generally known as As1--pyrite [Fe(As, S)2]. Direct analyses of the valence state of Au in pyrite are, however, difficult due to generally low (˜ppm level) Au concentrations. By means of X-ray photoelectron spectroscopy (XPS), this study obtained reliable valence states of As in pyrite from the Yang-shan gold deposit, a giant "Carlin-type" Au deposit in the western Qinling orogen, central China. The arsenian pyrite specimens were sputtered with Ar+ beam in the vacuum chamber of an XPS to obtain pristine surfaces and to avoid As oxidation during sample preparation. Analyses before and after sputtering show that the As3+ peak are only present on surface that was once exposed to the air. In contrast, the peak of As-1 was essentially unchanged during continuous sputtering. The results indicated that As- is the predominant state on the pristine surface of arsenian pyrite; the peak of As3+ previously reported for Au-bearing arsenian pyrite was probably due to oxidation when exposed to air during sample preparation. It is unlikely that the coupled substitution of (Au+ + As3+) for 2Fe2+ takes place in the pyrite lattice. The so-called As3+-pyrite proposed by previous studies may occur in some special (oxidizing) geologic settings, but it is not observed in the Yang-shan gold deposit, and is unlikely to be important in typical orogenic or Carlin-type gold deposits, in which arsenian pyrite is a dominant Au carrier. Combining previous studies on Carlin-type Au deposits with our XPS experimental results, we suggest that the most likely state of Au in the Yang-shan Au deposit is lattice-bounded Au with or without nanoparticles (Au0).

  15. Beneficial effect of melatonin treatment on inflammation, apoptosis and oxidative stress on pancreas of a senescence accelerated mice model.

    PubMed

    Cuesta, Sara; Kireev, Roman; García, Cruz; Forman, Katherine; Escames, Germaine; Vara, Elena; Tresguerres, Jesús A F

    2011-01-01

    This study has investigated the effect of aging on parameters of inflammation, oxidative stress and apoptosis in pancreas obtained from two types of male mice models: senescence-accelerated prone (SAMP8) and resistant mice (SAMR1). Animals of 2 (young) and 10 months of age (old) were used (n = 64). The influence of the administration of melatonin in the drinking water for one month at two different dosages (1 and 10mg/(kg day) on old SAMP8 mice on these parameters was also studied. SAMP8 mice showed with age a significant increase in the relative expression of pancreatic genes involved in inflammation, oxidative stress and apoptosis. Furthermore the protein expression of several NFκB subunits was also enhanced. On the contrary aged SAMR1 mice did not show significant increases in these parameters. Melatonin administration to SAMP8 mice was able to reduce these age related alterations at the two used dosages.

  16. Spirulina prevents memory dysfunction, reduces oxidative stress damage and augments antioxidant activity in senescence-accelerated mice.

    PubMed

    Hwang, Juen-Haur; Lee, I-Te; Jeng, Kee-Ching; Wang, Ming-Fu; Hou, Rolis Chien-Wei; Wu, Su-Mei; Chan, Yin-Ching

    2011-01-01

    Spirulina has proven to be effective in treating certain cancers, hyperlipidemia, immunodeficiency, and inflammatory processes. In this study, we aimed to investigate the effects of Spirulina on memory dysfunction, oxidative stress damage and antioxidant enzyme activity. Three-month-old male senescence-accelerated prone-8 (SAMP8) mice were randomly assigned to either a control group or to one of two experimental groups (one receiving daily dietary supplementation with 50 mg/kg BW and one with 200 mg/kg BW of Spirulina platensis water extract). Senescence-accelerated-resistant (SAMR1) mice were used as the external control. Results showed that the Spirulina-treated groups had better passive and avoidance scores than the control group. The amyloid β-protein (Aβ) deposition was significantly reduced at the hippocampus and whole brain in both Spirulina groups. The levels of lipid peroxidation were significantly reduced at the hippocampus, striatum, and cortex in both Spirulina groups, while catalase activity was significantly higher only in the 200 mg/kg BW Spirulina group than in the control group. Glutathione peroxidase activity was significantly higher only in the cortex of the 200 mg/kg group than in that of the SAMP8 control group. However, superoxide dismutase activity in all parts of the brain did not significantly differ among all groups. In conclusion, Spirulina platensis may prevent the loss of memory possibly by lessening Aβ protein accumulation, reducing oxidative damage and mainly augmenting the catalase activity.

  17. Iron sulfide ink for the growth of pyrite crystals.

    PubMed

    Kirkeminde, Alec; Gingrich, Phillip; Gong, Maogang; Cui, Huizhong; Ren, Shenqiang

    2014-05-23

    Iron pyrite (FeS2, Fool's Gold) is a non-toxic, earth abundant semiconductor that exhibits promise for use in energy conversion and storage devices, such as the cathode material for batteries, thermoelectrics and optoelectronics. However, pyrite's potential as an energy-critical material is being curbed due to problems with controlling composition, stoichiometry and bulk and surface defects. To overcome these problems, simple and scalable methods to grow high quality crystalline pyrite for in-depth studies are necessary. In this study, we report a facile approach to create high quality, micron sized pyrite crystals from the FeS wire molecular ink. Growth of high quality pyrite crystals is examined and a model for growth and surface facet dependent activation energy is proposed. Unique thermal measurements are preformed that allow for insight into the pyrite's crystallinity and thermoconductive properties. It is shown that as made pyrite crystals exhibit high crystallinity which will be vital for future in-depth studies and device fabrication.

  18. 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

  19. 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

  20. 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.

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

    PubMed

    Abida, Otman; Osthoff, Hans D

    2012-06-21

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

  2. Accelerated tissue aging and increased oxidative stress in broiler chickens fed allopurinol.

    PubMed

    Klandorf, H; Rathore, D S; Iqbal, M; Shi, X; Van Dyke, K

    2001-06-01

    Uric acid has been hypothesized as being one of the more important antioxidants in limiting the accumulation of glycosylated endproducts in birds. Study 1 was designed to quantitatively manipulate the plasma concentrations of uric acid using hemin and allopurinol while study 2 determined their effects on skin pentosidine, the shear force value of Pectoralis major muscle, plasma glucose, body weight and chemiluminescence monitored oxidative stress in broiler chickens. Hemin was hypothesized to raise uric acid concentrations thereby lowering oxidative stress whereas allopurinol was hypothesized to lower uric acid concentrations and raise measures of oxidative stress. In study 1 feeding allopurinol (10 mg/kg body weight) to 8-week-old broiler chicks (n=50) for 10 days decreased plasma uric acid by 57%. However, hemin (10 mg/kg body weight) increased uric acid concentrations 20%. In study 2, 12-week-old broiler chicks (n=90) were randomly assigned to either an ad libitum (AL) diet or a diet restricted (DR) group. Each group was further divided into three treatments (control, allopurinol or hemin fed). Unexpectedly, hemin did not significantly effect uric acid concentrations but increased (P<0.05) measures of chemiluminescence dependent oxidative stress in both the DR and AL birds probably due to the ability of iron to generate oxygen radicals. Allopurinol lowered concentrations of uric acid and increased (P<0.05) the oxidative stress in the AL birds at week 22, reduced (P<0.05) body weight in both the AL and DR fed birds at 16 and 22 weeks of age, and markedly increased (P<0.001) shear force values of the pectoralis major muscle. Skin pentosidine levels increased (P<0.05) in AL birds fed allopurinol or hemin fed birds, but not in the diet restricted birds at 22 weeks. The significance of these studies is that concentrations of plasma uric acid can be related to measures of oxidative stress, which can be linked to tissue aging.

  3. 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.

  4. 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.

  5. Accelerated CCl4-Induced Liver Fibrosis in Hjv-/- Mice, Associated with an Oxidative Burst and Precocious Profibrogenic Gene Expression

    PubMed Central

    Sebastiani, Giada; Gkouvatsos, Kostas; Maffettone, Carmen; Busatto, Graziella; Guido, Maria; Pantopoulos, Kostas

    2011-01-01

    Hereditary hemochromatosis is commonly associated with liver fibrosis. Likewise, hepatic iron overload secondary to chronic liver diseases aggravates liver injury. To uncover underlying molecular mechanisms, hemochromatotic hemojuvelin knockout (Hjv-/-) mice and wild type (wt) controls were intoxicated with CCl4. Hjv-/- mice developed earlier (by 2-4 weeks) and more acute liver damage, reflected in dramatic levels of serum transaminases and ferritin and the development of severe coagulative necrosis and fibrosis. These responses were associated with an oxidative burst and early upregulation of mRNAs encoding α1-(I)-collagen, the profibrogenic cytokines TGF-β1, endothelin-1 and PDGF and, notably, the iron-regulatory hormone hepcidin. Hence, CCl4-induced liver fibrogenesis was exacerbated and progressed precociously in Hjv−/− animals. Even though livers of naïve Hjv−/− mice were devoid of apparent pathology, they exhibited oxidative stress and immunoreactivity towards α-SMA antibodies, a marker of hepatic stellate cells activation. Furthermore, they expressed significantly higher (2–3 fold vs. wt, p<0.05) levels of α1-(I)-collagen, TGF-β1, endothelin-1 and PDGF mRNAs, indicative of early fibrogenesis. Our data suggest that hepatic iron overload in parenchymal cells promotes oxidative stress and triggers premature profibrogenic gene expression, contributing to accelerated onset and precipitous progression of liver fibrogenesis. PMID:21966437

  6. Kinetics of pyrite, pyrrhotite, and chalcopyrite dissolution by Acidithiobacillus ferrooxidans.

    PubMed

    Kocaman, Ayse Tuba; Cemek, Mustafa; Edwards, Katrina Jane

    2016-08-01

    The main objective of this study was to investigate the dissolution kinetics of pyrite, pyrrhotite, and chalcopyrite. Crushed minerals were reacted with Acidithiobacillus ferrooxidans (25 °C). The kinetics of dissolution was investigated by monitoring pH and Fe(2+) and Fe(3+) ion concentrations in the leaching solutions. Pyrite, pyrrhotite, and chalcopyrite dissolution by A. ferrooxidans was found to be a chemically controlled process. With bacteria, the dissolution rates of the minerals increased in the order of pyrrhotite, pyrite, and chalcopyrite. The number of cells attached to mineral surfaces increased in the same order. Acidithiobacillus ferrooxidans was found to enhance the dissolution rates of the minerals. The acid-insoluble trait of pyrite and acid-soluble trait of the other 2 minerals affected the pH changes in the leaching solutions.

  7. 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.

  8. 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

  9. 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.

  10. 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.

  11. Inhibition of nitric oxide synthesis accelerates the recovery of polysynaptic reflex potentials after transient spinal cord ischemia in cats.

