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Sample records for metastable iron sulfide

  1. Iron-sulfide redox flow batteries

    SciTech Connect

    Xia, Guan-Guang; Yang, Zhenguo; Li, Liyu; Kim, Soowhan; Liu, Jun; Graff, Gordon L

    2013-12-17

    Iron-sulfide redox flow battery (RFB) systems can be advantageous for energy storage, particularly when the electrolytes have pH values greater than 6. Such systems can exhibit excellent energy conversion efficiency and stability and can utilize low-cost materials that are relatively safer and more environmentally friendly. One example of an iron-sulfide RFB is characterized by a positive electrolyte that comprises Fe(III) and/or Fe(II) in a positive electrolyte supporting solution, a negative electrolyte that comprises S.sup.2- and/or S in a negative electrolyte supporting solution, and a membrane, or a separator, that separates the positive electrolyte and electrode from the negative electrolyte and electrode.

  2. Iron-sulfide redox flow batteries

    DOEpatents

    Xia, Guanguang; Yang, Zhenguo; Li, Liyu; Kim, Soowhan; Liu, Jun; Graff, Gordon L

    2016-06-14

    Iron-sulfide redox flow battery (RFB) systems can be advantageous for energy storage, particularly when the electrolytes have pH values greater than 6. Such systems can exhibit excellent energy conversion efficiency and stability and can utilize low-cost materials that are relatively safer and more environmentally friendly. One example of an iron-sulfide RFB is characterized by a positive electrolyte that comprises Fe(III) and/or Fe(II) in a positive electrolyte supporting solution, a negative electrolyte that comprises S.sup.2- and/or S in a negative electrolyte supporting solution, and a membrane, or a separator, that separates the positive electrolyte and electrode from the negative electrolyte and electrode.

  3. Sulfidation of iron at high temperatures and diffusion kinetics in ferrous sulfide

    SciTech Connect

    Danielewski, M.; Mrowec, S.; Stoklosa, A.

    1982-02-01

    The kinetics and mechanism of iron sulfidation have been studied as a function of temperature (950-1200 K) and sulfur pressure (10/sup -3/ 0.065 atm). It has been stated that a compact Fe/sub 1-y/ S scale on iron grows according to the parabolic rate law as a result of outward lattice diffusion of metal ions through cation vacancies. The activation energy of sulfidation increases with sulfur pressure and the 1/n exponent increases with temperature. This nontypical dependence of iron sulfidation kinetics on temperature and pressure results from the analogous effect of both these parameters on defect concentration in ferrous sulfide. The chemical diffusion coefficients, D/sub FeS/ , and diffusion coefficients of defects, D/sub d/ , in ferrous sulfide have been calculated on the basis of parabolic rate contacts of iron sulfidation and deviations from stoichiometry in ferrous sulfide. It has been shown that D/sub FeS/ is practically independent of cation vacancy concentration whereas the diffusion coefficient of defects depends strongly on that parameter. A comparison of self-diffusion coefficients of iron in Fe/sub 1-y/ S calculated from the kinetics of iron sulfidation to those obtained from radioisotopic studies indicates that within the range studied of temperatures and sulfur vapor pressures the outward diffusion of iron across the scale occurs preferentially along the c axis of columnar ferrous sulfide crystals.

  4. Physical and microstructural aspects of iron sulfide degradation in concrete

    SciTech Connect

    Schmidt, Thomas; Gallucci, Emanuel; Scrivener, Karen

    2011-03-15

    The microstructural aspects of iron sulfide degradation in dam concrete were investigated by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) in both dam concrete samples and laboratory concrete. The results show that iron sulfide inclusions with a diameter of a few micrometers in the aggregates are reactive and appear to generate expansion first in the aggregates and consequently in the cement paste. The expansion from the iron sulfides is a consequence of the increase in volume of the reaction products formed. The types of iron sulfide present in the aggregate, mainly pyrrhotite (FeS) and pyrite (FeS{sub 2}), show similar reaction behavior in the aggregates. The released sulfate can lead to a secondary ettringite formation in the concrete matrix, but the degradation associated with this appears to be minor. The reaction of the iron sulfides was found to be very slow even when laboratory samples were exposed to elevated temperatures.

  5. Influence of iron on sulfide inhibition in dark biohydrogen fermentation.

    PubMed

    Dhar, Bipro Ranjan; Elbeshbishy, Elsayed; Nakhla, George

    2012-12-01

    Sulfide impact on biohydrogen production using dark fermentation of glucose at 37 °C was investigated. Dissolved sulfide (S(2-)) at a low concentration (25mg/L) increased biohydrogen production by 54% relative to the control (without iron addition). Whereas on initial dissolved S(2-) concentration of 500 mg/L significantly inhibited the biohydrogen production with total cumulative biohydrogen decreasing by 90% compared to the control (without iron addition). At sulfide concentrations of 500 mg S(2-)/L, addition of Fe(2+) at 3-4 times the theoretical requirement to precipitate 100% of the dissolved S(2-) entirely eliminated the inhibitory effect of sulfide.

  6. The Sulfide Capacity of Iron Oxide-Rich Slags

    NASA Astrophysics Data System (ADS)

    Motlagh, M.

    1988-03-01

    The relationship between the sulfide capacity of slags rich in iron oxide and the sulfur partition ratio between the metal and slag is strongly related to the slag's iron oxide concentration. For slags containing little or no lime, this relationship is linear for a constant concentration of iron oxide in the slag. The effect of silica on changes in the sulfide capacity of slags rich in iron oxide is similar to that of basic steel-making slags, particularly at low activity of silica in slag.

  7. Enhanced reductive dechlorination of trichloroethylene by sulfidated nanoscale zerovalent iron.

    PubMed

    Rajajayavel, Sai Rajasekar C; Ghoshal, Subhasis

    2015-07-01

    Direct injection of reactive nanoscale zerovalent iron particles (NZVI) is considered to be a promising approach for remediation of aquifers contaminated by chlorinated organic pollutants. In this study we show that the extent of sulfidation of NZVI enhances the rate of dechlorination of trichloroethylene (TCE) compared to that by unamended NZVI, and the enhancement depends on the Fe/S molar ratio. Experiments where TCE was reacted with NZVI sulfidated to different extents (Fe/S molar ratios 0.62-66) showed that the surface-area normalized first-order TCE degradation rate constant increased up to 40 folds compared to non-sulfidated NZVI. Fe/S ratios in the range of 12-25 provided the highest TCE dechlorination rates, and rates decreased at both higher and lower Fe/S. In contrast, sulfidated NZVI exposed to water in the absence of TCE showed significantly lower hydrogen evolution rate (2.75 μmol L(-1) h(-1)) compared to that by an unamended NZVI (6.92 μmol L(-1) h(-1)), indicating that sulfidation of NZVI suppressed corrosion reactions with water. Sulfide (HS(-)) ions reacted rapidly with NZVI and X-ray photoelectron spectroscopy analyses showed formation of a surface layer of FeS and FeS2. We propose that more electrons are preferentially conducted from sulfidated NZVI than from unamended NZVI to TCE, likely because of greater binding of TCE on the reactive sites of the iron sulfide outer layer. Resuspending sulfidated NZVI in sulfide-free or sulfide containing solutions altered the TCE degradation rate constants because of changes in the FeS layer thickness. Sulfidated NZVI maintained its high reactivity in the presence of multiple mono and divalent ions and with polyelectrolyte coatings. Thus, sulfide ions in groundwater can significantly alter NZVI reactivity.

  8. Adsorption of hydrogen sulfide on montmorillonites modified with iron.

    PubMed

    Nguyen-Thanh, Danh; Block, Karin; Bandosz, Teresa J

    2005-04-01

    Sodium-rich montmorillonite was modified with iron in order to introduce active centers for hydrogen sulfide adsorption. In the first modification, interlayer sodium cations were exchanged with iron. In another modification, iron oxocations were introduced to the clay surface. The most elaborated modification was based on doping of iron within the interlayer space of aluminum-pillared clay. The modified clay samples were tested as hydrogen sulfide adsorbents. Iron-doped samples showed a significant improvement in the capacity for H2S removal, despite of a noticeable decrease in microporosity compared to the initial pillared clay. The smallest capacity was obtained for the clay modified with iron oxocations. Variations in adsorption capacity are likely due to differences in the chemistry of iron species, degree of their dispersion on the surface, and accessibility of small pores for H2S molecule. The results suggest that on the surface of iron-modified clay hydrogen sulfide reacts with Fe(+3) forming sulfides or it is catalytically oxidized to SO2 on iron (hydro)oxides. Subsequent oxidation may lead to sulfate formation.

  9. Comparison of Carbon XANES Spectra from an Iron Sulfide from Comet Wild 2 with an Iron Sulfide Interplanetary Dust Particle

    NASA Technical Reports Server (NTRS)

    Wirick, S.; Flynn, G. J.; Keller, L. P.; Sanford, S. A.; Zolensky, M. E.; Messenger, Nakamura K.; Jacobsen, C.

    2008-01-01

    Among one of the first particles removed from the aerogel collector from the Stardust sample return mission was an approx. 5 micron sized iron sulfide. The majority of the spectra from 5 different sections of this particle suggests the presence of aliphatic compounds. Due to the heat of capture in the aerogel we initially assumed these aliphatic compounds were not cometary but after comparing these results to a heated iron sulfide interplanetary dust particle (IDP) we believe our initial interpretation of these spectra was not correct. It has been suggested that ice coating on iron sulfides leads to aqueous alteration in IDP clusters which can then lead to the formation of complex organic compounds from unprocessed organics in the IDPs similar to unprocessed organics found in comets [1]. Iron sulfides have been demonstrated to not only transform halogenated aliphatic hydrocarbons but also enhance the bonding of rubber to steel [2,3]. Bromfield and Coville (1997) demonstrated using Xray photoelectron spectroscopy that "the surface enhancement of segregated sulfur to the surface of sulfided precipitated iron catalysts facilitates the formation of a low-dimensional structure of extraordinary properties" [4]. It may be that the iron sulfide acts in some way to protect aliphatic compounds from alteration due to heat.

  10. Lithium-aluminum/iron sulfide batteries

    NASA Astrophysics Data System (ADS)

    Henriksen, G. L.; Vissers, D. R.

    Lithium-alloy/metal sulfide batteries have been under development at Argonne National Laboratory since 1972. ANL's technology employs a two-phase Li alloy negative electrode, low-melting point LiCl-rich LiCl-LiBr-KBr molten salt electrolyte, and either an FeS or an upper-plateau (UP) FeS 2 positive electrode. These components are assembled in an 'electrolyte-starved' bipolar cell configuration. Use of the multi-phase Li alloy ((α+β)-Li-Al and Li 5Al 5Fe 2) negative electrode provides in situ overcharge tolerance that renders the bipolar design viable. Employing LiCl-rich LiCl-LiBr-KBr electrolyte is 'electrolyte-starved" cells achieves low-burdened cells that possess low area-specific impedance, comparable with that of flooded cells using LiCl-LiBr-KBr eutectic electrolyte. The combination of dense UP FeS 2 electrodes and low-melting electrolyte produces a stable and reversible couple, achieving over 1000 cycles in flooded cells, with high power capabilities. In addition, a new class of stable chalcogenide ceramic/sealant materials was developed. These materials produce high-strength bonds between a variety of metals and ceramics, which make fabrication of lithium/iron sulfide bipolar stacks practical. Bipolar Li-Al/FeS and Li-Al/FeS 2 cells and four-cell stacks using these seals have been built and tested for electric vehicle (EV) applications. When cell performance characteristics are used to model full-scale EV ad hybrid vehicle (HV) batteries, they are projected to meet or exceed the performance requirements for a large variety of EV and HV applications. In 1992, the US Advanced Battery Consortium awarded contracts to ANL and SAFT America to continue the development of the bipolar Li-Al/FeS 2 battery to meet their long-term criteria. Both ANL and sAFT are working together to refine this technology for EV applications and scale it up to larger stacks and fully integrated battery modules.

  11. Removal of copper from carbon-saturated steel with an aluminum sulfide/iron sulfide slag

    SciTech Connect

    Cohen, A.; Blander, M.

    1995-12-01

    Scrap iron and steel has long been considered a resource in the steel-making industry, and its value is largely determined by its impurity content. As the mini-mills, the major consumers of scrap iron and steel, expand into producing flat-rolled sheet, the demand for high-quality scrap will increase. Of the impurities present in scrap, copper is particularly troublesome because of its role in causing hot shortness. Therefore, the copper content of scrap should be kept below {approx} 0.1 wt%. A method for removing copper from steel could be used to improve the quality of scrap and make it more available for use by mini-mills. To determine the effectiveness of a binary slag consisting of aluminum sulfide and iron sulfide on the removal of copper from steel and iron, the distribution coefficient of copper between the slag and a carbon-saturated iron melt was investigated at 1,365 C. The composition of the slag was varied from nearly pure aluminum sulfide to pure iron sulfide. A maximum distribution coefficient of 30 was found, and the copper level in the iron melt was reduced to as low as 0.07 wt.% with a 4:1 ratio of iron to slag.

  12. Iron sulfide deposits at Wadi Wassat, Kingdom of Saudi Arabia

    USGS Publications Warehouse

    Roberts, R.J.; Rossman, D.L.; Bagdady, A.Y.; Conway, C.M.; Helaby, A.M.

    1981-01-01

    Massive and disseminated iron sulfide deposits in Wadi Wassat form lenticular, stratabound deposits in cherty Precambrian sedimentary rocks interlayered with Precambrian calcareous sedimentary rocks, pyroclastic rocks, and andesitic flow rocks. These rocks have been cut by a wide variety of plutonic and dike rocks including gabbro, diorite, granodiorite, diabase, rhyolite, and granite. The zone containing the sulfide lenses is nearly 16 km long and is cut off by granitic rocks at both the northern and southern ends. The lenses are as much as 200 m thick; one can be traced along strike for more than 4 km. The lenses consist mostly of iron sulfides. Pyrite is the principal sulfide mineral; near intrusive bodies the pyrite has been partially converted to pyrrhotite and locally mobilized into fractures. The sulfides have been oxidized to a depth of about 25 m. Preliminary calculations indicate that about 107,500,000 tons of sulfides, averaging 40 percent iron and 35 percent sulfur, are available to a depth of i00 m. Small amounts of nickel, cobalt, zinc, and copper are also present, but at metal prices prevailing in early 1981, these do not constitute significant resources.

  13. Penning ionization electron spectroscopy of hydrogen sulfide by metastable helium and neon atoms.

    PubMed

    Falcinelli, Stefano; Candori, Pietro; Bettoni, Marta; Pirani, Fernando; Vecchiocattivi, Franco

    2014-08-21

    The dynamics of the Penning ionization of hydrogen sulfide molecules by collision with helium and metastable neon atoms, occurring in the thermal energy range, has been studied by analyzing the energy spectra of the emitted electrons obtained in our laboratory in a crossed beam experiment. These spectra are compared with the photoelectron spectra measured by using He(I) and Ne(I) photons under the same experimental conditions. In this way we obtained the negative energy shifts for the formation of H2S(+) ions in the first three accessible electronic states by He*(2(3,1)S1,0) and Ne*((3)P2,0) Penning ionization collisions: the 2b1 (X̃(2)B1) fundamental one, the first 5a1 (Ã(2)A1), and the second 2b2 (B̃(2)B2) excited states, respectively. The recorded energy shifts indicate that in the case of He* and Ne*-H2S the autoionization dynamics depends on the features of the collision complex and is mainly driven by an effective global attraction that comes from a balance among several non covalent intermolecular interaction components. This suggests that the Penning ionization should take place, in a specific range of intermolecular distances, as we have already observed in the case of Penning ionization of water molecules [Brunetti, B. G.; Candori, P.; Falcinelli, S.; Pirani, F.; Vecchiocattivi, F. J. Chem. Phys. 2013, 139, 164305-1-164305-8].

  14. Improved cleaning method safely removes pyrophoric iron sulfide

    SciTech Connect

    Vella, P.A.

    1997-02-24

    Refinery process and storage equipment often becomes contaminated with pyrophoric iron sulfide and various odor-causing materials. Traditionally, refiners have used mechanical or chemical methods for removing and controlling these contaminants. With increased focus on safety, efficiency, and the environment, however, new methods for equipment cleaning are required. Potassium permanganate, long used for industrial odor control, is finding increased acceptance among refiners for the destruction of pyrophoric iron sulfide and odorous compounds. A number of facilities have found that use of potassium permanganate results in increased productivity, improved safety, and significant cost savings. The paper describes the process and gives two examples of its use.

  15. Impact of Iron Sulfide Transformation on Trichloroethylene Degradation

    EPA Science Inventory

    Trichloroethylene (TCE) is one of the most common and persistent groundwater contaminants encountered at hazardous waste sites around the world. A growing body of evidence indicates that iron sulfides play an important role in degrading TCE in natural environments and in enginee...

  16. A new nanoscale metastable iron phase in carbon steels

    PubMed Central

    Liu, Tianwei; Zhang, Danxia; Liu, Qing; Zheng, Yanjun; Su, Yanjing; Zhao, Xinqing; Yin, Jiang; Song, Minghui; Ping, Dehai

    2015-01-01

    Metastable ω phase is common in body-centred cubic (bcc) metals and alloys, including high-alloying steels. Recent theoretical calculations also suggest that the ω structure may act as an intermediate phase for face-centred cubic (fcc)-to-bcc transformation. Thus far, the role of the ω phase played in fcc-bcc martensitic transformation in carbon steels has not been reported. In previous investigations on martensitic carbon steels, extra electron diffraction spots were frequently observed by transmission electron microscopy (TEM), and these spots were historically ascribed to the diffraction arising from either internal twins or carbides. In this paper, an intensive TEM investigation revealed that the extra spots are in fact attributed to the metastable ω phase in particle-like morphology with an overall size of several or dozens of nanometres. The strict orientation relationships between the ω phase and the ferrite matrix are in good agreement with those of the hexagonal (P6/mmm) ω phase in other bcc metals and alloys. The identification of the ω phase as well as the extra diffraction spots might provide a clue to help understand the physical mechanism of martensitic transformation in steels. PMID:26503890

  17. Physical properties of superconducting single crystal iron sulfide

    NASA Astrophysics Data System (ADS)

    Rodriguez, Efrain E.; Borg, Christopher K. H.; Zhou, Xiuquan; Paglione, Johnpierre; University of Maryland Collaboration

    Recently, the simple binary tetragonal iron sulfide, FeS, was found to be a superconductor with a Tc = 5 K. We have prepared single crystals of tetragonal iron sulfide through hydrothermal de-intercalation of KxFe2-yS2. The KxFe2-yS2 single crystal precursors were grown by slow cooling of stoichiometric melts of K, Fe and S. The silver, plate-like FeS single crystals were highly crystalline with a superconducting transition temperature (Tc) of 4 K. The high quality of the FeS crystals revealed highly anisotropic nature of the magnetic and electronic properties intrinsic to FeS. The physical properties and thermal stability of single crystal FeS will be discussed in detail.

  18. Uniform yolk-shell iron sulfide–carbon nanospheres for superior sodium–iron sulfide batteries

    PubMed Central

    Wang, Yun-Xiao; Yang, Jianping; Chou, Shu-Lei; Liu, Hua Kun; Zhang, Wei-xian; Zhao, Dongyuan; Dou, Shi Xue

    2015-01-01

    Sodium–metal sulfide battery holds great promise for sustainable and cost-effective applications. Nevertheless, achieving high capacity and cycling stability remains a great challenge. Here, uniform yolk-shell iron sulfide–carbon nanospheres have been synthesized as cathode materials for the emerging sodium sulfide battery to achieve remarkable capacity of ∼545 mA h g−1 over 100 cycles at 0.2 C (100 mA g−1), delivering ultrahigh energy density of ∼438 Wh kg−1. The proven conversion reaction between sodium and iron sulfide results in high capacity but severe volume changes. Nanostructural design, including of nanosized iron sulfide yolks (∼170 nm) with porous carbon shells (∼30 nm) and extra void space (∼20 nm) in between, has been used to achieve excellent cycling performance without sacrificing capacity. This sustainable sodium–iron sulfide battery is a promising candidate for stationary energy storage. Furthermore, this spatially confined sulfuration strategy offers a general method for other yolk-shell metal sulfide–carbon composites. PMID:26507613

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

    NASA Astrophysics Data System (ADS)

    Personna, Yves Robert; Ntarlagiannis, Dimitrios; Slater, Lee; Yee, Nathan; O'Brien, Michael; Hubbard, Susan

    2008-06-01

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

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

    SciTech Connect

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

    2008-02-15

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

  1. Formation, stability, and reactivity studies of neutral iron sulfide clusters

    NASA Astrophysics Data System (ADS)

    Yin, Shi; Wang, Zhechen; Bernstein, Elliot

    2014-03-01

    Different methods are used to generate neutral iron sulfide clusters to study their formation, stability, and reactivity, employing a time of flight mass spectrometer (TOFMS) with VUV (118 nm) radiation single photon ionization (SPI). Neutral FemSn (m = 1-4, n = 1-6), and hydrogen containing FemSnHx (x >0, n > m) clusters are generated by the reaction of seeded H2S in a helium carrier gas with laser ablated iron metal within a supersonic nozzle. The observed strong signal of association products Fe2S2(SH)0,1 M (M = CO, C2H4, C3H6) suggest that the Fe2S2(SH)0,1 clusters have the high activity for interactions with these small molecules. In order to avoid the effect for reactivity from hydrogen containing clusters, pure FemSnclusters are generated through laser ablation of a mixed iron/sulfur target in the presence of a pure helium carrier gas. (FeS)m (m = 1-4) is observed to be the most stable series. Reaction of CO and H2 on neutral (FeS)1,2clusters is farther investigated both experimentally and theoretically. A size dependent reactivity of iron sulfide clusters toward CO is characterized. The reaction FeS + CO --> Fe + OCS is found for the FeS cluster. Products Fe2S 213COH2 and Fe2S 213COH4 are identified for reactions of 13CO and H2 on Fe2S2 clusters: this suggests that the Fe2S2 cluster has a high catalytic activity for hydrogenation reactions of CO to form formaldehyde and methanol. DFT calculations are performed to explore the potential energy surfaces for the two reactions: Fe2S2 + CO + 2H2 --> Fe2S2 + CH3OH; and Fe2S2 + CO + H2 --> Fe2S2 + CH2O.

  2. Arsenic Bioremediation by Biogenic Iron Oxides and Sulfides

    PubMed Central

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

    2013-01-01

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

  3. Arsenic bioremediation by biogenic iron oxides and sulfides.

    PubMed

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

    2013-07-01

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

  4. Synthesis of metastable rare-earth-iron mixed oxide with the hexagonal crystal structure

    SciTech Connect

    Nishimura, Tatsuya; Hosokawa, Saburo; Masuda, Yuichi; Wada, Kenji; Inoue, Masashi

    2013-01-15

    Rare-earth-iron mixed oxides with the rare earth/iron ratio=1 have either orthorhombic (o-REFeO{sub 3}) or hexagonal (h-REFeO{sub 3}) structure. h-REFeO{sub 3} is a metastable phase and the synthesis of h-REFeO{sub 3} is usually difficult. In this work, the crystallization process of the precursors obtained by co-precipitation and Pechini methods was investigated in detail to synthesize h-REFeO{sub 3}. It was found that the crystallization from amorphous to hexagonal phase and the phase transition from hexagonal to orthorhombic phase occurred at a similar temperature range for rare earth elements with small ionic radii (Er-Lu, Y). For both co-precipitation and Pechini methods, single-phase h-REFeO{sub 3} was obtained by shortening the heating time during calcination process. The hexagonal-to-orthorhombic phase transition took place by a nucleation growth mechanism and vermicular morphology of the thus-formed orthorhombic phase was observed. The hexagonal YbFeO{sub 3} had higher catalytic activity for C{sub 3}H{sub 8} combustion than orthorhombic YbFeO{sub 3}. - Graphical abstract: Although the synthesis of metastable hexagonal REFeO{sub 3} by the conventional method is difficult, we found that this phase is obtained by shortening the heating time of the precursor prepared by co-precipitation method. Highlights: Black-Right-Pointing-Pointer Synthesis of metastable REFeO{sub 3} with hexagonal structure by the co-precipitation method. Black-Right-Pointing-Pointer Hexagonal REFeO{sub 3} is obtained for the rare earth elements with small ionic radii. Black-Right-Pointing-Pointer Hexagonal-to-orthorhombic transformation of REFeO{sub 3}. Black-Right-Pointing-Pointer Catalytic activity of hexagonal REFeO{sub 3} for C{sub 3}H{sub 8} combustion.

  5. Geomicrobiological Regeneration of Iron Sulfides in Engineered barrier Systems

    NASA Astrophysics Data System (ADS)

    Vannela, R.; Adriaens, P.; Hayes, K. F.

    2005-12-01

    The reactive capacity of iron sulfide-based permeable reactive barriers (PRB) to complex and co-precipitate heavy metal ions from groundwater will depend on the potential for regeneration of reactive FeS during the expected lifetime of the PRB. FeS reactivity may decrease in a PRB in time as the result of the following processes: (i) oxidation of FeS and the formation of ferric iron (Fe(III)) oxide solids in the presence of oxygenated groundwater at the entrance of the PRB, (ii) oxidation of FeS in the presence of redox active metals like As(V) with the formation of ferric solids, (iii) co-precipitation of heavy metals within the PRB with the reactive FeS leading to the formation of insoluble metal sulfides co-precipitates with the concomitant release of ferrous iron and formation of ferrous (Fe(II) oxide, hydroxide, or carbonate solids, (iv) clogging of the PRB structure due to formation of precipitate products from processes (i) - (iii).. We have demonstrated the formation of triolite in the presence of an oxidized form of hydrous ferric oxide (HFO), various sulfate concentrations, and biomass densities for the sulfate reducing bacterium (SRB) Desulfovibrio vulgaris. This result has allowed us to demonstrate the feasibility of regeneration of FeS from the ferric oxide and hydroxide solids that may be produced under scenarios (i) and (ii) above as well as to establish the electron donor and acceptor requirements for this SRB. Using Desulfobacterium autotrophicum, both HFO and soluble complexed forms of ferric iron gave rise to the formation of mackinawite. The latter have been shown to react with As (V) and Cd (II) to form ferric solids. Both organisms will be used to generate FeS solids in the presence of crystalline forms of ferric solids expected to form from scenarios (i) and (ii) (e.g., goethite and the mixed Fe(II)/(Fe(III) magnetite, and green rusts) and ferrous iron solids from scenarios (iii) and (iv) (Fe(II) oxides and siderite). Similar to the study

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

    NASA Astrophysics Data System (ADS)

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

    2014-09-01

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

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

    PubMed

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

    2014-09-15

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

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

    PubMed Central

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

    2014-01-01

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

  9. [Investigation of nitrobenzene removal by iron sulfide (FeS)].

    PubMed

    Wang, Xia-Lin; Li, Rui-Hua

    2012-12-01

    The nitrobenzene removal performance by iron sulfide was investigated in batch experiments. The effects of different factors were studied. The results showed that the removal efficiency of nitrobenzene was 90% as initial nitrobenzene concentration was 0.96 mmol x L(-1), dosage of FeS was 1.2 g and the reaction time was 180 minutes. Initial nitrobenzene concentration, dosage of FeS, temperature and reused times of FeS had a significant influence on the removal efficiency of nitrobenzene. As the initial nitrobenzene concentration was in range of 0.74 to 1.74 mmol x L(-1), the removal efficiency of nitrobenzene decreased by 4.7% with every 0.1 mmol x L(-1) increasing of initial nitrobenzene concentration. As the dosage of FeS was in the range of 0.3 to 1.5 g, the removal efficiency of nitrobenzene increased by 20% with every 0.3 g increasing of FeS. As the dosage of FeS was 1.8 g, the removal efficiency of nitrobenzene was 100%. In the temperature range of 10 to 25 degrees C, the removal efficiency of nitrobenzene increased by 1.6% with 1 degrees C increasing. As the temperature was 30 degrees C, the removal efficiency of nitrobenzene was 100%. The removal efficiency of nitrobenzene decreased as the reused times of FeS increased. Rotational speed hardly had any influence on the removal efficiency of nitrobenzene. As the rotational speed was in the range of 10 to 80 r x min(-1), the removal efficiency of nitrobenzene was around 75%. The nitrobenzene removal performance by iron sulfide was satisfied in the treatment of simulated chemical industrial wastewater, and after 60 min, the removal efficiency of nitrobenzene was 100%.

  10. Impact of iron sulfide transformation on trichloroethylene degradation

    NASA Astrophysics Data System (ADS)

    He, Y. Thomas; Wilson, John T.; Wilkin, Richard T.

    2010-04-01

    Trichloroethylene (TCE) is one of the most common and persistent groundwater contaminants encountered at hazardous waste sites around the world. A growing body of evidence indicates that iron sulfides play an important role in degrading TCE in natural environments and in engineered systems designed for groundwater cleanup. In this study, we investigate transformation processes of iron sulfides and consequent impacts on TCE degradation using batch experimental techniques, transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray absorption spectroscopy (XAS). Our results show that mackinawite is highly reactive toward TCE and no detectable mineralogical changes were detected during the course of reaction. However, freeze-dried FeS transformed to a mixture of mackinawite and greigite during the freeze drying process, with further mineralogical changes during reaction with TCE to lepidocrocite, goethite and pyrite. Newly formed lepidocrocite is a transient phase, with conversion to goethite over time. TCE transformation kinetics show that freeze-dried FeS is 20-50 times less reactive in degrading TCE than non-freeze-dried FeS, and the TCE degradation rate increases with pH (from 5.4 to 8.3), possibly due to an increase of surface deprotonation or electron transfer at higher pH. Results suggest that freeze drying could cause FeS particle aggregation, decreased surface area and availability of reactive sites; it also could change FeS mineralogy and accelerate mineral transformation. These aspects could contribute to the lower reactivity of freeze-dried FeS toward TCE degradation. Modeling results show that FeS transformation in natural environments depends on specific biogeochemical conditions, and natural FeS transformation may affect mineral reactivity in a similar way as compared to the freeze drying process. Rapid transformation of FeS to FeS 2 could significantly slow down TCE degradation in both natural and engineered systems.

  11. What do we really know about the role of microorganisms in iron sulfide mineral formation?

    NASA Astrophysics Data System (ADS)

    Picard, Aude; Gartman, Amy; Girguis, Peter

    2016-06-01

    Iron sulfide mineralization in low-temperature systems is a result of biotic and abiotic processes, though the delineation between these two modes of formation is not always straightforward. Here we review the role of microorganisms in the precipitation of extracellular iron sulfide minerals. We summarize the evidence that links sulfur-metabolizing microorganisms and sulfide minerals in nature and we present a critical overview of laboratory-based studies of the nucleation and growth of iron sulfide minerals in microbial cultures. We discuss whether biologically derived minerals are distinguishable from abiotic minerals, possessing attributes that are uniquely diagnostic of biomineralization. These inquiries have revealed the need for additional thorough, mechanistic and high-resolution studies to understand microbially mediated formation of a variety of sulfide minerals across a range of natural environments.

  12. Sulfidation of a Novel Iron Sorbent Supported on Lignite Chars during Hot Coal Gas Desulfurization

    NASA Astrophysics Data System (ADS)

    Yin, Fengkui; Yu, Jianglong; Gupta, Sushil; Wang, Shaoyan; Wang, Dongmei; Yang, Li; Tahmasebi, Arash

    The sulfidation behavior of novel iron oxide sorbents supported using activated-chars during desulfurization of hot coal gases has been studied. The sulfidation of the char-supported sorbents was investigated using a fixed-bed quartz reactor in the temperature range of 673K to 873K. The product gases were analyzed using a GC equipped with a TCD and a FPD detector. The sorbent samples before and after sulfidation were examined using SEM and XRD.

  13. Characterization of lacustrine iron sulfide particles with proton-induced X-ray emission

    SciTech Connect

    Davison, W. ); Grime, G.W. ); Woof, C. )

    1992-12-01

    Black particles, collected by filtration (1.2-[mu] pore size) from the anoxic waters of a soft-water lake, were examined by a scanning proton microprobe which permitted quantitative elemental analysis by proton-induced X-ray emission (PIXE) and Rutherford backscattering (RBS). There was a uniform distribution of sulfur across the filter, but Fe, and to a lesser extent, Mn, was localized in [approximately]5-[mu]m diameter clusters. Elemental analysis with 1-[mu]m-diameter beams revealed that the Fe clusters were mainly comprised of iron oxides. Iron sulfide material not in the Fe clusters had stoichiometric proportions of Fe[sub 1.0]S[sub 0.60]P[sub 0.60]Ca[sub 0.24]K[sub 0.14]. Although a purely biogenic origin for P, Ca, and K cannot be ruled out, the composition is consistent with the particles originating as authigenic iron oxides which react with sulfide as they sink through the water column. The iron sulfide particles are richer in Cu (4,000 ppm) and Zn (6,000 ppm) than the iron oxides, suggesting that these elements are also concentrated as their insoluble sulfides. The coexistence of iron oxides and sulfides indicates that either the supply of sulfide is limiting or that some iron oxide particles are unreactive. 20 refs., 2 figs., 1 tab.