    PubMed

    Nemoto, T; Sekikawa, T; Suzuki, T; Moriya, H; Nakaya, H

    1997-04-01

    Nitric Oxide (NO) has been implicated as a mediator of neuronal injury in vascular stroke. On the other hand, NO is suggested to play a neuroprotective role by increasing blood flow during cerebral ischemia. In order to evaluate the role of NO in the spinal cord ischemia, effects of nitric oxide synthase (NOS) inhibition on the recovery of reflex potentials after a transient spinal cord ischemia were examined in urethane-chloralose anesthetized spinal cats. Spinal cord ischemia was produced by occlusion of the thoracic aorta and the both internal mammary arteries for 10 min. Regional blood flow (RBF) in the spinal cord was continuously measured with a laser-Doppler flow meter. The monosynaptic (MSR) and polysynaptic reflex (PSR) potentials elicited by electrical stimulation of the tibial nerve, were recorded from the L7 or S1 ventral root. The recovery process of spinal reflex potentials was reproducible when the oclusion was repeated twice at an interval of 120 min. Pretreatment with N(G)-monomethyl-L-arginine (L-NMMA, 10 mg/kg), a NOS inhibitor significantly accelerated the recovery of PSR potentials after spinal cord ischemia. The accelerating effect of L-NMMA on the recovery of PSR potentials was abolished by co-administration of L-arginine (1 mg/kg/min) but not by that of D-arginine (1 mg/kg/min). L-NMMA failed to improve RBF in the spinal cord during ischemia and reperfusion. Nitroprusside (10 microg/kg/min), a NO donor, retarded the recovery of PSR potentials after spinal cord ischemia. These results suggest that NO production has a significant influence on the functional recovery after transient spinal cord ischemia.

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

    PubMed

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

    2015-08-15

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

  13. 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

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

    PubMed

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

    2015-05-15

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

  15. 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

  16. 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.

  17. 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

  18. 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.

  19. 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

  20. 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.

  1. 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.

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

    NASA Astrophysics Data System (ADS)

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

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

  3. 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.

  4. 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

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

    NASA Astrophysics Data System (ADS)

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

    2010-09-01

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

  6. Deep subsurface sulfate reduction and methanogenesis in the Iberian Pyrite Belt revealed through geochemistry and molecular biomarkers.

    PubMed

    Puente-Sánchez, F; Moreno-Paz, M; Rivas, L A; Cruz-Gil, P; García-Villadangos, M; Gómez, M J; Postigo, M; Garrido, P; González-Toril, E; Briones, C; Fernández-Remolar, D; Stoker, C; Amils, R; Parro, V

    2014-01-01

    The Iberian Pyrite Belt (IPB, southwest of Spain), the largest known massive sulfide deposit, fuels a rich chemolithotrophic microbial community in the Río Tinto area. However, the geomicrobiology of its deep subsurface is still unexplored. Herein, we report on the geochemistry and prokaryotic diversity in the subsurface (down to a depth of 166 m) of the Iberian Pyritic belt using an array of geochemical and complementary molecular ecology techniques. Using an antibody microarray, we detected polymeric biomarkers (lipoteichoic acids and peptidoglycan) from Gram-positive bacteria throughout the borehole. DNA microarray hybridization confirmed the presence of members of methane oxidizers, sulfate-reducers, metal and sulfur oxidizers, and methanogenic Euryarchaeota. DNA sequences from denitrifying and hydrogenotrophic bacteria were also identified. FISH hybridization revealed live bacterial clusters associated with microniches on mineral surfaces. These results, together with measures of the geochemical parameters in the borehole, allowed us to create a preliminary scheme of the biogeochemical processes that could be operating in the deep subsurface of the Iberian Pyrite Belt, including microbial metabolisms such as sulfate reduction, methanogenesis and anaerobic methane oxidation.

  7. 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.

  8. 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.

  9. Iron pyrite nanocubes: size and shape considerations for photovoltaic application.

    PubMed

    Macpherson, H Alex; Stoldt, Conrad R

    2012-10-23

    Multiple lines of recent research indicate that iron pyrite (FeS(2)) requires a {100}-terminated crystal morphology in order to maintain semiconducting properties. Additionally, the large absorption coefficient of pyrite allows for the near complete absorption of above band gap radiation in <50 nm layers. However, to our knowledge <50 nm pyrite nanocubes have yet to be isolated. Herein, we demonstrate the synthesis of ~37 nm phase pure pyrite nanocubes by manipulating the sulfur chemical potential and ligand environment of the system. Ultraviolet-visible (UV-vis) absorption spectroscopy gives a signal of resonant light scattering indicating strong electronic coupling between nanocubes, which may allow for nanocube films with superior electron mobility. The absorption spectroscopies of cubic and irregular nanocrystals are contrasted and compared with recent theoretical work in order to investigate the effect of shape on electronic properties. Specifically, nanocubes have been found to have absorption characteristics closer to theory as compared to irregular nanocrystals, especially for UV radiation: 250-350 nm. Pyrite nanocubes display an indirect band gap at ~1.1 eV in addition to two direct transitions at ~1.9 and ~3.0 eV, correlating well to theoretical values.

  10. Selective adsorption of Mycobacterium Phlei on pyrite and sphalerite.

    PubMed

    Jia, C Y; Wei, D Z; Li, P J; Li, X J; Tai, P D; Liu, W; Gong, Z Q

    2011-04-01

    The adsorption of Mycobacterium Phlei cells on the surfaces of pyrite and sphalerite was studied as functions of time and pH. The results indicated that a higher amount of cells adsorbing onto pyrite compared with that onto sphalerite under neutral and alkaline conditions, and it was also observed from photographs of scanning electron micrograph. To gain a better insight into the mechanisms of differential adsorption, the functional groups on cell surfaces and the chemical states of each element on mineral surfaces before and after interaction with bacterial cells were investigated. The results showed that many groups presented on cells surface, such as C-O-H, C-O-C, C=O, C-N, N-H and P=O. The change in state of each element on pyrite and sphalerite surfaces after interaction with bacterial cells revealed that there were chemical reactions between metal ions and S on mineral surface and atoms like N, O, P, etc. on cell surface, and the shifts in binding energy of each element on pyrite surface is larger than that of sphalerite. Possible mechanisms for selective adsorption of bacterial cells onto pyrite and sphalerite were discussed in the latter part of this paper.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. Effect of Satureja khuzestanica essential oil on oxidative stability of sunflower oil during accelerated storage.

    PubMed

    Hashemi, Mohammad Bagher; Niakousari, Mehrdad; Saharkhiz, Mohammad Jamal; Eskandari, Mohammad Hadi

    2012-01-01

    In this study, the application of various concentrations (0.02%, 0.04%, 0.06% and 0.08%) of Satureja khuzestanica essential oil (EO) was examined on the oxidative stability of sunflower oil and compared to butylated hydroxyanisole (BHA) during storage at 60°C. Gas chromatography (GC) and GC-mass spectrometry analyses of the oils revealed that carvacrol (87.7%) was the major component of EO. Peroxide value and anisidine value measurements in sunflower oil showed that all concentrations of EO had antioxidant effects in comparison to BHA. Oil samples supplemented with EO concentration of 0.08% were the most stable during storage (p < 0.05). EO also was able to reduce the stable free radical 2, 2-diphenyl-1-picrylhydrazyl with a 50% inhibition concentration (IC₅₀) of 31.5 ± 0.6 µg mL⁻¹. Therefore, the results indicate that EO could be used as a natural antioxidant in food lipids.

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

    SciTech Connect

    Kim, Eun Jung; Batchelor, Bill

    2009-07-01

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

  17. Graphene oxide scaffold accelerates cellular proliferative response and alveolar bone healing of tooth extraction socket.

    PubMed

    Nishida, Erika; Miyaji, Hirofumi; Kato, Akihito; Takita, Hiroko; Iwanaga, Toshihiko; Momose, Takehito; Ogawa, Kosuke; Murakami, Shusuke; Sugaya, Tsutomu; Kawanami, Masamitsu

    2016-01-01

    Graphene oxide (GO) consisting of a carbon monolayer has been widely investigated for tissue engineering platforms because of its unique properties. For this study, we fabricated a GO-applied scaffold and assessed the cellular and tissue behaviors in the scaffold. A preclinical test was conducted to ascertain whether the GO scaffold promoted bone induction in dog tooth extraction sockets. For this study, GO scaffolds were prepared by coating the surface of a collagen sponge scaffold with 0.1 and 1 µg/mL GO dispersion. Scaffolds were characterized using scanning electron microscopy (SEM), physical testing, cell seeding, and rat subcutaneous implant testing. Then a GO scaffold was implanted into a dog tooth extraction socket. Histological observations were made at 2 weeks postsurgery. SEM observations show that GO attached to the surface of collagen scaffold struts. The GO scaffold exhibited an interconnected structure resembling that of control subjects. GO application improved the physical strength, enzyme resistance, and adsorption of calcium and proteins. Cytocompatibility tests showed that GO application significantly increased osteoblastic MC3T3-E1 cell proliferation. In addition, an assessment of rat subcutaneous tissue response revealed that implantation of 1 µg/mL GO scaffold stimulated cellular ingrowth behavior, suggesting that the GO scaffold exhibited good biocompatibility. The tissue ingrowth area and DNA contents of 1 µg/mL GO scaffold were, respectively, approximately 2.5-fold and 1.4-fold greater than those of the control. Particularly, the infiltration of ED2-positive (M2) macrophages and blood vessels were prominent in the GO scaffold. Dog bone-formation tests showed that 1 µg/mL GO scaffold implantation enhanced bone formation. New bone formation following GO scaffold implantation was enhanced fivefold compared to that in control subjects. These results suggest that GO was biocompatible and had high bone-formation capability for the scaffold

  18. 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

  19. 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

  20. 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.

  1. Pyrite Nanocrystal Solar Cells: Promising, or Fool's Gold?

    PubMed

    Steinhagen, Chet; Harvey, Taylor B; Stolle, C Jackson; Harris, Justin; Korgel, Brian A

    2012-09-06

    Pyrite-phase iron sulfide (FeS2) nanocrystals were synthesized to form solvent-based dispersions, or "solar paint," to fabricate photovoltaic devices (PVs). Nanocrystals were sprayed onto substrates as absorber layers in devices with several different architectures, including Schottky barrier, heterojunction, and organic/inorganic hybrid architectures, to explore their viability as a PV material. None of the devices exhibited PV response. XRD and Raman spectroscopy confirmed the pyrite composition and phase purity of the nanocrystals. The electrical conductivity of the nanocrystal films was about 4 to 5 S/cm, more typical of metal nanocrystal films than semiconductor nanocrystal films, and the lack of PV response appears to derive from the highly conductive surface-related defects in pyrite that have been proposed.

  2. Electrochemical Evaluation of Pyrite Films Prepared by Plasma Spraying

    SciTech Connect

    Guidotti, R.A.; Reinhardt, F.W.

    1998-10-30

    Thermally activated batteries use electrodes that are typically fabricated by cold pressing of powder. In the LiSi/FeS2 system, natural (mineral) pyrite is used for the cathode. In an effort to increase the energy density and specific energy of these batteries, flame and plasma spraying to form thin films of pyrite cathodes were evaluated. The films were deposited on a 304 stainless steel substrate (current collector) and were characterized by scanning electron microscopy and x-ray dlfllaction. The films were electrochemically tested in single cells at 5000C and the petiormance compared to that of standard cells made with cold-pressed powders. The best results were obtained with material deposited by de-arc plasma spraying with a proprietq additive to suppress thermal decomposion of the pyrite.

  3. 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.

  4. 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

  5. Biogenic syngenetic pyrite from tuffaceous sedimentary RF3-V rocks

    NASA Astrophysics Data System (ADS)

    Kozyreva, Irina; Nikulova, Natalia

    2015-04-01

    Biogenic framboidal pyrite was found in intraformational tuffaceous sedimentary gravelites, within basic volcanites (RF3-V) in Subpolar Urals (Sablya Ridge). Pyrite grains (Fe 44.07-44,33, S 50.22-53.31 wt. %) are composed of ball-like microconcretions, sometimes intergrown with crystals of pentagondodecahedron and cubic habit. The microconcretions (20 to 40 mcm) are roundish and composed of microcrystals, which end faces form spherical surface. The nuclei of the microconcretions are represented by frambohedrons 4-5 mcm in size, which are pyritized cells of sulphate-reducing colonial coccoid microfossils. The formation of the frambohedrons occurred synchronously to sedimentation in stagnant reducing environment at interaction of biogenic hydrogen sulphide with water-dissolved iron. The biogenic hydrogen sulphide is reduced by microorganisms in the conditions of free and unrestricted access of dissolved sulphate ions sourced from sulphur of fumarole gases. Iron came from washed-out basic volcanites. The growth of outer radial parts of microconcretions occurred during compaction of sediments in diagenetic stage. The quantity of dissolved sulphate and iron during pyrite formation exceeded possibilitites of bacterial "starters" which resulted in the formation of pyrites of other morphological varieties. This is confirmed by the accretion of concentric rays of the concretions and cubic microcrystals of pyrite in the aggregate grains. The formation of tuffaceous sediments occurred during temporary decrease of volcanic activity in a continuous linear water flow with stagnant areas composed of water-displaced pebbles from underlying metaterrigenous rocks (RF 1-2), which were exposed beyond the development area of volcanic strata, unchanged clasts of recent and synchronously formed basic and medium volcanites with participation of air-driven ashes and influence of volcanic gases in the presence of sulphate-reducing bacteria. The work is financially supported by the Program

  6. 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.

  7. 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.

  8. Isolation and characterization of a novel Acidithiobacillus ferrivorans strain from the Chilean Altiplano: attachment and biofilm formation on pyrite at low temperature.

    PubMed

    Barahona, Sergio; Dorador, Cristina; Zhang, Ruiyong; Aguilar, Pablo; Sand, Wolfgang; Vera, Mario; Remonsellez, Francisco

    2014-11-01

    Microorganisms are used to aid the extraction of valuable metals from low-grade sulfide ores in mines worldwide, but relatively little is known about this process in cold environments. This study comprises a preliminary analysis of the bacterial diversity of the polyextremophilic acid River Aroma located in the Chilean Altiplano, and revealed that Betaproteobacteria was the most dominant bacterial group (Gallionella-like and Thiobacillus-like). Taxa characteristic of leaching environments, such Acidithiobacillus and Leptospirillum, were detected at low abundances. Also, bacteria not associated with extremely acidic, metal-rich environments were found. After enrichment in iron- and sulfur-oxidizing media, we isolated and identified a novel psychrotolerant Acidithiobacillus ferrivorans strain ACH. This strain can grow using ferrous iron, sulfur, thiosulfate, tetrathionate and pyrite, as energy sources. Optimal growth was observed in the presence of pyrite, where cultures reached a cell number of 6.5 · 10(7) cells mL(-1). Planktonic cells grown with pyrite showed the presence of extracellular polymeric substances (10 °C and 28 °C), and a high density of cells attached to pyrite grains were observed at 10 °C by electron microscopy. The attachment of cells to pyrite coupons and the presence of capsular polysaccharides were visualized by using epifluorescence microscopy, through nucleic acid and lectin staining with Syto(®)9 and TRITC-Con A, respectively. Interestingly, we observed high cell adhesion including the formation of microcolonies within 21 days of incubation at 4 °C, which was correlated with a clear induction of capsular polysaccharides production. Our data suggests that attachment to pyrite is not temperature-dependent in At. ferrivorans ACH. The results of this study highlight the potential of this novel psychrotolerant strain in oxidation and attachment to minerals under low-temperature conditions.

  9. 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.

  10. 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.

  11. Variscan tectonics in the Iberian Pyrite Belt, South Portuguese Zone

    NASA Astrophysics Data System (ADS)

    Soriano, C.; Casas, J. M.

    2002-10-01

    This paper aims to discuss the structural evolution of the Iberian Pyrite Belt during the Variscan Orogeny. It provides new structural data, maps and cross sections from the eastern part of the Iberian Pyrite Belt. Regional geology of the South Portuguese Zone and lithostratigraphy of the Iberian Pyrite Belt are first briefly summarised. Three roughly homoaxial deformation phases are distinguished, and are mainly characterised by south-verging multi-order folds, axial planar cleavages and thrusts. Three structural units are distinguished: the La Puebla de Guzmán and Valverde del Camino antiforms are rooted units related to the propagation of southward-directed thrust systems that may branch onto the lower décollement level of the South Portuguese Zone; El Cerro de Andévalo is a structurally higher unit, mainly composed of allochthonous D1 thrust nappes. No evidence of sinistral transpression has been found in the transected cleavage and the strike of S3 with respect to S2. Better evidence of transpression is the moderately to steeply westerly plunging folds that show S-type asymmetry in down-plunge view. Variscan deformation in the Iberian Pyrite Belt is defined as the combination of a dominant southwards shear and a sinistral E-shear caused by oblique continental collision between the South Portuguese plate and the Iberian Massif.

  12. GW calculations of the bandgap of pyrite under various conditions

    NASA Astrophysics Data System (ADS)

    Kolb, Brian; Kolpak, Alexie

    2013-03-01

    Iron pyrite holds great promise as a solar cell material because of it's near optimal bandgap (0.95 eV) and its high optical absorbance. Nevertheless, real solar cells made from this material suffer from poor performance. In particular, the low open circuit voltage of around 200 meV precludes pyrite's use in effective solar cell devices. Several theories have been proposed to explain this low open-circuit voltage including bulk defects, intrinsic surface states within the gap, and surface defects. Careful DFT calculations have shown that bulk defects are exceedingly rare. Further, the calculations do not exhibit intrinsic surface states within the gap. Researchers disagree about the effect of surface defects, particularly sulfur deficiencies, on the bandgap. This work combines DFT with GW calculations of the bandgap to address some of the most fundamental and important questions about the cause of the low open-circuit voltage of pyrite solar cells including the true role of surface defects, the nature of the interface with metal electrodes, and the effect of phonons on the bandgap. This investigation is undertaken with an eye toward engineering a pyrite-based material that can perform well in real solar cell applications.

  13. TRANSFORMATION OF CARBON TETRACHLORIDE BY PYRITE IN AQUEOUS SOLUTION

    EPA Science Inventory

    The reactivity of Cc4 with pyrite was investigated by measuring the CC14 transformation rates and products under aerobic and anaerobic conditions. Under all reaction conditions, >90% of the CC14 was transformed within 12- 36 days in the presence o...

  14. Sulfidation Roasting of Hemimorphite with Pyrite for the Enrichment of Zn and Pb

    NASA Astrophysics Data System (ADS)

    Min, Xiao-Bo; Xue, Ke; Ke, Yong; Zhou, Bo-Sheng; Li, Yang-Wen-Jun; Wang, Qing-Wei

    2016-09-01

    With the increasing consumption of zinc and the depletion of zinc sulfide ores, the exploitation of low-grade zinc oxide ores may be important for the sustainability of the zinc industry. Hemimorphite, a zinc hydroxyl silicate hydrate, is a significant source of Zn and Pb. It is difficult to obtain Zn and Pb from the hemimorphite using traditional technology. In this work, for the first time, sulfidation roasting of hemimorphite with pyrite was studied for the enrichment of Zn and Pb by a flotation process. Four stages of sulfidation roasting were determined based on x-ray diffraction and thermogravimetry analysis. Then, the effects of sulfidation temperature, pyrite dosage and reaction time on the sulfidation percentages were investigated at the laboratory scale. The experimental results showed that the sulfidation percentages of Pb and Zn were as high as 98.08% and 90.55% under optimum conditions, respectively. Finally, a flotation test was performed to enrich Zn and Pb in the sulfidation product. A flotation concentrate with 8.78% Zn and 9.25% Pb was obtained, and the recovery of Zn and Pb reached 56.14% and 75.94%, respectively.

  15. 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.

  16. Sulfur isotope variability in biogenic pyrite: Reflections of heterogeneous bacterial colonization?

    SciTech Connect

    Kohn, M.J.; Riciputi, L.R.; Stakes, D.; Orange, D.L.

    1998-11-01

    The top 20 cm of sediments at active cold seeps in Monterey Bay, coastal California, contain framboidal pyrite that occurs as infillings and pseudomorphs of the chambers of the tests of foraminifera and rarely as irregularly shaped grains. Sulfur isotope compositions obtained with the ion microprobe show depletions in {sup 34}S and large variations both within and among these pyrite grains. Backscattered-electron imaging reveals three types of pyrite: isolated framboids in a porous aggregation, agglomerated framboids with cementing interstitial pyrite, and recrystallized pyrite with isolated relicts of framboids. In individual grains, RF-pyrite cores grade into F+I-pyrite toward grain rims, and F+I-pyrite grades into PF-pyrite at the grain edges. These textures are consistent with a paragenetic sequence whereby framboids first agglomerate (PF-pyrite), then cement (F+I-pyrite), and finally recrystallize (RF-pyrite). The {delta}{sup 34}S values of RF-pyrite are generally lower than that of F+I-pyrite; if the paragenetic sequence is correct, then this trend parallels the regular core-rim isotopic zoning observed in some grains. The implied increase in {delta}{sup 14}S with time is consistent with Rayleigh fractionation of sulfur in a closed system. Bacteria are intimately involved in the production of pyrite from the samples, and heterogeneous colonization by bacteria provides a simple explanation for the sulfur isotope heterogeneity among and within grains: The foraminifera provide open space for colonization and local nutrients for bacterial growth, whereas the cell walls of the bacteria may provide a local nucleation site for sulfides.