  14. VAPOR PHASE MERCURY SORPTION BY ORGANIC SULFIDE MODIFIED BIMETALLIC IRON-COPPER NANOPARTICLE AGGREGATES

    EPA Science Inventory

    Novel organic sulfide modified bimetallic iron-copper nanoparticle aggregate sorbent materials have been synthesized for removing elemental mercury from vapor streams at elevated temperatures (120-140 °C). Silane based (disulfide silane and tetrasulfide silane) and alkyl sulfide ...

  15. Dissolved Oxygen and Sulfide Define the Boundaries of Thermophilic Microbial Iron Mats

    NASA Astrophysics Data System (ADS)

    St Clair, B.; Shock, E.

    2014-12-01

    Microbial iron cycling can be found in hot springs throughout Yellowstone National Park, where the process is often visibly apparent as red iron oxyhydroxide staining. We measured rates of microbial and abiotic iron oxidation and reduction in systems ranging from pH 2 to 6 and 40° to 90°C. Measurements of numerous solutes, including oxygen, sulfide, and iron, were also made on outflow channels of springs containing apparent iron metabolism. In all cases, > 16 μM dissolved oxygen was required for visible iron oxidation products to occur. Oxygen concentrations below this level do not necessarily preclude microbial iron oxidation coupled to oxygen, only the accumulation of oxidation products. Kinetics experiments conducted at these iron mats suggest that the rate of microbial iron oxidation falls below the rate of microbial reduction when dissolved oxygen falls below this concentration. In outflow channels, this is often visibly apparent as a sharp boundary between the presence and lack of red iron oxidation products. Locations with changing temperature, pH, flow rate and other factors experience changing oxygen concentrations, which causes the boundary to shift from year to year. The boundaries of iron mats are also influenced in several locations by the concentration of total dissolved sulfide. Experiments with enrichment cultures and field observations show that sulfide is not toxic to iron oxidizers, but rather inhibits the accumulation of dissolved oxygen. Microbial and abiotic sulfide oxidation, leading to visible sulfur precipitation, together with degassing of hydrogen sulfide, contribute to keeping oxygen levels low. Typically, only where sulfide concentrations fall below 20 μM are iron mats able to form. Enrichment cultures of iron oxidizers, however, grow easily at levels exceeding 100 μM sulfide. Only a handful of field locations appear to have simultaneous sulfur and iron precipitation zones. Formation of iron oxidation mats occurs at highly

  16. Reductive transformation of tetrabromobisphenol A by sulfidated nano zerovalent iron.

    PubMed

    Li, Dan; Mao, Zhe; Zhong, Yin; Huang, Weilin; Wu, Yundang; Peng, Ping'an

    2016-10-15

    Recent studies showed that sulfidated nano zerovalent iron (S-nZVI) is a better alternative to non-sulfidated nano zerovalent iron (NS-nZVI) commonly used for contaminated site remediation. However, its reactivity with different halogenated pollutants such as tetrabromobisphenol A (TBBPA) remains unclear. In this study, we explored the reductive transformation of TBBPA by S-nZVI and compared it with that by NS-nZVI. The results showed that over 90% of the initial TBBPA (20 mg L(-1)) was transformed by S-nZVI within 24 h of reaction, which was 1.65 times as high as that for NS-nZVI. The TBBPA transformation by S-nZVI was well described by a pseudo-first-order kinetic model, whilst that by NS-nZVI was well fitted by a three-parameter single exponential decay model. After 11 weeks of aging, S-nZVI was still able to transform up to 56% of the initial TBBPA within 24 h of reaction; by contrast, the two-week aged NS-nZVI lost more than 95% of its original capacity to transform TBBPA. Moreover, S-nZVI showed only an approximately 20% decrease in its capacity to transform TBBPA in the seventh cycle, while NS-nZVI was no longer able to transform TBBPA in the fourth cycle. XPS analysis suggested the formation of FeS layer on S-nZVI surface and electrochemical analysis revealed an elevated electron transfer capacity of S-nZVI, which were likely responsible for the superior performances of S-nZVI in TBBPA transformation. While the transformation rate of TBBPA by S-nZVI decreased with increasing initial concentration of TBBPA, it showed an increasing trend with increasing S/Fe ratio and initial concentration of S-nZVI. The study indicated that S-nZVI has the potential to be a promising alternative to NS-nZVI for remediation of TBBPA-contaminated aquatic environments. PMID:27423531

  17. Synthesis and characterization of hybrid materials containing iron oxide for removal of sulfides from water.

    PubMed

    Jacukowicz-Sobala, Irena; Wilk, Łukasz J; Drabent, Krzysztof; Kociołek-Balawejder, Elżbieta

    2015-12-15

    Hybrid materials containing iron oxides based on macroporous and gel-type sulfonic and carboxylic cation exchangers as supporting materials were obtained. Multiple factors, including the kind of functional groups, ion exchange capacity, and polymer matrix type (chemical constitution and porous structure), affected the amount of iron oxides introduced into their matrix (7.8-35.2% Fe). Products containing the highest iron content were obtained using carboxylic cation exchangers, with their inorganic deposit being mostly a mixture of iron(III) oxides, including maghemite. Obtained hybrid polymers were used for removal of sulfides from anoxic aqueous solutions (50-200mgS(2-)/dm(3)). The research showed that the form (Na(+) or H(+)) of ionic groups of hybrid materials had a crucial impact on the sulfide removal process. Due to high iron oxide content (35% Fe), advantageous chemical constitution and porous structure, the highest removal efficiency (60mgS(2-)/g) was exhibited by a hybrid polymer obtained using a macroporous carboxylic cation exchanger as the host material. The process of sulfide removal was very complex and proceeded with heterogeneous oxidation, iron(III) oxide reductive dissolution and formation of sulfide oxidation and precipitation products such as iron(II) sulfides, thiosulfates and polysulfides.

  18. Feasibility of sulfide control in sewers by reuse of iron rich drinking water treatment sludge.

    PubMed

    Sun, Jing; Pikaar, Ilje; Sharma, Keshab Raj; Keller, Jürg; Yuan, Zhiguo

    2015-03-15

    Dosage of iron salt is the most commonly used method for sulfide control in sewer networks but incurs high chemical costs. In this study, we experimentally investigate the feasibility of using iron rich drinking water treatment sludge for sulfide control in sewers. A lab-scale rising main sewer biofilm reactor was used. The sulfide concentration in the effluent decreased from 15.5 to 19.8 mgS/L (without dosing) to below 0.7-2.3 mgS/L at a sludge dosing rate achieving an iron to total dissolved inorganic sulfur molar ratio (Fe:S) of 1:1, with further removal of sulfide possible by prolonging the reaction time. In fact, batch tests revealed an Fe consumption to sulfide removal ratio of 0.5 ± 0.02 (mole:mole), suggesting the possible occurrence of other reactions involving the removal of sulfide. Modelling revealed that the reaction between iron in sludge and sulfide has reaction orders of 0.65 ± 0.01 and 0.77 ± 0.02 with respect to the Fe and sulfide concentrations, respectively. The addition of sludge slightly increased the total chemical oxidation demand (tCOD) concentration (by approximately 12%) as expected, but decreased the soluble chemical oxidation demand (sCOD) concentration and methane formation by 7% and 20%, respectively. Some phosphate removal (13%) was also observed at the sludge dosing rate of 1:1 (Fe:S), which is beneficial to nutrient removal from the wastewater. Overall, this study suggests that dosing iron-rich drinking water sludge to sewers could be an effective strategy for sulfide removal in sewer systems, which would also reduce the sludge disposal costs for drinking water treatment works. However, its potential side-effects on sewer sedimentation and on the wastewater treatment plant effluent remain to be investigated.

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

    SciTech Connect

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

    2013-09-07

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

  20. After more than a century, iron sponge still soaks up hydrogen sulfide problems

    SciTech Connect

    Anerousis, J.P. )

    1994-09-01

    The oldest and simplest method for removing H[sub 2]S and other sulfur compounds, such as mercaptans, from gaseous streams is the iron sponge process. The basic technique consists of passing a sour gas stream (one containing H[sub 2]S or mercaptans, or both) across a bed of hydrated iron oxide. The chemical reaction produces iron sulfide and a small amount of by-product water. Although not a common practice, the spent material may be regenerated by exposing it to oxygen, which converts the mixed iron sulfides to their original iron oxide form. The iron sponge technique originated in Europe more than 100 years ago, and the earliest operators used a naturally occurring form of hydrated iron oxide known as bog iron or bog ore. As refinements were made in the process, it was found that more efficient sulfur removal could be attained by uniformly distributing the iron oxide hydrate across a substrate, and that active iron oxide could be prepared synthetically. Continual improvements in the synthetic iron sponge's composition focused on such issues as the crystalline forms of the hydrated iron oxide, size distribution of the active iron oxide particulates, overall chemical composition, size and nature of the typical wood substrate, moisture content, and degree of buffering. Modern iron sponge products are prepared with careful attention to each of these issues. The synthetic materials are characterized by high quality and uniform composition, and their overall characteristics optimize performance in typical gas-sweetening applications.

  1. VAPOR PHASE MERCURY SORPTION BY ORGANIC-SULFIDE COATED BIMETALLIC IRON-COPPER NANOPARTICLE AGGREGATES

    EPA Science Inventory

    Tetra sulfide silane coated iron-copper nano-particle aggregates are found to be potentially very high capacity sorbents for vapor phase mercury capture. High equilibrium capacities were obtained for the silane coated iron copper nano-aggregate sorbent at 70 oC and 120 oC. Even a...

  2. Iron sulfide oxidation and the chemistry of acid generation

    SciTech Connect

    Sullivan, P.J.; Yelton, J.L. ); Reddy, K.J. )

    1988-06-01

    Acid mine drainage, produced from the oxidation of iron sulfides, often contains elevated levels of dissolved aluminum (Al), iron (Fe), and sulfate (SO{sub 4}) and low pH. Understanding the interactions of these elements associated with acid mine drainage is necessary for proper solid waste management planning. Two eastern oil shales were leached using humidity cell methods. This study used a New Albany Shale (4.6% pyrite) and a Chattanooga Shale (1.5% pyrite) were used. The leachates from the humidity cells were filtered, and the filtrates were analyzed for total concentrations of cations and anions. After correcting for significant solution species and complexes, ion activities were calculated from total concentrations. The results show that the activities of Fe{sup 3+}, Fe{sup 2+}, Al{sup 3+}, and SO{sub 4}{sup 2{minus}} increased due to the oxidation of pyrite. Furthermore, the oxidation of pyrite resulted in a decreased pH and an increased pe + pH (redox-potential). The Fe{sup 3+} and Fe{sup 2+} activities appeared to be controlled by amorphous Fe(OH){sub 3} solid phase above a pH of 6.0 and below pe + pH 11.0. The Fe{sup 3+}, Fe{sup 2+}, and SO{sub 4}{sup 2{minus}} activities reached saturation with respect to FeOHSO{sub 4} solid phase between pH 3.0 and 6.0 and below pe + pH 11.0. Below a pH of 3.0 and above a pe + pH of 11.0, Fe{sup 2+}, Fe{sup 3+}, and SO{sub 4}{sup 2{minus}} activities are supported by FeSO{sub 4}{center dot}7H{sub 2}O solid phase. Above a pH of 6.0, the Al{sup 3+} activity showed an equilibrium with amorphous Al(OH){sub 3} solid phase. Below pH 6.0, Al{sup 3+} and SO{sub 4}{sup 2{minus}} activities are regulated by the AlOHSO{sub 4} solid phase, irrespective of pe + pH. The results of this study suggest that under oxidizing conditions with low to high leaching potential, activities of Al and Fe can be predicted on the basis of secondary mineral formation over a wide range of pH and redox.

  3. Speciation and Distribution of Trace Metals Associated with Iron Sulfides in the Marcellus Shale

    NASA Astrophysics Data System (ADS)

    Singer, D. M.; Cahill, M.

    2014-12-01

    Black shales underlying the areas from Eastern Ohio, through Pennsylvania, and into Central New York State have become of economic interest lately due to the recent economic viability of shale gas extraction. Sulfide minerals such as pyrite and marcasite occurring in these shales are often the primary phases that trace metals are associated with. Trace metals can be incorporated into these sulfides via various pathways during initial shale deposition and secondary diagenesis including substitution for Fe (Co and Ni), substitution for S (As and Se), and excluded to form other sulfide phases (Cu and Zn). The manner in which these trace metals are incorporated directly influences how they are released into the environment during sulfide oxidation following shale weathering or hydraulic fracturing. The aim of this research is to examine the distribution of trace metals in iron sulfides from black shales using Synchrotron-based X-ray microprobe techniques including micro-X-ray fluorescence and micro-X-ray diffraction of shale thin sections. Marcellus Shale samples were collected from: (1) outcrops from the Oatka member in Leroy, NY and Jersey Shore, PA and the Union Springs member in Lewiston, PA, and (2) drilling core sample from Beaver Meadow, NY and Hancock Co, TN (Chattanooga shale). Analyses have shown that the sulfide grains are a combination of pyrite and marcasite. As and Se are spatially correlated with each other and within the pyrite grains. Ni is spatially correlated with larger euhedral pyrite, as well as smaller non-iron sulfide grains. Cu and Zn are not spatially correlated with the pyrite and form separate Cu- and Zn- sulfides. During iron sulfide oxidative dissolution, these differences in distribution of trace metals will affect the order and rate in which they are released into the environment.

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

  5. Potential for biogeochemical cycling of sulfur, iron and carbon within massive sulfide deposits below the seafloor.

    PubMed

    Kato, Shingo; Ikehata, Kei; Shibuya, Takazo; Urabe, Tetsuro; Ohkuma, Moriya; Yamagishi, Akihiko

    2015-05-01

    Seafloor massive sulfides are a potential energy source for the support of chemosynthetic ecosystems in dark, deep-sea environments; however, little is known about microbial communities in these ecosystems, especially below the seafloor. In the present study, we performed culture-independent molecular analyses of sub-seafloor sulfide samples collected in the Southern Mariana Trough by drilling. The depth for the samples ranged from 0.52 m to 2.67 m below the seafloor. A combination of 16S rRNA and functional gene analyses suggested the presence of chemoautotrophs, sulfur-oxidizers, sulfate-reducers, iron-oxidizers and iron-reducers. In addition, mineralogical and thermodynamic analyses are consistent with chemosynthetic microbial communities sustained by sulfide minerals below the seafloor. Although distinct bacterial community compositions were found among the sub-seafloor sulfide samples and hydrothermally inactive sulfide chimneys on the seafloor collected from various areas, we also found common bacterial members at species level including the sulfur-oxidizers and sulfate-reducers, suggesting that the common members are widely distributed within massive sulfide deposits on and below the seafloor and play a key role in the ecosystem function.

  6. Use of iron salts to control dissolved sulfide in trunk sewers

    SciTech Connect

    Padival, N.A.; Kimbell, W.A.; Redner, J.A.

    1995-11-01

    Sewer headspace H{sub 2}S reduction by precipitating dissolved sulfide in wastewater was investigated using iron salt (FeCl{sub 3} and FeCl{sub 2}). Full-scale experiments were conducted in a 40-km (25 mi) sewer with an average flow of 8.7 m{sup 3}/s (200 mgd). Results were sensitive to total Fe dosages and Fe(III)/Fe(II) blend ratios injected. A concentration of 16 mg/L total Fe and a blend ratio of 1.9:1 [Fe(III):Fe(II)] reduced dissolved sulfide levels by 97%. Total sulfide and headspace H{sub 2}S were reduced by 63% and 79%, respectively. Liquid and gas-phase sulfide reductions were largely due to the effective precipitation of sulfide with Fe(III) and Fe(II) and the limited volatilization of H{sub 2}S, respectively. Oxidation of sulfide in the presence of Fe(II) and minute amounts of O{sub 2} may have occurred. A combination of Fe(III) and Fe(II) proved more effective than either salt alone. By using excess Fe(III), dissolved sulfide can be reduced to undetectable levels. No specific relation between the concentration of Fe or Fe(III)/Fe(II) blend ratio and sewer crown pH was inferred. Iron salts may retard crown corrosion rates by precipitating free sulfide and reducing its release to the sewer headspace as H{sub 2}S. A mechanism to inhibit certain responsible bacteria was not established in the 40-km (25 mi) sewer.

  7. Rotational Remanent Magnetization (RRM) to Identify Pyrrhotite in Natural Iron-Sulfide-Bearing Samples

    NASA Astrophysics Data System (ADS)

    Slotznick, S. P.; Kirschvink, J. L.; Fischer, W. W.; Webb, S. M.

    2014-12-01

    Pyrrhotite has been known for several decades to have anomalous demagnetization behavior when using tumbling AF techniques. This was quantified by Thomson (1990) to show that pyrrhotite can acquire rotational remanent magnetization (RRM) similar to the more intensely-studied iron sulfide, greigite. Use of RRM as an identification tool in natural samples has not become standard practice, perhaps due to the decrease in use of tumbling AF techniques. However, using the 2G SQuID magnetometer with in-line AF/ARM coils and RAPID automated protocols (Kirschvink et al. 2008), one can easily produce and measure RRM. This method of measuring RRM has been used to identify greigite (Suzuki et al. 2006), but not pyrrhotite. We present room temperature RRM measurements for samples spinning from -20 to +20 rev/sec, perpendicular to peak AF fields of 90mT (at 950 Hz) in iron-sulfide-bearing shales, argillites, and carbonates throughout Earth History (Miocene, Cretaceous, Mesoproterozoic, Late Archean). Presence of pyrrhotite was confirmed using AF demagnetization of NRM (GRM), IRM acquisition/AF demagnetization (Cisowski plots), Kappabridge thermal susceptibility, ultra-high resolution scanning SQuID microscopy (UHRSSM), and/or X-ray absorption near edge spectroscopy (XANES)/multiple energy X-ray fluorescence (XRF) imaging. Although the total absence of pyrrhotite cannot be proven, the same techniques were applied to rocks that do not gain RRM easily to identify their iron sulfides and ferromagnetic minerals, and no magnetic iron sulfides were found. The RRM signal for pyrrhotite is distinct from that of greigite, suggesting it could be used as a tool for distinguishing these magnetic iron sulfides from each other. Further work on room temperature RRM could define a unique non-destructive rock magnetic test for pyrrhotite.

  8. Transformations of mercury, iron, and sulfur during the reductive dissolution of iron oxyhydroxide by sulfide

    NASA Astrophysics Data System (ADS)

    Slowey, Aaron J.; Brown, Gordon E.

    2007-02-01

    Methylmercury can accumulate in fish to concentrations unhealthy for humans and other predatory mammals. Most sources of mercury (Hg) emit inorganic species to the environment. Therefore, ecological harm occurs when inorganic Hg is converted to methylmercury. Sulfate- and iron-reducing bacteria (SRB and FeRB) methylate Hg, but the effects of processes involving oxidized and reduced forms of sulfur and iron on the reactivity of Hg, including the propensity of inorganic Hg to be methylated, are poorly understood. Under abiotic conditions, using a laboratory flow reactor, bisulfide (HS -) was added at 40 to 250 μM h -1 to 5 g L -1 goethite (α-FeOOH) suspensions to which Hg(II) was adsorbed (30-100 nmol m -2) at pH 7.5. Dissolved Hg initially decreased from 10 3 or 10 4 nM (depending on initial conditions) to 10 -1 nM, during which the concentration of Hg(II) adsorbed to goethite decreased by 80% and metacinnabar (β-HgS (s)) formed, based on identification using Hg L III-edge extended X-ray absorption fine structure (EXAFS) spectroscopic analysis. The apparent coordination of oxygens surrounding Hg(II), measured with EXAFS spectroscopy, increased during one flow experiment, suggesting desorption of monodentate-bound Hg(II) while bidentate-bound Hg(II) persisted on the goethite surface. Further sulfidation increased dissolved Hg concentrations by one to two orders of magnitude (0.5 to 10 nM or 30 nM), suggesting that byproducts of bisulfide oxidation and Fe(III) reduction, primarily polysulfide and potentially Fe(II), enhanced the dissolution of β-HgS (s) and/or desorption of Hg(II). Rapid accumulation of Fe(II) in the solid phase (up to 40 μmol g -1) coincided with faster elevation of dissolved Hg concentrations. Fe(II) served as a proxy for elemental sulfur [S(0)], as S(0) was the dominant bisulfide oxidation product coupled to Fe(III) reduction, based on sulfur K-edge X-ray absorption near edge structure (XANES) spectroscopy. In one experiment, dissolved Hg

  9. Iron-Nickel Sulfide Compositional Ranges in CM Chondrites: No Simple Plan

    NASA Technical Reports Server (NTRS)

    Zolensky, Michael; Le, Loan

    2003-01-01

    Iron-nickel sulfides are found in most or all solar system environments, and are probably the only minerals found in all extraterrestrial materials on hand. Despite this ubiquity, they have only just begun the attention they deserve. The most common Fe-Ni sulfides in chondrites are troilite (FeS), pyrrhotite (Fe(1-x)S) and pentlandite (Fe,Ni)9S8. Troilite is believed to have resulted from sulfidation of metal (Fe-Ni) grains in an H2S-containing environment. Pyrrhotite is produced when friable troilite grains, which are exfoliated from the metal nucleus, are submitted to continued sulfidation. Some asteroids are known to have experienced aqueous alteration, forming products including new generations of sulfides (pyrrhotite and pentlandite). Pentlandite in particular is known to form during such alteration. However, experimental work by Lauretta has indicated that pentlandite may also have been formed during the initial sulfidation process, due to the faster diffusion rate of nickel into the forming sulfide, as compared to iron. Finally, there is considerable evidence for a family of phases intermediate between pyrrhotite and pentlandite, following the trend of the high temperature monosulfide solid solution, something not encountered in terrestrial rocks. Each sulfide has its own particular stability conditions, which have been determined for most phases. The long-term objective of our research is to characterize sulfides in chondritic materials in order to better establish the conditions under which they formed, and the subsequent processes they experienced. Ultimately, it will be possible to infer whether the sulfides in the chondrites were formed in the solar nebula or on asteroids, and if formed on the asteroids, deduce how much alteration has occurred there. Here we explore the relationships between the finest grain size portions of carbonaceous chondrites, these being matrix and chondrule rims; fine-grained materials are the most sensitive to their environment

  10. Combined Raman-LIBS Studies on Iron Sulfides to Investigate the Effect of the LIBS Plasma on the Mineral Composition

    NASA Astrophysics Data System (ADS)

    Alsemgeest, J.; Schröder, S.; Böttger, U.; Pavlov, S. G.; Weber, I.; Greshake, A.; Knöfler, H.-R.; Altenberger, U.; Hübers, H.-W.

    2016-08-01

    Iron sulfides, analyzed under martian conditions, show alteration caused by LIBS. This means that, during robotic planetary exploration by combined LIBS-Raman, effects must be taken into account with the interpretation of post-LIBS Raman data.

  11. Experimental segregation of iron-nickel metal, iron-sulfide, and olivine in a thermal gradient: Preliminary results

    NASA Technical Reports Server (NTRS)

    Jurewicz, Stephen R.; Jones, J. H.

    1993-01-01

    Speculation about the possible mechanisms for core formation in small asteroids raises more questions than answers. Petrologic evidence from iron meteorites, pallasites, and astronomical observations of M asteroids suggests that many small bodies were capable of core formation. Recent work by Taylor reviews the geochemical evidence and examines the possible physical/mechanical constraints on segregation processes. Taylor's evaluation suggests that extensive silicate partial melting (preferably 50 vol. percent or greater) is required before metal can segregate from the surrounding silicate and form a metal core. The arguments for large degrees of silicate partial melting are two-fold: (1) elemental trends in iron meteorites require that the metal was at is liquidus; and (2) experimental observations of metal/sulfide inclusions in partially molten silicate meteorites show that the metal/sulfide tends to form spherules in the liquid silicate due to surface tension effects. Taylor points out that for these metal spherules to sink through a silicate mush, high degrees of silicate partial melting are required to lower the silicate yield strength. Although some qualitative experimental data exists, little is actually known about the behavior of metals and liquid sulfides dispersed in silicate systems. In addition, we have been impressed with the ability of cumulative olivine to expel trapped liquid when placed in a thermal gradient. Consequently, we undertook to accomplish the following: (1) experimentally evaluate the potential for metal/sulfide/silicate segregation in a thermal gradient; and (2) obtain quantitative data of the wetting parameters of metal-sulfide melts among silicate grains.

  12. Selected methods for dissolved iron (II, III) and dissolved sulfide (-II) determinations in geothermal waters

    USGS Publications Warehouse

    Vivit, D.V.; Jenne, E.A.

    1985-01-01

    Dissolved sulfide (-II) and dissolved iron (II, III) were determined in geothermal well water samples collected at Cerro Prieto, Mexico. Most samples consisted of liquid and gas (two phases) at the instant of collection; and a subset of samples, referred to as ' flashed ' samples, consisted of pressurized steam samples which were allowed to condense. Sulfide was determined by sulfide specific ion electrode; Fe(II) and Fe(III) plus Fe(II) were determined spectrophotometrically. The precision and accuracy of the methods were evaluated for these high-silica waters with replicate analyses, spike recoveries, and an alternate method. Direct current (d.c.) argon plasma emission spectrometry was the alternate method used for Fe(III)-plus-Fe(II) analyses. Mean dissolved iron concentrations ranged from 20.2 to 834 micrograms/L (ug/L) as Fe(II) and 26.8 to 904 ug/L as Fe(III) plus Fe(II). Mean sulfide concentrations ranged from about 0.01 to 5.3 mg/L (S-II) Generally, higher S(-II) values and larger Fe(II)/Fe(III) ratios were found in the two-phase samples. These findings suggest that the ' flashed ' samples are at a less reduced state than the two-phase samples. (Author 's abstract)

  13. Electrochemical deposition of iron sulfide thin films and heterojunction diodes with zinc oxide

    SciTech Connect

    Kawai, Shoichi Sobue, Susumu; Okuno, Eiichi; Yamazaki, Ryuta; Ichimura, Masaya

    2014-03-01

    Iron sulfide thin films were fabricated by the electrochemical deposition method from an aqueous solution containing FeSO{sub 4} and Na{sub 2}S{sub 2}O{sub 3}. The composition ratio obtained was Fe:S:O = 36:56:8. In the photoelectrochemical measurement, a weak negative photo-current was observed for the iron sulfide films, which indicates that its conduction type is p-type. No peaks were observed in X-ray diffraction pattern, and thus the deposited films were considered to be amorphous. For a heterojunction with ZnO, rectification properties were confirmed in the current-voltage characteristics. Moreover, the current was clearly enhanced under AM1.5 illumination.

  14. Hydrogen sulfide removal from sediment and water in box culverts/storm drains by iron-based granules.

    PubMed

    Sun, J L; Shang, C; Kikkert, G A

    2013-01-01

    A renewable granular iron-based technology for hydrogen sulfide removal from sediment and water in box culverts and storm drains is discussed. Iron granules, including granular ferric hydroxide (GFH), granular ferric oxide (GFO) and rusted waste iron crusts (RWIC) embedded in the sediment phase removed aqueous hydrogen sulfide formed from sedimentary biological sulfate reduction. The exhausted iron granules were exposed to dissolved oxygen and this regeneration process recovered the sulfide removal capacities of the granules. The recovery is likely attributable to the oxidation of the ferrous iron precipitates film and the formation of new reactive ferric iron surface sites on the iron granules and sand particles. GFH and RWIC showed larger sulfide removal capacities in the sediment phase than GFO, likely due to the less ordered crystal structures on their surfaces. This study demonstrates that the iron granules are able to remove hydrogen sulfide from sediment and water in box culverts and storm drains and they have the potential to be regenerated and reused by contacting with dissolved oxygen.

  15. Hydrogen sulfide removal from sediment and water in box culverts/storm drains by iron-based granules.

    PubMed

    Sun, J L; Shang, C; Kikkert, G A

    2013-01-01

    A renewable granular iron-based technology for hydrogen sulfide removal from sediment and water in box culverts and storm drains is discussed. Iron granules, including granular ferric hydroxide (GFH), granular ferric oxide (GFO) and rusted waste iron crusts (RWIC) embedded in the sediment phase removed aqueous hydrogen sulfide formed from sedimentary biological sulfate reduction. The exhausted iron granules were exposed to dissolved oxygen and this regeneration process recovered the sulfide removal capacities of the granules. The recovery is likely attributable to the oxidation of the ferrous iron precipitates film and the formation of new reactive ferric iron surface sites on the iron granules and sand particles. GFH and RWIC showed larger sulfide removal capacities in the sediment phase than GFO, likely due to the less ordered crystal structures on their surfaces. This study demonstrates that the iron granules are able to remove hydrogen sulfide from sediment and water in box culverts and storm drains and they have the potential to be regenerated and reused by contacting with dissolved oxygen. PMID:24355850

  16. Geology of the Brick Flat massive sulfide body, Iron Mountain cluster, West Shasta district, California ( USA).

    USGS Publications Warehouse

    Albers, J.P.

    1985-01-01

    The Brick Flat massive sulfide body is one of a group of 8 individual bodies that constitute the Iron Mountain cluster in the S part of the West Shasta district. Before they were separated by postmineral faulting, 5 of the 8 sulfide bodies formed a single large deposit about 1375 m long with a mass of some 23 million metric tons. The pyritic Brick Flat sulfide body is one of the 5 faulted segements of this deposit. The Brick Flat massive sulfide lies within medium phenocryst rhyolite that is characteristic of the ore-bearing middle unit of the Balaklala Rhyolite. It is interpreted to be downfaulted a vertical distance of 75 to 85 m from the Old Mine sulfide-gossan orebody along the N-dipping Camden South fault. It is bounded in turn on its N side by another parallel fault, the Camden North, which drops the orebody down another 75 m to the level of the Richmond orebody. -from Author

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

    DOEpatents

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

    2003-08-19

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

  18. Pyrrhotite: an Iron Sulfide Mineral Formed During Growth of Sulfate-Reducing Bacteria at a Hematite Surface

    NASA Astrophysics Data System (ADS)

    Geesey, G.; Reardon, C.; Neal, A.

    2008-12-01

    Many bacteria are capable of respiring on sulfate and other oxidized forms of sulfur under anaerobic conditions. The hydrogen sulfide that is formed during dissimilatory sulfate reduction (DSR) readily reacts with metals in the surrounding environment to form insoluble metal sulfides. Iron oxides are common substrata for colonization by sulfate-reducing bacteria (SRB) in sedimentary aquatic systems as well as in subsurface environments. While numerous studies have characterized iron sulfides formed during dissimilatory sulfate reduction by suspended populations of these bacteria in the presence of soluble iron, not much is known about those formed in the presence of biofilm populations associated with solid phase iron, particularly crystalline forms such as hematite. Under the latter conditions, we have observed the formation of the iron sulfide pyrrhotite, typically present in very low abundance in sediments and ore deposits compared to pyrite. The formation of pyrrhotite over pyrite is favored at low redox potential and sulfide activity, conditions we hypothesize are achieved at an iron oxide surface colonized by biofilm-forming SRB. Higher levels of hydrogenase activity by hematite surface-associated SRB than suspended cell populations likely promotes the low redox potential that favors pyrrhotite formation. The tendency for SRB in nature to associate with mineral particle surfaces, including iron oxides, suggests that some pyrrotite may have originated through biotic reactions. A comparison of the fine structure of pyrrhotite formed through these biotic processes with that formed under abiotic processes may reveal differences that provide a signature for biotically-derived pyrrhotite in the biosphere.

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

    SciTech Connect

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

    1996-04-01

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

  20. Abrasive resistance of metastable V-Cr-Mn-Ni spheroidal carbide cast irons using the factorial design method

    NASA Astrophysics Data System (ADS)

    Efremenko, V. G.; Shimizu, K.; Cheiliakh, A. P.; Pastukhova, T. V.; Chabak, Yu. G.; Kusumoto, K.