  17. 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.

  18. A remediation strategy based on active phytoremediation followed by natural attenuation in a soil contaminated by pyrite waste.

    PubMed

    Clemente, Rafael; Almela, Concepción; Bernal, M Pilar

    2006-10-01

    Phytoremediation of metal-polluted soils can be promoted by the proper use of soil amendments and agricultural practices. A 4-year phytoremediation programme was applied to a site affected by the toxic spill of pyrite residue at Aznalcóllar (Spain) in 1998, contaminated with heavy metals (Zn, Cu, Pb, Cd) and arsenic. This consisted of active phytoremediation, using organic amendments (cow manure and compost) and lime and growing two successive crops of Brassica juncea (L.) Czern., followed by natural attenuation without further intervention. Changes in soil pH, extractable metal and As concentrations, organic carbon content and microbial biomass was evaluated. The initial oxidation of metal sulphides from pyrite residues released soluble metals and reduced soil pH to extremely acidic values (mean 4.1, range 2.0-7.0). The addition of lime (up to 64 t ha(-1)) increased soil pH to adequate values for plant growth, resulting in a significant decrease in DTPA-extractable metal concentrations in all plots. The natural attenuation phase showed also a decrease in extractable metals. Organic treatments increased the soil total organic carbon, which led to higher values of microbial biomass (11.6, 15.2 and 14.9 g kg(-1) TOC and 123, 170 and 275 microg g(-1) biomass-C in control, compost and manure plots, respectively). Active phytoremediation followed by natural attenuation, was effective for remediation of this pyrite-polluted soil.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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

  4. 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

  5. Microwave-Accelerated Rapid, Chemical Oxidant-Free, Material-Independent Surface Chemistry of Poly(dopamine).

    PubMed

    Lee, Mihyun; Lee, Si-Hwa; Oh, Il-Kwon; Lee, Haeshin

    2017-01-01

    A simple strategy for the rapid preparation of multifunctional polydopamine (pDA) coatings is demonstrated. Microwave irradiation of the coating solution enables the formation of a ≈18 nm thick, genuine pDA coating in 15 min, which is ≈18 times faster than conventional coating. The acceleration effect results from the radical generation and temperature increase, which facilitate thermally accelerated radical polymerization of dopamine.

  6. 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.

  7. 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.

  8. 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.

  9. Graphene-assisted room-temperature synthesis of 2D nanostructured hybrid electrode materials: dramatic acceleration of the formation rate of 2D metal oxide nanoplates induced by reduced graphene oxide nanosheets.

    PubMed

    Sung, Da-Young; Gunjakar, Jayavant L; Kim, Tae Woo; Kim, In Young; Lee, Yu Ri; Hwang, Seong-Ju

    2013-05-27

    A new prompt room temperature synthetic route to 2D nanostructured metal oxide-graphene-hybrid electrode materials can be developed by the application of colloidal reduced graphene oxide (RGO) nanosheets as an efficient reaction accelerator for the synthesis of δ-MnO2 2D nanoplates. Whereas the synthesis of the 2D nanostructured δ-MnO2 at room temperature requires treating divalent manganese compounds with persulfate ions for at least 24 h, the addition of RGO nanosheet causes a dramatic shortening of synthesis time to 1 h, underscoring its effectiveness for the promotion of the formation of 2D nanostructured metal oxide. To the best of our knowledge, this is the first example of the accelerated synthesis of 2D nanostructured hybrid material induced by the RGO nanosheets. The observed acceleration of nanoplate formation upon the addition of RGO nanosheets is attributable to the enhancement of the oxidizing power of persulfate ions, the increase of the solubility of precursor MnCO3, and the promoted crystal growth of δ-MnO2 2D nanoplates. The resulting hybridization between RGO nanosheets and δ-MnO2 nanoplates is quite powerful not only in increasing the surface area of manganese oxide nanoplate but also in enhancing its electrochemical activity. Of prime importance is that the present δ-MnO2 -RGO nanocomposites show much superior electrode performance over most of 2D nanostructured manganate systems including a similar porous assembly of RGO and layered MnO2 nanosheets. This result underscores that the present RGO-assisted solution-based synthesis can provide a prompt and scalable method to produce nanostructured hybrid electrode materials.

  10. 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.

  11. 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

  12. 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

  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. Temporal adaptation of neutrophil oxidative responsiveness to n-formyl-methionyl-leucyl-phenylalanine. Acceleration by granulocyte-macrophage colony stimulating factor.

    PubMed

    English, D; Broxmeyer, H E; Gabig, T G; Akard, L P; Williams, D E; Hoffman, R

    1988-10-01

    This investigation was undertaken to clarify the mechanism by which purified recombinant human granulocyte-macrophage colony stimulating factor (GM-CSF) potentiates neutrophil oxidative responses triggered by the chemotactic peptide, FMLP. Previous studies have shown that GM-CSF priming of neutrophil responses to FMLP is induced relatively slowly, requiring 90 to 120 min of incubation in vitro, is not associated with increased levels of cytoplasmic free Ca2+, but is associated with up-regulation of cell-surface FMLP receptors. We have confirmed these findings and further characterized the process of GM-CSF priming. We found that the effect of GM-CSF on neutrophil oxidative responsiveness was induced in a temperature-dependent manner and was not reversed when the cells were washed extensively to remove the growth factor before stimulation with FMLP. Extracellular Ca2+ was not required for functional enhancement by GM-CSF and GM-CSF alone effected no detectable alteration in the 32P-labeled phospholipid content of neutrophils during incubation in vitro. Our data indicate that GM-CSF exerts its influence on neutrophils by accelerating a process that occurs spontaneously and results in up-regulation of both cell-surface FMLP receptors and oxidative responsiveness to FMLP. Thus, the results demonstrate that, with respect to oxidative activation, circulating endstage polymorphonuclear leukocytes are nonresponsive or hyporesponsive to FMLP; functional responsiveness increases dramatically as surface FMLP receptors are gradually deployed after the cells leave the circulation. Thus, as neutrophils mature, their responsiveness to FMLP changes in a manner which may be crucial for efficient host defense. At 37 degrees C, this process is markedly potentiated by GM-CSF. We conclude that endogenous GM-CSF, released systemically or at sites of infection and inflammation, potentially plays an important role in host defense by accelerating functional maturation of responding

  15. Coupled Geochemical and Reactive Transport Modeling of Organic Contaminants in a Pyrite-Rich Aquifer

    NASA Astrophysics Data System (ADS)

    Sarioglu, S. M.; Copty, N. K.

    2004-12-01

    Although pH is recognized as a key factor influencing bacterial activity, existing groundwater transport models generally do not directly account for the effect of pH on the biodegradation of organic compounds. The purpose of this study is to develop a coupled reactive transport and geochemical model that explicitly incorporates the effect of spatial and temporal variations of the pH on the biodegradation of organic contaminants. The model consists of two modules: a transport module and a geochemical module. The transport module uses a Crank-Nicholson finite-difference formulation to solve the groundwater flow and transport equations for the hydrocarbon, dissolved oxygen, microbial mass and all reactive groundwater species influencing the hydrocarbon biodegradation and pH distribution. The geochemical module allows for the simulation of both kinetically defined as well as geochemical equilibrium reactions. The governing non-linear system of equations is solved using an iterative multi-step operator-splitting algorithm. Both modules account for heterogeneity in the definition of the hydrogeological and biochemical parameters. For demonstration, the model is applied to a hypothetical pyrite-rich aquifer contaminated with petroleum hydrocarbons. A commonly used practice for the remediation of aquifers contaminated with petroleum hydrocarbons is the delivery of oxygen for the enhanced aerobic biodegradation of the organic contaminant. However, the presence of pyrite may interfere with the intended purpose of the supplied oxygen, leading to undesirable side effects. Specifically, oxygen readily reacts with the sulfide minerals leading to depletion of oxygen and acidification of the subsurface environment and, subsequently, the inadvertent inhibition of the microbial activity. The developed coupled geochemical and reactive transport model is used to quantify these processes and assess the dominance of the various chemical reactions. Both abiotic and biotic pyrite

  16. 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.

  17. Comparison analysis of coal biodesulfurization and coal's pyrite bioleaching with Acidithiobacillus ferrooxidans.

    PubMed

    Hong, Fen-Fen; He, Huan; Liu, Jin-Yan; Tao, Xiu-Xiang; Zheng, Lei; Zhao, Yi-Dong

    2013-01-01

    Acidithiobacillus ferrooxidans (A. ferrooxidans) was applied in coal biodesulfurization and coal's pyrite bioleaching. The result showed that A. ferrooxidans had significantly promoted the biodesulfurization of coal and bioleaching of coal's pyrite. After 16 days of processing, the total sulfur removal rate of coal was 50.6%, and among them the removal of pyritic sulfur was up to 69.9%. On the contrary, after 12 days of processing, the coal's pyrite bioleaching rate was 72.0%. SEM micrographs showed that the major pyrite forms in coal were massive and veinlets. It seems that the bacteria took priority to remove the massive pyrite. The sulfur relative contents analysis from XANES showed that the elemental sulfur (28.32%) and jarosite (18.99%) were accumulated in the biotreated residual coal. However, XRD and XANES spectra of residual pyrite indicated that the sulfur components were mainly composed of pyrite (49.34%) and elemental sulfur (50.72%) but no other sulfur contents were detected. Based on the present results, we speculated that the pyrite forms in coal might affect sulfur biooxidation process.

  18. FTIR and XPS studies of surface chemistry of pyrite in flotation

    SciTech Connect

    Leppinen, J.; Laajalehto, K.; Kartio, I.; Suoninen, E.

    1995-12-31

    Efficient separation of pyrite is of great importance for the metallurgical performance of flotation processes. Presently, separation of pyrite by flotation is becoming more and more important for reduction of sulfur in coal. In this work Fourier Transform Infrared Spectroscopy (FTIR) and X-ray Photoelectron Spectroscopy (XPS) were used to study the surface chemistry of pyrite in depression, activation and xanthate adsorption under conditions of controlled potential. Modifications of pyrite surfaces after treatment with depressants (lime, sulfur dioxide, sodium cyanide) and after activation with metal ions (Cu, Pb) were studied. The principal adsorption product identified on pyrite was dixanthogen whose formation started at about +0.15 V and +0.25 V (vs, SHE) in ethyl and amyl xanthate solutions, respectively. Copper xanthate was formed on copper(II) activated pyrite. Activation mechanism of pyrite by copper(II) salts is likely to be electrochemical where copper occurs as copper(I) on the surface of pyrite. Effective depression is achieved by sulfur dioxide and sodium cyanide. Depression at high pH is due to formation of iron(III) hydroxides. Calcium ions do not affect the electrochemistry but adsorb on pyrite and reduce the surface sites for dixanthogen adsorption.

  19. Comparison Analysis of Coal Biodesulfurization and Coal's Pyrite Bioleaching with Acidithiobacillus ferrooxidans

    PubMed Central

    Hong, Fen-Fen; He, Huan; Liu, Jin-Yan; Tao, Xiu-Xiang; Zheng, Lei; Zhao, Yi-Dong

    2013-01-01

    Acidithiobacillus ferrooxidans (A. ferrooxidans) was applied in coal biodesulfurization and coal's pyrite bioleaching. The result showed that A. ferrooxidans had significantly promoted the biodesulfurization of coal and bioleaching of coal's pyrite. After 16 days of processing, the total sulfur removal rate of coal was 50.6%, and among them the removal of pyritic sulfur was up to 69.9%. On the contrary, after 12 days of processing, the coal's pyrite bioleaching rate was 72.0%. SEM micrographs showed that the major pyrite forms in coal were massive and veinlets. It seems that the bacteria took priority to remove the massive pyrite. The sulfur relative contents analysis from XANES showed that the elemental sulfur (28.32%) and jarosite (18.99%) were accumulated in the biotreated residual coal. However, XRD and XANES spectra of residual pyrite indicated that the sulfur components were mainly composed of pyrite (49.34%) and elemental sulfur (50.72%) but no other sulfur contents were detected. Based on the present results, we speculated that the pyrite forms in coal might affect sulfur biooxidation process. PMID:24288464

  20. Antisense directed against PS-1 gene decreases brain oxidative markers in aged senescence accelerated mice (SAMP8) and reverses learning and memory impairment: a proteomics study.

    PubMed

    Fiorini, Ada; Sultana, Rukhsana; Förster, Sarah; Perluigi, Marzia; Cenini, Giovanna; Cini, Chiara; Cai, Jian; Klein, Jon B; Farr, Susan A; Niehoff, Michael L; Morley, John E; Kumar, Vijaya B; Allan Butterfield, D

    2013-12-01

    Amyloid β-peptide (Aβ) plays a central role in the pathophysiology of Alzheimer's disease (AD) through the induction of oxidative stress. This peptide is produced by proteolytic cleavage of amyloid precursor protein (APP) by the action of β- and γ-secretases. Previous studies demonstrated that reduction of Aβ, using an antisense oligonucleotide (AO) directed against the Aβ region of APP, reduced oxidative stress-mediated damage and prevented or reverted cognitive deficits in senescence-accelerated prone mice (SAMP8), a useful animal model for investigating the events related to Aβ pathology and possibly to the early phase of AD. In the current study, aged SAMP8 were treated by AO directed against PS-1, a component of the γ-secretase complex, and tested for learning and memory in T-maze foot shock avoidance and novel object recognition. Brain tissue was collected to identify the decrease of oxidative stress and to evaluate the proteins that are differently expressed and oxidized after the reduction in free radical levels induced by Aβ. We used both expression proteomics and redox proteomics approaches. In brain of AO-treated mice a decrease of oxidative stress markers was found, and the proteins identified by proteomics as expressed differently or nitrated are involved in processes known to be impaired in AD. Our results suggest that the treatment with AO directed against PS-1 in old SAMP8 mice reverses learning and memory deficits and reduces Aβ-mediated oxidative stress with restoration to the normal condition and identifies possible pharmacological targets to combat this devastating dementing disease.

  1. 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.

  2. Mechanism of Pyrite Dissolution in the Presence of Thiobacillus ferrooxidans

    PubMed Central

    Fowler, T. A.; Holmes, P. R.; Crundwell, F. K.

    1999-01-01

    In spite of the environmental and commercial interests in the bacterial leaching of pyrite, two central questions have not been answered after more than 35 years of research: does Thiobacillus ferrooxidans enhance the rate of leaching above that achieved by ferric sulfate solutions under the same conditions, and if so, how do the bacteria affect such an enhancement? Experimental conditions of previous studies were such that the concentrations of ferric and ferrous ions changed substantially throughout the course of the experiments. This has made it difficult to interpret the data obtained from these previous works. The aim of this work was to answer these two questions by employing an experimental apparatus designed to maintain the concentrations in solution at a constant value. This was achieved by using the constant redox potential apparatus described previously (P. I. Harvey, and F. K. Crundwell, Appl. Environ. Microbiol. 63:2586–2592, 1997; T. A. Fowler, and F. K. Crundwell, Appl. Environ. Microbiol. 64:3570–3575, 1998). Experiments were conducted in both the presence and absence of T. ferrooxidans, maintaining the same conditions in solution. The rate of dissolution of pyrite with bacteria was higher than that without bacteria at the same concentrations of ferrous and ferric ions in solution. Analysis of the dependence of the rate of leaching on the concentration of ferric ions and on the pH, together with results obtained from electrochemical measurements, provided clear evidence that the higher rate of leaching with bacteria is due to the bacteria increasing the pH at the surface of the pyrite. PMID:10388693

  3. 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

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. Pyrite-based autotrophic denitrification for remediation of nitrate contaminated groundwater.

    PubMed

    Pu, Jiaoyang; Feng, Chuanping; Liu, Ying; Li, Rui; Kong, Zhe; Chen, Nan; Tong, Shuang; Hao, Chunbo; Liu, Ye

    2014-12-01

    In this study, pyrite-based denitrification using untreated pyrite (UP) and acid-pretreated pyrite (AP) was evaluated as an alternative to elemental sulfur based denitrification. Pyrite-based denitrification resulted in a favorable nitrate removal rate constant (0.95 d(-1)), sulfate production of 388.00 mg/L, and a stable pH. The pretreatment of pyrite with acid led to a further increase in the nitrate removal rate constant (1.03 d(-1)) and reduction in initial sulfate concentration (224.25±7.50 mg/L). By analyzing the microbial community structure using Denaturing Gradient Gel Electrophoresis, it was confirmed that Sulfurimonas denitrificans (S. denitrificans) could utilize pyrite as an electron donor. A stable pH was observed over the entire experimental period, indicating that the use of a pH buffer reagent would not be necessary for pyrite-based denitrification. Therefore, pyrite could effectively replace elemental sulfur as an electron donor in autotrophic denitrification for nitrate-contaminated groundwater remediation.

  9. Treatment of Actual Chemical Wastewater by a Heterogeneous Fenton Process Using Natural Pyrite.

    PubMed

    Sun, Liang; Li, Yan; Li, Aimin

    2015-10-28

    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.

  10. Thermal stability and mechanism of decomposition of emulsion explosives in the presence of pyrite.

    PubMed

    Xu, Zhi-Xiang; Wang, Qian; Fu, Xiao-Qi

    2015-12-30

    The reaction of emulsion explosives (ammonium nitrate) with pyrite was studied using techniques of TG-DTG-DTA. TG-DSC-MS was also used to analyze samples thermal decomposition process. When a mixture of pyrite and emulsion explosives was heated at a constant heating rate of 10K/min from room temperature to 350°C, exothermic reactions occurred at about 200°C. The essence of reaction between emulsion explosives and pyrite is the reaction between ammonium nitrate and pyrite. Emulsion explosives have excellent thermal stability but it does not mean it showed the same excellent thermal stability when pyrite was added. Package emulsion explosives were more suitable to use in pyrite shale than bulk emulsion explosives. The exothermic reaction was considered to take place between ammonium nitrate and pyrite where NO, NO2, NH3, SO2 and N2O gases were produced. Based on the analysis of the gaseous, a new overall reaction was proposed, which was thermodynamically favorable. The results have significant implication in the understanding of stability of emulsion explosives in reactive mining grounds containing pyrite minerals.

  11. 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.

  12. 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

  13. Relationship between pyrite Stability and arsenic mobility during aquifer storage and recovery in southwest central Florida.

    PubMed

    Jones, Gregg W; Pichler, Thomas

    2007-02-01

    Elevated arsenic concentrations are common in water recovered from aquifer storage and recovery (ASR) systems in west-central Florida that store surface water. Investigations of the Suwannee Limestone of the Upper Floridan aquifer, the storage zone for ASR systems, have shown that arsenic is highest in pyrite in zones of high moldic porosity. Geochemical modeling was employed to examine pyrite stability in limestone during simulated injections of surface water into wells open only to the Suwannee Limestone with known mineralogy and water chemistry. The goal was to determine if aquifer redox conditions could be altered to the degree of pyrite instability. Increasing amounts of injection water were added to native storage-zone water, and resulting reaction paths were plotted on pyrite stability diagrams. Native storage-zone water plotted within the pyrite stability field, indicating that conditions were sufficiently reducing to allow for pyrite stability. Thus, arsenic is immobilized in pyrite, and its groundwater concentration should be low. This was corroborated by analysis of water samples, none of which had arsenic concentrations above 0.036 microg/L. During simulation, however, as injection/native storage-zone water ratios increased, conditions became less reducing and pyrite became unstable. The result would be release of arsenic from limestone into storage-zone water.

  14. Iron isotope fractionation between pyrite (FeS 2), hematite (Fe 2O 3) and siderite (FeCO 3): A first-principles density functional theory study

    NASA Astrophysics Data System (ADS)

    Blanchard, Marc; Poitrasson, Franck; Méheut, Merlin; Lazzeri, Michele; Mauri, Francesco; Balan, Etienne

    2009-11-01

    In addition to equilibrium isotopic fractionation factors experimentally derived, theoretical predictions are needed for interpreting isotopic compositions measured on natural samples because they allow exploring more easily a broader range of temperature and composition. For iron isotopes, only aqueous species were studied by first-principles methods and the combination of these data with those obtained by different methods for minerals leads to discrepancies between theoretical and experimental isotopic fractionation factors. In this paper, equilibrium iron isotope fractionation factors for the common minerals pyrite, hematite, and siderite were determined as a function of temperature, using first-principles methods based on the density functional theory (DFT). In these minerals belonging to the sulfide, oxide and carbonate class, iron is present under two different oxidation states and is involved in contrasted types of interatomic bonds. Equilibrium fractionation factors calculated between hematite and siderite compare well with the one estimated from experimental data (ln α57Fe/ 54Fe = 4.59 ± 0.30‰ and 5.46 ± 0.63‰ at 20 °C for theoretical and experimental data, respectively) while those for Fe(III) aq-hematite and Fe(II) aq-siderite are significantly higher that experimental values. This suggests that the absolute values of the reduced partition functions ( β-factors) of aqueous species are not accurate enough to be combined with those calculated for minerals. When compared to previous predictions derived from Mössbauer or INRXS data [Polyakov V. B., Clayton R. N., Horita J. and Mineev S. D. (2007) Equilibrium iron isotope fractionation factors of minerals: reevaluation from the data of nuclear inelastic resonant X-ray scattering and Mössbauer spectroscopy. Geochim. Cosmochim. Acta71, 3833-3846], our iron β-factors are in good agreement for siderite and hematite while a discrepancy is observed for pyrite. However, the detailed investigation of the

  15. 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.