    2016-06-01

    Full factorial design was used to evaluate the two-body abrasive resistance of 3wt%C-4wt%Mn-1.5wt%Ni spheroidal carbide cast irons with varying vanadium (5.0wt%-10.0wt%) and chromium (up to 9.0wt%) contents. The alloys were quenched at 920°C. The regression equation of wear rate as a function of V and Cr contents was proposed. This regression equation shows that the wear rate decreases with increasing V content because of the growth of spheroidal VC carbide amount. Cr influences the overall response in a complex manner both by reducing the wear rate owing to eutectic carbides (M7C3) and by increasing the wear rate though stabilizing austenite to deformation-induced martensite transformation. This transformation is recognized as an important factor in increasing the abrasive response of the alloys. By analyzing the regression equation, the optimal content ranges are found to be 7.5wt%-10.0wt% for V and 2.5wt%-4.5wt% for Cr, which corresponds to the alloys containing 9vol%-15vol% spheroidal VC carbides, 8vol%-16vol% M7C3, and a metastable austenite/martensite matrix. The wear resistance is 1.9-2.3 times that of the traditional 12wt% V-13wt% Mn spheroidal carbide cast iron.

  1. Relationship between the properties of iron sulfides and their catalytic activity

    SciTech Connect

    Stohl, F. V.; Granoff, B.

    1981-01-01

    Iron sulfides, such as pyrite, are known catalysts in coal liquefaction and produce significant increases in both conversion and distillate (850 F/sup -/) yield. The main objective of this work is to increase the catalytic activity of iron sulfides by systematically changing the following properties: composition, source, particle size, surface area, morphology and defect level. Several iron sulfides have been synthesized including pyrite (FeS/sub 2/) with 46.6 wt % Fe, pyrrhotite (Fe/sub 1-x/S) with about 60 wt % Fe and mackinawite (Fe/sub 9/S/sub 8/) with 66.2 wt % Fe. The source variations have included commercial material and minerals. The pyrite particle sizes ranged from -350 to -5..mu..m, the pyrite surface areas varied from 2 to >10 m/sup 2//g, the mackinawite surface areas ranged from 40 to 80 m/sup 2//g, and pyrite morphologies included massive material and a concentrate of framboids from Iowa coal. Moessbauer studies of the pyrrhotites in coal liquefaction residues have shown that there is a direct correlation between conversion and the number of vacancies in the pyrrhotite. Pyrites with enhanced defect levels were prepared by explosively shock loading Robena pyrite at 15 GPa. All these materials have been tested in either tubing reactor or autoclave runs with West Virginia Blacksville No. 2 coal and SRC-II heavy distillate (550/sup 0/F/sup +/). The runs were carried out at 425/sup 0/C, 500 psi H/sub 2/ (cold charge) for 30 minutes with a 7.5 wt % catalyst loading. All these materials have shown catalytic effects as compared to uncatalyzed thermal runs.

  2. Prevention of iron-sulfide deposition in petroleum processing. Final CRADA report.

    SciTech Connect

    Doctor, R. D.; Panchal, C. B.; Energy Systems

    2010-03-25

    The purpose of this CRADA extension which effectively ended in 2003 was to quantify the effect of iron-sulfide formation on the fouling propensity of crude oil. The specific objectives are focused on fouling of the Crude Distillation Unit (CDU-1) at the Shell Refinery in Mobile, Alabama. The technical approach consists of analyzing the plant data, chemical analysis of crude oil to detect key precursors, performing refinery tests using the Argonne Field Fouling Unit, and verifying the effectiveness of a physical device of tube insert and enhanced tubes to change threshold conditions and thereby reducing fouling.

  3. Heterocyclic dithiocarbamato-iron(III) complexes: single-source precursors for aerosol-assisted chemical vapour deposition (AACVD) of iron sulfide thin films.

    PubMed

    Mlowe, Sixberth; Lewis, David J; Malik, Mohammad Azad; Raftery, James; Mubofu, Egid B; O'Brien, Paul; Revaprasadu, Neerish

    2016-02-14

    Tris-(piperidinedithiocarbamato)iron(III) (1) and tris-(tetrahydroquinolinedithiocarbamato)iron(iii) (2) complexes have been synthesized and their single-crystal X-ray structures were determined. Thermogravimetric analysis (TGA) of the complexes showed decomposition to iron sulfide. Both complexes were then used as single-source precursors for the deposition of iron sulfide thin films by aerosol-assisted chemical vapour deposition (AACVD). Energy-dispersive X-ray (EDX) spectroscopy confirmed the formation of iron sulfide films. The addition of tert-butyl thiol almost doubled the sulfur content in the deposited films. Scanning electron microscopy (SEM) images of the iron sulfide films from both complexes showed flakes/leaves/sheets, spherical granules and nanofibres. The sizes and shapes of these crystallites depended on the nature of the precursor, temperature, solvent and the amount of tert-butyl thiol used. The observed optical properties are dependent upon the variation of reaction parameters such as temperature and solvent. Powder X-ray diffraction (p-XRD) studies revealed that pyrrhotite, hexagonal (Fe0.975S), marcasite and smythite (Fe3S4) phases were differently deposited. PMID:26732865

  4. Discovery and Characterization of Iron Sulfide and Polyphosphate Bodies Coexisting in Archaeoglobus fulgidus Cells

    DOE PAGESBeta

    Toso, Daniel B.; Javed, Muhammad Mohsin; Czornyj, Elizabeth; Gunsalus, Robert P.; Zhou, Z. Hong

    2016-01-01

    Inorganic storage granules have long been recognized in bacterial and eukaryotic cells but were only recently identified in archaeal cells. Here, we report the cellular organization and chemical compositions of storage granules in the Euryarchaeon, Archaeoglobus fulgidusstrain VC16, a hyperthermophilic, anaerobic, and sulfate-reducing microorganism. Dense granules were apparent inA. fulgiduscells imaged by cryo electron microscopy (cryoEM) but not so by negative stain electron microscopy. Cryo electron tomography (cryoET) revealed that each cell contains one to several dense granules located near the cell membrane. Energy dispersive X-ray (EDX) spectroscopy and scanning transmission electron microscopy (STEM) show that, surprisingly, each cell containsmore » not just one but often two types of granules with different elemental compositions. One type, named iron sulfide body (ISB), is composed mainly of the elements iron and sulfur plus copper; and the other one, called polyphosphate body (PPB), is composed of phosphorus and oxygen plus magnesium, calcium, and aluminum. PPBs are likely used for energy storage and/or metal sequestration/detoxification. ISBs could result from the reduction of sulfate to sulfide via anaerobic energy harvesting pathways and may be associated with energy and/or metal storage or detoxification. The exceptional ability of these archaeal cells to sequester different elements may have novel bioengineering applications.« less

  5. Natural stressors in uncontaminated sediments of shallow freshwaters: the prevalence of sulfide, ammonia, and reduced iron.

    PubMed

    Kinsman-Costello, Lauren E; O'Brien, Jonathan M; Hamilton, Stephen K

    2015-03-01

    Potentially toxic levels of 3 naturally occurring chemical stressors (dissolved sulfide, ammonia, and iron) can appear in freshwater sediments, although their roles in shaping ecosystem structure (i.e., plant and animal communities) and function (e.g., biologically mediated elemental cycles) have received little study. The present critical review discusses the prevalence and ecological effects of potentially toxic concentrations of sulfide, ammonia, and iron in uncontaminated freshwater sediments, including a review of the literature as well as a case study presenting previously unpublished data on sediment porewaters from a diverse set of shallow (<2 m) freshwater ecosystems in southwest Michigan, USA. Measured concentrations are compared with surface water quality criteria established by the US Environmental Protection Agency (USEPA) and with acute and chronic toxic thresholds in the published literature, where available. Based on USEPA criteria for aquatic life for these 3 stressors, the benthic environment of almost every freshwater ecosystem sampled was theoretically stressful to some component of aquatic life in some area or at some time (i.e., in at least 1 sample), and 54% of samples exceeded more than 1 criterion simultaneously. Organismal tolerances to chemical stressors vary, so the observed concentrations are likely shaping benthic animal communities and influencing rates of ecosystem processes. Consideration of the role of natural chemical stressors is important in shaping freshwater benthic environments and in developing bioassessments, restoration goals, and remediation plans. Environ Toxicol Chem 2015;34:467-479. © 2014 SETAC.

  6. Magnetic sulfide-modified nanoscale zerovalent iron (S-nZVI) for dissolved metal ion removal.

    PubMed

    Su, Yiming; Adeleye, Adeyemi S; Keller, Arturo A; Huang, Yuxiong; Dai, Chaomeng; Zhou, Xuefei; Zhang, Yalei

    2015-05-01

    Sulfide-modified nanoscale zerovalent iron (S-nZVI) is attracting a lot of attention due to its ease of production and high reactivity with organic pollutants. However, its structure is still poorly understood and its potential application in heavy metal remediation has not been explored. Herein, the structure of S-nZVI and its cadmium (Cd) removal performance under different aqueous conditions were carefully investigated. Transmission electron microscopy (TEM) with an energy-dispersive X-ray spectroscopy (EDS) analysis suggested that sulfur was incorporated into the zerovalent iron core. Scanning electron microscopy (SEM) with EDS analysis demonstrated that sulfur was also homogeneously distributed within the nanoparticles. When the concentration of Na2S2O4 was increased during synthesis, a flake-like structure (FeSx) increased significantly. S-nZVI had an optimal Cd removal capacity of 85 mg/g, which was >100% higher than for pristine nZVI. Even at pH 5, over 95% removal efficiency was observed, indicating sulfide compounds played a crucial role in metal ion removal and particle chemical stability. Oxygen impaired the structure of S-nZVI but enhanced Cd removal capacity to about 120 mg/g. Particle aging had no negative effect on removal capacity of S-nZVI, and Cd-containing mixtures remained stable in a two months experiment. S-nZVI can efficiently sequester dissolved metal ions from different contaminated water matrices. PMID:25706223

  7. Discovery and Characterization of Iron Sulfide and Polyphosphate Bodies Coexisting in Archaeoglobus fulgidus Cells

    PubMed Central

    Toso, Daniel B.; Javed, Muhammad Mohsin; Czornyj, Elizabeth; Zhou, Z. Hong

    2016-01-01

    Inorganic storage granules have long been recognized in bacterial and eukaryotic cells but were only recently identified in archaeal cells. Here, we report the cellular organization and chemical compositions of storage granules in the Euryarchaeon, Archaeoglobus fulgidus strain VC16, a hyperthermophilic, anaerobic, and sulfate-reducing microorganism. Dense granules were apparent in A. fulgidus cells imaged by cryo electron microscopy (cryoEM) but not so by negative stain electron microscopy. Cryo electron tomography (cryoET) revealed that each cell contains one to several dense granules located near the cell membrane. Energy dispersive X-ray (EDX) spectroscopy and scanning transmission electron microscopy (STEM) show that, surprisingly, each cell contains not just one but often two types of granules with different elemental compositions. One type, named iron sulfide body (ISB), is composed mainly of the elements iron and sulfur plus copper; and the other one, called polyphosphate body (PPB), is composed of phosphorus and oxygen plus magnesium, calcium, and aluminum. PPBs are likely used for energy storage and/or metal sequestration/detoxification. ISBs could result from the reduction of sulfate to sulfide via anaerobic energy harvesting pathways and may be associated with energy and/or metal storage or detoxification. The exceptional ability of these archaeal cells to sequester different elements may have novel bioengineering applications. PMID:27194953

  8. Discovery and Characterization of Iron Sulfide and Polyphosphate Bodies Coexisting in Archaeoglobus fulgidus Cells.

    PubMed

    Toso, Daniel B; Javed, Muhammad Mohsin; Czornyj, Elizabeth; Gunsalus, Robert P; Zhou, Z Hong

    2016-01-01

    Inorganic storage granules have long been recognized in bacterial and eukaryotic cells but were only recently identified in archaeal cells. Here, we report the cellular organization and chemical compositions of storage granules in the Euryarchaeon, Archaeoglobus fulgidus strain VC16, a hyperthermophilic, anaerobic, and sulfate-reducing microorganism. Dense granules were apparent in A. fulgidus cells imaged by cryo electron microscopy (cryoEM) but not so by negative stain electron microscopy. Cryo electron tomography (cryoET) revealed that each cell contains one to several dense granules located near the cell membrane. Energy dispersive X-ray (EDX) spectroscopy and scanning transmission electron microscopy (STEM) show that, surprisingly, each cell contains not just one but often two types of granules with different elemental compositions. One type, named iron sulfide body (ISB), is composed mainly of the elements iron and sulfur plus copper; and the other one, called polyphosphate body (PPB), is composed of phosphorus and oxygen plus magnesium, calcium, and aluminum. PPBs are likely used for energy storage and/or metal sequestration/detoxification. ISBs could result from the reduction of sulfate to sulfide via anaerobic energy harvesting pathways and may be associated with energy and/or metal storage or detoxification. The exceptional ability of these archaeal cells to sequester different elements may have novel bioengineering applications. PMID:27194953

  9. Sorption of arsenite, arsenate, and thioarsenates to iron oxides and iron sulfides: a kinetic and spectroscopic investigation.

    PubMed

    Couture, R-M; Rose, J; Kumar, N; Mitchell, K; Wallschläger, D; Van Cappellen, P

    2013-06-01

    Sorption to iron (Fe) minerals determines the fate of the toxic metalloid arsenic (As) in many subsurface environments. Recently, thiolated As species have been shown to dominate aqueous As speciation under a range of environmentally relevant conditions, thus highlighting the need for a quantitative understanding of their sorption behavior. We conducted batch experiments to measure the time-dependent sorption of two S-substituted arsenate species, mono- and tetrathioarsenate, and compared it to the sorption of arsenite and arsenate, in suspensions containing 2-line ferrihydrite, goethite, mackinawite, or pyrite. All four As species strongly sorbed to ferrihydrite. For the other sorbents, binding of the thiolated As species was generally lower compared to arsenate and arsenite, with the exception of the near instantaneous and complete sorption of monothioarsenate to pyrite. Analysis of the X-ray absorption spectroscopy (XAS) spectra of sorbed complexes implied that monothioarsenate binds to Fe oxides as a monodentate, inner-sphere complex. In the presence of Fe sulfides, mono- and tetrathioarsenate were both unstable and partially reduced to arsenite. Adsorption of the thiolated As species to the Fe sulfide minerals also caused the substitution of surface sulfur (S) atoms by As and the formation of As-Fe bonds.

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

    NASA Astrophysics Data System (ADS)

    Sun, Fenglong

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

  11. Structure and properties of ultrathin iron films on Ru(10 overline10) : The formation of metastable surface phases of γ-Fe

    NASA Astrophysics Data System (ADS)

    Harrison, Kevin; Prince, Robert H.; Lambert, Richard M.

    1988-07-01

    The chemisorption and desorption of Fe at the (10 overline10) surface of Ru has been investigated by LEED, Auger spectroscopy, Δφ and thermal desorption measurements over a substrate temperature range of 300-900 K. The growth mode of the iron deposit was found to be strongly dependent on the temperature. At 300 K up to seven iron monolayers could be grown, these adopting the configuration of the fcc (111) plane of bulk γ-iron. The layers were metastable and heating of such films or deposition at elevated temperatures resulted in nucleation and growth of crystallites. Only a single Fe desorption peak ( Ed≈ 250 kJ mol-1) was observed over the whole coverage regime; this is assigned to the evaporation of iron atoms in contact with the ruthenium substrate, either pre-existing in the first monolayer or supplied from the Fe crystallites.

  12. Spectroscopic characterization of co-precipitated arsenic- and iron-bearing sulfide phases at circum-neutral pH

    NASA Astrophysics Data System (ADS)

    Illera, V.; Rivera, N. A.; O'Day, P. A.

    2009-12-01

    Precipitation of arsenic- and iron-sulfide phases from porewaters is an important mechanism for removing arsenic and other contaminant metals from solution, thus reducing their bioaccessibility and potential toxicity. Although sulfide phases form readily at low pH, the identity, crystallinity, and local structure of arsenic and iron co-precipitated phases that form at circum-neutral pH are less well known. In this study, co-precipitated As+Fe sulfide phases and end-member As-sulfides and Fe-sulfides were synthesized in batch experiments and in a gas-tight reaction vessel at 25°C. Reduced conditions were maintained by keeping a constant flow of a 95%N2 /5%H2 mixture gas. Fresh saturated solutions of 0.3 M Fe(II) or Fe(III), 0.3 M S2- and 0.2 M As(III) ions were mixed and pH was maintained at pH 4, 6 and 8 by small additions of concentrated HCl or NaOH. At different time intervals, aliquots were extracted from suspensions aged from hours to 1 month and analyzed for total iron, arsenic and sulfur (by ICP-OES and ICP-MS). The Fe-S-As precipitates were characterized by X-ray diffraction (XRD) and synchrotron X-ray absorption spectroscopy (XAS). X-ray diffraction and Fe k-edge EXAFS showed the precipitation of amorphous to poorly crystalline iron sulfide when Fe(II) was co-precipitated with sulfide (no arsenic) at pH 4, 6, and 8. The precipitate that formed in ~1-4 h was nanoparticle-sized and disordered mackinawite (FeS), which showed a characteristic broad, low-intensity Bragg peaks in the XRD patterns. After aging for ~7 d, XRD patterns showed a change to more crystalline mackinawite. In contrast, co-precipitation of As(III) with Fe(II) and sulfide resulted in x-ray amorphous (both synchrotron and laboratory XRD) precipitates for all pH and aging times (~4 h to 1 m). Arsenic and iron XANES and EXAFS spectra of precipitates at pH 4 showed a mixture of amorphous orpiment-type (As2S3) and mackinawite-type (FeS) phases. At pH 6 and 8, XANES showed As sulfide and a

  13. Rates of microbial sulfate reduction control the sizes of biogenic iron sulfide aggregates

    NASA Astrophysics Data System (ADS)

    Jin, Q.

    2005-12-01

    Sulfide minerals occur widely in freshwater and marine sediments as byproducts of microbial sulfate reduction and as end products of heavy metal bioremediation. They form when metals in the environments combine with sulfide produced from the metabolism of sulfate reducing bacteria. We used chemostat bioreactors to study sizes and crystal structures of iron sulfide (FeS) minerals produced by Desulfovibrio vulgaris, D. desulfuricans strain G20, and subspecies desulfuricans. FeS nanoparticles and their aggregates are characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and dynamic light scattering (DLS). FeS nanoparticles produced by sulfate reducing bacteria are extremely small, usually less than around 10 nm in diameter. Nanoparticles do not occur as individual nanoparticles, but as aggregates. The sizes of FeS aggregates are affected by sulfate reduction rates, Fe(II) concentration, pH, ionic strength, organic matter concentration, bacterial species, etc. Aggregate size ranges from about 500 nm at very large sulfate reduction rates to about 1,500 nm at very small rates. Variations in Fe(II) concentration also lead to a difference up to 500 nm in FeS aggregate size. Different bacterial species produce nanoparticle aggregates of different sizes under similar growth conditions. For example, D. vulgaris produces FeS aggregates with sizes 500 nm smaller than those by strain G20. The inverse relationship between FeS aggregate sizes and sulfate reduction rates is important in evaluating metal bioremediation strategies. Previous approaches have focused on stimulating microbial activities in natural environments. However, our experimental results suggest that increasing metabolic rates may decrease the aggregate size, increasing the mobility of colloidal aggregates. Therefore, the balance between microbial activities and sizes of biogenic aggregates may be an important consideration in the design and

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

    PubMed

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

    2014-07-01

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

  15. Application of iron sulfide particles for groundwater and soil remediation: A review.

    PubMed

    Gong, Yanyan; Tang, Jingchun; Zhao, Dongye

    2016-02-01

    Rapid industrialization and urbanization have resulted in elevated concentrations of hazardous inorganic and organic contaminants in groundwater and soil, which has become a paramount concern to the environment and the public health. In recent years, iron sulfide (FeS), a major constituent of acid-volatile sulfides, has elicited extensive interests in environmental remediation due to its ubiquitous presence and high treatment efficiency in anoxic environment. This paper provides a comprehensive review on recent advances in: (1) synthesis of FeS particles (including nanoscale FeS); and (2) reactivity of FeS towards a variety of common environmental contaminants in groundwater and soil over extended periods of time, namely, heavy metals (Hg(II), Cu(II), Pb(II), and Cr(VI)), oxyanions (arsenite, arsenate, selenite, and selenate), radionuclides (e.g., uranium (U) and neptunium (Np)), chlorinated organic compounds (e.g., trichloroethane, trichloroethylene, and p-chloroaniline), nitroaromatic compounds, and polychlorinated biphenyls. Different physiochemical and biological methods for preparing FeS with desired particle size, structure, and surface properties are discussed. Reaction principles and removal effectiveness/constraints are discussed in details. Special attention is placed to the application of nanoscale FeS particles because of their unique properties, such as small particle size, large specific surface area, high surface reactivity, and soil deliverability in the subsurface. Moreover, current knowledge gaps and further research needs are identified. PMID:26707732

  16. Application of iron sulfide particles for groundwater and soil remediation: A review.

    PubMed

    Gong, Yanyan; Tang, Jingchun; Zhao, Dongye

    2016-02-01

    Rapid industrialization and urbanization have resulted in elevated concentrations of hazardous inorganic and organic contaminants in groundwater and soil, which has become a paramount concern to the environment and the public health. In recent years, iron sulfide (FeS), a major constituent of acid-volatile sulfides, has elicited extensive interests in environmental remediation due to its ubiquitous presence and high treatment efficiency in anoxic environment. This paper provides a comprehensive review on recent advances in: (1) synthesis of FeS particles (including nanoscale FeS); and (2) reactivity of FeS towards a variety of common environmental contaminants in groundwater and soil over extended periods of time, namely, heavy metals (Hg(II), Cu(II), Pb(II), and Cr(VI)), oxyanions (arsenite, arsenate, selenite, and selenate), radionuclides (e.g., uranium (U) and neptunium (Np)), chlorinated organic compounds (e.g., trichloroethane, trichloroethylene, and p-chloroaniline), nitroaromatic compounds, and polychlorinated biphenyls. Different physiochemical and biological methods for preparing FeS with desired particle size, structure, and surface properties are discussed. Reaction principles and removal effectiveness/constraints are discussed in details. Special attention is placed to the application of nanoscale FeS particles because of their unique properties, such as small particle size, large specific surface area, high surface reactivity, and soil deliverability in the subsurface. Moreover, current knowledge gaps and further research needs are identified.

  17. Highly siderophile elements were stripped from Earth's mantle by iron sulfide segregation.

    PubMed

    Rubie, David C; Laurenz, Vera; Jacobson, Seth A; Morbidelli, Alessandro; Palme, Herbert; Vogel, Antje K; Frost, Daniel J

    2016-09-01

    Highly siderophile elements (HSEs) are strongly depleted in the bulk silicate Earth (BSE) but are present in near-chondritic relative abundances. The conventional explanation is that the HSEs were stripped from the mantle by the segregation of metal during core formation but were added back in near-chondritic proportions by late accretion, after core formation had ceased. Here we show that metal-silicate equilibration and segregation during Earth's core formation actually increased HSE mantle concentrations because HSE partition coefficients are relatively low at the high pressures of core formation within Earth. The pervasive exsolution and segregation of iron sulfide liquid from silicate liquid (the "Hadean matte") stripped magma oceans of HSEs during cooling and crystallization, before late accretion, and resulted in slightly suprachondritic palladium/iridium and ruthenium/iridium ratios. PMID:27609889

  18. The role of iron in sulfide induced corrosion of sewer concrete.

    PubMed

    Jiang, Guangming; Wightman, Elaine; Donose, Bogdan C; Yuan, Zhiguo; Bond, Philip L; Keller, Jurg

    2014-02-01

    The sulfide-induced corrosion of concrete sewer is a widespread and expensive problem for water utilities worldwide. Fundamental knowledge of the initiation and propagation of sewer corrosion, especially the interactions between chemical reactions and physical structure changes, is still largely unknown. Advanced mineral analytical techniques were applied to identify the distribution of corrosion products and the micro-cracking that developed along the corrosion boundary. It was found that sewer concrete corrosion caused by reactions with sulfuric acid progressed uniformly in the cement of concrete. In contrast to conventional knowledge, iron rust rather than gypsum and ettringite was likely the factor responsible for cracking ahead of the corrosion front. The analysis also allowed quantitative determination of the major corrosion products, i.e., gypsum and ettringite, with the latter found closer to the corrosion front. The conceptual model based on these findings clearly demonstrated the complex interactions among different chemical reactions, diffusion, and micro-structure changes. PMID:24326021

  19. Mössbauer study of electrochemically deposited amorphous iron-sulfide-oxide thin films

    NASA Astrophysics Data System (ADS)

    Ichimura, Masaya; Kajima, Takahiro; Kawai, Shoichi; Mibu, Ko

    2016-03-01

    Iron-sulfide-oxide thin films, which are promising candidates for solar cell materials, were deposited by electrochemical deposition. As-deposited and annealed films were characterized by Mössbauer spectroscopy, X-ray diffraction (XRD), and Raman scattering at room temperature. The as-deposited film is amorphous, and the oxygen content is about 1/4 of the sulfur content (S/Fe ≈ 1.5, O/Fe ≈ 0.4). The Mössbauer spectrum for the as-deposited film is a doublet with a broad line profile having hyperfine parameters similar to those of FeS2 pyrite or marcasite. This indicates that Fe atoms are in the Fe2+ low-spin state, as in FeS2.

  20. Highly siderophile elements were stripped from Earth's mantle by iron sulfide segregation.

    PubMed

    Rubie, David C; Laurenz, Vera; Jacobson, Seth A; Morbidelli, Alessandro; Palme, Herbert; Vogel, Antje K; Frost, Daniel J

    2016-09-01

    Highly siderophile elements (HSEs) are strongly depleted in the bulk silicate Earth (BSE) but are present in near-chondritic relative abundances. The conventional explanation is that the HSEs were stripped from the mantle by the segregation of metal during core formation but were added back in near-chondritic proportions by late accretion, after core formation had ceased. Here we show that metal-silicate equilibration and segregation during Earth's core formation actually increased HSE mantle concentrations because HSE partition coefficients are relatively low at the high pressures of core formation within Earth. The pervasive exsolution and segregation of iron sulfide liquid from silicate liquid (the "Hadean matte") stripped magma oceans of HSEs during cooling and crystallization, before late accretion, and resulted in slightly suprachondritic palladium/iridium and ruthenium/iridium ratios.

  1. Highly siderophile elements were stripped from Earth’s mantle by iron sulfide segregation

    NASA Astrophysics Data System (ADS)

    Rubie, David C.; Laurenz, Vera; Jacobson, Seth A.; Morbidelli, Alessandro; Palme, Herbert; Vogel, Antje K.; Frost, Daniel J.

    2016-09-01

    Highly siderophile elements (HSEs) are strongly depleted in the bulk silicate Earth (BSE) but are present in near-chondritic relative abundances. The conventional explanation is that the HSEs were stripped from the mantle by the segregation of metal during core formation but were added back in near-chondritic proportions by late accretion, after core formation had ceased. Here we show that metal-silicate equilibration and segregation during Earth’s core formation actually increased HSE mantle concentrations because HSE partition coefficients are relatively low at the high pressures of core formation within Earth. The pervasive exsolution and segregation of iron sulfide liquid from silicate liquid (the “Hadean matte”) stripped magma oceans of HSEs during cooling and crystallization, before late accretion, and resulted in slightly suprachondritic palladium/iridium and ruthenium/iridium ratios.

  2. The role of iron in sulfide induced corrosion of sewer concrete.

    PubMed

    Jiang, Guangming; Wightman, Elaine; Donose, Bogdan C; Yuan, Zhiguo; Bond, Philip L; Keller, Jurg

    2014-02-01

    The sulfide-induced corrosion of concrete sewer is a widespread and expensive problem for water utilities worldwide. Fundamental knowledge of the initiation and propagation of sewer corrosion, especially the interactions between chemical reactions and physical structure changes, is still largely unknown. Advanced mineral analytical techniques were applied to identify the distribution of corrosion products and the micro-cracking that developed along the corrosion boundary. It was found that sewer concrete corrosion caused by reactions with sulfuric acid progressed uniformly in the cement of concrete. In contrast to conventional knowledge, iron rust rather than gypsum and ettringite was likely the factor responsible for cracking ahead of the corrosion front. The analysis also allowed quantitative determination of the major corrosion products, i.e., gypsum and ettringite, with the latter found closer to the corrosion front. The conceptual model based on these findings clearly demonstrated the complex interactions among different chemical reactions, diffusion, and micro-structure changes.

  3. Aqueous Iron-Sulfide Clusters in Variably Saturated Soil Systems: Implications for Iron Cycling and Fluid Flow

    NASA Astrophysics Data System (ADS)

    McGuire, J. T.; Hansen, D. J.; Mohanty, B. P.

    2008-12-01

    Iron and sulfur cycling is an important control on contaminant fate and transport, the availability of micronutrients and the physics of water flow. This study explores the effects of soil structure (i.e. layers, lenses, macropores, or fractures) on linked biogeochemical and hydrological processes involving Fe and S cycling in the vadose zone using packed soil columns. Three laboratory soil columns were constructed: a homogenized medium-grained sand, homogenized organic-rich loam, and a sand-over-loam layered column. Both upward and downward infiltration of water was evaluated during experiments to simulate rising water table and rainfall events respectively. Water samples extracted by lysimeter were analyzed for reduced species (including total sulfide, Fe(II), and FeSaq) voltammetrically using a mercury drop electrode. In addition to other reduced species, aqueous FeS clusters (FeSaq) were observed in two of the columns, with the greatest concentrations of FeSaq occurring in close proximity to the soil interface in the layered column. To our knowledge, this is the first documentation of aqueous FeS clusters in partially saturated sediments. The aqueous nature of FeSaq allows it to be transported instead of precipitating and suggests that current conceptual models of iron-sulfur cycling may need to be adapted to account for an aqueous phase. The presence of iron-rich soil aggregates near the soil interface may indicate that FeS clusters played a critical role in the formation of soil aggregates that subsequently caused up to an order of magnitude decrease in hydraulic conductivity.

  4. Immobilization of heavy metals in electroplating sludge by biochar and iron sulfide.

    PubMed

    Lyu, Honghong; Gong, Yanyan; Tang, Jingcshun; Huang, Yao; Wang, Qilin

    2016-07-01

    Electroplating sludge (ES) containing large quantities of heavy metals is regarded as a hazardous waste in China. This paper introduced a simple method of treating ES using environmentally friendly fixatives biochar (BC) and iron sulfide (FeS), respectively. After 3 days of treatment with FeS at a FeS-to-ES mass ratio of 1:5, the toxicity characteristic leaching procedure (TCLP)-based leachability of total Cr (TCr), Cu(II), Ni(II), Pb(II), and Zn(II) was decreased by 59.6, 100, 63.8, 73.5, and 90.5 %, respectively. After 5 days of treatment with BC at a BC-to-ES mass ratio of 1:2, the TCLP-based leachability was declined by 35.1, 30.6, 22.3, 23.1, and 22.4 %, respectively. Pseudo first-order kinetic model adequately simulated the sorption kinetic data. Structure and morphology analysis showed that adsorption, electrostatic attraction, surface complexation, and chemical precipitation were dominant mechanisms for heavy metals immobilization by BC, and that chemical precipitation (formation of metal sulfide and hydroxide precipitates), iron exchange (formation of CuFeS2), and surface complexation were mainly responsible for heavy metals removal by FeS. Economic costs of BC and FeS were 500 and 768 CNY/t, lower than that of Na2S (940 CNY/t). The results suggest that BC and FeS are effective, economic, and environmentally friendly fixatives for immobilization of heavy metals in ES before landfill disposal.