  16. Oxidative stability of sunflower oil supplemented with medicinal split gill mushroom, Schizophyllum commune Fr.:Fr. extract during accelerated storage.

    PubMed

    Yim, Hip Seng; Chye, Fook Yee; Heng, Pei Ying; Ho, Chun Wai

    2011-01-01

    The oxidative stability of sunflower oil supplemented with medicinal split gill mushroom, Schizophyllum commune's crude extract (CE), the formic acid (FA) fraction and semipurified subfractions (SF) II and IV were tested, compared to BHA and alpha-tocopherol, by measuring their peroxide value, iodine value, p-anisidine value, thiobarbituric acid-reactive substances, and free fatty acid content. Their total phenolic content (TPC), 2,2-diphenyl-1-picryhydrazyl (DPPH) radical scavenging, and ferric reducing/antioxidant power (FRAP) were also evaluated. FA and CE exhibited highest DPPH* scavenging, while FA and SFIV showed the highest FRAP; TPC was found to be highest in CE, FA, and SFIV. BHA and alpha-tocopherol are more protective in stabilizing the sunflower oil; SFII and SFIV had short-term protective effect in secondary oxidation for 1 year, while CE and FA retarded secondary oxidation and extended the shelf life 1 1/2 years and 2 years, respectively. HPLC-DAD analysis found (+)-catechin in Sch. commune's extracts. Sch. commune's extracts did not show similar retardation of lipid oxidation in sunflower oil as compared to alpha-tocopherol and BHA at the 200 ppm level. However, the higher concentration of Sch. commune's extract that provided the protective effect in stabilizing sunflower oil can be further studied.

  17. Quantifying Fenton reaction pathways driven by self-generated H2O2 on pyrite surfaces

    PubMed Central

    Gil-Lozano, C.; Davila, A. F.; Losa-Adams, E.; Fairén, A. G.; Gago-Duport, L.

    2017-01-01

    Oxidation of pyrite (FeS2) plays a significant role in the redox cycling of iron and sulfur on Earth and is the primary cause of acid mine drainage (AMD). It has been established that this process involves multi-step electron-transfer reactions between surface defects and adsorbed O2 and H2O, releasing sulfoxy species (e.g., S2O32−, SO42−) and ferrous iron (Fe2+) to the solution and also producing intermediate by-products, such as hydrogen peroxide (H2O2) and other reactive oxygen species (ROS), however, our understanding of the kinetics of these transient species is still limited. We investigated the kinetics of H2O2 formation in aqueous suspensions of FeS2 microparticles by monitoring, in real time, the H2O2 and dissolved O2 concentration under oxic and anoxic conditions using amperometric microsensors. Additional spectroscopic and structural analyses were done to track the dependencies between the process of FeS2 dissolution and the degradation of H2O2 through the Fenton reaction. Based on our experimental results, we built a kinetic model which explains the observed trend of H2O2, showing that FeS2 dissolution can act as a natural Fenton reagent, influencing the oxidation of third-party species during the long term evolution of geochemical systems, even in oxygen-limited environments. PMID:28262831

  18. Quantifying Fenton reaction pathways driven by self-generated H2O2 on pyrite surfaces

    NASA Astrophysics Data System (ADS)

    Gil-Lozano, C.; Davila, A. F.; Losa-Adams, E.; Fairén, A. G.; Gago-Duport, L.

    2017-03-01

    Oxidation of pyrite (FeS2) plays a significant role in the redox cycling of iron and sulfur on Earth and is the primary cause of acid mine drainage (AMD). It has been established that this process involves multi-step electron-transfer reactions between surface defects and adsorbed O2 and H2O, releasing sulfoxy species (e.g., S2O32‑, SO42‑) and ferrous iron (Fe2+) to the solution and also producing intermediate by-products, such as hydrogen peroxide (H2O2) and other reactive oxygen species (ROS), however, our understanding of the kinetics of these transient species is still limited. We investigated the kinetics of H2O2 formation in aqueous suspensions of FeS2 microparticles by monitoring, in real time, the H2O2 and dissolved O2 concentration under oxic and anoxic conditions using amperometric microsensors. Additional spectroscopic and structural analyses were done to track the dependencies between the process of FeS2 dissolution and the degradation of H2O2 through the Fenton reaction. Based on our experimental results, we built a kinetic model which explains the observed trend of H2O2, showing that FeS2 dissolution can act as a natural Fenton reagent, influencing the oxidation of third-party species during the long term evolution of geochemical systems, even in oxygen-limited environments.

  19. The influence of reagent dosage on the floatability of pyrite during coal flotation

    SciTech Connect

    Bonner, C.M.; Aplan, F.F.

    1993-01-01

    In general, as the quantity of frother and/or coal collector is increased, so too, does the flotation of the undesired pyrite. The problem is particularly serious with oil reagents. For some coals, however, a collector, such as fuel oil, is required to achieve a high coal recovery. This requires a compromise between the competing desires of a high coal recovery and a high pyrite rejection. This study gives the quantitative effect of reagent dosage on coal and pyrite floatability and details several means of minimizing pyrite floatability during coal flotation. The effect of fuel oil on coal flotation is especially interesting in that the flotation process changes from froth flotation to emulsion or agglomerative flotation as the amount of oil is increased. This phenomenon provides an additional method of rejecting pyritic sulfur.

  20. Remnant colloform pyrite at the haile gold deposit, South Carolina: A textural key to genesis

    USGS Publications Warehouse

    Foley, N.; Ayuso, R.A.; Seal, R.R.

    2001-01-01

    Auriferous iron sulfide-bearing deposits of the Carolina slate belt have distinctive mineralogical and textural features-traits that provide a basis to construct models of ore deposition. Our identification of paragenetically early types of pyrite, especially remnant colloform, crustiform, and layered growth textures of pyrite containing electrum and pyrrhotite, establishes unequivocally that gold mineralization was coeval with deposition of host rocks and not solely related to Paleozoic tectonic events. Ore horizons at the Haile deposit, South Carolina, contain many remnants of early pyrite: (1) fine-grained cubic pyrite disseminated along bedding; (2) fine- grained spongy, rounded masses of pyrite that may envelop or drape over pyrite cubes; (3) fragments of botryoidally and crustiform layered pyrite, and (4) pyritic infilling of vesicles and pumice. Detailed mineral chemistry by petrography, microprobe, SEM, and EDS analysis of replaced pumice and colloform structures containing both arsenic compositional banding and electrum points to coeval deposition of gold and the volcanic host rocks and, thus, confirms a syngenetic origin for the gold deposits. Early pyrite textures are present in other major deposits of the Carolina slate belt, such as Ridgeway and Barite Hill, and these provide strong evidence for models whereby the sulfide ores formed prior to tectonism. The role of Paleozoic metamorphism was to remobilize and concentrate gold and other minerals in structurally prepared sites. Recognizing the significance of paragenetically early pyrite and gold textures can play an important role in distinguishing sulfide ores that form in volcanic and sedimentary environments from those formed solely by metamorphic processes. Exploration strategies applied to the Carolina slate belt and correlative rocks in the eastern United States in the Avalonian basement will benefit from using syngenetic models for gold mineralization.

  1. 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.

  2. Accelerated biodegradation of cement by sulfur-oxidizing bacteria as a bioassay for evaluating immobilization of low-level radioactive waste.

    PubMed

    Aviam, Orli; Bar-Nes, Gabi; Zeiri, Yehuda; Sivan, Alex

    2004-10-01

    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 Ca(2+) and Si(2+), 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 Sr(2+) 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.

  3. 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

  4. Warburg Meets Autophagy: Cancer-Associated Fibroblasts Accelerate Tumor Growth and Metastasis via Oxidative Stress, Mitophagy, and Aerobic Glycolysis

    PubMed Central

    Pavlides, Stephanos; Vera, Iset; Gandara, Ricardo; Sneddon, Sharon; Pestell, Richard G.; Mercier, Isabelle; Martinez-Outschoorn, Ubaldo E.; Whitaker-Menezes, Diana; Howell, Anthony

    2012-01-01

    Abstract Significance: Here, we review certain recent advances in oxidative stress and tumor metabolism, which are related to understanding the contributions of the microenvironment in promoting tumor growth and metastasis. In the early 1920s, Otto Warburg, a Nobel Laureate, formulated a hypothesis to explain the “fundamental basis” of cancer, based on his observations that tumors displayed a metabolic shift toward glycolysis. In 1963, Christian de Duve, another Nobel Laureate, first coined the phrase auto-phagy, derived from the Greek words “auto” and “phagy,” meaning “self” and “eating.” Recent Advances: Now, we see that these two ideas (autophagy and aerobic glycolysis) physically converge in the tumor stroma. First, cancer cells secrete hydrogen peroxide. Then, as a consequence, oxidative stress in cancer-associated fibroblasts drives autophagy, mitophagy, and aerobic glycolysis. Critical Issues: This “parasitic” metabolic coupling converts the stroma into a “factory” for the local production of recycled and high-energy nutrients (such as L-lactate)—to fuel oxidative mitochondrial metabolism in cancer cells. We believe that Warburg and de Duve would be pleased with this new two-compartment model for understanding tumor metabolism. It adds a novel stromal twist to two very well-established cancer paradigms: aerobic glycolysis and autophagy. Future Directions: Undoubtedly, these new metabolic models will foster the development of novel biomarkers, and corresponding therapies, to achieve the goal of personalized cancer medicine. Given the central role that oxidative stress plays in this process, new powerful antioxidants should be developed in the fight against cancer. Antioxid. Redox Signal. 16, 1264–1284. PMID:21883043

  5. Extremely long nonradiative relaxation of photoexcited graphane is greatly accelerated by oxidation: time-domain ab initio study.