  5. Immobilization of heavy metals in electroplating sludge by biochar and iron sulfide.

    PubMed

    Lyu, Honghong; Gong, Yanyan; Tang, Jingcshun; Huang, Yao; Wang, Qilin

    2016-07-01

    Electroplating sludge (ES) containing large quantities of heavy metals is regarded as a hazardous waste in China. This paper introduced a simple method of treating ES using environmentally friendly fixatives biochar (BC) and iron sulfide (FeS), respectively. After 3 days of treatment with FeS at a FeS-to-ES mass ratio of 1:5, the toxicity characteristic leaching procedure (TCLP)-based leachability of total Cr (TCr), Cu(II), Ni(II), Pb(II), and Zn(II) was decreased by 59.6, 100, 63.8, 73.5, and 90.5 %, respectively. After 5 days of treatment with BC at a BC-to-ES mass ratio of 1:2, the TCLP-based leachability was declined by 35.1, 30.6, 22.3, 23.1, and 22.4 %, respectively. Pseudo first-order kinetic model adequately simulated the sorption kinetic data. Structure and morphology analysis showed that adsorption, electrostatic attraction, surface complexation, and chemical precipitation were dominant mechanisms for heavy metals immobilization by BC, and that chemical precipitation (formation of metal sulfide and hydroxide precipitates), iron exchange (formation of CuFeS2), and surface complexation were mainly responsible for heavy metals removal by FeS. Economic costs of BC and FeS were 500 and 768 CNY/t, lower than that of Na2S (940 CNY/t). The results suggest that BC and FeS are effective, economic, and environmentally friendly fixatives for immobilization of heavy metals in ES before landfill disposal. PMID:27068904

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

    PubMed

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

    2016-04-01

    Iron-rich organic flocs are frequently observed in surface waters of wetlands and show a high affinity for trace metal(loid)s. Under low-flow stream conditions, flocs may settle, become buried, and eventually be subjected to reducing conditions facilitating trace metal(loid) release. In this study, we reacted freshwater flocs (704-1280 mg As/kg) from a minerotrophic peatland (Gola di Lago, Switzerland) with sulfide (5.2 mM, S(-II)spike/Fe = 0.75-1.62 mol/mol) at neutral pH and studied the speciation changes of Fe, S, and As at 25 ± 1 °C over 1 week through a combination of synchrotron X-ray techniques and wet-chemical analyses. Sulfidization of floc ferrihydrite and nanocrystalline lepidocrocite caused the rapid formation of mackinawite (52-81% of Fesolid at day 7) as well as solid-phase associated S(0) and polysulfides. Ferrihydrite was preferentially reduced over lepidocrocite, although neoformation of lepidocrocite from ferrihydrite could not be excluded. Sulfide-reacted flocs contained primarily arsenate (47-72%) which preferentially adsorbed to Fe(III)-(oxyhydr)oxides, despite abundant mackinawite precipitation. At higher S(-II)spike/Fe molar ratios (≥1.0), the formation of an orpiment-like phase accounted for up to 35% of solid-phase As. Despite Fe and As sulfide precipitation and the presence of residual Fe(III)-(oxyhydr)oxides, mobilization of As was recorded in all samples (Asaq = 0.45-7.0 μM at 7 days). Aqueous As speciation analyses documented the formation of thioarsenates contributing up to 33% of Asaq. Our findings show that freshwater flocs from the Gola di Lago peatland may become a source of As under sulfate-reducing conditions and emphasize the pivotal role Fe-rich organic freshwater flocs play in trace metal(loid) cycling in S-rich wetlands characterized by oscillating redox conditions. PMID:26967672

  7. Effect of iron sulfides on space weathering: Lessons from the Itokawa particles and laboratory simulations

    NASA Astrophysics Data System (ADS)

    Okazaki, M.; Sasaki, S.; Tsuchiyama, A.; Miyake, A.; Matsumoto, T.; Hirata, T.; Hiroi, T.

    2014-07-01

    Space weathering is the process invoked to explain the spectral mismatch between S-type asteroids and ordinary chondrites: darkening, spectral reddening, and attenuation of absorption bands in the reflectance spectra. These changes of optical properties of the surface of airless silicate bodies are explained by nanophase metallic iron (nanoFe) particles, which are formed on regolith particles by high-velocity dust impacts as well as irradiation of the solar-wind ions (Hapke 2001). Those nanoFe particles were discovered in lunar soils, Kapoeta meteorite, and regolith grains from the surface of S-type asteroid Itokawa. Experimental studies using a nano-second-pulse laser confirmed that nanoFe should control the spectral darkening and reddening. The observed reddening of S-type asteroid families is correlated with dynamical asteroid ages after family-forming disruption (Jedicke, et al. 2004). Still, experiments showed that the weathering degree should depend on the composition such as the olivine/pyroxene ratio (Hiroi and Sasaki 2001). In ordinary chondrites, iron sulfides, typically, troilite FeS is the main sulfur-bearing mineral. TEM observation of a dust grain of Itokawa showed the presence of not only iron, but also nanophase FeS particles, which are embedded within a vapor-deposited thin surface layer (thinner than 10-15 nm; Noguchi et al. 2011). One of the Itokawa grains is composed mainly of FeS (about 40 microns) with smaller olivine and pyroxene particles (Yada et al., 2014). On the other hand, the surface sulfur depletion of S-type asteroid Eros was explained by the same mechanism (high-velocity dust and solar-wind particle impacts) of space weathering (Loeffler et al. 2008). To examine the effect of FeS on the surface optical properties of silicate bodies, we conducted pulse-laser irradiation experiments on mixtures of olivine (and pyroxene) and FeS particles with typical sizes of 45--75 micron, for varying FeS fractions (0--0.2 by weight). We find that

  8. Evaluation of the diagenetic role of iron as a sulfide buffer at Cape Lookout Bight, North Carolina (USA)

    NASA Astrophysics Data System (ADS)

    He, B.; Meyers, S. R.; Alperin, M.

    2009-12-01

    Iron availability has critical impacts on primary productivity (micronutrient for cyanobacteria) and organic matter decomposition, as well as sedimentary diagenesis. This study is investigating the hypothesis that changes in iron concentration within marine sediments can control organic matter burial, via early diagenetic processes that impact pore water sulfide concentration (iron sulfidization), and phosphorus return flux to the water column (iron scavenging phosphorus and changing redox condition within sediments). The initial phase of this study is specifically focused on the diagenetic role of iron as a sulfide buffer in pore water, and its impact on bioturbation/bioirrigation. In this presentation, we outline a new approach to investigate the biogeochemistry of iron during early diagenesis, using controlled laboratory macrocosm experiments. Organic-rich coastal marine sediments were collected from Cape Lookout Bight (Outer Banks, North Carolina), a shallow coastal marine environment (depth < 8m) with an oxygenated water column, but organic-rich sediments dominated by sulfate reduction and methanogenesis. The uppermost portion of each sediment core was amended with synthetic sediment composed of kaolinite, variable amounts of hematite, and a geochemical tracer used to monitor bioturbation (samarium). The impact of iron concentration on oxygen penetration depth and bioturbation/bioirrigation is assessed using (1) detailed contour mapping of oxygen microelectrode measurements, and (2) X-ray fluorescence scanning of sub cores, which allows quantification for bioturbation induced samarium redistribution. The results from the experiments and employed statistical approaches (linear regressions and ANOVA) suggest that the oxygen penetration depth is determined by the number of the organisms in the sediments and the amount of iron addition. Future macrocosm study will develop quantitative diagenetic models that can provide insights for investigations of ancient

  9. Sulfidation of Nano Zerovalent Iron (nZVI) for Improved Selectivity During In-Situ Chemical Reduction (ISCR).

    PubMed

    Fan, Dimin; O'Brien Johnson, Graham; Tratnyek, Paul G; Johnson, Richard L

    2016-09-01

    The high reactivity of nano zerovalent iron (nZVI) leads to inefficient treatment due to competition with various natural reductant demand (NRD) processes, especially the reduction of water to hydrogen. Here we show that this limitation can be alleviated by sulfidation (i.e., modification by reducing sulfur compounds). nZVI synthesized on carboxylmethylcelluose (CMC-nZVI) was sulfidated with either sulfide or dithionite. The reactivity of the resulting materials was examined with three complementary assays: (i) direct measurement of hydrogen production, (ii) reduction of a colorimetric redox probe (indigo disulfonate, I2S), and (iii) dechlorination of trichloroethylene (TCE). The results indicate that sulfidation at S/Fe molar ratios of ≥0.3, effectively eliminates reaction with water, but retains significant reactivity with TCE. However, sulfidation with sulfide leaves most of the nZVI as Fe(0), whereas dithionite converts a majority of the nZVI to FeS (thus consuming much of the reducing capacity originally provided by the Fe(0)). Simplified numerical models show that the reduction kinetics of I2S and TCE are mainly dependent on the initial reducing equivalents and that the TCE reduction rate is affected by the aging of FeS. Overall, the results suggest that pretreatment of nZVI with reducing sulfur compounds could result in substantial improvement in nZVI selectivity. PMID:27454131

  10. Sulfur isotope patterns of iron sulfide and barite nodules in the Upper Cretaceous Chalk of England and their regional significance in the origin of coloured chalks

    NASA Astrophysics Data System (ADS)

    Jeans, Christopher V.; Turchyn, Alexandra V.; Hu, Xu-Fang

    2016-06-01

    The relationship between the development of iron sulfide and barite nodules in the Cenomanian Chalk of England and the presence of a red hematitic pigment has been investigated using sulfur isotopes. In southern England where red and pink chalks are absent, iron sulfide nodules are widespread. Two typical large iron sulfide nodules exhibit δ34S ranging from -48.6‰ at their core to -32.6‰ at their outer margins. In eastern England, where red and pink chalks occur in three main bands, there is an antipathetic relationship between the coloured chalks and the occurrence of iron sulfide or barite nodules. Here iron sulfide, or its oxidised remnants, are restricted to two situations: (1) in association with hard grounds that developed originally in chalks that contained the hematite pigment or its postulated precursor FeOH3, or (2) in regional sulfidization zones that cut across the stratigraphy. In the Cenomanian Chalk exposed in the cliffs at Speeton, Yorkshire, pyrite and marcasite (both iron sulfide) nodules range in δ34S from -34.7‰ to +40.0‰. In the lower part of the section δ34S vary from -34.8‰ to +7.8‰, a single barite nodule has δ34S between +26.9‰ and +29.9‰. In the middle part of the section δ34S ranges from +23.8‰ to +40.0‰. In the sulfidization zones that cut across the Cenomanian Chalk of Lincolnshire the iron sulfide nodules are typically heavily weathered but these may contain patches of unoxidised pyrite. In these zones, δ34S ranges from -32.9‰ to +7.9‰. The cross-cutting zones of sulfidization in eastern England are linked to three basement faults - the Flamborough Head Fault Zone, the Caistor Fault and the postulated Wash Line of Jeans (1980) - that have affected the deposition of the Chalk. It is argued that these faults have been both the conduits by which allochthonous fluids - rich in hydrogen sulfide/sulfate, hydrocarbons and possibly charged with sulfate-reducing bacteria - have penetrated the Cenomanian Chalk as

  11. Deposition of iron sulfide thin films by AACVD from single source precursors

    NASA Astrophysics Data System (ADS)

    Akhtar, Masood; Abdelhady, Ahmed Lutfi; Azad Malik, M.; O'Brien, Paul

    2012-05-01

    The unsymmetrical [Fe(S2CNEtiPr)3] (1), [Fe(S2CNEtMe)3] (2) and symmetrical [Fe(S2CN(Hex)2)3] (3), [Fe(S2CN(Et)2)3] (4) tris(dialkyldithiocarbamato)iron(III) complexes were used as single source precursors for the deposition of iron sulfide thin films by the aerosol assisted chemical vapor Deposition (AACVD) method. The unsymmetrical complexes deposited the mixed phases (pyrite and marcasite) at all deposition temperatures except the complex (2) which deposited pyrite and pyrrhotite at 400 °C. The symmetrical complex (3) with longer alkyl groups produced a mixture of pyrite and pyrrhotite phases at 350 and 450 °C but pyrite and mackinawite at 400 °C whereas the complex (4) with shorter alkyl groups deposited a mixture of pyrite and marcasite at 350 °C but a pure pyrrhotite phase at 400 and 450 °C.

  12. Permeability of iron sulfide (FeS)-based materials for groundwater remediation.

    PubMed

    Henderson, Andrew D; Demond, Avery H

    2013-03-01

    Iron sulfide (FeS) has been extensively assessed as a reactive medium to remove both metals and halogenated organics from groundwater. However, to address its suitability as a material for permeable reactive barriers (PRBs), its propensity for solids and gas production, which result in reduced permeability, must be evaluated. The reduction in permeability for sands coated with FeS (as mackinawite), under the anoxic conditions often encountered at contaminated groundwater sites, was examined through column experiments and geochemical modeling under conditions of high calcium and nitrate, which have been previously shown to cause significant permeability reduction in zero-valent iron (ZVI) systems. The column experiments showed negligible production of both solids and gases. The geochemical modeling predicted a maximum reduction in permeability of 1% due to solids and about 30% due to gas formation under conditions for which a complete loss of permeability was predicted for ZVI systems. This difference in permeability reduction is driven by the differences in thermodynamic stability of ZVI and FeS in aqueous solutions. The results suggest that geochemical conditions that result in high permeability losses for ZVI systems will likely not be problematic for FeS-based reactive materials.

  13. A fuel-cell-assisted iron redox process for simultaneous sulfur recovery and electricity production from synthetic sulfide wastewater.

    PubMed

    Zhai, Lin-Feng; Song, Wei; Tong, Zhong-Hua; Sun, Min

    2012-12-01

    Sulfide present in wastewaters and waste gases should be removed due to its toxicity, corrosivity, and malodorous property. Development of effective, stable, and feasible methods for sulfur recovery from sulfide attains a double objective of waste minimization and resource recovery. Here we report a novel fuel-cell-assisted iron redox (FC-IR) process for simultaneously recovering sulfur and electricity from synthetic sulfide wastewater. The FC-IR system consists of an oxidizing reactor where sulfide is oxidized to elemental sulfur by Fe(III), and a fuel cell where Fe(III) is regenerated from Fe(II) concomitantly with electricity producing. The oxidation of sulfide by Fe(III) is significantly dependent on solution pH. Increasing the pH from 0.88 to 1.96 accelerates the oxidation of sulfide, however, lowers the purity of the produced elemental sulfur. The performance of fuel cell is also a strong function of solution pH. Fe(II) is completely oxidized to Fe(III) when the fuel cell is operated at a pH above 6.0, whereas only partially oxidized below pH 6.0. At pH 6.0, the highest columbic efficiency of 75.7% is achieved and electricity production maintains for the longest time of 106 h. Coupling operation of the FC-IR system obtains sulfide removal efficiency of 99.90%, sulfur recovery efficiency of 78.6 ± 8.3%, and columbic efficiency of 58.6 ± 1.6%, respectively. These results suggest that the FC-IR process is a promising tool to recover sulfur and energy from sulfide.

  14. Iron sulfides and sulfur species produced at hematite surfaces in the presence of sulfate-reducing bacteria 1

    NASA Astrophysics Data System (ADS)

    Neal, Andrew L.; Techkarnjanaruk, Somkiet; Dohnalkova, Alice; McCready, David; Peyton, Brent M.; Geesey, Gill G.

    2001-01-01

    In the presence of sulfate-reducing bacteria ( Desulfovibrio desulfuricans) hematite (α-Fe 2O 3) dissolution is affected potentially by a combination of enzymatic (hydrogenase) reduction and hydrogen sulfide oxidation. As a consequence, ferrous ions are free to react with excess H 2S to form insoluble ferrous sulfides. X-ray photoelectron spectra indicate binding energies similar to ferrous sulfides having pyrrhotite-like structures (Fe2 p3/2 708.4 eV; S2 p3/2 161.5 eV). Other sulfur species identified at the surface include sulfate, sulfite and polysulfides. Thin film X-ray diffraction identifies a limited number of peaks, the principal one of which may be assigned to the hexagonal pyrrhotite (102) peak (d = 2.09 Å; 2θ = 43.22°), at the hematite surface within 3 months exposure to sulfate-reducing bacteria (SRB). High-resolution transmission electron microscopy identifies the presence of a hexagonal structure associated with observed crystallites. Although none of the analytical techniques employed provide unequivocal evidence as to the nature of the ferrous sulfide formed in the presence of SRB at hematite surfaces, we conclude from the available evidence that a pyrrhotite stiochiometry and structure is the best description of the sulfides we observe. Such ferrous sulfide production is inconsistent with previous reports in which mackinawite and greigite were products of biological sulfate reduction (Rickard 1969a; Herbert et al., 1998; Benning et al., 1999). The apparent differences in stoichiometry may be related to sulfide activity at the mineral surface, controlled in part by H 2S autooxidation in the presence of iron oxides. Due to the relative stability of pyrrhotite at low temperatures, ferrous sulfide dissolution is likely to be reduced compared to the more commonly observed products of SRB activity. Additionally, biogenic pyrrhotite formation will also have implications for geomagnetic field behavior of sediments.

  15. Polymersomes Containing Iron Sulfide (FeS) as Primordial Cell Model. For the investigation of energy providing redox reactions

    NASA Astrophysics Data System (ADS)

    Alpermann, Theodor; Rüdel, Kristin; Rüger, Ronny; Steiniger, Frank; Nietzsche, Sandor; Filiz, Volkan; Förster, Stephan; Fahr, Alfred; Weigand, Wolfgang

    2011-04-01

    According to Wächtershäuser's "Iron-Sulfur-World" one major requirement for the development of life on the prebiotic Earth is compartmentalization. Vesicles spontaneously formed from amphiphilic components containing a specific set of molecules including sulfide minerals may have lead to the first autotrophic prebiotic units. The iron sulfide minerals may have been formed by geological conversions in the environment of deep-sea volcanos (black smokers), which can be observed even today. Wächtershäuser postulated the evolution of chemical pathways as fundamentals of the origin of life on earth. In contrast to the classical Miller-Urey experiment, depending on external energy sources, the "Iron-Sulfur-World" is based on the catalytic and energy reproducing redox system FeS + {H_2}S to FeS{}_2 + {H_2} . The energy release out of this redox reaction (∆RG° = -38 kJ/mol, pH 0) could be the cause for the subsequent synthesis of complex organic molecules and the precondition for the development of more complex units similar to cells known today. Here we show the possibility for precipitating iron sulfide inside vesicles composed of amphiphilic block-copolymers as a model system for a first prebiotic unit. Our findings could be an indication for a chemoautotrophic FeS based origin of life.

  16. Polymersomes containing iron sulfide (FeS) as primordial cell model : for the investigation of energy providing redox reactions.

    PubMed

    Alpermann, Theodor; Rüdel, Kristin; Rüger, Ronny; Steiniger, Frank; Nietzsche, Sandor; Filiz, Volkan; Förster, Stephan; Fahr, Alfred; Weigand, Wolfgang

    2011-04-01

    According to Wächtershäuser's "Iron-Sulfur-World" one major requirement for the development of life on the prebiotic Earth is compartmentalization. Vesicles spontaneously formed from amphiphilic components containing a specific set of molecules including sulfide minerals may have lead to the first autotrophic prebiotic units. The iron sulfide minerals may have been formed by geological conversions in the environment of deep-sea volcanos (black smokers), which can be observed even today. Wächtershäuser postulated the evolution of chemical pathways as fundamentals of the origin of life on earth. In contrast to the classical Miller-Urey experiment, depending on external energy sources, the "Iron-Sulfur-World" is based on the catalytic and energy reproducing redox system FeS+H2S-->FeS2+H2. The energy release out of this redox reaction (∆RG°=-38 kJ/mol, pH 0) could be the cause for the subsequent synthesis of complex organic molecules and the precondition for the development of more complex units similar to cells known today. Here we show the possibility for precipitating iron sulfide inside vesicles composed of amphiphilic block-copolymers as a model system for a first prebiotic unit. Our findings could be an indication for a chemoautotrophic FeS based origin of life. PMID:20697814

  17. Polymersomes containing iron sulfide (FeS) as primordial cell model : for the investigation of energy providing redox reactions.

    PubMed

    Alpermann, Theodor; Rüdel, Kristin; Rüger, Ronny; Steiniger, Frank; Nietzsche, Sandor; Filiz, Volkan; Förster, Stephan; Fahr, Alfred; Weigand, Wolfgang

    2011-04-01

    According to Wächtershäuser's "Iron-Sulfur-World" one major requirement for the development of life on the prebiotic Earth is compartmentalization. Vesicles spontaneously formed from amphiphilic components containing a specific set of molecules including sulfide minerals may have lead to the first autotrophic prebiotic units. The iron sulfide minerals may have been formed by geological conversions in the environment of deep-sea volcanos (black smokers), which can be observed even today. Wächtershäuser postulated the evolution of chemical pathways as fundamentals of the origin of life on earth. In contrast to the classical Miller-Urey experiment, depending on external energy sources, the "Iron-Sulfur-World" is based on the catalytic and energy reproducing redox system FeS+H2S-->FeS2+H2. The energy release out of this redox reaction (∆RG°=-38 kJ/mol, pH 0) could be the cause for the subsequent synthesis of complex organic molecules and the precondition for the development of more complex units similar to cells known today. Here we show the possibility for precipitating iron sulfide inside vesicles composed of amphiphilic block-copolymers as a model system for a first prebiotic unit. Our findings could be an indication for a chemoautotrophic FeS based origin of life.

  18. Possible Evidence for Iron Sulfates, Iron Sulfides, and Elemental Sulfur at Gusev Crater, Mars, from Mer, Crism, and Analog Data

    NASA Technical Reports Server (NTRS)

    Morris, R. V.; Ming, D. W.; Yen, A.; Arvidson, R. E.; Gruener, J.; Humm, D.; Klingelhoefer, G.; Murchie, S.; Schroeder, C.; Seelos, F., IV; Squyres, S.; Wiseman, S.; Wolff, M.

    2007-01-01

    The Mossbauer (MB) spectrometers on the Mars Exploration Rovers (MER) Spirit (Gusev crater) and Opportunity (Meridiani Planum) have detected 14 Fe-bearing phases, and mineralogical assignments have been made for all except 3. Identified Fe2+-bearing phases are olivine, pyroxene, ilmenite, and troilite. Magnetite and chromite are present as mixed Fe(2+) and Fe(3+) phases. Identified Fe(3+) phase are jarosite, hematite, goethite, and nanophase ferric oxide (npOx). Fe(sup 0) (iron metal) is present as kamacite. Nanophase ferric oxide (npOx) is a generic name for octahedrally coordinated Fe(3+) alteration products that cannot be otherwise mineralogically assigned on the basis of MER data. On the Earth, npOx would include ferrihydrite, iddingsite, schwertmannite, akaganeite, and superparamagnetic hematite and goethite. The Mars Reconnaissance Orbiter CRISM instrument, a visible, near-IR hyperspectral imager (approximately 0.35 to 4 micron) enables mineralogical examination of Mars with a tool that is sensitive to H2O and to M-OH (M = Al, Si, Fe, Mg, etc.) at spatial resolution of about 20 m/pixel. We examined a CRISM image of the MER region of Gusev crater (Columbia Hills and plains to the west), looking for spectral evidence of the aqueous process apparent from the MER analyses. We also searched for spectral constraints for the mineralogical composition of our unidentified Fe-bearing phases and the forms of npOx present on Mars. We also consider evidence from analogue samples that the precursor for the goethite detected by MB in Clovis Class rocks is an iron sulfide. We suggest that there is some indirect evidence that elemental sulfur might be present to different extents in Clovis Class rocks, the Fe3Sulfate-rich soils, and perhaps even typical (Laguna Class) surface soils.

  19. Role of morphology and structure in the kinetic evolution of iron-sulfide films on Fe-base alloys

    SciTech Connect

    Pareek, V.K.; Ramanarayanan, T.A.; Mumford, J.D.; Ozekcin, A.; Scanlon, J.C. )

    1994-06-01

    Sulfidation corrosion of 4130 steel in CH[sub 3]SH was studied in the temperature range 250-550[degree]C. The rate of sulfidation attack was found to be a function of temperature and sulfur activity. Investigations of the corrosion process led to the proposal of two mechanisms of sulfidation, dependent on temperature. Cation diffusion through the iron sulfide corrosion product is the rate-determining step at higher temperatures (> 370[degree]C), while a surface reaction was identified as the rate-limiting step at lower temperatures. The corrosion scale has preferred orientation as determined by X-ray diffraction and morphological observations. The lower-temperature corrosion product is made up of columnar grains of pyrrholite crystals with the c-axis aligned nearly perpendicular to the steel substrate. At high temperatures, a whisker morphology developed with the whiskers having variable texture with respect to the steel substrate. A preformed-surface-oxide layer on 4130 steel does not appear to significantly reduce sulfidation corrosion. 28 refs., 16 figs.

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

    SciTech Connect

    Rittman, Bruce; Zhou, Chen; Vannela, Raveender

    2013-12-31

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

  1. Diurnal shifts in co-distributions of sulfide and iron(II) and profiles of phosphate and ammonium in the rhizosphere of Zostera capricorni

    NASA Astrophysics Data System (ADS)

    Pagès, Anaïs; Welsh, David T.; Robertson, David; Panther, Jared G.; Schäfer, Jörg; Tomlinson, Rodger B.; Teasdale, Peter R.

    2012-12-01

    High resolution, two dimensional distributions of porewater iron(II) and sulfide were measured, using colourimetric DET (diffusive equilibration in a thin film) and DGT (diffusive gradients in a thin film) techniques, respectively, in Zostera capricorni colonised sediments under both light and dark conditions. Low resolution depth profiles of ammonium and phosphate were measured using conventional DET and DGT methods, respectively. Porewater iron(II) and sulfide distributions showed a high degree of spatial heterogeneity under both light and dark conditions, and distributions were characterised by a complex mosaic of sediment zones dominated by either iron(II) or sulfide. However, there was a clear shift in overall redox conditions between light and dark conditions. During light deployments, iron(II) and sulfide concentrations were generally low throughout the rhizosphere, apart from a few distinct "hotspots" of high concentration. Whereas during dark deployments, high concentrations of iron(II) were sometimes measured in the near surface sediments and sulfide depth distributions migrated towards the sediment surface. Profiles of porewater ammonium and phosphate demonstrated an increase in ammonium concentrations under dark compared to light conditions. Surprisingly, despite the large changes in iron(II) distributions between light and dark conditions, phosphate profiles remained similar, indicating that adsorption/release of phosphate by iron(III) hydr(oxide) mineral formation and reduction was not a major factor regulating porewater phosphate concentrations in these sediments or that phosphate uptake by the seagrass roots persisted during the dark period. Overall, the results demonstrate that the photosynthetic activity of the seagrass played a significant role in regulating sulfide, iron(II) and ammonium concentrations in the rhizosphere, due to rates of radial oxygen loss and ammonium uptake by the roots and rhizomes being lower under dark compared to light

  2. Iron-Sulfide-Associated Products Formed during Reductive Dechlorination of Carbon Tetrachloride.

    PubMed

    Lan, Ying; Butler, Elizabeth C

    2016-06-01

    This paper investigated the mackinawite (FeS)-associated products formed during reaction between FeS and carbon tetrachloride (CT) at pH 7 and 8. At pH 8, reaction of FeS with CT led to formation of abundant spherical particles with diameters between 50 and 400 nm on the FeS surface and in solution; far fewer such particles were observed at pH 7. Analysis of the FeS surface by energy dispersive X-ray spectroscopy after reaction with CT at pH 8 showed decreased sulfur and elevated oxygen compared to unreacted FeS. The spherical particles that formed upon FeS reaction with CT were mostly amorphous with localized areas of poorly crystalline two-line ferrihydrite. X-ray photoelectron spectroscopy indicated that the predominant Fe surface species after reaction with CT at pH 8 was Fe(III)-O, consistent with ferrihydrite and other amorphous iron (hydr)oxides as major products. Powder X-ray diffraction analysis suggested formation of greigite upon reaction of FeS with CT at pH 7. Both ferrihydrite and Fe(2+), which is a product of greigite dissolution, can react with dissolved HS(-) to form FeS, suggesting that, after oxidation by chlorinated aliphatics, FeS can be regenerated by addition or microbial generation of sulfide.

  3. Kinetics and mechanisms of iron sulfide reductions in hydrogen and in carbon monoxide

    USGS Publications Warehouse

    Wiltowski, T.; Hinckley, C.C.; Smith, Gerard V.; Nishizawa, T.; Saporoschenko, Mykola; Shiley, R.H.; Webster, J.R.

    1987-01-01

    The reduction of iron sulfides by hydrogen and by carbon monoxide has been studied using plug flow and thermogravimetric methods. The reactions were studied in the 523-723??K temperature range and were found to be first-order processes. Plug flow studies were used to correlate reaction rates between pyrite and the gases as a function of the surface area of the pyrite. The rate of H2S formation increases with the surface area of the pyrite sample. The results of thermogravimetric experiments indicate that the reactions consist of several steps. Rate constants for the pyrite reduction by H2 and by CO were obtained. The activation energies increased with degree of reduction. Values of Ea were 113.2 (step I) and 122.5 kJ/mole (step II) for pyrite reduction with CO and 99.4 (step I), 122.4 (step II), 125.2 (step III), and 142.6 kJ/mole (step IV) for pyrite reduction with hydrogen. ?? 1987.

  4. Failure analysis of Mark IA lithium/iron sulfide battery. [Two 20-kWh modules

    SciTech Connect

    Kolba, V M; Battles, J E; Geller, J D; Gentry, K

    1980-10-01

    The Mark IA lithium/iron sulfide electric-vehicle battery, which consisted of two 20-kWh modules containing 60 cells each, was fabricated by Eagle-Picher Industries, Inc. and delivered to ANL for testing in May 1979. During startup heating prior to electrical testing, a short circuit developed in one of the modules, which resulted in a progressive failure of the cells. The other module, which was alongside and connected in series, was unaffected by the failure. The initial indication of difficulty was a small drop in the voltage of several cells, followed by short circuits in the balance of the cells and localized temperatures above 1000/sup 0/C. A team consisting of ANL and Eagle-Picher personnel conducted a detailed failure analysis as the failed module was disassembled. The other module was also examined for purposes of comparison. The general conclusion was that the short circuit was initiated by electrolyte leakage and resulting corrosion in the nearby region which formed metallic bridges between cells and the cell tray, or arcing between cells and the cell tray through the butt joints in the electrical insulation. The above two mechanisms were also believed to be responsible for the failure propagation. 66 figures, 11 tables.

  5. SULFIDE MINERALS IN SEDIMENTS

    EPA Science Inventory

    The formation processes of metal sulfides in sediments, especially iron sulfides, have been the subjects of intense scientific research because of linkages to the global biogeochemical cycles of iron, sulfur, carbon, and oxygen. Transition metal sulfides (e.g., NiS, CuS, ZnS, Cd...

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

    SciTech Connect

    Hayes, Kim F.; Bi, Yuqiang; Carpenter, Julian; Hyng, Sung Pil; Rittmann, Bruce E.; Zhou, Chen; Vannela, Raveender; Davis, James A.

    2014-01-01

    This overarching aim of this project was to identify the role of biogenic and synthetic iron-sulfide minerals in the long-term sequestration of reduced U(IV) formed under sulfate-reducing conditions when subjected to re-oxidizing conditions. The work reported herein was achieved through the collaborative research effort conducted at Arizona State University (ASU) and the University of Michigan (UM). Research at ASU, focused on the biogenesis aspects, examined the biogeochemical bases for iron-sulfide production by Desulfovibrio vulgaris, a Gram-negative bacterium that is one of the most-studied strains of sulfate-reducing bacteria. A series of experimental studies were performed to investigate comprehensively important metabolic and environmental factors that affect the rates of sulfate reduction and iron-sulfide precipitation, the mineralogical characteristics of the iron sulfides, and how uranium is reduced or co-reduced by D. vulagaris. FeS production studies revealed that controlling the pH affected the growth of D. vulgaris and strongly influenced the formation and growth of FeS solids. In particular, lower pH produced larger-sized mackinawite (Fe1+xS). Greater accumulation of free sulfide, from more sulfate reduction by D. vulgaris, also led to larger-sized mackinawite and stimulated mackinawite transformation to greigite (Fe3S4) when the free sulfide concentration was 29.3 mM. On the other hand, using solid Fe(III) (hydr)oxides as the iron source led to less productivity of FeS due to their slow and incomplete dissolution and scavenging of sulfide. Furthermore, sufficient free Fe2+, particularly during Fe(III) (hydr)oxide reductions, led to the additional formation of vivianite [Fe3(PO4)2•8(H2O)]. The U(VI) reduction studies revealed that D. vulgaris reduced U(VI) fastest when accumulating sulfide from concomitant sulfate reduction, since direct enzymatic and sulfide-based reductions of U(VI) occurred in parallel. The UO2 produced in presence of ferrous

  7. Potassium Partitioning Between Iron Sulfide and Peridotite Melt at 2.0 GPa

    NASA Astrophysics Data System (ADS)

    Rama Murthy, V.; van Westrenen, W.; Fei, Y.

    2001-12-01

    Radioactive decay of potassium-40 in the Earth's core could provide the heat required to sustain the Earth's magnetic field. If potassium is present in the core, it was incorporated early in Earth's history, during segregation of a sulfur-bearing iron metal liquid. Recent studies by Gessmann and Wood (Spring AGU 1999) and Chabot and Drake (EPSL, 1999) have started to provide constraints on the concentration of K in the core through measurements of K partitioning between Fe-S and silicate liquids at relatively low pressure (1.5 - 2.5 GPa). As a further step towards designing high-pressure experiments at conditions relevant for metal segregation during core formation, we have studied extensively the effects of capsule material and experiment duration on measured metal-silicate distribution coefficients (Kd values) of K. Experiments were performed at pressures of 2 GPa, temperatures between 1423 and 2673 K, and run durations between 5 seconds and 1 hour. Starting material for all our experiments is a mixture of KLB-1 peridotite, K2Si2O5 silicate glass, FeS and Fe, with a bulk composition close to Bulk Earth estimates for all elements except K (2.31 wt% K2O). All experiments were performed in a piston cylinder apparatus, using either single graphite capsules, or graphite inner capsules within a noble metal outer capsule. In all runs, the metal phase quenches to a mixture of Fe and Fe-S blebs. At 2073 K, a minimum of 15 minutes experimental duration is needed to achieve equilibrium Fe-S liquid compositions. At high temperature, the peridotite melt quenches to an intimate mixture of olivine quench crystals and interstitial quench glass, while occasionally large pools of homogeneous glass are formed. K contents in metal and silicate phases were measured using an electron microprobe. During all stages of the experimental and analytical process, any contact with water and ethanol was avoided to prevent dissolution of potassium sulfides. Nevertheless, duplicate measurements

  8. Stabilization of Sulfur and Arsenic Species in Sulfidic, Iron-rich Geothermal Waters Using Solid Phase Extraction

    NASA Astrophysics Data System (ADS)

    Ullrich, M. K.; Gayout, A.; Misiari, V.; Planer-Friedrich, B.

    2015-12-01

    Iron-rich geothermal waters pose a special challenge regarding sample stabilization for sulfur and arsenic speciation analysis. Standard stabilization techniques fail to preserve speciation due to precipitating iron oxyhydroxides and thus adsorption of arsenic when flash-freezing a sample or precipitation of orpiment (As2S3)-like phases when adding HNO3. Solid phase extraction has the potential to extract anionic sulfur and arsenic species from solution and consequently separate them from cationic iron. This method was tested by applying synthetic solutions of sulfur and arsenic species onto Bio-Rad AG2-X8 resin and eluting the target species using 0.5 M Na-Salicylate. Complete retention of the initially applied amount on the resin was found for sulfate, thiosulfate, arsenate, monothioarsenate and trithioarsenate with 100.0 %, 99.7 %, 95.1 %, 98.9 %, and 99.8 %, respectively. Arsenite passed the resin without binding (3.0 % retention). All species bound to the resin could be eluted quantitatively and species-conserving with a recovery of 98.4 %, 102.8 %, 95.3 %, 90.5 % and 85.3 % for sulfate, thiosulfate, arsenate, monothioarsenate and trithioarsenate, respectively. Addition of 5 ppm FeCl2 did not reduce method efficiency with 98.7 % retention and 105.1 % recovery for monothioarsenate, while all of the applied iron passed the resin without binding as hypothesized. However, in solutions containing a mixture of arsenite, arsenate, monothioarsenate and trithioarsenate we found arsenite retention up to 59.1 % both in the presence and absence of iron. This effect cannot be fully explained yet and might be attributed to free sulfide in these mixed solutions facilitating arsenite binding via sulfide sorbed onto the resin. The interaction between different species needs to be further investigated. Samples from geothermal features in Yellowstone and mineral springs in the Czech Republic have been collected and results of immediate elution and stability during storage will

  9. Application of MC-ICPMS to the precise determination of tellurium isotope compositions in chondrites, iron meteorites and sulfides

    NASA Astrophysics Data System (ADS)

    Fehr, Manuela A.; Rehkämper, Mark; Halliday, Alex N.

    2004-03-01

    New mass spectrometric techniques have been developed for the precise and accurate determination of Te isotope compositions. The methods are suitable for the analysis of stony and iron meteorites as well as sulfide mineral separates, such that they can be applied to search for Te isotope anomalies in various solar system materials. Tellurium is first separated from its matrix with a two-stage liquid chromatographic procedure. For iron meteorites, solvent-extraction is used to isolate Te from Fe prior to the column separation. The isotope composition of Te is then determined by multiple-collector inductively coupled plasma-mass spectrometry (MC-ICPMS). Tellurium has a very high first ionization potential and thus MC-ICPMS is much more suitable for the isotopic analyses than positive ion thermal ionization mass spectrometry (TIMS). Only about 100 ng Te are required for a single high precision measurement. Analyses of two terrestrial sulfides, the carbonaceous chondrite Allende and the iron meteorite Canyon Diablo reveal that these have Te isotope compositions that are identical to the terrestrial standard within uncertainty. The Te isotope data acquired for standard solutions as well as meteorites and sulfides display reproducibilities (2[sigma]) of approximately +/-4500 ppm for 120Te/128Te, +/-140 ppm for 122Te/128Te, +/-100 ppm for 124Te/128Te, +/-30 ppm for 126Te/128Te, and +/-60 ppm for 130Te/128Te. Compared to published results for meteorite samples obtained by TIMS, this represents an improvement in precision of about one to two orders of magnitude for 122-130Te/128Te and by a factor of 4 for 120Te/128Te. A number of experiments furthermore demonstrate that the isotope data acquired by MC-ICPMS are accurate, even for complex geological samples.

  10. Study on application of biological iron sulfide composites in treating vanadium-extraction wastewater containing chromium (VI) and chromium reclamation.

    PubMed

    Xie, Yi-Fei; Li, Xu-Dong; Li, Fu-De

    2013-04-01

    In this study, the Cr(VI)-resistant properties and regeneration characteristics of biological iron sulfide composites were investigated, which consist of sulfate reducing bacteria (SRB) and its in situ synthesized nanosized iron sulfides. Then the application of the composites in treating vanadium-extraction wastewater containing high concentration Cr(VI) and reclaiming Cr were performed. It was found that SRB in composites still survived after being used to treat vanadium-extraction wastewater, which could reduce reaction products Fe3+ and sulphur into Fe2+ and S2 by using them as the electron accepters and thus regenerating biological iron sulfide composites. The SRB also could be resistant to 600 mgl(-1) Cr(VI) and reduce it gradually. Based on the Cr(VI)-resistant properties and regeneration characteristics of the composites, a reduction-regeneration recirculation process for treating vanadium-extraction wastewater and reclamation of Cr was developed. The results indicated that the contaminants in effluent reached the Chinese discharge standard of pollutants for vanadium industry (GB 26452-2011), i.e. the concentration of total Cr(TCr) was less than 0.912 mgl(-1), Cr(VI) was less than 0.017 mgl(-1) and V was less than 0.260 mgl(-1). After 10 cycles of treatment, the Cr2O3 content in sludge reached 41.03%, and the ratio of Cr2O3/FeO was 7.35. The sludge reached the chemical and metallurgical (hydrometallurgy) grade of chromite ore and could be reclaimed. PMID:24620597

  11. Study on application of biological iron sulfide composites in treating vanadium-extraction wastewater containing chromium (VI) and chromium reclamation.

    PubMed

    Xie, Yi-Fei; Li, Xu-Dong; Li, Fu-De

    2013-04-01

    In this study, the Cr(VI)-resistant properties and regeneration characteristics of biological iron sulfide composites were investigated, which consist of sulfate reducing bacteria (SRB) and its in situ synthesized nanosized iron sulfides. Then the application of the composites in treating vanadium-extraction wastewater containing high concentration Cr(VI) and reclaiming Cr were performed. It was found that SRB in composites still survived after being used to treat vanadium-extraction wastewater, which could reduce reaction products Fe3+ and sulphur into Fe2+ and S2 by using them as the electron accepters and thus regenerating biological iron sulfide composites. The SRB also could be resistant to 600 mgl(-1) Cr(VI) and reduce it gradually. Based on the Cr(VI)-resistant properties and regeneration characteristics of the composites, a reduction-regeneration recirculation process for treating vanadium-extraction wastewater and reclamation of Cr was developed. The results indicated that the contaminants in effluent reached the Chinese discharge standard of pollutants for vanadium industry (GB 26452-2011), i.e. the concentration of total Cr(TCr) was less than 0.912 mgl(-1), Cr(VI) was less than 0.017 mgl(-1) and V was less than 0.260 mgl(-1). After 10 cycles of treatment, the Cr2O3 content in sludge reached 41.03%, and the ratio of Cr2O3/FeO was 7.35. The sludge reached the chemical and metallurgical (hydrometallurgy) grade of chromite ore and could be reclaimed.

  12. Iron Sulfide as a Sustainable Reactive Material for Permeable Reactive Barriers

    NASA Astrophysics Data System (ADS)

    Henderson, A. D.; Demond, A. H.

    2012-12-01

    Permeable reactive barriers (PRBs) are gaining acceptance for groundwater remediation, as they operate in situ and do not require continuous energy input. The majority of PRBs use zero-valent iron (ZVI). However, some ZVI PRBs have hydraulically failed [1,2], due to the fact that ZVI may reduce not only contaminants but also water and non-contaminant solutes. These reactions may form precipitates or gas phases that reduce permeability. Therefore, there is a need to assess the hydraulic suitability of possible alternatives, such as iron sulfide (FeS). The capability of FeS to remove both metals and halogenated organics from aqueous systems has been demonstrated previously [3,4], and FeS formed in situ within a ZVI PRB has been linked to contaminant removal [5]. These results suggest possible applications in groundwater remediation as a permeable reactive barrier (PRB) material. However, the propensity of FeS for permeability loss, due to solids and gas production, must be evaluated in order to address its suitability for PRBs. The reduction in permeability for FeS-coated sands under the anoxic conditions often encountered at contaminated groundwater sites was examined through column experiments and geochemical modeling under conditions of high calcium and nitrate, which have been previously shown to cause significant permeability reduction in zero-valent iron (ZVI) systems [6]. The column experiments showed negligible production of both solids and gases. The geochemical model was used to estimate solid and gas volumes generated under conditions of varying FeS concentration. Then, the Kozeny-Carman equation and a power-law relationship was used to predict permeability reduction, with a maximum reduction in permeability of 1% due to solids and about 30% due to gas formation under conditions for which a complete loss of permeability was predicted for ZVI systems. This difference in permeability reduction is driven by the differences in thermodynamic stability of ZVI

  13. Reduction and sulfidation properties of iron species in iron-supported Y-zeolite by temperature-programmed reduction and sulfiding

    SciTech Connect

    Inamura, Kazuhiro; Iwamoto, Ryuichiro; Iino, Akira; Takyu, Toshiyuki )

    1993-07-01

    Temperature-programmed reduction (TPR) and temperature-programmed sulfiding (TPS) were used to characterize reduction and sulfiding properties of Fe-exchanged Y-zeolites and Fe-treated Y-zeolites, which were prepared by treating NH[sub 4]Y-zeolite with an aqueous ferric nitrate solution (Fe-treatment). By considering their unique TPR and TPS patterns, it was confirmed that the Fe[sup 2+]-species in the Fe-exchanged Y-zeolites are stabilized inside the sodalite cages and the hexagonal prisms. On the basis of the TPR and TPS characterizations, it was demonstrated that three types of the Fe-species are present in the Fe-treated Y-zeolite framework (including aggregated ferric oxide), the proportion of which is dependent on the extent of the Fe-treatment. Prolonged Fe-treatment weakens the interaction between the Fe-species and the framework oxygen atoms by hydrolysis, and leads to the aggregation of the Fe oxides and to the formation of bulk ferric oxide. The small Fe-oxide clusters, which are probably situated inside the supercages through a coordination with the framework oxygen atoms, are responsible for the high activity for toluene disproportionation in the presence of H[sub 2]S. 31 refs., 10 figs., 2 tabs.

  14. Nonaqueous System of Iron-Based Ionic Liquid and DMF for the Oxidation of Hydrogen Sulfide and Regeneration by Electrolysis.

    PubMed

    Guo, Zhihui; Zhang, Tingting; Liu, Tiantian; Du, Jun; Jia, Bing; Gao, Shujing; Yu, Jiang

    2015-05-01

    To improve the hydrogen sulfide removal efficiency with the application of an iron-based imidazolium chloride ionic liquid (Fe(III)-IL) as desulfurizer, Fe(II) and N,N-dimethylformamide (DMF) are introduced to Fe(III)-IL to construct a new nonaqueous desulfurization system (Fe(III/II)-IL/DMF). Following desulfurization, the system can be regenerated using the controlled-potential electrolysis method. The addition of Fe(II) in Fe(III)-IL is beneficial for the hydrogen sulfide removal and the electrochemical regeneration of the desulfurizer. The addition of DMF in Fe(III/II)-IL does not change the structure of Fe(III/II)-IL but clearly decreases the acidity, increases the electrolytic current, and decreases the stability of the Fe-Cl bond in Fe(III/II)-IL. Fe(III/II)-IL/DMF can remove hydrogen sulfide and can be regenerated through an electrochemical method more efficiently than can Fe(III/II)-IL. After six cycles, the desulfurization efficiency remains higher than 98%, and the average conversion rate of Fe(II) is essentially unchanged. No sulfur peroxidation occurs, and the system remains stable. Therefore, this new nonaqueous system has considerable potential for removing H2S in pollution control applications.

  15. Stereodynamics in the Collisional Autoionization of Water, Ammonia, and Hydrogen Sulfide with Metastable Rare Gas Atoms: Competition Between Intermolecular Halogen and Hydrogen Bonds.

    PubMed

    Falcinelli, Stefano; Bartocci, Alessio; Cavalli, Simonetta; Pirani, Fernando; Vecchiocattivi, Franco

    2016-01-11

    Recent experiments on the title subject, performed with a high-resolution crossed-beam apparatus, have provided the total ionization cross sections as a function of the collision energy between noble gas atoms, electronically excited in their metastable states (Ng*), and H2 O, H2 S, and NH3 reagents, as well as the emitted electron energy spectra. This paper presents a rationalization of all the experimental findings in a unifying picture to cast light on the basic chemical properties of Ng* under conditions of great relevance both from a fundamental and from an applied point of view. The importance of this investigation is that it isolates the selective role of the intermolecular halogen and hydrogen bonds, to assess their anisotropic effects on the stereodynamics of the promoted ionization reactions, and to model energy transfer and reactivity in systems of applied interest, such as planetary atmospheres, plasmas, lasers, and flames.

  16. Ferrous Iron and Sulfur Oxidation and Ferric Iron Reduction Activities of Thiobacillus ferrooxidans Are Affected by Growth on Ferrous Iron, Sulfur, or a Sulfide Ore

    PubMed Central

    Suzuki, Isamu; Takeuchi, Travis L.; Yuthasastrakosol, Trin D.; Oh, Jae Key

    1990-01-01

    Eight strains of Thiobacillus ferrooxidans (laboratory strains Tf-1 [= ATCC 13661] and Tf-2 [= ATCC 19859] and mine isolates SM-1, SM-2, SM-3, SM-4, SM-5, and SM-8) and three strains of Thiobacillus thiooxidans (laboratory strain Tt [= ATCC 8085] and mine isolates SM-6 and SM-7) were grown on ferrous iron (Fe2+), elemental sulfur (S0), or sulfide ore (Fe, Cu, and Zn). The cells were studied for their aerobic Fe2+ - and S0-oxidizing activities (O2 consumption) and anaerobic S0-oxidizing activity with ferric iron (Fe3+) (Fe2+ formation). Fe2+-grown T. ferrooxidans cells oxidized S0 aerobically at a rate of 2 to 4% of the Fe2+ oxidation rate. The rate of anaerobic S0 oxidation with Fe3+ was equal to the aerobic oxidation rate in SM-1, SM-3, SM-4, and SM-5, but was only one-half or less that in Tf-1, Tf-2, SM-2, and SM-8. Transition from growth on Fe2+ to that on S0 produced cells with relatively undiminished Fe2+ oxidation activities and increased S0 oxidation (both aerobic and anaerobic) activities in Tf-2, SM-4, and SM-5, whereas it produced cells with dramatically reduced Fe2+ oxidation and anaerobic S0 oxidation activities in Tf-1, SM-1, SM-2, SM-3, and SM-8. Growth on ore 1 of metal-leaching Fe2+-grown strains and on ore 2 of all Fe2+-grown strains resulted in very high yields of cells with high Fe2+ and S0 oxidation (both aerobic and anaerobic) activities with similar ratios of various activities. Sulfur-grown Tf-2, SM-1, SM-4, SM-6, SM-7, and SM-8 cultures leached metals from ore 3, and Tf-2 and SM-4 cells recovered showed activity ratios similar to those of other ore-grown cells. It is concluded that all the T. ferrooxidans strains studied have the ability to produce cells with Fe2+ and S0 oxidation and Fe3+ reduction activities, but their levels are influenced by growth substrates and strain differences. PMID:16348205

  17. Suboxic deep seawater in the late Paleoproterozoic: Evidence from hematitic chert and iron formation related to seafloor-hydrothermal sulfide deposits, central Arizona, USA

    USGS Publications Warehouse

    Slack, J.F.; Grenne, Tor; Bekker, A.; Rouxel, O.J.; Lindberg, P.A.

    2007-01-01

    A current model for the evolution of Proterozoic deep seawater composition involves a change from anoxic sulfide-free to sulfidic conditions 1.8??Ga. In an earlier model the deep ocean became oxic at that time. Both models are based on the secular distribution of banded iron formation (BIF) in shallow marine sequences. We here present a new model based on rare earth elements, especially redox-sensitive Ce, in hydrothermal silica-iron oxide sediments from deeper-water, open-marine settings related to volcanogenic massive sulfide (VMS) deposits. In contrast to Archean, Paleozoic, and modern hydrothermal iron oxide sediments, 1.74 to 1.71??Ga hematitic chert (jasper) and iron formation in central Arizona, USA, show moderate positive to small negative Ce anomalies, suggesting that the redox state of the deep ocean then was at a transitional, suboxic state with low concentrations of dissolved O2 but no H2S. The presence of jasper and/or iron formation related to VMS deposits in other volcanosedimentary sequences ca. 1.79-1.69??Ga, 1.40??Ga, and 1.24??Ga also reflects oxygenated and not sulfidic deep ocean waters during these time periods. Suboxic conditions in the deep ocean are consistent with the lack of shallow-marine BIF ??? 1.8 to 0.8??Ga, and likely limited nutrient concentrations in seawater and, consequently, may have constrained biological evolution. ?? 2006 Elsevier B.V. All rights reserved.

  18. A novel solvent-free thermal reaction of ferrocene and sulfur for one-step synthesis of iron sulfide and carbon nanocomposites and their electrochemical performance

    NASA Astrophysics Data System (ADS)

    Fei, Ling; Jiang, Yufeng; Xu, Yun; Chen, Gen; Li, Yuling; Xu, Xun; Deng, Shuguang; Luo, Hongmei

    2014-11-01

    A novel solvent-free thermal reaction of ferrocene and sulfur is developed for preparing iron sulfide and carbon nanocomposites, where ferrocene acts as both iron and carbon source. The prepared composite has iron sulfide sandwiched in carbon matrix. Moreover, ferrocene and sulfur can turn to vapor phase at an elevated temperature, resulting in easy deposition of product on the surface of templates. Sodium chloride was selected as a template due to its nontoxic and water-soluble nature. The NaCl-templated composite shows "sphere on mattress" morphology and exhibits the highest capacity and the longest cyclability ever reported for iron pyrite anode. To obtain mesoporous nanocomposites, SBA-15 was also applied as templates. The mesoporous nanocomposite demonstrates excellent capacity retention capability, indicating the robust structural stability.

  19. High-Nickel Iron-Sulfides in Anhydrous, GEMS-Rich IDPs

    NASA Astrophysics Data System (ADS)

    Flynn, G. J.; Keller, L. P.; Wirick, S.; Hu, W.; Li, L.; Yan, H.; Huang, X.; Nazaretski, E.; Lauer, K.; Chu, Y. S.

    2016-08-01

    We used the new Hard X-ray Nanoprobe at the NSLS II to map the element distributions, with ~15 nm spatial resolution, in anhydrous, GEMS-rich IDPs and found high-Ni, Fe-sulfides, previously thought only to form by hydrous alteration on parent bodies.

  20. GEOCHEMICAL AND BIOLOGICAL ASPECTS OF SULFIDE MINERAL DISSOLUTION: LESSONS FROM IRON MOUNTAIN, CALIFORNIA. (R826189)

    EPA Science Inventory

    Abstract

    The oxidative dissolution of sulfide minerals leading to acid mine drainage (AMD) involves a complex interplay between microorganisms, solutions, and mineral surfaces. Consequently, models that link molecular level reactions and the microbial communities that ...

  1. Reference design of 100 MW-h lithium/iron sulfide battery system for utility load leveling

    SciTech Connect

    Zivi, S.M.; Kacinskas, H.; Pollack, I.; Chilenskas, A.A.; Barney, D.L.; Grieve, W.; McFarland, B.L.; Sudar, S.; Goldstein, E.; Adler, E.

    1980-03-01

    The first year in a two-year cooperative effort between Argonne National Laboratory and Rockwell International to develop a conceptual design of a lithium alloy/iron sulfide battery for utility load leveling is presented. A conceptual design was developed for a 100 MW-h battery system based upon a parallel-series arrangement of 2.5 kW-h capacity cells. The sales price of such a battery system was estimated to be very high, $80.25/kW-h, exclusive of the cost of the individual cells, the dc-to-ac converters, site preparation, or land acquisition costs. Consequently, the second year's efforts were directed towards developing modified designs with significantly lower potential costs.

  2. Metallic Iron-Nickel Sulfide Ultrathin Nanosheets As a Highly Active Electrocatalyst for Hydrogen Evolution Reaction in Acidic Media.

    PubMed

    Long, Xia; Li, Guixia; Wang, Zilong; Zhu, HouYu; Zhang, Teng; Xiao, Shuang; Guo, Wenyue; Yang, Shihe

    2015-09-23

    We report on the synthesis of iron-nickel sulfide (INS) ultrathin nanosheets by topotactic conversion from a hydroxide precursor. The INS nanosheets exhibit excellent activity and stability in strong acidic solutions as a hydrogen evolution reaction (HER) catalyst, lending an attractive alternative to the Pt catalyst. The metallic α-INS nanosheets show an even lower overpotential of 105 mV at 10 mA/cm(2) and a smaller Tafel slope of 40 mV/dec. With the help of DFT calculations, the high specific surface area, facile ion transport and charge transfer, abundant electrochemical active sites, suitable H(+) adsorption, and H2 formation kinetics and energetics are proposed to contribute to the high activity of the INS ultrathin nanosheets toward HER.

  3. Metallic Iron-Nickel Sulfide Ultrathin Nanosheets As a Highly Active Electrocatalyst for Hydrogen Evolution Reaction in Acidic Media.

    PubMed

    Long, Xia; Li, Guixia; Wang, Zilong; Zhu, HouYu; Zhang, Teng; Xiao, Shuang; Guo, Wenyue; Yang, Shihe

    2015-09-23

    We report on the synthesis of iron-nickel sulfide (INS) ultrathin nanosheets by topotactic conversion from a hydroxide precursor. The INS nanosheets exhibit excellent activity and stability in strong acidic solutions as a hydrogen evolution reaction (HER) catalyst, lending an attractive alternative to the Pt catalyst. The metallic α-INS nanosheets show an even lower overpotential of 105 mV at 10 mA/cm(2) and a smaller Tafel slope of 40 mV/dec. With the help of DFT calculations, the high specific surface area, facile ion transport and charge transfer, abundant electrochemical active sites, suitable H(+) adsorption, and H2 formation kinetics and energetics are proposed to contribute to the high activity of the INS ultrathin nanosheets toward HER. PMID:26338434

  4. Micrometeorite dynamic pyrometamorphism: Observation of a thermal gradient in iron-nickel sulfide

    NASA Technical Reports Server (NTRS)

    Rietmeijer, Frans J. M.

    1993-01-01

    Dynamic pyrometamorphism describes the mineralogical changes in a micrometeorite that occur in response to flash-heating during atmospheric entry. Mineral reactions during this event will be endothermic and act as local sinks for thermal energy which delays a uniform temperature distribution in decelerating micrometeorites. The most common pyrometamorphic reaction is formation of magnetite nanocrystal decorations on Mg,Fe-silicate grains and magnetite or (partial) maghemite rims. Constituent silicates also respond to this thermal event and show formation of olivine-maghemite symplectites and growth of garnet and partial laihunitisation. In continued effort to constrain dynamic pyrometamorphism of unmelted interplanetary dust particles (IDP's), I determined the mineralogical composition, and Fe,Ni-sulfide chemistry, in the sulfide-rich particles L2005C39, L2005E40, and L2006A28 using a JEOL 2000FX analytical electron microscope equipped with a TN5500 energy dispersive spectrometer for in situ microanalysis. Sulfide compositions in these three IDP's are distinctly different from those in silicate-rich particle L2005T13 which might suggest a delicate balance of the fO2/fS2 ratios during dynamic pyrometamorphism.

  5. IRON SULFIDE-ARSENITE INTERACTIONS: ADSORPTION BEHAVIOR ONTO IRON MONOSULFIDES AND CONTROLS ON ARSENIC ACCUMULATION IN PYRITE

    EPA Science Inventory

    Because arsenic in ground water and surface water poses a risk to ecosystem and human health, more detailed information is needed on the factors that govern arsenic fate and transport in the environment. Arsenic mobility in natural systems is often linked to iron and sulfur cycl...

  6. Toxic metal(loid) speciation during weathering of iron sulfide mine tailings under semi-arid climate

    PubMed Central

    Root, Robert A.; Hayes, Sarah M.; Hammond, Corin M.; Maier, Raina M.; Chorover, Jon

    2015-01-01

    Toxic metalliferous mine-tailings pose a significant health risk to ecosystems and neighboring communities from wind and water dispersion of particulates containing high concentrations of toxic metal(loid)s (e.g., Pb, As, Zn). Tailings are particularly vulnerable to erosion before vegetative cover can be reestablished, i.e., decades or longer in semi-arid environments without intervention. Metal(loid) speciation, linked directly to bioaccessibility and lability, is controlled by mineral weathering and is a key consideration when assessing human and environmental health risks associated with mine sites. At the semi-arid Iron King Mine and Humboldt Smelter Superfund site in central Arizona, the mineral assemblage of the top 2 m of tailings has been previously characterized. A distinct redox gradient was observed in the top 0.5 m of the tailings and the mineral assemblage indicates progressive transformation of ferrous iron sulfides to ferrihydrite and gypsum, which, in turn weather to form schwertmannite and then jarosite accompanied by a progressive decrease in pH (7.3 to 2.3). Within the geochemical context of this reaction front, we examined enriched toxic metal(loid)s As, Pb, and Zn with surficial concentrations 41.1, 10.7, 39.3 mM kg-1 (3080, 2200, and 2570 mg kg-1), respectively. The highest bulk concentrations of As and Zn occur at the redox boundary representing a 1.7 and 4.2 fold enrichment relative to surficial concentrations, respectively, indicating the translocation of toxic elements from the gossan zone to either the underlying redox boundary or the surface crust. Metal speciation was also examined as a function of depth using X-ray absorption spectroscopy (XAS). The deepest sample (180 cm) contains sulfides (e.g., pyrite, arsenopyrite, galena, and sphalerite). Samples from the redox transition zone (25-54 cm) contain a mixture of sulfides, carbonates (siderite, ankerite, cerrusite, and smithsonite) and metal(loid)s sorbed to neoformed secondary Fe

  7. Iron-sulfides, iron-oxides and aqueous processing of organic materials in CM and CI meteorites and IDPs

    NASA Astrophysics Data System (ADS)

    Rietmeijer, F. J.

    Why do CM meteorites have such a rich variety of organics? D/H isotope ratios prove an interstellar component of the organic matter in CM and CI carbonaceous meteorites wherein the complex ``organics'' could in part be due to Fischer-Tropsch type (FTT) processes and processing of organic precursors on Fe-sulfide, Fe-oxide or clay catalysts. ``Origin of Life'' scenarios refer to the richly varied organics in CM (Murchison) meteorites as the precursor materials delivered to the Earth 4.2-3.9 Gyrs ago. Aggregate interplanetary dust particles (IDPs) have more carbon, incl. an interstellar component, than CI and CM meteorites but their original ``organics'' and amounts are modified by pyrolysis during atmospheric entry. Here, I will assume that anhydrous aggregate IDPs formed the originally anhydrous CI and CM matrix. These IDPs contain submicron CHON, mixed and `silicate' principal components (PCs), e.g. Fe-rich serpentine dehydroxylate, (Mg,Fe)3Si2O7, PCs [Fe/(Mg+Fe)(fe) = 0.3-0.8], and micron-size Fe-sulfides, olivine and pyroxenes. In a Mg-Fe-Si diagram with an Fe-apex, these PC compositions plot on a serpentine, (Mg,Fe)/Si line. The hydrated CI matrix compositions also define a straight line that, anchored at serpentine, fe = 0.3, is rotated towards higher (Mg,Fe)/Si ratios with increasing serpentine fe-ratio when during hydration of an initially ``serpentine dehydroxylate PC'' CI matrix reacted with Fe-sulfide, Fe-oxide, or both. The straight line defining hydrated CM matrix compositions is rotated even more towards higher (Mg,Fe)/Si ratios when hydrated CI-like material continued reacting with Fe-oxide and Fe-sulfide and formed tochilinite, a mineral unique to CM meteorites. Continuous hydration of IDP-like material with an ample supply of Fe-minerals acting as catalysts for formation and processing ``organics'' would have affected the redox conditions of a buffered C-H-O-S aqueous fluid during the time ``organics' were modified to the unique mélanges of CM

  8. Temporal trends in vent fluid iron and sulfide chemistry following the 2005/2006 eruption at East Pacific Rise, 9°50'N

    NASA Astrophysics Data System (ADS)

    Yücel, Mustafa; Luther, George W.

    2013-04-01

    The chemistry of vent fluids that emanate to the seafloor undergoes dramatic changes after volcanic eruptions. Data on these changes are still limited, but the best studied example is the East Pacific Rise (EPR) at 9°50'N, where the temporal evolution of the vent fluid chemistry after the 1991/1992 eruption was documented. The area underwent another eruption sequence during late 2005/early 2006, and here we show that a similar evolution is recurring in the iron and sulfide contents of the high-temperature fluids sampled in June 2006, January 2007, and June 2008. The vents have had increasing dissolved iron and decreasing acid-volatile sulfide (free sulfide plus FeS) concentrations with 1 order of magnitude variation. In addition, chromium reducible sulfide (mainly pyrite) also had fivefold decreasing concentrations over the 3 years. Our results confirm a pattern that was noted only once before for 9°50'N EPR and emphasize the dramatic yearly variability in the concentrations of iron-sulfur species emanating from vents.

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

    SciTech Connect

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

    2014-06-02

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

  10. Iron isotope fractionation during sulfide-rich felsic partial melting in early planetesimals

    NASA Astrophysics Data System (ADS)

    Wang, Kun; Day, James M. D.; Korotev, Randy L.; Zeigler, Ryan A.; Moynier, Frédéric

    2014-04-01

    New Fe isotope data of feldspar-rich meteorites Graves Nunataks 06128 and 06129 (GRA 06128/9) reveal that they are the only known examples of crustal materials with isotopically light Fe isotope compositions (δFe56=-0.08±0.06‰; δ56Fe is defined as the per mille deviation of a sample's 56Fe/54Fe ratio from the IRMM-014 standard) in the Solar System. In contrast, associated brachinites, as well as brachinite-like achondrites, have Fe isotope compositions (δFe56=+0.01±0.02‰) that are isotopically similar to carbonaceous chondrites and the bulk terrestrial mantle. In order to understand the cause of Fe isotope variations in the GRA 06128/9 and brachinite parent body, we also report the Fe isotope compositions of metal, silicate and sulfide fractions from three ordinary chondrites (Semarkona, Kernouve, Saint-Séverin). Metals from ordinary chondrites are enriched in the heavier isotopes of Fe (average δFe56=0.15‰), sulfide fractions are enriched in the lighter isotopes of Fe (average δFe56=-0.14‰), and the δ56Fe values of the silicates are coincident with that of the bulk rock (average δFe56=0.03‰). The enrichment of light isotopes of Fe isotopes in GRA 06128/9 is consistent with preferential melting of sulfides in precursor chondritic source materials leading to the formation of Fe-S-rich felsic melts. Conceptual models show that melt generation to form a GRA 06128/9 parental melt occurred prior to the onset of higher-temperature basaltic melting (<1200 °C) in a volatile-rich precursor and led to the generation of buoyant felsic melt with a strong Fe-S signature. These models not only reveal the origin of enrichment in light isotopes of Fe for GRA 06128/9, but are also consistent with petrological and geochemical observations, experimental studies for the origin of Fe-S-rich felsic melts, and for the cessation of early melting on some asteroidal parent bodies because of the effective removal of the major radioactive heat-source, 26Al. The mode of

  11. Removal of EDB and 1,2-DCA by Abiotic Reaction with Iron (II) Sulfide

    EPA Science Inventory

    To properly evaluate the risk associated with exposure to EDB and 1,2-DCA in ground water from old spills of leaded gasoline, it is necessary to understand the mechanisms that may attenuate concentrations of these compounds in ground water. TCE reacts rapidly with iron (II) sulf...