    PubMed

    Nelson, Tammie R; Prezhdo, Oleg V

    2013-03-06

    Graphane and its derivatives are stable and extremely thin, wide band gap semiconductors that promise to replace conventional semiconductors in electronics, catalysis, and energy applications, greatly reducing device size and power consumption. In order to be useful, band-gap excitations in these materials should be long lived and nonradiative energy losses to heat should be slow. We use state-of-the-art nonadiabatic molecular dynamics combined with time-dependent density functional theory in order to determine the nonradiative lifetime and radiative line width of the lowest energy singlet excitations in pure and oxidized graphanes. We predict that pure graphane has a very long nonradiative decay time, on the order of 100 ns, while epoxy- and hydroxy-graphanes lose electronic excitation energy to heat 10-20 times faster. The luminescence line width is 1.5 times larger in pristine graphane compared to its oxidized forms, and at room temperature, it is on the order of 50 meV. Hydroxylation lowers graphane's band gap, while epoxidation increases the gap. The nonradiative decay and luminescence line width of pure graphane are governed by electron coupling to the 1200 cm(-1) vibrational mode. In the oxidized forms of graphane, the electronic excitations couple to a broad range of vibrational modes, rationalizing the more rapid nonradiative decay in these systems. The slow electron-phonon energy losses in graphane compared to other graphene derivatives, such as carbon nanotubes and nanoribbons, indicate that graphanes are excellent candidates for semiconductor applications.

  6. Intermediates in assembly by photoactivation after thermally accelerated disassembly of the manganese complex of photosynthetic water oxidation.

    PubMed

    Barra, Marcos; Haumann, Michael; Loja, Paola; Krivanek, Roland; Grundmeier, Alexander; Dau, Holger

    2006-12-05

    The Mn4Ca complex bound to photosystem II (PSII) is the active site of photosynthetic water oxidation. Its assembly involves binding and light-driven oxidation of manganese, a process denoted as photoactivation. The disassembly of the Mn complex is a thermally activated process involving distinct intermediates. Starting from intermediate states of the disassembly, which was initiated by a temperature jump to 47 degrees C, we photoactivated PSII membrane particles and monitored the activity recovery by O2 polarography and delayed chlorophyll fluorescence measurements. Oxidation state and structural features of the formed intermediates of the Mn complex were assayed by X-ray absorption spectroscopy at the Mn K-edge. The photoactivation time courses, which exhibit a lag phase characteristic of intermediate formation only when starting with the apo-PSII, suggest that within approximately 5 min of photoactivation of apo-PSII, a binuclear Mn complex is formed. It is proposed that a MnIII2(di-mu-oxo) complex is a key intermediate both in the disassembly and in the assembly reaction paths.

  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. All inorganic iron pyrite nano-heterojunction solar cells

    NASA Astrophysics Data System (ADS)

    Kirkeminde, Alec; Scott, Randall; Ren, Shenqiang

    2012-11-01

    The large absorption coefficient of iron pyrite (FeS2) nanocrystals coupled with their low-cost and vast-abundance shows great promise as a potential photovoltaic absorber. Here, we demonstrate that bulk heterojunction (BHJ) nanostructures consisting of 80 nm FeS2 nanocubes (NCs) and 4 nm CdS quantum dot (QD) matrix, lead to a well-defined percolation network, which significantly improved open-circuit voltage (Voc) to 0.79 V and power conversion efficiency of 1.1% under AM 1.5 solar illumination. The localized surface plasmon resonances (LSPRs) arising from p-type colloidal FeS2 NCs exhibit plasmonic photoelectron conversion. Our approach can be applied to a wide range of colloidal nanocrystals exhibiting the LSPRs effect and is compatible with solution processing, thereby offering a general tactic to enhancing the efficiency of all inorganic BHJ solar cells and LSPRs-based NIR photodetectors.The large absorption coefficient of iron pyrite (FeS2) nanocrystals coupled with their low-cost and vast-abundance shows great promise as a potential photovoltaic absorber. Here, we demonstrate that bulk heterojunction (BHJ) nanostructures consisting of 80 nm FeS2 nanocubes (NCs) and 4 nm CdS quantum dot (QD) matrix, lead to a well-defined percolation network, which significantly improved open-circuit voltage (Voc) to 0.79 V and power conversion efficiency of 1.1% under AM 1.5 solar illumination. The localized surface plasmon resonances (LSPRs) arising from p-type colloidal FeS2 NCs exhibit plasmonic photoelectron conversion. Our approach can be applied to a wide range of colloidal nanocrystals exhibiting the LSPRs effect and is compatible with solution processing, thereby offering a general tactic to enhancing the efficiency of all inorganic BHJ solar cells and LSPRs-based NIR photodetectors. Electronic supplementary information (ESI) available. See DOI: 10.1039/c2nr32097e

  9. 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.

  10. 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.

  11. 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

  12. Constitutive gp130 activation rapidly accelerates the transformation of human hepatocytes via an impaired oxidative stress response

    PubMed Central

    Herden, Johannes; Parplys, Ann Christin; Borgmann, Kerstin; Schmidt-Arras, Dirk; Lohse, Ansgar W.; Rose-John, Stefan; Wege, Henning

    2016-01-01

    Pro-inflammatory signaling pathways, especially interleukin 6 (IL-6), and reactive oxygen species (ROS) promote carcinogenesis in the liver. In order to elucidate the underlying oncogenic mechanism, we activated the IL-6 signal transducer glycoprotein 130 (gp130) via stable expression of a constitutively active gp130 construct (L-gp130) in untransformed telomerase-immortalized human fetal hepatocytes (FH-hTERT). As known from hepatocellular adenomas, forced gp130 activation alone was not sufficient to induce malignant transformation. However, additional challenge of FH-hTERT L-gp130 clones with oxidative stress resulted in 2- to 3-fold higher ROS levels and up to 6-fold more DNA-double strand breaks (DSB). Despite increased DNA damage, ROS-challenged FH-hTERT L-gp130 clones displayed an enhanced proliferation and rapidly developed colony growth capabilities in soft agar. As driving gp130-mediated oncogenic mechanism, we detected a decreased expression of antioxidant genes, in particular glutathione peroxidase 3 and apolipoprotein E, and an absence of P21 upregulation following ROS-conferred induction of DSB. In summary, an impaired oxidative stress response in hepatocytes with gp130 gain-of-function mutations, as detected in dysplastic intrahepatic nodules and hepatocellular adenomas, is one of the central oncogenic mechanisms in chronic liver inflammation. PMID:27489351

  13. Accelerated migration and invasion of prostate cancer cells after a photodynamic therapy-like challenge: Role of nitric oxide.

    PubMed

    Fahey, Jonathan M; Girotti, Albert W

    2015-09-15

    Employing an in vitro model for 5-aminolevulinic acid (ALA)-based photodynamic therapy (PDT), we recently reported that human prostate cancer PC3 cells rapidly and persistently overexpressed inducible nitric oxide synthase (iNOS) and nitric oxide (NO) after a moderate ALA/light challenge. The upregulated iNOS/NO was shown to play a key role in cell resistance to apoptotic photokilling and also in the dramatic growth spurt observed in surviving cells. In the present study, we found that PC3 cells surviving an ALA/light insult not only proliferated faster than non-stressed controls, but migrated and invaded faster as well, these effects being abrogated by an iNOS inhibitor or NO scavenger. Photostressed prostate DU145 cells exhibited similar behavior. Using in-gel zymography, we showed that PC3 extracellular matrix metalloproteinase-9 (MMP-9) was strongly activated 24 h after ALA/light treatment and that MMP-9 inhibitor TIMP-1 was downregulated, consistent with MMP-9 involvement in enhanced invasiveness. We also observed a photostress-induced upregulation of α6 and β1 integrins, implying their involvement as well. The MMP-9, TIMP-1, and integrin effects were strongly attenuated by iNOS inhibition, confirming NO's role in photostress-enhanced migration/invasion. This study reveals novel, potentially tumor-promoting, side-effects of prostate cancer PDT which may be averted through use of iNOS inhibitors as PDT adjuvants.

  14. 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

  15. Macroscopic and X-ray photoelectron spectroscopic investigation of interactions of arsenic with synthesized pyrite.

    PubMed

    Kim, Eun Jung; Batchelor, Bill

    2009-04-15

    Interactions of arsenic with synthesized pyrite were investigated using macroscopic (solution phase experiments) and microscopic (X-ray photoelectron spectroscopic investigation) approaches. Arsenic removal by pyrite was strongly dependent on pH and arsenic species. Both arsenite (As(III)) and arsenate (As(V)) had a strong affinity for the pyrite surface under acidic conditions, but As(III) was more effectively removed than As(V). A BET isotherm equation provided the best fit to arsenic removal data, suggesting that surface precipitation occurred at a high arsenic/pyrite ratio. The addition of competing ions did not substantially affect the ultimate distribution of arsenic between the pyrite surface and the solution, but changing the pH affected arsenic stability on pyrite. X-ray photoelectron spectroscopy (XPS) revealed that under acidic conditions, arsenic was removed by reaction with pyrite to form solid phases similar to As2S3 and As4S4. However, under neutral to alkaline conditions, arsenic was removed by sorption and precipitation to form solid phases that are similar to FeAsS and As2S3/As4S4.

  16. 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.

  17. 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.

  18. 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.

  19. Synthesis, characterization, and variable range hopping transport of pyrite (FeS₂) nanorods, nanobelts, and nanoplates.

    PubMed

    Cabán-Acevedo, Miguel; Liang, Dong; Chew, Kit S; Degrave, John P; Kaiser, Nicholas S; Jin, Song

    2013-02-26

    We report the growth, structural, and electrical characterization of single-crystalline iron pyrite (FeS₂) nanorods, nanobelts, and nanoplates synthesized via sulfidation reaction with iron dichloride (FeCl₂) and iron dibromide (FeBr₂). The as-synthesized products were confirmed to be single-crystal phase pure cubic iron pyrite using powder X-ray diffraction, Raman spectroscopy, and transmission electron microscopy. An intermediate reaction temperature of 425 °C or a high sulfur vapor pressure under high temperatures was found to be critical for the formation of phase pure pyrite. Field effect transport measurements showed that these pyrite nanostructures appear to behave as a moderately p-doped semiconductor with an average resistivity of 2.19 ± 1.21 Ω·cm, an improved hole mobility of 0.2 cm² V⁻¹ s⁻¹, and a lower carrier concentration on the order of 10¹⁸-10¹⁹ cm⁻³ compared with previous reported pyrite nanowires. Temperature-dependent electrical transport measurements reveal Mott variable range hopping transport in the temperature range 40-220 K and transport via thermal activation of carriers with an activation energy of 100 meV above room temperature (300-400 K). Most importantly, the transport properties of the pyrite nanodevices do not change if highly pure (99.999%) precursors are utilized, suggesting that the electrical transport is dominated by intrinsic defects in pyrite. These single-crystal pyrite nanostructures are nice platforms to further study the carrier conduction mechanisms, semiconductor defect physics, and surface properties in depth, toward improving the physical properties of pyrite for efficient solar energy conversion.