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

    PubMed

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

    2016-04-01

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

  13. Covalent entrapment of cobalt-iron sulfides in N-doped mesoporous carbon: extraordinary bifunctional electrocatalysts for oxygen reduction and evolution reactions.

    PubMed

    Shen, Mengxia; Ruan, Changping; Chen, Yan; Jiang, Chunhuan; Ai, Kelong; Lu, Lehui

    2015-01-21

    To alleviate the kinetic barriers associated with ORR (oxygen reduction reaction) and OER (oxygen evolution reaction) in electrochemical systems, efficient nonprecious electrocatalysts are urgently required. Here we report a facile soft-template mediated approach for fabrication of nanostructured cobalt-iron double sulfides that are covalently entrapped in nitrogen-doped mesoporous graphitic carbon (Co0.5Fe0.5S@N-MC). Notably, with a positive half-wave potential (0.808 V) and a high diffusion-limiting current density, the composite material delivers unprecedentedly striking ORR electrocatalytic activity among recently reported nonprecious late transition metal chalcogenide materials in alkaline medium. Various characterization techniques, including X-ray absorption spectroscopy, X-ray photoelectron spectroscopy, and X-ray diffraction, are conducted to elucidate the correlation between structural features and catalytic activities of the composite. Moderate substitution and well-dispersion of iron in bimetallic sulfide composites are believed to have positive effect on the adsorption and activation of oxygen-containing species, thus leading to conspicuous ORR and OER catalytic enhancement compared to their monometallic counterparts. Besides, the covalent bridge between active sulfide particles and mesoporous carbon shells provides facile pathways for electron and mass transport. Beneficially, the intimate coupling interaction renders prolonged electrocatalytic performances to the composite. Our results may possibly lend a new impetus to the rational design of bi- or multimetallic sulfides encapsulated in porous carbon with improved performance for electrocatalysis and energy storage applications.

  14. Nanometer-Size Iron Sulfides Biomineralized by a Deep-Sea Hydrothermal Vent Gastropod in Cooperation with Endosymbiotic Sulfate-Reducing Bacteria

    NASA Astrophysics Data System (ADS)

    Suzuki, Y.; Kogure, T.; Takai, K.; Tsuchida, S.; Nealson, K. H.; Horikoshi, K.

    2003-12-01

    The _gscaly-foot_h gastropod has been discovered only from a deep-sea hydrothermal field in the Central Indian Ridge among the global Mid Ocean Ridges (MOR) and found to be peculiar, because it has scale-shaped sclerites composed of hard proteins and iron sulfides that covered the sides of the foot. As the product and mechanism of the iron sulfide biomineralization have not been elucidated in any details, yet, we conducted crystallographic and molecular phylogenetic characterizations of the sclerites._@It was revealed that nanometer-scale (1) mackinawite (FeS) + greigite (Fe3S4), (2) pyrite (FeS2) and (3) mackinawite formed in distinct strata from the outer to inner parts of the sclerites, respectively. This study demonstrated for the first time that pyrite occurred in nature as exceedingly small crystalline nanoparticles (around 3 nm in diameter) and to grow via the aggregation-based pathway._@Phylogenetic analyses based on 16S rRNA and dissimilatory sulfite reductase (DSR) genes detected predominant occurrence of bacteria that have the sequences of both genes closely related to sulfate-reducing Desulfobulbus spp. Fluorescence in-situ hybridization analysis using a probe specific to the retrieved 16S rRNA gene sequences of the Desulfobulbus-related bacteria revealed the localized occurrence of the bacteria in the most inner part of the sclerites, which represents a novel structural integration between bacteria and metazoans. The results strongly suggested the potential contribution of endosymbiotic SRB to formation of stratified nanometer-scale iron sulfides inside the gastropod_fs scaly. As mackinawite that is easily oxidized under slightly oxic conditions and persisted, pyrite seems to have formed via the strictly anoxic pathway. The results presented here may provide aid in deciphering important, but still partially understood formation mechanisms and biochemical and geochemical roles of iron sulfides.

  15. Coordinated Analysis of Two Graphite Grains from the CO3.0 LAP 031117 Meteorite: First Identification of a CO Nova Graphite and a Presolar Iron Sulfide Subgrain

    NASA Astrophysics Data System (ADS)

    Haenecour, Pierre; Floss, Christine; José, Jordi; Amari, Sachiko; Lodders, Katharina; Jadhav, Manavi; Wang, Alian; Gyngard, Frank

    2016-07-01

    Presolar grains constitute the remnants of stars that existed before the formation of the solar system. In addition to providing direct information on the materials from which the solar system formed, these grains provide ground-truth information for models of stellar evolution and nucleosynthesis. Here we report the in situ identification of two unique presolar graphite grains from the primitive meteorite LaPaz Icefield 031117. Based on these two graphite grains, we estimate a bulk presolar graphite abundance of {5}-3+7 ppm in this meteorite. One of the grains (LAP-141) is characterized by an enrichment in 12C and depletions in 33,34S, and contains a small iron sulfide subgrain, representing the first unambiguous identification of presolar iron sulfide. The other grain (LAP-149) is extremely 13C-rich and 15N-poor, with one of the lowest 12C/13C ratios observed among presolar grains. Comparison of its isotopic compositions with new stellar nucleosynthesis and dust condensation models indicates an origin in the ejecta of a low-mass CO nova. Grain LAP-149 is the first putative nova grain that quantitatively best matches nova model predictions, providing the first strong evidence for graphite condensation in nova ejecta. Our discovery confirms that CO nova graphite and presolar iron sulfide contributed to the original building blocks of the solar system.

  16. Nickel-cobalt-iron-copper sulfides and arsenides in solution-collapse breccia pipes, northwestern Arizona

    SciTech Connect

    Wenrich, K.J. ); Hlava, P.F. )

    1993-04-01

    An extensive suite of Ni-Co-Fe-Cu sulfides and arsenides lies within the matrix of solution-collapse breccias buried deep within the plateaus of the Grand Canyon region. Ceilings over large caverns in the Redwall collapsed, brecciating the overlying sandstone and forming cylindrical breccia pipes up to 300 ft in diameter that extend vertically as much as 3,000 ft. These highly permeable breccias served as a host for the precipitation of a suite of over 100 minerals, including uraninite, sphalerite, galena and various copper phases, in addition to the Ni-Co-bearing-phase discussed here. Intricately zoned crystals of small (<1 mm), euhedral Ni-Co-Fe-As-S minerals were the first to form during the second major episode of mineralization in these pipes. Several of these phases replace minerals, such as barite and anhydrite, from the first episode. Extensive microprobe work has been done on samples from two breccia pipe mines, the Hack 2 and Orphan, which are about 50 miles apart. Mineral compositions are similar except that no copper is found in the Ni-Co-Fe phases from the Hack 2 mine, while pyrites containing 1 wt % Cu are common from the Orphan, which was mined for copper. In some of these pyrites', Cu is dominant and the mineral is actually villamaninite. Pyrites from both mines characteristically contain 0.5 to 3 wt % As. Metal contents in zones pyrite-bravoite-vaesite (M[sub 1]S[sub 2]) crystals at the Hack 2 mine range from Fe[sub 1] to Fe[sub .12], Ni[sub 0] to Ni[sub .86], and Co[sub 0] to Co[sub .10]. The metal content for polydymite-siegenite-violarite averages about (Ni[sub 2.33]Co[sub .39]Fe[sub .23])(S[sub 3.9]As[sub .1]). Orphan mine pyrite-bravoite-vaesite-villamaninite ranges in composition from pure FeS[sub 2] to (Ni[sub .6]Fe[sub .21]Co[sub .17])S[sub 2], and (Cu[sub .46]Ni[sub .27]Fe[sub .21]Co[sub .13])S[sub 2]. Of all the sulfides or arsenides found in these breccia pipes, only nickeline consistently occurs as the pure end member.

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

    PubMed

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

    2016-05-25

    Sulfidic off-odors arising during wine production are frequently removed by Cu(II) fining. In part 1 of this study ( 10.1021/acs.jafc.6b00641 ), the reaction of H2S and thiols with Cu(II) was examined; however, the interaction of iron and copper is also known to play an important synergistic role in mediating non-enzymatic wine oxidation. The interaction of these two metals in the oxidation of H2S and thiols (cysteine, 3-sulfanylhexan-1-ol, and 6-sulfanylhexan-1-ol) was therefore examined under wine-like conditions. H2S and thiols (300 μM) were reacted with Fe(III) (100 or 200 μM) alone and in combination with Cu(II) (25 or 50 μM), and concentrations of H2S and thiols, oxygen, and acetaldehyde were monitored over time. H2S and thiols were shown to be slowly oxidized in the presence of Fe(III) alone and were not bound to Fe(III) under model wine conditions. However, Cu(II) added to model wine containing Fe(III) was quickly reduced by H2S and thiols to form Cu(I) complexes, which then rapidly reduced Fe(III) to Fe(II). Oxidation of Fe(II) in the presence of oxygen regenerated Fe(III) and completed the iron redox cycle. In addition, sulfur-derived oxidation products were observed, and the formation of organic polysulfanes was demonstrated. PMID:27133088

  18. Immobilization of mercury by carboxymethyl cellulose stabilized iron sulfide nanoparticles: reaction mechanisms and effects of stabilizer and water chemistry.

    PubMed

    Gong, Yanyan; Liu, Yuanyuan; Xiong, Zhong; Zhao, Dongye

    2014-04-01

    Iron sulfide (FeS) nanoparticles were prepared with sodium carboxymethyl cellulose (CMC) as a stabilizer, and tested for enhanced removal of aqueous mercury (Hg(2+)). CMC at ≥0.03 wt % fully stabilized 0.5 g/L of FeS (i.e., CMC-to-FeS molar ratio ≥0.0006). FTIR spectra suggested that CMC molecules were attached to the nanoparticles through bidentate bridging and hydrogen bonding. Increasing the CMC-to-FeS molar ratio from 0 to 0.0006 enhanced mercury sorption capacity by 20%; yet, increasing the ratio from 0.0010 to 0.0025 diminished the sorption by 14%. FTIR and XRD analyses suggested that precipitation (formation of cinnabar and metacinnabar), ion exchange (formation of Hg0.89Fe0.11S), and surface complexation were important mechanisms for mercury removal. A pseudo-second-order kinetic model was able to interpret the sorption kinetics, whereas a dual-mode isotherm model was proposed to simulate the isotherms, which considers precipitation and adsorption. High mercury uptake was observed over the pH range of 6.5-10.5, whereas significant capacity loss was observed at pH < 6. High concentrations of Cl(-) (>106 mg/L) and organic matter (5 mg/L as TOC) modestly inhibited mercury uptake. The immobilized mercury remained stable when preserved for 2.5 years at pH above neutral. PMID:24568693

  19. Lithium/iron sulfide batteries for electric-vehicle propulsion and other applications. Progress report, October 1979-March 1980

    SciTech Connect

    Barney, D. L.; Steunenberg, R. K.; Chilenskas, A. A.; Gay, E. C.; Battles, J. E.; Miller, W. E.; Vissers, D. R.; Shimotake, H.

    1980-08-01

    The research and development activities of the program at Argonne National Laboratory (ANL) on lithium/iron sulfide batteries during the period October 1979-March 1980 is described. Although the major emphasis is currently on batteries for electric-vehicle propulsion, stationary energy-storage applications are also under investigation. The individual battery cells, which operate at 400 to 500/sup 0/C, are of a vertically oriented, prismatic design with two or more positive electrodes of FeS or FeS/sub 2/, facing negative electrodes of lithium-aluminum or lithium-silicon alloy, and molten LiCl-KCl electrolyte. The ANL program consists of cell chemistry studies, materials engineering, and component and auxiliary systems development. Important elements of this program are studies of the effects of design modifications on cell performance and post-test examinations of cells. During the reporting period, cell and battery development work has been aimed primarily at the first phase of the Mark II electric-vehicle battery program, which consists of an effort to develop high-reliability cells having boron nitride felt separators. Later in the Mark II program, the cells will be tested in 10-cell modules. Work on stationary energy-storage batteries during this period has consisted mainly of conceptual design studies. 23 figures, 9 tables.

  20. Hard X-ray photoelectron and X-ray absorption spectroscopy characterization of oxidized surfaces of iron sulfides

    NASA Astrophysics Data System (ADS)

    Mikhlin, Yuri; Tomashevich, Yevgeny; Vorobyev, Sergey; Saikova, Svetlana; Romanchenko, Alexander; Félix, Roberto

    2016-11-01

    Hard X-ray photoelectron spectroscopy (HAXPES) using an excitation energy range of 2 keV to 6 keV in combination with Fe K- and S K-edge XANES, measured simultaneously in total electron (TEY) and partial fluorescence yield (PFY) modes, have been applied to study near-surface regions of natural polycrystalline pyrite FeS2 and pyrrhotite Fe1-xS before and after etching treatments in an acidic ferric chloride solution. It was found that the following near-surface regions are formed owing to the preferential release of iron from oxidized metal sulfide lattices: (i) a thin, no more than 1-4 nm in depth, outer layer containing polysulfide species, (ii) a layer exhibiting less pronounced stoichiometry deviations and low, if any, concentrations of polysulfide, the composition and dimensions of which vary for pyrite and pyrrhotite and depend on the chemical treatment, and (iii) an extended almost stoichiometric underlayer yielding modified TEY XANES spectra, probably, due to a higher content of defects. We suggest that the extended layered structure should heavily affect the near-surface electronic properties, and processes involving the surface and interfacial charge transfer.

  1. Reaction sequence of iron sulfide minerals in bacteria and their use as biomarkers.

    PubMed

    Pósfai, M; Buseck, P R; Bazylinski, D A; Frankel, R B

    1998-05-01

    Some bacteria form intracellular nanometer-scale crystals of greigite (Fe3S4) that cause the bacteria to be oriented in magnetic fields. Transmission electron microscope observations showed that ferrimagnetic greigite in these bacteria forms from nonmagnetic mackinawite (tetragonal FeS) and possibly from cubic FeS. These precursors apparently transform into greigite by rearrangement of iron atoms over a period of days to weeks. Neither pyrrhotite nor pyrite was found. These results have implications for the interpretation of the presence of pyrrhotite and greigite in the martian meteorite ALH84001. PMID:9572727

  2. Reflectance spectroscopy of natural organic solids, iron sulfides and their mixtures as refractory analogues for Rosetta/VIRTIS' surface composition analysis of 67P/CG

    NASA Astrophysics Data System (ADS)

    Moroz, Lyuba V.; Markus, Kathrin; Arnold, Gabriele; Henckel, Daniela; Kappel, David; Schade, Ulrich; Rousseau, Batiste; Quirico, Eric; Schmitt, Bernard; Capaccioni, Fabrizio; Bockelee-Morvan, Dominique; Filacchione, Gianrico; Érard, Stéphane; Leyrat, Cedric; VIRTIS Team

    2016-10-01

    Analysis of 0.25-5 µm reflectance spectra provided by the Visible and InfraRed Thermal Imaging Spectrometer (VIRTIS) onboard Rosetta orbiter revealed that the surface of 67P/CG is dark from the near-UV to the IR and is enriched in refractory phases such as organic and opaque components. The broadness and complexity of the ubiquitous absorption feature around 3.2 µm suggest a variety of cometary organic constituents. For example, complex hydrocarbons (aliphatic and polycyclic aromatic) can contribute to the feature between 3.3 and 3.5 µm and to the low reflectance of the surface in the visible. Here we present the 0.25-5 µm reflectance spectra of well-characterized terrestrial hydrocarbon materials (solid oil bitumens, coals) and discuss their relevance as spectral analogues for a hydrocarbon part of 67P/CG's complex organics. However, the expected low degree of thermal processing of cometary hydrocarbons (high (H+O+N+S)/C ratios and low carbon aromaticities) suggests high IR reflectance, intense 3.3-3.5 µm absorption bands and steep red IR slopes that are not observed in the VIRTIS spectra. Fine-grained opaque refractory phases (e.g., iron sulfides, Fe-Ni alloys) intimately mixed with other surface components are likely responsible for the low IR reflectance and low intensities of absorption bands in the VIRTIS spectra of the 67P/CG surface. In particular, iron sulfides are common constituents of cometary dust, "cometary" chondritic IDPs, and efficient darkening agents in primitive carbonaceous chondrites. Their effect on reflectance spectra of an intimate mixture is strongly affected by grain size. We report and discuss the 0.25-5 µm reflectance spectra of iron sulfides (meteoritic troilite and several terrestrial pyrrhotites) ground and sieved to various particle sizes. In addition, we present reflectance spectra of several intimate mixtures of powdered iron sulfides and solid oil bitumens. Based on the reported laboratory data, we discuss the ability of

  3. Reductive sequestration of pertechnetate (⁹⁹TcO₄⁻) by nano zerovalent iron (nZVI) transformed by abiotic sulfide.

    PubMed

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

    2013-05-21

    Under anoxic conditions, soluble pertechnetate (⁹⁹TcO₄⁻) can be reduced to less soluble TcO₂·nH₂O, but the oxide is highly susceptible to reoxidation. Here we investigate an alternative strategy for remediation of Tc-contaminated groundwater whereby sequestration as Tc sulfide is favored by sulfidic conditions stimulated by nano zerovalent iron (nZVI). nZVI was pre-exposed to increasing concentrations of sulfide in simulated Hanford groundwater for 24 h to mimic the onset of aquifer biotic sulfate reduction. Solid-phase characterizations of the sulfidated nZVI confirmed the formation of nanocrystalline FeS phases, but higher S/Fe ratios (>0.112) did not result in the formation of significantly more FeS. The kinetics of Tc sequestration by these materials showed faster Tc removal rates with increasing S/Fe between 0 and 0.056, but decreasing Tc removal rates with S/Fe > 0.224. The more favorable Tc removal kinetics at low S/Fe could be due to a higher affinity of TcO₄⁻ for FeS than iron oxides, and electron microscopy confirmed that the majority of the Tc was associated with FeS phases. The inhibition of Tc removal at high S/Fe appears to have been caused by excess HS(-). X-ray absorption spectroscopy revealed that as S/Fe increased, the pathway for Tc(IV) formation shifted from TcO₂·nH2₂ to Tc sulfide phases. The most substantial change of Tc speciation occurred at low S/Fe, coinciding with the rapid increase in Tc removal rate. This agreement further confirms the importance of FeS in Tc sequestration.

  4. From Suicide Enzyme to Catalyst: The Iron-Dependent Sulfide Transfer in Methanococcus jannaschii Thiamin Thiazole Biosynthesis.

    PubMed

    Eser, Bekir E; Zhang, Xuan; Chanani, Prem K; Begley, Tadhg P; Ealick, Steven E

    2016-03-23

    Bacteria and yeast utilize different strategies for sulfur incorporation in the biosynthesis of the thiamin thiazole. Bacteria use thiocarboxylated proteins. In contrast, Saccharomyces cerevisiae thiazole synthase (THI4p) uses an active site cysteine as the sulfide source and is inactivated after a single turnover. Here, we demonstrate that the Thi4 ortholog from Methanococcus jannaschii uses exogenous sulfide and is catalytic. Structural and biochemical studies on this enzyme elucidate the mechanistic details of the sulfide transfer reactions.

  5. Direct Synthesis of Novel and Reactive Sulfide-modified Nano Iron through Nanoparticle Seeding for Improved Cadmium-Contaminated Water Treatment.

    PubMed

    Su, Yiming; Adeleye, Adeyemi S; Huang, Yuxiong; Zhou, Xuefei; Keller, Arturo A; Zhang, Yalei

    2016-01-01

    Magnetic sulfide-modified nanoscale zerovalent iron (S-nZVI) is of great technical and scientific interest because of its promising application in groundwater remediation, although its synthesis is still a challenge. We develop a new nanoparticle seeding method to obtain a novel and reactive nanohybrid, which contains an Fe(0) core covered by a highly sulfidized layer under high extent of sulfidation. Syntheses monitoring experiments show that seeding accelerates the reduction rate from Fe(2+) to Fe(0) by 19%. X-ray adsorption near edge structure (XANES) spectroscopy and extended X-ray absorption fine structure analyses demonstrate the hexahedral Fe-Fe bond (2.45 and 2.83 Å) formation through breaking down of the 1.99 Å Fe-O bond both in crystalline and amorphous iron oxide. The XANES analysis also shows 24.2% (wt%) of FeS with bond length of 2.4 Å in final nanohybrid. Both X-ray diffraction and Mössbauer analyses further confirm that increased nanoparticle seeding results in formation of more Fe(0) crystals. Nano-SiO2 seeding brings down the size of single Fe(0) grain from 32.4 nm to 18.7 nm, enhances final Fe(0) content from 5.9% to 55.6%, and increases magnetization from 4.7 to 65.5 emu/g. The synthesized nanohybrid has high cadmium removal capacity and holds promising prospects for treatment of metal-contaminated water.

  6. Changing Distributions of Methyl Halides, Nonmethane Hydrocarbons, Alkyl Nitrates, and Dimethyl Sulfide during the SOFeX Iron Fertilization Experiment

    NASA Astrophysics Data System (ADS)

    Wingenter, O. W.; Haase, K. B.; Strutton, P.; Friederich, G.; Meinardi, S.; Blake, D. R.; Rowland, F. S.

    2002-12-01

    Concentrations for selected volatile organic compounds (VOCs) including methyl halides, nonmethane hydrocarbons, alkyl nitrates, and dimethyl sulfide were determined from whole air samples collected simultaneously from surface ocean water and 15 meters above the water during a mesoscale Fe enrichment experiment. The Southern Ocean Iron Experiment (SOFeX) (January-February, 2002) involved the research vessels Revelle, Melville, and Polar Star. Previous Fe enhancement experiments have induced intense phytoplankton blooms that consumed significant amounts of CO2, resulting in the uptake of additional CO2 from the atmosphere. During SOFeX, two areas of the Southern Ocean (SO) were fertilized, one north of the Antarctic Polar Front and the other south of the front. The northern patch (NP) was low in silicate with high concentrations of nitrate and other nutrients, while the southern patch (SP) contained high concentrations of both nitrate and silicate. It was expected that the addition of Fe to waters low in silicate would not stimulate diatom production because diatoms require silicate to form. It is believed that diatoms remove most of the CO2 from surface waters, therefore little CO2 uptake was expected in the NP. Most of the HNLC water in the SO is found north of the front. Oceanic phytoplankton and other microorganisms are known to produce and consume certain VOCs. The question that we seek to address is: What impact does Fe fertilization in the SO have on the oceanic production and losses of trace gases that can affect stratospheric ozone and global climate? A total of 420 whole air samples (half from an equilibrator and half from above the bow of the ship) were collected aboard the Revelle, in and outside of the two iron-enriched sites. The samples were later returned to the UCI laboratory for gas chromatographic analysis. Approximately 30 days elapsed between the first Fe addition in the NP and the final VOC sampling in the NP on the return leg. Fourteen days

  7. Reductive Sequestration Of Pertechnetate (99TcO4–) By Nano Zerovalent Iron (nZVI) Transformed By Abiotic Sulfide

    SciTech Connect

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

    2013-04-24

    Under anoxic conditions, soluble 99TcO4– can be reduced to less soluble TcO2•nH2O, but the oxide is highly susceptible to reoxidation. Here we investigate an alternative strategy for remediation of Tc-contaminated groundwater whereby sequestration as Tc sulfide is favored by sulfidic conditions stimulated by nano zero-valent iron (nZVI). nZVI was pre-exposed to increasing concentrations of sulfide in simulated Hanford groundwater for 24 hrs to mimic the stages of aquifer sulfate reduction and onset of biotic sulfidogenesis. Solid-phase characterizations of the sulfidated nZVI confirmed the formation of nanocrystalline FeS phases, but higher S/Fe ratios (>0.112) did not result in the formation of significantly more FeS. The kinetics of Tc sequestration by these materials showed faster Tc removal rates with increasing S/Fe between S/Fe = 0–0.056, but decreasing Tc removal rates with S/Fe > 0.224. The more favorable Tc removal kinetics at low S/Fe could be due to a higher affinity of TcO4– for FeS (over iron oxides), and electron microscopy confirmed that the majority of the Tc was associated with FeS phases. The inhibition of Tc removal at high S/Fe appears to have been caused by excess HS–. X-ray absorption spectroscopy revealed that as S/Fe increased, Tc speciation shifted from TcO2•nH2O to TcS2. The most substantial change of Tc speciation occurred at low S/Fe, coinciding with the rapid increase of Tc removal rate. This agreement further confirms the importance of FeS in Tc sequestration.

  8. Environmental control on the occurrence of high-coercivity magnetic minerals and formation of iron sulfides in a 640 ka sediment sequence from Lake Ohrid (Balkans)

    NASA Astrophysics Data System (ADS)

    Just, Janna; Nowaczyk, Norbert R.; Sagnotti, Leonardo; Francke, Alexander; Vogel, Hendrik; Lacey, Jack H.; Wagner, Bernd

    2016-04-01

    The bulk magnetic mineral record from Lake Ohrid, spanning the past 637 kyr, reflects large-scale shifts in hydrological conditions, and, superimposed, a strong signal of environmental conditions on glacial-interglacial and millennial timescales. A shift in the formation of early diagenetic ferrimagnetic iron sulfides to siderites is observed around 320 ka. This change is probably associated with variable availability of sulfide in the pore water. We propose that sulfate concentrations were significantly higher before ˜ 320 ka, due to either a higher sulfate flux or lower dilution of lake sulfate due to a smaller water volume. Diagenetic iron minerals appear more abundant during glacials, which are generally characterized by higher Fe / Ca ratios in the sediments. While in the lower part of the core the ferrimagnetic sulfide signal overprints the primary detrital magnetic signal, the upper part of the core is dominated by variable proportions of high- to low-coercivity iron oxides. Glacial sediments are characterized by high concentration of high-coercivity magnetic minerals (hematite, goethite), which relate to enhanced erosion of soils that had formed during preceding interglacials. Superimposed on the glacial-interglacial behavior are millennial-scale oscillations in the magnetic mineral composition that parallel variations in summer insolation. Like the processes on glacial-interglacial timescales, low summer insolation and a retreat in vegetation resulted in enhanced erosion of soil material. Our study highlights that rock-magnetic studies, in concert with geochemical and sedimentological investigations, provide a multi-level contribution to environmental reconstructions, since the magnetic properties can mirror both environmental conditions on land and intra-lake processes.

  9. Effective sulfur and energy recovery from hydrogen sulfide through incorporating an air-cathode fuel cell into chelated-iron process.

    PubMed

    Sun, Min; Song, Wei; Zhai, Lin-Feng; Cui, Yu-Zhi

    2013-12-15

    The chelated-iron process is among the most promising techniques for the hydrogen sulfide (H2S) removal due to its double advantage of waste minimization and resource recovery. However, this technology has encountered the problem of chelate degradation which made it difficult to ensure reliable and economical operation. This work aims to develop a novel fuel-cell-assisted chelated-iron process which employs an air-cathode fuel cell for the catalyst regeneration. By using such a process, sulfur and electricity were effectively recovered from H2S and the problem of chelate degradation was well controlled. Experiment on a synthetic sulfide solution showed the fuel-cell-assisted chelated-iron process could maintain high sulfur recovery efficiencies generally above 90.0%. The EDTA was preferable to NTA as the chelating agent for electricity generation, given the Coulombic efficiencies (CEs) of 17.8 ± 0.5% to 75.1 ± 0.5% for the EDTA-chelated process versus 9.6 ± 0.8% to 51.1 ± 2.7% for the NTA-chelated process in the pH range of 4.0-10.0. The Fe (III)/S(2-) ratio exhibited notable influence on the electricity generation, with the CEs improved by more than 25% as the Fe (III)/S(2-) molar ratio increased from 2.5:1 to 3.5:1. Application of this novel process in treating a H2S-containing biogas stream achieved 99% of H2S removal efficiency, 78% of sulfur recovery efficiency, and 78.6% of energy recovery efficiency, suggesting the fuel-cell-assisted chelated-iron process was effective to remove the H2S from gas streams with favorable sulfur and energy recovery efficiencies.

  10. Effective sulfur and energy recovery from hydrogen sulfide through incorporating an air-cathode fuel cell into chelated-iron process.

    PubMed

    Sun, Min; Song, Wei; Zhai, Lin-Feng; Cui, Yu-Zhi

    2013-12-15

    The chelated-iron process is among the most promising techniques for the hydrogen sulfide (H2S) removal due to its double advantage of waste minimization and resource recovery. However, this technology has encountered the problem of chelate degradation which made it difficult to ensure reliable and economical operation. This work aims to develop a novel fuel-cell-assisted chelated-iron process which employs an air-cathode fuel cell for the catalyst regeneration. By using such a process, sulfur and electricity were effectively recovered from H2S and the problem of chelate degradation was well controlled. Experiment on a synthetic sulfide solution showed the fuel-cell-assisted chelated-iron process could maintain high sulfur recovery efficiencies generally above 90.0%. The EDTA was preferable to NTA as the chelating agent for electricity generation, given the Coulombic efficiencies (CEs) of 17.8 ± 0.5% to 75.1 ± 0.5% for the EDTA-chelated process versus 9.6 ± 0.8% to 51.1 ± 2.7% for the NTA-chelated process in the pH range of 4.0-10.0. The Fe (III)/S(2-) ratio exhibited notable influence on the electricity generation, with the CEs improved by more than 25% as the Fe (III)/S(2-) molar ratio increased from 2.5:1 to 3.5:1. Application of this novel process in treating a H2S-containing biogas stream achieved 99% of H2S removal efficiency, 78% of sulfur recovery efficiency, and 78.6% of energy recovery efficiency, suggesting the fuel-cell-assisted chelated-iron process was effective to remove the H2S from gas streams with favorable sulfur and energy recovery efficiencies. PMID:24220197

  11. Mineralogy of iron sulfides in CM1 and CI1 lithologies of the Kaidun breccia: Records of extreme to intense hydrothermal alteration

    NASA Astrophysics Data System (ADS)

    Harries, Dennis; Zolensky, Michael E.

    2016-06-01

    The polymict Kaidun microbreccia contains lithologies of C-type chondrites with euhedral iron sulfide crystals of hydrothermal origin. Our FIB-TEM study reveals that acicular sulfides in a CM1 lithology are composed of Fe-rich pyrrhotite with nonintegral vacancy superstructures (NC-pyrrhotite), troilite, and pentlandite, all showing distinct exsolution textures. Based on phase relations in the Fe-Ni-S system, we constrain the temperature of formation of the originally homogeneous monosulfide solid solution to the range of 100-300 °C. In some crystals the exsolution of pentlandite and the microtextural equilibration was incomplete, probably due to rapid cooling. We use thermodynamic modeling to constrain the physicochemical conditions of the extreme hydrothermal alteration in this lithology. Unless the CM1 lithology was sourced from a large depth in the parent body (internal pressure >85 bar) or the temperatures were in the lower range of the interval determined, the water was likely present as vapor. Previously described light δ34S compositions of sulfides in Kaidun's CM1 lithology are likely due to the loss of 34S-enriched H2S during boiling. Platy sulfide crystals in an adjacent, intensely altered CI1 lithology are composed of Fe-poor, monoclinic 4C-pyrrhotite and NC-pyrrhotite and probably formed at lower temperatures and higher fS2 relative to the CM1 lithology. However, a better understanding of the stability of Fe-poor pyrrhotites at temperatures below 300 °C is required to better constrain these conditions.

  12. Direct Synthesis of Novel and Reactive Sulfide-modified Nano Iron through Nanoparticle Seeding for Improved Cadmium-Contaminated Water Treatment

    NASA Astrophysics Data System (ADS)

    Su, Yiming; Adeleye, Adeyemi S.; Huang, Yuxiong; Zhou, Xuefei; Keller, Arturo A.; Zhang, Yalei

    2016-04-01

    Magnetic sulfide-modified nanoscale zerovalent iron (S-nZVI) is of great technical and scientific interest because of its promising application in groundwater remediation, although its synthesis is still a challenge. We develop a new nanoparticle seeding method to obtain a novel and reactive nanohybrid, which contains an Fe(0) core covered by a highly sulfidized layer under high extent of sulfidation. Syntheses monitoring experiments show that seeding accelerates the reduction rate from Fe2+ to Fe0 by 19%. X-ray adsorption near edge structure (XANES) spectroscopy and extended X-ray absorption fine structure analyses demonstrate the hexahedral Fe-Fe bond (2.45 and 2.83 Å) formation through breaking down of the 1.99 Å Fe-O bond both in crystalline and amorphous iron oxide. The XANES analysis also shows 24.2% (wt%) of FeS with bond length of 2.4 Å in final nanohybrid. Both X-ray diffraction and Mössbauer analyses further confirm that increased nanoparticle seeding results in formation of more Fe0 crystals. Nano-SiO2 seeding brings down the size of single Fe0 grain from 32.4 nm to 18.7 nm, enhances final Fe0 content from 5.9% to 55.6%, and increases magnetization from 4.7 to 65.5 emu/g. The synthesized nanohybrid has high cadmium removal capacity and holds promising prospects for treatment of metal-contaminated water.

  13. Direct Synthesis of Novel and Reactive Sulfide-modified Nano Iron through Nanoparticle Seeding for Improved Cadmium-Contaminated Water Treatment

    PubMed Central

    Su, Yiming; Adeleye, Adeyemi S.; Huang, Yuxiong; Zhou, Xuefei; Keller, Arturo A.; Zhang, Yalei

    2016-01-01

    Magnetic sulfide-modified nanoscale zerovalent iron (S-nZVI) is of great technical and scientific interest because of its promising application in groundwater remediation, although its synthesis is still a challenge. We develop a new nanoparticle seeding method to obtain a novel and reactive nanohybrid, which contains an Fe(0) core covered by a highly sulfidized layer under high extent of sulfidation. Syntheses monitoring experiments show that seeding accelerates the reduction rate from Fe2+ to Fe0 by 19%. X-ray adsorption near edge structure (XANES) spectroscopy and extended X-ray absorption fine structure analyses demonstrate the hexahedral Fe-Fe bond (2.45 and 2.83 Å) formation through breaking down of the 1.99 Å Fe-O bond both in crystalline and amorphous iron oxide. The XANES analysis also shows 24.2% (wt%) of FeS with bond length of 2.4 Å in final nanohybrid. Both X-ray diffraction and Mössbauer analyses further confirm that increased nanoparticle seeding results in formation of more Fe0 crystals. Nano-SiO2 seeding brings down the size of single Fe0 grain from 32.4 nm to 18.7 nm, enhances final Fe0 content from 5.9% to 55.6%, and increases magnetization from 4.7 to 65.5 emu/g. The synthesized nanohybrid has high cadmium removal capacity and holds promising prospects for treatment of metal-contaminated water. PMID:27095387

  14. Direct Synthesis of Novel and Reactive Sulfide-modified Nano Iron through Nanoparticle Seeding for Improved Cadmium-Contaminated Water Treatment.

    PubMed

    Su, Yiming; Adeleye, Adeyemi S; Huang, Yuxiong; Zhou, Xuefei; Keller, Arturo A; Zhang, Yalei

    2016-01-01

    Magnetic sulfide-modified nanoscale zerovalent iron (S-nZVI) is of great technical and scientific interest because of its promising application in groundwater remediation, although its synthesis is still a challenge. We develop a new nanoparticle seeding method to obtain a novel and reactive nanohybrid, which contains an Fe(0) core covered by a highly sulfidized layer under high extent of sulfidation. Syntheses monitoring experiments show that seeding accelerates the reduction rate from Fe(2+) to Fe(0) by 19%. X-ray adsorption near edge structure (XANES) spectroscopy and extended X-ray absorption fine structure analyses demonstrate the hexahedral Fe-Fe bond (2.45 and 2.83 Å) formation through breaking down of the 1.99 Å Fe-O bond both in crystalline and amorphous iron oxide. The XANES analysis also shows 24.2% (wt%) of FeS with bond length of 2.4 Å in final nanohybrid. Both X-ray diffraction and Mössbauer analyses further confirm that increased nanoparticle seeding results in formation of more Fe(0) crystals. Nano-SiO2 seeding brings down the size of single Fe(0) grain from 32.4 nm to 18.7 nm, enhances final Fe(0) content from 5.9% to 55.6%, and increases magnetization from 4.7 to 65.5 emu/g. The synthesized nanohybrid has high cadmium removal capacity and holds promising prospects for treatment of metal-contaminated water. PMID:27095387

  15. Chemical insights into the synthesis and properties of polycrystalline and single crystal iron scandium sulfide (FeSc2S4)

    NASA Astrophysics Data System (ADS)

    Morey, Jennifer R.; Plumb, Kemp W.; Koohpayeh, Seyed M.; Broholm, Collin L.; McQueen, Tyrel M.

    Iron scandium sulfide, FeSc2S4, has recently attracted significant theoretical and experimental interest as a candidate spin-orbital liquid. An AB2X4 spinel, FeSc2S4 (space group Fd-3m, No. 227) features a high degree of frustration associated with the Fe2+, which occupies the A-site diamond sublattice and is tetrahedrally coordinated by sulfur. The Fe2+ ion is in a high spin (S =2) state, resulting in orbital degeneracy due to a single hole on the e orbitals. We report the strides we have made to produce material in powder and single crystal form, and the relationship between the chemistry and the structural, magnetic, and thermodynamic properties of FeSc2S4. This work was supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Material Sciences and Engineering, under Grant No. DEFG02-08ER46544.

  16. Laboratory Measurements of Synthetic Pyroxenes and their Mixtures with Iron Sulfides as Inorganic Refractory Analogues for Rosetta/VIRTIS' Surface Composition Analysis of 67P/CG

    NASA Astrophysics Data System (ADS)

    Markus, Kathrin; Arnold, Gabriele; Moroz, Ljuba; Henckel, Daniela; Kappel, David; Capaccioni, Fabrizio; Filacchione, Gianrico; Schmitt, Bernard; Tosi, Federico; Érard, Stéphane; Bockelee-Morvan, Dominique; Leyrat, Cedric; VIRTIS Team

    2016-10-01

    The Visible and InfraRed Thermal Imaging Spectrometer VIRTIS on board Rosetta provided 0.25-5.1 µm spectra of 67P/CG's surface (Capaccioni et al., 2015). Thermally corrected reflectance spectra display a low albedo of 0.06 at 0.65 µm, different red VIS and IR spectral slopes, and a broad 3.2 µm band. This absorption feature is due to refractory surface constituents attributed to organic components, but other refractory constituents influence albedo and spectral slopes. Possible contributions of inorganic components to spectral characteristics and spectral variations across the surface should be understood based on laboratory studies and spectral modeling. Although a wide range of silicate compositions was found in "cometary" anhydrous IDPs and cometary dust, Mg-rich crystalline mafic minerals are dominant silicate components. A large fraction of silicate grains are Fe-free enstatites and forsterites that are not found in terrestrial rocks but can be synthesized in order to provide a basis for laboratory studies and comparison with VIRTIS data. We report the results of the synthesis, analyses, and spectral reflectance measurements of Fe-free low-Ca pyroxenes (ortho- and clinoenstatites). These minerals are generally very bright and almost spectrally featureless. However, even trace amounts of Fe-ions produce a significant decrease in the near-UV reflectance and hence can contribute to slope variations. Iron sulfides (troilite, pyrrhotite) are among the most plausible phases responsible for the low reflectance of 67P's surface from the VIS to the NIR. The darkening efficiency of these opaque phases is strongly particle-size dependent. Here we present a series of reflectance spectra of fine-grained synthetic enstatite powders mixed in various proportions with iron sulfide powders. The influence of dark sulfides on reflectance in the near-UV to near-IR spectral ranges is investigated. This study can contribute to understand the shape of reflectance spectra of 67P

  17. The metastable brain.

    PubMed

    Tognoli, Emmanuelle; Kelso, J A Scott

    2014-01-01

    Neural ensembles oscillate across a broad range of frequencies and are transiently coupled or "bound" together when people attend to a stimulus, perceive, think, and act. This is a dynamic, self-assembling process, with parts of the brain engaging and disengaging in time. But how is it done? The theory of Coordination Dynamics proposes a mechanism called metastability, a subtle blend of integration and segregation. Tendencies for brain regions to express their individual autonomy and specialized functions (segregation, modularity) coexist with tendencies to couple and coordinate globally for multiple functions (integration). Although metastability has garnered increasing attention, it has yet to be demonstrated and treated within a fully spatiotemporal perspective. Here, we illustrate metastability in continuous neural and behavioral recordings, and we discuss theory and experiments at multiple scales, suggesting that metastable dynamics underlie the real-time coordination necessary for the brain's dynamic cognitive, behavioral, and social functions.

  18. The metastable brain.

    PubMed

    Tognoli, Emmanuelle; Kelso, J A Scott

    2014-01-01

    Neural ensembles oscillate across a broad range of frequencies and are transiently coupled or "bound" together when people attend to a stimulus, perceive, think, and act. This is a dynamic, self-assembling process, with parts of the brain engaging and disengaging in time. But how is it done? The theory of Coordination Dynamics proposes a mechanism called metastability, a subtle blend of integration and segregation. Tendencies for brain regions to express their individual autonomy and specialized functions (segregation, modularity) coexist with tendencies to couple and coordinate globally for multiple functions (integration). Although metastability has garnered increasing attention, it has yet to be demonstrated and treated within a fully spatiotemporal perspective. Here, we illustrate metastability in continuous neural and behavioral recordings, and we discuss theory and experiments at multiple scales, suggesting that metastable dynamics underlie the real-time coordination necessary for the brain's dynamic cognitive, behavioral, and social functions. PMID:24411730

  19. Iron

    MedlinePlus

    ... cereals and breads. White beans, lentils, spinach, kidney beans, and peas. Nuts and some dried fruits, such as raisins. Iron in food comes in two forms: heme iron and nonheme iron. Nonheme iron is found in plant foods and iron-fortified food products. Meat, seafood, ...

  20. Iron

    MedlinePlus

    Iron is a mineral that our bodies need for many functions. For example, iron is part of hemoglobin, a protein which carries ... It helps our muscles store and use oxygen. Iron is also part of many other proteins and ...

  1. Sulfide detoxification in plant mitochondria.

    PubMed

    Birke, Hannah; Hildebrandt, Tatjana M; Wirtz, Markus; Hell, Rüdiger

    2015-01-01

    In contrast to animals, which release the signal molecule sulfide in small amounts from cysteine and its derivates, phototrophic eukaryotes generate sulfide as an essential intermediate of the sulfur assimilation pathway. Additionally, iron-sulfur cluster turnover and cyanide detoxification might contribute to the release of sulfide in mitochondria. However, sulfide is a potent inhibitor of cytochrome c oxidase in mitochondria. Thus, efficient sulfide detoxification mechanisms are required in mitochondria to ensure adequate energy production and consequently survival of the plant cell. Two enzymes have been recently described to catalyze sulfide detoxification in mitochondria of Arabidopsis thaliana, O-acetylserine(thiol)lyase C (OAS-TL C), and the sulfur dioxygenase (SDO) ethylmalonic encephalopathy protein 1 (ETHE1). Biochemical characterization of sulfide producing and consuming enzymes in mitochondria of plants is fundamental to understand the regulatory network that enables mitochondrial sulfide homeostasis under nonstressed and stressed conditions. In this chapter, we provide established protocols to determine the activity of the sulfide releasing enzyme β-cyanoalanine synthase as well as sulfide-consuming enzymes OAS-TL and SDO. Additionally, we describe a reliable and efficient method to purify OAS-TL proteins from plant material.

  2. Iron-control additives improve acidizing

    SciTech Connect

    Walker, M.; Dill, W. ); Besler, M. )

    1989-07-24

    Iron sulfide and sulfur precipitation in sour wells can be controlled with iron-sequestering agents and sulfide modifiers. Oil production has been routinely increased in sour wells where precipitation of iron sulfide and elemental sulfur has been brought under control. Production increases have been especially noteworthy on wells that had a history of rapid production decline after acid stimulation. Twenty-fold production increases have been recorded. Key to the production increase has been to increase permeability with: Iron chelating agents that control precipitation of iron sulfide. A sulfide modifier that reduces precipitation of solids in the presence of excessive amounts of hydrogen sulfide and prevents precipitation of elemental sulfur.

  3. Oxidation of Aryl Diphenylmethyl Sulfides Promoted by a Nonheme Iron(IV)-Oxo Complex: Evidence for an Electron Transfer-Oxygen Transfer Mechanism.

    PubMed

    Barbieri, Alessia; De Carlo Chimienti, Rosemilia; Del Giacco, Tiziana; Di Stefano, Stefano; Lanzalunga, Osvaldo; Lapi, Andrea; Mazzonna, Marco; Olivo, Giorgio; Salamone, Michela

    2016-03-18

    The oxidation of a series of aryl diphenylmethyl sulfides (4-X-C6H4SCH(C6H5)2, where X = OCH3 (1), X = CH3 (2), X = H (3), and X = CF3 (4)) promoted by the nonheme iron(IV)-oxo complex [(N4Py)Fe(IV)═O](2+) occurs by an electron transfer-oxygen transfer (ET-OT) mechanism as supported by the observation of products (diphenylmethanol, benzophenone, and diaryl disulfides) deriving from α-C-S and α-C-H fragmentation of radical cations 1(+•)-4(+•), formed besides the S-oxidation products (aryl diphenylmethyl sulfoxides). The fragmentation/S-oxidation product ratios regularly increase through a decrease in the electron-donating power of the aryl substituents, that is, by increasing the fragmentation rate constants of the radical cations as indicated by a laser flash photolysis (LFP) study of the photochemical oxidation of 1-4 carried out in the presence of N-methoxyphenanthridinium hexafluorophosphate (MeOP(+)PF6(-)). PMID:26886491

  4. Oxidation of Aryl Diphenylmethyl Sulfides Promoted by a Nonheme Iron(IV)-Oxo Complex: Evidence for an Electron Transfer-Oxygen Transfer Mechanism.

    PubMed

    Barbieri, Alessia; De Carlo Chimienti, Rosemilia; Del Giacco, Tiziana; Di Stefano, Stefano; Lanzalunga, Osvaldo; Lapi, Andrea; Mazzonna, Marco; Olivo, Giorgio; Salamone, Michela

    2016-03-18

    The oxidation of a series of aryl diphenylmethyl sulfides (4-X-C6H4SCH(C6H5)2, where X = OCH3 (1), X = CH3 (2), X = H (3), and X = CF3 (4)) promoted by the nonheme iron(IV)-oxo complex [(N4Py)Fe(IV)═O](2+) occurs by an electron transfer-oxygen transfer (ET-OT) mechanism as supported by the observation of products (diphenylmethanol, benzophenone, and diaryl disulfides) deriving from α-C-S and α-C-H fragmentation of radical cations 1(+•)-4(+•), formed besides the S-oxidation products (aryl diphenylmethyl sulfoxides). The fragmentation/S-oxidation product ratios regularly increase through a decrease in the electron-donating power of the aryl substituents, that is, by increasing the fragmentation rate constants of the radical cations as indicated by a laser flash photolysis (LFP) study of the photochemical oxidation of 1-4 carried out in the presence of N-methoxyphenanthridinium hexafluorophosphate (MeOP(+)PF6(-)).

  5. Iron isotope composition of particles produced by UV-femtosecond laser ablation of natural oxides, sulfides, and carbonates.

    PubMed

    d'Abzac, Francois-Xavier; Beard, Brian L; Czaja, Andrew D; Konishi, Hiromi; Schauer, James J; Johnson, Clark M

    2013-12-17

    The need for femtosecond laser ablation (fs-LA) systems coupled to MC-ICP-MS to accurately perform in situ stable isotope analyses remains an open question, because of the lack of knowledge concerning ablation-related isotopic fractionation in this regime. We report the first iron isotope analysis of size-resolved, laser-induced particles of natural magnetite, siderite, pyrrhotite, and pyrite, collected through cascade impaction, followed by analysis by solution nebulization MC-ICP-MS, as well as imaging using electron microscopy. Iron mass distributions are independent of mineralogy, and particle morphology includes both spheres and agglomerates for all ablated phases. X-ray spectroscopy shows elemental fractionation in siderite (C-rich agglomerates) and pyrrhotite/pyrite (S-rich spheres). We find an increase in (56)Fe/(54)Fe ratios of +2‰, +1.2‰, and +0.8‰ with increasing particle size for magnetite, siderite, and pyrrhotite, respectively. Fe isotope differences in size-sorted aerosols from pyrite ablation are not analytically resolvable. Experimental data are discussed using models of particles generation by Hergenröder and elemental/isotopic fractionation by Richter. We interpret the isotopic fractionation to be related to the iron condensation time scale, dependent on its saturation in the gas phase, as a function of mineral composition. Despite the isotopic variations across aerosol size fractions, total aerosol composition, as calculated from mass balance, confirms that fs-LA produces a stoichiometric sampling in terms of isotopic composition. Specifically, both elemental and isotopic fractionation are produced by particle generation processes and not by femtosecond laser-matter interactions. These results provide critical insights into the analytical requirements for laser-ablation-based stable isotope measurements of high-precision and accuracy in geological samples, including the importance of quantitative aerosol transport to the ICP. PMID

  6. The iron isotope composition of enstatite meteorites: Implications for their origin and the metal/sulfide Fe isotopic fractionation factor

    NASA Astrophysics Data System (ADS)

    Wang, Kun; Savage, Paul S.; Moynier, Frédéric

    2014-10-01

    Despite their unusual chemical composition, it is often proposed that the enstatite chondrites represent a significant component of Earth’s building materials, based on their terrestrial similarity for numerous isotope systems. In order to investigate a possible genetic relationship between the Fe isotope composition of enstatite chondrites and the Earth, we have analyzed 22 samples from different subgroups of the enstatite meteorites, including EH and EL chondrites, aubrites (main group and Shallowater) and the Happy Canyon impact melt. We have also analyzed the Fe isotopic compositions of separated (magnetic and non-magnetic) phases from both enstatite chondrites and achondrites. On average, EH3-5 chondrites (δ56Fe = 0.003 ± 0.042‰; 2 standard deviation; n = 9; including previous literature data) as well as EL3 chondrites (δ56Fe = 0.030 ± 0.038‰; 2 SD; n = 2) have identical and homogeneous Fe isotopic compositions, indistinguishable from those of the carbonaceous chondrites and average terrestrial peridotite. In contrast, EL6 chondrites display a larger range of isotopic compositions (-0.180‰ < δ56Fe < 0.181‰; n = 11), a result of mixing between isotopically distinct mineral phases (metal, sulfide and silicate). The large Fe isotopic heterogeneity of EL6 is best explained by chemical/mineralogical fragmentation and brecciation during the complex impact history of the EL parent body. Enstatite achondrites (aubrites) also exhibit a relatively large range of Fe isotope compositions: all main group aubrites are enriched in the light Fe isotopes (δ56Fe = -0.170 ± 0.189‰; 2 SD; n = 6), while Shallowater is, isotopically, relatively heavy (δ56Fe = 0.045 ± 0.101‰; 2 SD; n = 4; number of chips). We take this variation to suggest that the main group aubrite parent body formed a discreet heavy Fe isotope-enriched core, whilst the Shallowater meteorite is most likely from a different parent body where core and silicate material remixed. This could be

  7. Micro-scale Complexity in Iron-Sulfide Phases in Precambrian Sedimentary Rocks Determined by Synchrotron Microprobe Spectroscopy

    NASA Astrophysics Data System (ADS)

    Webb, S.; Johnson, J. E.; Slotznick, S. P.; Roach, C.; Fischer, W. W.

    2014-12-01

    The record of sedimentary pyrite forms the foundation for most isotope records working to define the coupled evolution and behavior of the ancient iron and sulfur cycles. In order to assess the strengths and limitations of records derived from pyrite-rich rocks (e.g. iron speciation, sulfur isotope ratios), we need to understand more about the processes that form and alter sedimentary pyrite. From samples of the Archean/early Proterozoic Transvaal and middle Proterozoic Belt Supergroups, petrography reveals that what might operationally be called sedimentary pyrite has complex textures that hint at a rich process history of sulfur mineralization. A common limitation of virtually all proxy measurements employed to date is that they operate on 'bulk' samples, typically gram-sized or larger pieces. As such, they lose the ability to relate geochemistry to petrography at the scale of mineral grains. Many of the sedimentary pyrites in the Transvaal Supergroup exhibit complex redox and electronic structures of S and Fe, with crystals of pyrite, pyrrhotite, and sulfate-bearing minerals throughout. Parallel application of multiple techniques on the same samples across micron bases spatial scales, provide an opportunity to diagnose issues resulting from post-depositional alteration of sedimentary rocks. We have integrated light and electron microscopy for petrography, electron microprobe and synchrotron XRF for elemental composition, synchrotron X-ray spectroscopy for redox and chemical state, and secondary ion mass spectrometry (SIMS) for isotopic composition. The coupling of these tools allows in essence "images" of the proxy data at the micrometer scale, giving a wide array of textural and mineralogical information designed to inform and untangle the complicated histories of these early Precambrian rocks.

  8. Hydrogen Sulfide Oxidation by Myoglobin.

    PubMed

    Bostelaar, Trever; Vitvitsky, Victor; Kumutima, Jacques; Lewis, Brianne E; Yadav, Pramod K; Brunold, Thomas C; Filipovic, Milos; Lehnert, Nicolai; Stemmler, Timothy L; Banerjee, Ruma

    2016-07-13

    Enzymes in the sulfur network generate the signaling molecule, hydrogen sulfide (H2S), from the amino acids cysteine and homocysteine. Since it is toxic at elevated concentrations, cells are equipped to clear H2S. A canonical sulfide oxidation pathway operates in mitochondria, converting H2S to thiosulfate and sulfate. We have recently discovered the ability of ferric hemoglobin to oxidize sulfide to thiosulfate and iron-bound hydropolysulfides. In this study, we report that myoglobin exhibits a similar capacity for sulfide oxidation. We have trapped and characterized iron-bound sulfur intermediates using cryo-mass spectrometry and X-ray absorption spectroscopy. Further support for the postulated intermediates in the chemically challenging conversion of H2S to thiosulfate and iron-bound catenated sulfur products is provided by EPR and resonance Raman spectroscopy in addition to density functional theory computational results. We speculate that the unusual sensitivity of skeletal muscle cytochrome c oxidase to sulfide poisoning in ethylmalonic encephalopathy, resulting from the deficiency in a mitochondrial sulfide oxidation enzyme, might be due to the concentration of H2S by myoglobin in this tissue. PMID:27310035

  9. Selenium Sulfide

    MedlinePlus

    Selenium sulfide comes in a lotion and is usually applied as a shampoo. As a shampoo, selenium sulfide usually is used twice a week for the first ... it is irritating. Rinse off all of the lotion.Do not use this medication on children younger ...

  10. Reactive iron sulfide (FeS)-supported ultrafiltration for removal of mercury (Hg(II)) from water.

    PubMed

    Han, Dong Suk; Orillano, Maria; Khodary, Ahmed; Duan, Yuhang; Batchelor, Bill; Abdel-Wahab, Ahmed

    2014-04-15

    This study investigated removal of Hg(II) from water using FeS(s) with batch and continuous contact filtration systems. For the batch system, kinetic experiments showed that removal of Hg(II) by FeS(s) was rapid at lower concentration (500 μM), but at higher concentration (1000 and 1250 μM), more time was required to achieve greater than 99% removal. The concentration of iron released to the solution remained relatively low, typically below 3 μM. This would theoretically present less than 1% of the Hg(II) removed. Thus, a simple exchange of Hg(II) for Fe(II) in the solid (FeS(s)) does not explain the results, but if the Fe(II) released could react to form another solids, low concentrations of Fe do not preclude a mechanism in which Hg(II) reacts to form HgS and release Fe(II). A continuous contact dead-end ultrafiltration (DE/UF) system was developed to treat water containing Hg(II) by applying a FeS(s) suspension with stirred or non-stirred modes. A major reason for applying stirring to the system was to investigate the role of "shear" flow in rejection of Hg(II)-contacted FeS(s) by a UF membrane and the stability of Hg on the FeS(s). The Hg(II)-contacted FeS(s) was completely rejected by the DE/UF system and mercury was strongly retained on the FeS(s) particles. Almost no release of Hg(II) (≈0 mM) from the FeS(s) solids was observed when they were contacted with 0.1M-thiosulfate, regardless of whether the system was operated in stirred or non-stirred mode. However, rapid oxidation of FeS(s) was observed in the stirred system but not in the non-stirred system. Determining the mechanism of oxidation requires further study, but it is important because oxidation reduces the ability of the solids to remove additional Hg(II).

  11. Reactive iron sulfide (FeS)-supported ultrafiltration for removal of mercury (Hg(II)) from water.

    PubMed

    Han, Dong Suk; Orillano, Maria; Khodary, Ahmed; Duan, Yuhang; Batchelor, Bill; Abdel-Wahab, Ahmed

    2014-04-15

    This study investigated removal of Hg(II) from water using FeS(s) with batch and continuous contact filtration systems. For the batch system, kinetic experiments showed that removal of Hg(II) by FeS(s) was rapid at lower concentration (500 μM), but at higher concentration (1000 and 1250 μM), more time was required to achieve greater than 99% removal. The concentration of iron released to the solution remained relatively low, typically below 3 μM. This would theoretically present less than 1% of the Hg(II) removed. Thus, a simple exchange of Hg(II) for Fe(II) in the solid (FeS(s)) does not explain the results, but if the Fe(II) released could react to form another solids, low concentrations of Fe do not preclude a mechanism in which Hg(II) reacts to form HgS and release Fe(II). A continuous contact dead-end ultrafiltration (DE/UF) system was developed to treat water containing Hg(II) by applying a FeS(s) suspension with stirred or non-stirred modes. A major reason for applying stirring to the system was to investigate the role of "shear" flow in rejection of Hg(II)-contacted FeS(s) by a UF membrane and the stability of Hg on the FeS(s). The Hg(II)-contacted FeS(s) was completely rejected by the DE/UF system and mercury was strongly retained on the FeS(s) particles. Almost no release of Hg(II) (≈0 mM) from the FeS(s) solids was observed when they were contacted with 0.1M-thiosulfate, regardless of whether the system was operated in stirred or non-stirred mode. However, rapid oxidation of FeS(s) was observed in the stirred system but not in the non-stirred system. Determining the mechanism of oxidation requires further study, but it is important because oxidation reduces the ability of the solids to remove additional Hg(II). PMID:24530550

  12. Sulfur and sulfides in chondrules

    NASA Astrophysics Data System (ADS)

    Marrocchi, Yves; Libourel, Guy

    2013-10-01

    The nature and distribution of sulfides within type I PO, POP and PP chondrules of the carbonaceous chondrite Vigarano (CV3) have been studied by secondary electron microscopy and electron microprobe. They occur predominantly as spheroidal blebs composed entirely of low-Ni iron sulfide (troilite, FeS) or troilite + magnetite but in less abundance in association with metallic Fe-Ni beads in opaque assemblages. Troilites are mainly located within the low-Ca pyroxene outer zone and their amounts increase with the abundance of low-Ca pyroxene within chondrules, suggesting co-crystallization of troilite and low-Ca pyroxene during high-temperature events. We show that sulfur concentration and sulfide occurrence in chondrules obey high temperature sulfur solubility and saturation laws. Depending on the fS2 and fO2 of the surrounding gas and on the melt composition, mainly the FeO content, sulfur dissolved in chondrule melts may eventually reach a concentration limit, the sulfur content at sulfide saturation (SCSS), at which an immiscible iron sulfide liquid separates from the silicate melt. The occurrence of both a silicate melt and an immiscible iron sulfide liquid is further supported by the non-wetting behavior of sulfides on silicate phases in chondrules due to the high interfacial tension between their precursor iron-sulfide liquid droplets and the surrounding silicate melt during the high temperature chondrule-forming event. The evolution of chondrule melts from PO to PP towards more silicic compositions, very likely due to high PSiO(g) of the surrounding nebular gas, induces saturation of FeS at much lower S content in PP than in PO chondrules, leading to the co-crystallization of iron sulfides and low-Ca pyroxenes. Conditions of co-saturation of low-Ca pyroxene and FeS are only achieved in non canonical environments characterized by high partial pressures of sulfur and SiO and redox conditions more oxidizing than IW-3. Fe and S mass balance calculations also

  13. Nanostructured metal sulfides for energy storage.

    PubMed

    Rui, Xianhong; Tan, Huiteng; Yan, Qingyu

    2014-09-01

    Advanced electrodes with a high energy density at high power are urgently needed for high-performance energy storage devices, including lithium-ion batteries (LIBs) and supercapacitors (SCs), to fulfil the requirements of future electrochemical power sources for applications such as in hybrid electric/plug-in-hybrid (HEV/PHEV) vehicles. Metal sulfides with unique physical and chemical properties, as well as high specific capacity/capacitance, which are typically multiple times higher than that of the carbon/graphite-based materials, are currently studied as promising electrode materials. However, the implementation of these sulfide electrodes in practical applications is hindered by their inferior rate performance and cycling stability. Nanostructures offering the advantages of high surface-to-volume ratios, favourable transport properties, and high freedom for the volume change upon ion insertion/extraction and other reactions, present an opportunity to build next-generation LIBs and SCs. Thus, the development of novel concepts in material research to achieve new nanostructures paves the way for improved electrochemical performance. Herein, we summarize recent advances in nanostructured metal sulfides, such as iron sulfides, copper sulfides, cobalt sulfides, nickel sulfides, manganese sulfides, molybdenum sulfides, tin sulfides, with zero-, one-, two-, and three-dimensional morphologies for LIB and SC applications. In addition, the recently emerged concept of incorporating conductive matrices, especially graphene, with metal sulfide nanomaterials will also be highlighted. Finally, some remarks are made on the challenges and perspectives for the future development of metal sulfide-based LIB and SC devices. PMID:25073046

  14. Nanostructured metal sulfides for energy storage.

    PubMed

    Rui, Xianhong; Tan, Huiteng; Yan, Qingyu

    2014-09-01

    Advanced electrodes with a high energy density at high power are urgently needed for high-performance energy storage devices, including lithium-ion batteries (LIBs) and supercapacitors (SCs), to fulfil the requirements of future electrochemical power sources for applications such as in hybrid electric/plug-in-hybrid (HEV/PHEV) vehicles. Metal sulfides with unique physical and chemical properties, as well as high specific capacity/capacitance, which are typically multiple times higher than that of the carbon/graphite-based materials, are currently studied as promising electrode materials. However, the implementation of these sulfide electrodes in practical applications is hindered by their inferior rate performance and cycling stability. Nanostructures offering the advantages of high surface-to-volume ratios, favourable transport properties, and high freedom for the volume change upon ion insertion/extraction and other reactions, present an opportunity to build next-generation LIBs and SCs. Thus, the development of novel concepts in material research to achieve new nanostructures paves the way for improved electrochemical performance. Herein, we summarize recent advances in nanostructured metal sulfides, such as iron sulfides, copper sulfides, cobalt sulfides, nickel sulfides, manganese sulfides, molybdenum sulfides, tin sulfides, with zero-, one-, two-, and three-dimensional morphologies for LIB and SC applications. In addition, the recently emerged concept of incorporating conductive matrices, especially graphene, with metal sulfide nanomaterials will also be highlighted. Finally, some remarks are made on the challenges and perspectives for the future development of metal sulfide-based LIB and SC devices.

  15. Nanostructured metal sulfides for energy storage

    NASA Astrophysics Data System (ADS)

    Rui, Xianhong; Tan, Huiteng; Yan, Qingyu

    2014-08-01

    Advanced electrodes with a high energy density at high power are urgently needed for high-performance energy storage devices, including lithium-ion batteries (LIBs) and supercapacitors (SCs), to fulfil the requirements of future electrochemical power sources for applications such as in hybrid electric/plug-in-hybrid (HEV/PHEV) vehicles. Metal sulfides with unique physical and chemical properties, as well as high specific capacity/capacitance, which are typically multiple times higher than that of the carbon/graphite-based materials, are currently studied as promising electrode materials. However, the implementation of these sulfide electrodes in practical applications is hindered by their inferior rate performance and cycling stability. Nanostructures offering the advantages of high surface-to-volume ratios, favourable transport properties, and high freedom for the volume change upon ion insertion/extraction and other reactions, present an opportunity to build next-generation LIBs and SCs. Thus, the development of novel concepts in material research to achieve new nanostructures paves the way for improved electrochemical performance. Herein, we summarize recent advances in nanostructured metal sulfides, such as iron sulfides, copper sulfides, cobalt sulfides, nickel sulfides, manganese sulfides, molybdenum sulfides, tin sulfides, with zero-, one-, two-, and three-dimensional morphologies for LIB and SC applications. In addition, the recently emerged concept of incorporating conductive matrices, especially graphene, with metal sulfide nanomaterials will also be highlighted. Finally, some remarks are made on the challenges and perspectives for the future development of metal sulfide-based LIB and SC devices.