  20. Formation of n-type pyrite films from electrodeposited iron sulphides: effect of annealing temperature

    SciTech Connect

    Gomes, A.; Ares, J.R.; Ferrer, I.J.; Silva Pereira, M.I. da; Sanchez, C

    2003-06-19

    The n-type polycrystalline pyrite films were obtained by annealing mackinawite electrodeposited on metallic titanium substrates in sulphur atmosphere in the temperature range 523-773 K. The detailed structural and morphological characterisation of the films shows that an increase of crystallite size and a porosity decrease was achieved by increasing the sulphuration temperature. The measurement of thermoelectric effect indicates that pyrite films present n-type conduction, which is attributed to the diffusion of Ti atoms from the substrate. The Seebeck coefficient varies from -54 to -24 {mu}V/K, depending on pyrite grain size.

  1. A sulfur isotope study of pyrite genesis: The mid-proterozoic Newland formation, belt supergroup, Montana

    NASA Astrophysics Data System (ADS)

    Strauss, Harald; Schieber, Jürgen

    1990-01-01

    Different generations of sedimentary pyrite from the Mid-Proterozoic Newland Formation, USA, have been analysed for their sulfur isotopic compositions. The results indicate bacterial sulfate reduction as the pyrite forming process. The δ 34S values for early diagenetic pyrite, around -14%., are in contrast to dominantly more positive values for many other Middle Proterozoic units. A progressive reduction of sulfate availability during diagenesis can be recognized by an increase in 34S content (Rayleigh Distillation) as well as through detailed petrographic observations. Contemporaneous seawater had a sulfur isotopic ratio between +14 and +18%. as measured from sedimentary barite within the unit.

  2. 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

  3. Pyrite and organic matter in normal marine sediments of Middle Cambrian age, southern Georgina Basin, Australia

    SciTech Connect

    Donnelly, T.H.; Shergold, J.H.; Southgate, P.N.

    1988-02-01

    Normal marine sedimentary rocks of Middle Cambrian, Floran-Undillan, age from the southern Georgina Basin have pyrite S/organic C ratios with a mean value of 0.65 and show a significant positive correlations with an extension of the line of best fit through zero. The S/C ratio of 0.65 determined in this study is close to the mean ratio for all Cambrian sediments of 0.7, but differs markedly from the recently reported S/C ratio of 2 for normal marine early Paleozoic rocks mainly from the United Kingdom. The variations shown by these figures indicate that if the oxidation state of the crust-ocean-atmosphere over geological time is to be fully understood, and related to possible world-wide trends, further assessment of early Paleozoic sulfur and carbon burial rates is needed. Furthermore, as S/C burial rates are known to vary, the ages of the sediments being analyzed need to be more precisely known.

  4. Composition and spectra of copper-carotenoid sediments from a pyrite mine stream in Spain.

    PubMed

    Garcia-Guinea, Javier; Furio, Marta; Sanchez-Moral, Sergio; Jurado, Valme; Correcher, Virgilio; Saiz-Jimenez, Cesareo

    2015-01-25

    Mine drainages of La Poderosa (El Campillo, Huelva, Spain), located in the Rio Tinto Basin (Iberian Pyrite Belt) generate carotenoid complexes mixed with copper sulfates presenting good natural models for the production of carotenoids from microorganisms. The environmental conditions of Rio Tinto Basin include important environmental stresses to force the microorganisms to accumulate carotenoids. Here we show as carotenoid compounds in sediments can be analyzed directly in the solid state by Raman and Luminescence spectroscopy techniques to identify solid carotenoid, avoiding dissolution and pre-concentration treatments, since the hydrous copper-salted paragenesis do not mask the Raman emission of carotenoids. Raman spectra recorded from one of these specimens' exhibit major features at approximately 1006, 1154, and 1520 cm(-1). The bands at 1520 cm(-1) and 1154 cm(-1) can be assigned to in-phase C=C (γ(-1)) and C-C stretching (γ(-2)) vibrations of the polyene chain in carotenoids. The in-plane rocking deformations of CH3 groups linked to this chain coupled with C-C bonds are observed in the 1006 cm(-1) region. X-irradiation pretreatments enhance the cathodoluminescence spectra emission of carotenoids enough to distinguish organic compounds including hydroxyl and carboxyl groups. Carotenoids in copper-sulfates could be used as biomarkers and useful proxies for understanding remote mineral formations as well as for terrestrial environmental investigations related to mine drainage contamination including biological activity and photo-oxidation processes.

  5. 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.

  6. 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

  7. 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

  8. Aerobic and Anaerobic Thiosulfate Oxidation by a Cold-Adapted, Subglacial Chemoautotroph.

    PubMed

    Harrold, Zoë R; Skidmore, Mark L; Hamilton, Trinity L; Desch, Libby; Amada, Kirina; van Gelder, Will; Glover, Kevin; Roden, Eric E; Boyd, Eric S

    2015-12-28

    Geochemical data indicate that protons released during pyrite (FeS2) oxidation are important drivers of mineral weathering in oxic and anoxic zones of many aquatic environments, including those beneath glaciers. Oxidation of FeS2 under oxic, circumneutral conditions proceeds through the metastable intermediate thiosulfate (S2O3 (2-)), which represents an electron donor capable of supporting microbial metabolism. Subglacial meltwaters sampled from Robertson Glacier (RG), Canada, over a seasonal melt cycle revealed concentrations of S2O3 (2-) that were typically below the limit of detection, despite the presence of available pyrite and concentrations of the FeS2 oxidation product sulfate (SO4 (2-)) several orders of magnitude higher than those of S2O3 (2-). Here we report on the physiological and genomic characterization of the chemolithoautotrophic facultative anaerobe Thiobacillus sp. strain RG5 isolated from the subglacial environment at RG. The RG5 genome encodes genes involved with pathways for the complete oxidation of S2O3 (2-), CO2 fixation, and aerobic and anaerobic respiration with nitrite or nitrate. Growth experiments indicated that the energy required to synthesize a cell under oxygen- or nitrate-reducing conditions with S2O3 (2-) as the electron donor was lower at 5.1°C than 14.4°C, indicating that this organism is cold adapted. RG sediment-associated transcripts of soxB, which encodes a component of the S2O3 (2-)-oxidizing complex, were closely affiliated with soxB from RG5. Collectively, these results suggest an active sulfur cycle in the subglacial environment at RG mediated in part by populations closely affiliated with RG5. The consumption of S2O3 (2-) by RG5-like populations may accelerate abiotic FeS2 oxidation, thereby enhancing mineral weathering in the subglacial environment.

  9. 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

  10. Phase-pure iron pyrite nanocrystals for low-cost photodetectors.

    PubMed

    Liu, Shenting; Wu, Jiang; Yu, Peng; Ding, Qinghua; Zhou, Zhihua; Li, Handong; Lai, Chih-Chung; Chueh, Yu-Lun; Wang, Zhiming M

    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 (>10(5) 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.

  11. A unifying model for Neoproterozoic-Palaeozoic exceptional fossil preservation through pyritization and carbonaceous compression.

    PubMed

    Schiffbauer, James D; Xiao, Shuhai; Cai, Yaoping; Wallace, Adam F; Hua, Hong; Hunter, Jerry; Xu, Huifang; Peng, Yongbo; Kaufman, Alan J

    2014-12-17

    Soft-tissue fossils capture exquisite biological detail and provide our clearest views onto the rise of animals across the Ediacaran-Cambrian transition. The processes contributing to fossilization of soft tissues, however, have long been a subject of debate. The Ediacaran Gaojiashan biota displays soft-tissue preservational styles ranging from pervasive pyritization to carbonaceous compression, and thus provides an excellent opportunity to dissect the relationships between these taphonomic pathways. Here geochemical analyses of the Gaojiashan fossil Conotubus hemiannulatus show that pyrite precipitation was fuelled by the degradation of labile tissues through bacterial sulfate reduction (BSR). Pyritization initiated with nucleation on recalcitrant tube walls, proceeded centripetally, decelerated with exhaustion of labile tissues and possibly continued beneath the BSR zone. We propose that pyritization and kerogenization are regulated principally by placement and duration of the decaying organism in different microbial zones of the sediment column, which hinge on post-burial sedimentation rate and/or microbial zone thickness.

  12. 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

  13. 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

  14. Chalcophile Siderophile Trace Element Systematics of Hydrothermal Pyrite from Martian Regolith Breccia NWA 7533

    NASA Astrophysics Data System (ADS)

    Lorand, J.-P.; Hewins, R. H.; Humayun, M.; Remusat, L.; Zanda, B.; La, C.; Pont, S.

    2016-08-01

    Martian impact breccia NWA 7533 contains hydrothermal pyrite. Laser ablation ICPMS analyses show that its chalcophile siderophile element content was inherited from both early meteorite bombardment and later hydrothermal inputs from H2S fluids.

  15. The 57Fe Mössbauer parameters of pyrite and marcasite with different provenances

    USGS Publications Warehouse

    Evans, B.J.; Johnson, R.G.; Senftle, F.E.; Cecil, C.B.; Dulong, F.

    1982-01-01

    The Mössbauer parameters of pyrite and marcasite exhibit appreciable variations, which bear no simple relationship to the geological environment in which they occur but appear to be selectively influenced by impurities, especially arsenic, in the pyrite lattice. Quantitative and qualitative determinations of pyrite/marcasite mechanical mixtures are straightforward at 298 K and 77 K but do require least-squares computer fittings and are limited to accuracies ranging from ±5 to ±15 per cent by uncertainties in the parameter values of the pure phases. The methodology and results of this investigation are directly applicable to coals for which the presence and relative amounts of pyrite and marcasite could be of considerable genetic significance.

  16. 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

  17. Future accelerators (?)

    SciTech Connect

    John Womersley

    2003-08-21

    I describe the future accelerator facilities that are currently foreseen for electroweak scale physics, neutrino physics, and nuclear structure. I will explore the physics justification for these machines, and suggest how the case for future accelerators can be made.

  18. Structure of selenium incorporated in pyrite and mackinawite as determined by XAFS analyses.

    PubMed

    Diener, A; Neumann, T; Kramar, U; Schild, D

    2012-05-15

    Selenium has a toxic potential leading to diseases by ingestion and a radiotoxic potential as (79)Se 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 Se(2-) and Se(4+) 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 Se(2-) 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 S(2-) was substituted by Se(2-), 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 Se(2-) and Se(4+) predominantly as Se(0). 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, Se(0) is expected to be the most stable species.

  19. 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.

  20. 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.