  16. Process for removing technetium from iron and other metals

    DOEpatents

    Leitnaker, James M.; Trowbridge, Lee D.

    1999-01-01

    A process for removing technetium from iron and other metals comprises the steps of converting the molten, alloyed technetium to a sulfide dissolved in manganese sulfide, and removing the sulfide from the molten metal as a slag.

  17. Process for removing technetium from iron and other metals

    DOEpatents

    Leitnaker, J.M.; Trowbridge, L.D.

    1999-03-23

    A process for removing technetium from iron and other metals comprises the steps of converting the molten, alloyed technetium to a sulfide dissolved in manganese sulfide, and removing the sulfide from the molten metal as a slag. 4 figs.

  18. Digital Synchronizer without Metastability

    NASA Technical Reports Server (NTRS)

    Simle, Robert M.; Cavazos, Jose A.

    2009-01-01

    A proposed design for a digital synchronizing circuit would eliminate metastability that plagues flip-flop circuits in digital input/output interfaces. This metastability is associated with sampling, by use of flip-flops, of an external signal that is asynchronous with a clock signal that drives the flip-flops: it is a temporary flip-flop failure that can occur when a rising or falling edge of an asynchronous signal occurs during the setup and/or hold time of a flip-flop. The proposed design calls for (1) use of a clock frequency greater than the frequency of the asynchronous signal, (2) use of flip-flop asynchronous preset or clear signals for the asynchronous input, (3) use of a clock asynchronous recovery delay with pulse width discriminator, and (4) tying the data inputs to constant logic levels to obtain (5) two half-rate synchronous partial signals - one for the falling and one for the rising edge. Inasmuch as the flip-flop data inputs would be permanently tied to constant logic levels, setup and hold times would not be violated. The half-rate partial signals would be recombined to construct a signal that would replicate the original asynchronous signal at its original rate but would be synchronous with the clock signal.

  19. Synchrotron X-Ray Fluorescence Analysis of Trace Elements in Focused Ion Beam Prepared Sections of Carbonaceous Chondrite Iron Sulfides (CM and CR) and Associated Metal (CR)

    NASA Astrophysics Data System (ADS)

    Singerling, S. A.; Sutton, S. R.; Lanzirotti, A.; Newville, M.; Brearley, A. J.

    2016-08-01

    This study presents data on trace element abundances in CM and CR sulfides and metals. We determined that Ge and Zn were observed to be depleted relative to CI chondrite while the more volatile Se was observed to be enriched.

  20. Desensitization of metastable intermolecular composites

    DOEpatents

    Busse, James R.; Dye, Robert C.; Foley, Timothy J.; Higa, Kelvin T.; Jorgensen, Betty S.; Sanders, Victor E.; Son, Steven F.

    2011-04-26

    A method to substantially desensitize a metastable intermolecular composite material to electrostatic discharge and friction comprising mixing the composite material with an organic diluent and removing enough organic diluent from the mixture to form a mixture with a substantially putty-like consistency, as well as a concomitant method of recovering the metastable intermolecular composite material.

  1. Platinum metals magmatic sulfide ores.

    PubMed

    Naldrett, A J; Duke, J M

    1980-06-27

    Platinum-group elements (PGE) are mined predominantly from deposits that have formed by the segregation of molten iron-nickel-copper sulfides from silicate magmas. The absolute concentrations of PGE in sulfides from different deposits vary over a range of five orders of magnitude, whereas those of other chalcophile elements vary by factors of only 2 to 100. However, the relative proportions of the different PGE in a given deposit are systematically related to the nature of the parent magma. The absolute and relative concentrations of PGE in magmatic sulfides are explained in terms of the degree of partial melting of mantle peridotite required to produce the parent magma and the processes of batch equilibration and fractional segregation of sulfides. The Republic of South Africa and the U.S.S.R. together possess more than 97 percent of the world PGE reserves, but significant undeveloped resources occur in North America. The Stillwater complex in Montana is perhaps the most important example.

  2. Complexity, Metastability and Nonextensivity

    NASA Astrophysics Data System (ADS)

    Beck, C.; Benedek, G.; Rapisarda, A.; Tsallis, C.

    Work and heat fluctuations in systems with deterministic and stochastic forces / E. G. D. Cohen and R. Van Zon -- Is the entropy S[symbol] extensive or nonextensive? / C. Tsallis -- Superstatistics: recent developments and applications / C. Beck -- Two stories outside Boltzmann-Gibbs statistics: Mori's Q-phase transitions and glassy dynamics at the onset of chaos / A. Robledo, F. Baldovin and E. Mayoral -- Time-averages and the heat theorem / A. Carati -- Fundamental formulae and numerical evidences for the central limit theorem in Tsallis statistics / H. Suyari -- Generalizing the Planck distribution / A. M. C. Soma and C. Tsallis -- The physical roots of complexity: renewal or modulation? / P. Grigolini -- Nonequivalent ensembles and metastability / H. Touchette and R. S. Ellis -- Statistical physics for cosmic structures / L. Pietronero and F. Sylos Labini -- Metastability and anomalous behavior in the HMF model: connections to nonextensive thermodynamics and glassy dynamics / A. Pluchino, A. Rapisarda and V. Latora -- Vlasov analysis of relaxation and meta-equilibrium / C. Anteneodo and R. O. Vallejos -- Weak chaos in large conservative systems - infinite-range coupled standard maps / L. G. Moyano, A. P. Majtey and C. Tsallis -- Deterministc aging / E. Barkai -- Edge of chaos of the classical kicked top map: sensitivity to initial conditions / S. M. Duarte Queirós and C. Tsallis -- What entropy at the edge of chaos? / M. Lissia, M. Coraddu and R. Tonelli -- Fractal growth of carbon schwarzites / G. Benedek ... [et al.] -- Clustering and interface propagation in interacting particle dynamics / A. Provata and V. K. Noussiou -- Resonant activation and noise enhanced stability in Josephson junctions / A. L. Pankratov and B. Spagnolo -- Symmetry breaking induced directed motions / C.-H. Chang and T. Y. Tsong -- General theory of Galilean-invariant entropic lattic Boltzmann models / B. M. Boghosian -- Unifying approach to the jamming transition in granular media and

  3. Iron Transformation Pathways and Redox Micro-Environments in Seafloor Sulfide-Mineral Deposits: Spatially Resolved Fe XAS and δ(57/54)Fe Observations.

    PubMed

    Toner, Brandy M; Rouxel, Olivier J; Santelli, Cara M; Bach, Wolfgang; Edwards, Katrina J

    2016-01-01

    Hydrothermal sulfide chimneys located along the global system of oceanic spreading centers are habitats for microbial life during active venting. Hydrothermally extinct, or inactive, sulfide deposits also host microbial communities at globally distributed sites. The main goal of this study is to describe Fe transformation pathways, through precipitation and oxidation-reduction (redox) reactions, and examine transformation products for signatures of biological activity using Fe mineralogy and stable isotope approaches. The study includes active and inactive sulfides from the East Pacific Rise 9°50'N vent field. First, the mineralogy of Fe(III)-bearing precipitates is investigated using microprobe X-ray absorption spectroscopy (μXAS) and X-ray diffraction (μXRD). Second, laser-ablation (LA) and micro-drilling (MD) are used to obtain spatially-resolved Fe stable isotope analysis by multicollector-inductively coupled plasma-mass spectrometry (MC-ICP-MS). Eight Fe-bearing minerals representing three mineralogical classes are present in the samples: oxyhydroxides, secondary phyllosilicates, and sulfides. For Fe oxyhydroxides within chimney walls and layers of Si-rich material, enrichments in both heavy and light Fe isotopes relative to pyrite are observed, yielding a range of δ(57)Fe values up to 6‰. Overall, several pathways for Fe transformation are observed. Pathway 1 is characterized by precipitation of primary sulfide minerals from Fe(II)aq-rich fluids in zones of mixing between vent fluids and seawater. Pathway 2 is also consistent with zones of mixing but involves precipitation of sulfide minerals from Fe(II)aq generated by Fe(III) reduction. Pathway 3 is direct oxidation of Fe(II) aq from hydrothermal fluids to form Fe(III) precipitates. Finally, Pathway 4 involves oxidative alteration of pre-existing sulfide minerals to form Fe(III). The Fe mineralogy and isotope data do not support or refute a unique biological role in sulfide alteration. The findings

  4. Iron Transformation Pathways and Redox Micro-Environments in Seafloor Sulfide-Mineral Deposits: Spatially Resolved Fe XAS and δ(57/54)Fe Observations.

    PubMed

    Toner, Brandy M; Rouxel, Olivier J; Santelli, Cara M; Bach, Wolfgang; Edwards, Katrina J

    2016-01-01

    Hydrothermal sulfide chimneys located along the global system of oceanic spreading centers are habitats for microbial life during active venting. Hydrothermally extinct, or inactive, sulfide deposits also host microbial communities at globally distributed sites. The main goal of this study is to describe Fe transformation pathways, through precipitation and oxidation-reduction (redox) reactions, and examine transformation products for signatures of biological activity using Fe mineralogy and stable isotope approaches. The study includes active and inactive sulfides from the East Pacific Rise 9°50'N vent field. First, the mineralogy of Fe(III)-bearing precipitates is investigated using microprobe X-ray absorption spectroscopy (μXAS) and X-ray diffraction (μXRD). Second, laser-ablation (LA) and micro-drilling (MD) are used to obtain spatially-resolved Fe stable isotope analysis by multicollector-inductively coupled plasma-mass spectrometry (MC-ICP-MS). Eight Fe-bearing minerals representing three mineralogical classes are present in the samples: oxyhydroxides, secondary phyllosilicates, and sulfides. For Fe oxyhydroxides within chimney walls and layers of Si-rich material, enrichments in both heavy and light Fe isotopes relative to pyrite are observed, yielding a range of δ(57)Fe values up to 6‰. Overall, several pathways for Fe transformation are observed. Pathway 1 is characterized by precipitation of primary sulfide minerals from Fe(II)aq-rich fluids in zones of mixing between vent fluids and seawater. Pathway 2 is also consistent with zones of mixing but involves precipitation of sulfide minerals from Fe(II)aq generated by Fe(III) reduction. Pathway 3 is direct oxidation of Fe(II) aq from hydrothermal fluids to form Fe(III) precipitates. Finally, Pathway 4 involves oxidative alteration of pre-existing sulfide minerals to form Fe(III). The Fe mineralogy and isotope data do not support or refute a unique biological role in sulfide alteration. The findings

  5. Iron transformation pathways and redox micro-environments in seafloor sulfide-mineral deposits: Spatially resolved Fe XAS and δ57/54Fe observations

    DOE PAGESBeta

    Toner, Brandy M.; Rouxel, Olivier J.; Santelli, Cara M.; Bach, Wolfgang; Edwards, Katrina J.

    2016-05-10

    Hydrothermal sulfide chimneys located along the global system of oceanic spreading centers are habitats for microbial life during active venting. Hydrothermally extinct, or inactive, sulfide deposits also host microbial communities at globally distributed sites. The main goal of this study is to describe Fe transformation pathways, through precipitation and oxidation-reduction (redox) reactions, and examine transformation products for signatures of biological activity using Fe mineralogy and stable isotope approaches. The study includes active and inactive sulfides from the East Pacific Rise 9°50'N vent field. First, the mineralogy of Fe(III)-bearing precipitates is investigated using microprobe X-ray absorption spectroscopy (μXAS) and X-ray diffractionmore » (μXRD). Second, laser-ablation (LA) and micro-drilling (MD) are used to obtain spatially-resolved Fe stable isotope analysis by multicollector-inductively coupled plasma-mass spectrometry (MC-ICP-MS). Eight Fe-bearing minerals representing three mineralogical classes are present in the samples: oxyhydroxides, secondary phyllosilicates, and sulfides. For Fe oxyhydroxides within chimney walls and layers of Si-rich material, enrichments in both heavy and light Fe isotopes relative to pyrite are observed, yielding a range of δ57Fe values up to 6‰. Overall, several pathways for Fe transformation are observed. Pathway 1 is characterized by precipitation of primary sulfide minerals from Fe(II)aq-rich fluids in zones of mixing between vent fluids and seawater. Pathway 2 is also consistent with zones of mixing but involves precipitation of sulfide minerals from Fe(II)aq generated by Fe(III) reduction. Pathway 3 is direct oxidation of Fe(II) aq from hydrothermal fluids to form Fe(III) precipitates. Finally, Pathway 4 involves oxidative alteration of pre-existing sulfide minerals to form Fe(III). The Fe mineralogy and isotope data do not support or refute a unique biological role in sulfide alteration. The

  6. Iron Transformation Pathways and Redox Micro-Environments in Seafloor Sulfide-Mineral Deposits: Spatially Resolved Fe XAS and δ57/54Fe Observations

    PubMed Central

    Toner, Brandy M.; Rouxel, Olivier J.; Santelli, Cara M.; Bach, Wolfgang; Edwards, Katrina J.

    2016-01-01

    Hydrothermal sulfide chimneys located along the global system of oceanic spreading centers are habitats for microbial life during active venting. Hydrothermally extinct, or inactive, sulfide deposits also host microbial communities at globally distributed sites. The main goal of this study is to describe Fe transformation pathways, through precipitation and oxidation-reduction (redox) reactions, and examine transformation products for signatures of biological activity using Fe mineralogy and stable isotope approaches. The study includes active and inactive sulfides from the East Pacific Rise 9°50′N vent field. First, the mineralogy of Fe(III)-bearing precipitates is investigated using microprobe X-ray absorption spectroscopy (μXAS) and X-ray diffraction (μXRD). Second, laser-ablation (LA) and micro-drilling (MD) are used to obtain spatially-resolved Fe stable isotope analysis by multicollector-inductively coupled plasma-mass spectrometry (MC-ICP-MS). Eight Fe-bearing minerals representing three mineralogical classes are present in the samples: oxyhydroxides, secondary phyllosilicates, and sulfides. For Fe oxyhydroxides within chimney walls and layers of Si-rich material, enrichments in both heavy and light Fe isotopes relative to pyrite are observed, yielding a range of δ57Fe values up to 6‰. Overall, several pathways for Fe transformation are observed. Pathway 1 is characterized by precipitation of primary sulfide minerals from Fe(II)aq-rich fluids in zones of mixing between vent fluids and seawater. Pathway 2 is also consistent with zones of mixing but involves precipitation of sulfide minerals from Fe(II)aq generated by Fe(III) reduction. Pathway 3 is direct oxidation of Fe(II) aq from hydrothermal fluids to form Fe(III) precipitates. Finally, Pathway 4 involves oxidative alteration of pre-existing sulfide minerals to form Fe(III). The Fe mineralogy and isotope data do not support or refute a unique biological role in sulfide alteration. The findings

  7. Metallic sulfide additives for positive electrode material within a secondary electrochemical cell

    DOEpatents

    Walsh, William J.; McPheeters, Charles C.; Yao, Neng-ping; Koura, Kobuyuki

    1976-01-01

    An improved active material for use within the positive electrode of a secondary electrochemical cell includes a mixture of iron disulfide and a sulfide of a polyvalent metal. Various metal sulfides, particularly sulfides of cobalt, nickel, copper, cerium and manganese, are added in minor weight proportion in respect to iron disulfide for improving the electrode performance and reducing current collector requirements.

  8. 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.

  9. Modulated voltage metastable ionization detector

    NASA Technical Reports Server (NTRS)

    Carle, G. C.; Kojiro, D. R.; Humphrey, D. E. (Inventor)

    1985-01-01

    The output current from a metastable ionization detector (MID) is applied to a modulation voltage circuit. An adjustment is made to balance out the background current, and an output current, above background, is applied to an input of a strip chart recorder. For low level concentrations, i.e., low detected output current, the ionization potential will be at a maximum and the metastable ionization detector will operate at its most sensitive level. When the detected current from the metastable ionization detector increases above a predetermined threshold level, a voltage control circuit is activated which turns on a high voltage transistor which acts to reduce the ionization potential. The ionization potential applied to the metastable ionization detector is then varied so as to maintain the detected signal level constant. The variation in ionization potential is now related to the concentration of the constituent and a representative amplitude is applied to another input of said strip chart recorder.

  10. Nickel sulfide hollow whisker formation

    SciTech Connect

    Holcomb, G.R.; Cramer, S.D.

    1997-02-01

    Hollow, high-aspect-ratio nickel sulfide whiskers were formed during aqueous corrosion experiments at 250 C by the US Department of Energy. The whiskers grew radially from Teflon thread at the waterline in acidic sodium sulfate solutions containing chloride additions. The hollow morphology is consistent with that reported for the mineral millerite found in nature in hematite cavities. The data suggest that iron and chloride impurities are necessary for the observed whisker structure. Hollow nickel sulfide whiskers were observed only in high-temperature corrosion experiments conducted on stainless steels; they were not observed in similar experiments on nickel-base alloys.

  11. Carbonyl sulfide

    Integrated Risk Information System (IRIS)

    Carbonyl sulfide ; CASRN 463 - 58 - 1 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic

  12. Hydrogen sulfide

    Integrated Risk Information System (IRIS)

    Hydrogen sulfide ; 7783 - 06 - 4 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Effec

  13. Selenium sulfide

    Integrated Risk Information System (IRIS)

    Selenium sulfide ; CASRN 7446 - 34 - 6 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic

  14. Hydrothermal ore-forming processes in the light of studies in rock- buffered systems: I. Iron-copper-zinc-lead sulfide solubility relations

    USGS Publications Warehouse

    Hemley, J.J.; Cygan, G.L.; Fein, J.B.; Robinson, G.R.; d'Angelo, W. M.

    1992-01-01

    Experimental studies, using cold-seal and extraction vessel techniques, were conducted on Fe, Pb, Zn, and Cu sulfide solubilities in chloride soultions at temperatures from 300?? to 700??C and pressures from 0.5 to 2 kbars. The solutions were buffered in pH by quartz monzonite and the pure potassium feldspar-muscovite-quartz assemblage and in fS2-fO2 largely by the assemblage pyrite-pyrrhotite-magnetite. Solubilities increase with increasing temperature and total chloride, and decrease with increasing pressure. The effect of increasing chloride concentration on solubility reflects primarily a shift to lower pH via the silicate buffer reactions. Similarity in behaviour with respect to the temperature and pressure of Fe, Zn, and Pb sulfide solubilities points to similarity in chloride speciation, and the neutral species appear to be dominant in the high-temperature region. -from Authors

  15. Pulsed discharge production Ar* metastables

    NASA Astrophysics Data System (ADS)

    Han, Jiande; Heaven, Michael C.; Emmons, Daniel; Perram, Glen P.; Weeks, David E.; Bailey, William F.

    2016-03-01

    The production of relatively high densities of Ar* metastables (>1012 cm-3) in Ar/He mixtures, at total pressures close to 1 atm, is essential for the efficient operation of an optically pumped Ar* laser. We have used emission spectroscopy and diode laser absorption spectroscopy measurements to observe the production and decay of Ar* in a parallel plate pulsed discharge. With discharge pulses of 1 μs duration we find that metastable production is dominated by processes occurring within the first 100 ns of the gas break-down. Application of multiple, closely spaced discharge pulses yields insights concerning conditions that favor metastable production. This information has been combined with time-resolved measurements of voltage and current. The experimental results and preliminary modeling of the discharge kinetics are presented.

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

    USGS Publications Warehouse

    Sato, M.

    1992-01-01

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

  17. Selective formation of metastable ferrihydrite in the chiton tooth.

    PubMed

    Gordon, Lyle M; Román, Jessica K; Everly, R Michael; Cohen, Michael J; Wilker, Jonathan J; Joester, Derk

    2014-10-20

    Metastable precursors are thought to play a major role in the ability of organisms to create mineralized tissues. Of particular interest are the hard and abrasion-resistant teeth formed by chitons, a class of rock-grazing mollusks. The formation of chiton teeth relies on the precipitation of metastable ferrihydrite (Fh) in an organic scaffold as a precursor to magnetite. In vitro synthesis of Fh under physiological conditions has been challenging. Using a combination of X-ray absorption and electron paramagnetic resonance spectroscopy, we show that, prior to Fh formation in the chiton tooth, iron ions are complexed by the organic matrix. In vitro experiments demonstrate that such complexes facilitate the formation of Fh under physiological conditions. These results indicate that acidic molecules may be integral to controlling Fh formation in the chiton tooth. This biological approach to polymorph selection is not limited to specialized proteins and can be expropriated using simple chemistry.

  18. Selective formation of metastable ferrihydrite in the chiton tooth.

    PubMed

    Gordon, Lyle M; Román, Jessica K; Everly, R Michael; Cohen, Michael J; Wilker, Jonathan J; Joester, Derk

    2014-10-20

    Metastable precursors are thought to play a major role in the ability of organisms to create mineralized tissues. Of particular interest are the hard and abrasion-resistant teeth formed by chitons, a class of rock-grazing mollusks. The formation of chiton teeth relies on the precipitation of metastable ferrihydrite (Fh) in an organic scaffold as a precursor to magnetite. In vitro synthesis of Fh under physiological conditions has been challenging. Using a combination of X-ray absorption and electron paramagnetic resonance spectroscopy, we show that, prior to Fh formation in the chiton tooth, iron ions are complexed by the organic matrix. In vitro experiments demonstrate that such complexes facilitate the formation of Fh under physiological conditions. These results indicate that acidic molecules may be integral to controlling Fh formation in the chiton tooth. This biological approach to polymorph selection is not limited to specialized proteins and can be expropriated using simple chemistry. PMID:25196134

  19. Metastable Phases in Ice Clouds

    NASA Astrophysics Data System (ADS)

    Weiss, Fabian; Baloh, Philipp; Kubel, Frank; Hoelzel, Markus; Parker, Stewart; Grothe, Hinrich

    2014-05-01

    Polar Stratospheric Clouds and Cirrus Clouds contain both, pure water ice and phases of nitric acid hydrates. Preferentially for the latter, the thermodynamically stable phases have intensively been investigated in the past (e.g. nitric acid trihydrate, beta-NAT). As shown by Peter et al. [1] the water activity inside clouds is higher than expected, which might be explained by the presence of metastable stable phases (e.g. cubic ice). However, also metastable nitric acid hydrates might be important due to the inherent non-equilibrium freezing conditions in the upper atmosphere. The delta ice theory of Gao et al. [2] presents a model approach to solve this problem by involving both metastable ice and NAT as well. So it is of high interest to investigate the metastable phase of NAT (i.e. alpha-NAT), the structure of which was unknown up to the presence. In our laboratory a production procedure for metastable alpha-NAT has been developed, which gives access to neutron diffraction and X-ray diffraction measurements, where sample quantities of several Gramm are required. The diffraction techniques were used to solve the unknown crystalline structure of metastable alpha-NAT, which in turn allows the calculation of the vibrational spectra, which have also been recorded by us in the past. Rerefences [1] Peter, T., C. Marcolli, P. Spichtinger, T. Corti, M. B. Baker, and T. Koop. When dry air is too humid. Science, 314:1399-1402, 2006. [2] Gao, R., P. Popp, D. Fahey, T. Marcy, R. L. Herman, E. Weinstock, D. Baumgardener, T. Garrett, K. Rosenlof, T. Thompson, T. P. Bui, B. Ridley, S. C. Wofsy, O. B. Toon, M. Tolbert, B. Kärcher, Th. Peter, P. K. Hudson, A. Weinheimer, and A. Heymsfield. Evidence That Nitric Acid Increases Relative Humidity in Low-Temperature Cirrus Clouds, Science, 303:516-520, 2004. [3] Tizek, H., E. Knözinger, and H. Grothe. Formation and phase distribution of nitric acid hydrates in the mole fraction range xHNO3<0.25: A combined XRD and IR study, PCCP, 6

  20. Sulfide chemiluminescence detection

    DOEpatents

    Spurlin, Stanford R.; Yeung, Edward S.

    1985-01-01

    A method of chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction and a specifically designed chemiluminescence detection cell for the reaction.

  1. Sulfide chemiluminescence detection

    DOEpatents

    Spurlin, S.R.; Yeung, E.S.

    1985-11-26

    A method is described for chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction and a specifically designed chemiluminescence detection cell for the reaction. 4 figs.

  2. Platinum metals magmatic sulfide ores.

    PubMed

    Naldrett, A J; Duke, J M

    1980-06-27

    Platinum-group elements (PGE) are mined predominantly from deposits that have formed by the segregation of molten iron-nickel-copper sulfides from silicate magmas. The absolute concentrations of PGE in sulfides from different deposits vary over a range of five orders of magnitude, whereas those of other chalcophile elements vary by factors of only 2 to 100. However, the relative proportions of the different PGE in a given deposit are systematically related to the nature of the parent magma. The absolute and relative concentrations of PGE in magmatic sulfides are explained in terms of the degree of partial melting of mantle peridotite required to produce the parent magma and the processes of batch equilibration and fractional segregation of sulfides. The Republic of South Africa and the U.S.S.R. together possess more than 97 percent of the world PGE reserves, but significant undeveloped resources occur in North America. The Stillwater complex in Montana is perhaps the most important example. PMID:17796685

  3. Potassium-bearing Iron-Nickel Sulfides in Nature and High-Pressure Experiments: Geochemical Consequences of Potassium in the Earth's Core

    NASA Technical Reports Server (NTRS)

    Keshav, S.; Corgne, A.; McDonough, W. F.; Fei, Y.

    2005-01-01

    Introduction: Potassium (K) as a large ion lithophile element has dominantly been concentrated in the Earth s crust and the mantle through differentiation, and in the form of K-40 contributes to the planet s heat budget. However, whether or not K also enters core-forming phases, has been debated for over three decades. Arguments favoring entry of K in the core are based on: (1) K-sulfide (with Fe, Ni, Cu, Na, and Cl; djerfisherite) found in highly reduced enstatite chondrites (or aubrites, enstatite achondrites); (2) demonstration that K, owing to an s-d electronic switch at high-pressure, exhibits transition- element like character, (3) solubility of measurable K in Fe-Ni-S liquids at high pressure, temperature conditions, and (4) models of cooling of the core that seem to require, besides convection, some form of radioactivity, and thus lending support to the experimental work. In this contribution, we assess the effect of sequestering K in the core, as it is perhaps an element that is a key to reconciling geochemistry, paleomagnetism, accretion, and thermal evolution models for the planet.

  4. Metal-atom fluorescence from the quenching of metastable rare gases by metal carbonyls

    SciTech Connect

    Hollingsworth, W.E.

    1982-11-01

    A flowing afterglow apparatus was used to study the metal fluorescence resulting from the quenching of metastable rare-gas states by metal carbonyls. The data from the quenching or argon, neon, and helium by iron and nickel carbonyl agreed well with a restricted degree of freedom model indicating a concerted bond-breaking dissociation.

  5. Iron-Nitride-Based Magnets: Synthesis and Phase Stabilization of Body Center Tetragonal (BCT) Metastable Fe-N Anisotropic Nanocomposite Magnet- A Path to Fabricate Rare Earth Free Magnet

    SciTech Connect

    2012-01-01

    REACT Project: The University of Minnesota will develop an early stage prototype of an iron-nitride permanent magnet material for EVs and renewable power generators. This new material, comprised entirely of low-cost and abundant resources, has the potential to demonstrate the highest energy potential of any magnet to date. This project will provide the basis for an entirely new class of rare-earth-free magnets capable of generating power without costly and scarce rare earth materials. The ultimate goal of this project is to demonstrate a prototype with magnetic properties exceeding state-of-the-art commercial magnets.

  6. Marine diagenesis of hydrothermal sulfide

    SciTech Connect

    Moammar, M.O.

    1985-01-01

    An attempt is made to discuss the artificial and natural oxidation and hydrolysis of hydrothermal sulfide upon interaction with normal seawater. Synthetic and natural ferrosphalerite particles used in kinetic oxidation and hydrolysis studies in seawater develop dense, crystalline coatings consisting of ordered and ferrimagnetic delta-(Fe, Zn)OOH. Due to the formation of this reactive diffusion barrier, the release of Zn into solution decreases rapidly, and sulfide oxidation is reduced to a low rate determined by the diffusion of oxygen through the oxyhydroxide film. This also acts as an efficient solvent for ions such as Zn/sup 2 +/, Ca/sup 2 +/, and possibly Cd/sup 2 +/, which contribute to the stabilization of the delta-FeOOH structure. The oxidation of sulfide occurs in many seafloor spreading areas, such as 21/sup 0/N on the East Pacific Ridge. In these areas the old surface of the sulfide chimneys are found to be covered by an orange stain, and sediment near the base of nonactive vents is also found to consist of what has been referred to as amorphous iron oxide and hydroxide. This thesis also discusses the exceedingly low solubility of zinc in seawater, from delta-(Fe, Zn)OOH and the analogous phase (zinc-ferrihydroxide) and the zinc exchange minerals, 10-A manganate and montmorillonite. The concentrations of all four are of the same magnitude (16, 36.4, and 12 nM, respectively) as the zinc concentration in deep ocean water (approx. 10 nM), which suggests that manganates and montmorillonite with iron oxyhydroxides control zinc concentration in the deep ocean.

  7. Production of glycolic acid by chemolithotrophic iron- and sulfur-oxidizing bacteria and its role in delineating and sustaining acidophilic sulfide mineral-oxidizing consortia.

    PubMed

    Nancucheo, Ivan; Johnson, D Barrie

    2010-01-01

    Glycolic acid was detected as an exudate in actively growing cultures of three chemolithotrophic acidophiles that are important in biomining operations, Leptospirillum ferriphilum, Acidithiobacillus (At.) ferrooxidans, and At. caldus. Although similar concentrations of glycolic acid were found in all cases, the concentrations corresponded to ca. 24% of the total dissolved organic carbon (DOC) in cultures of L. ferriphilum but only ca. 5% of the total DOC in cultures of the two Acidithiobacillus spp. Rapid acidification (to pH 1.0) of the culture medium of At. caldus resulted in a large increase in the level of DOC, although the concentration of glycolic acid did not change in proportion. The archaeon Ferroplasma acidiphilum grew in the cell-free spent medium of At. caldus; glycolic acid was not metabolized, although other unidentified compounds in the DOC pool were metabolized. Glycolic acid exhibited levels of toxicity with 21 strains of acidophiles screened similar to those of acetic acid. The most sensitive species were chemolithotrophs (L. ferriphilum and At. ferrivorans), while the most tolerant species were chemoorganotrophs (Acidocella, Acidobacterium, and Ferroplasma species), and the ability to metabolize glycolic acid appeared to be restricted (among acidophiles) to Firmicutes (chiefly Sulfobacillus spp.). Results of this study help explain why Sulfobacillus spp. rather than other acidophiles are the main organic carbon-degrading bacteria in continuously fed stirred tanks used to bioprocess sulfide mineral concentrates and also why temporary cessation of pH control in these systems, resulting in rapid acidification, often results in a plume of the archaeon Ferroplasma.

  8. Optically enhanced production of metastable xenon.

    PubMed

    Hickman, G T; Franson, J D; Pittman, T B

    2016-09-15

    Metastable states of noble gas atoms are typically produced by electrical discharge techniques or "all-optical" excitation methods. Here we combine electrical discharges with optical pumping to demonstrate "optically enhanced" production of metastable xenon (Xe*). We experimentally measure large increases in Xe* density with relatively small optical control field powers. This technique may have applications in systems where large metastable state densities are desirable. PMID:27628400

  9. New treatment of quantum metastability

    NASA Astrophysics Data System (ADS)

    Defendi, Antonio; Roncadelli, Marco

    1995-02-01

    We explore the implications of the recently proposed Langevin quantization for quantum metastability, working within the semiclassical approximation. As far as we can see, the present treatment is simpler and more straightforward than the path integral approach. Indeed, no extra trick is needed and the correct result follows at once - as a consequence of general principles - from the representation of the propagator supplied by the Langevin quantization. Moreover, the imaginary part of the semiclassical propagator emerges naturally form the formalism and no analytic continuation has to be performed in order to make sense out of a divergent expression. Further applications of the strategy discussed in this Letter are pointed out.

  10. Geometrically induced metastability and holography

    SciTech Connect

    Aganagic, Mina; Aganagic, Mina; Beem, Christopher; Seo, Jihye; Vafa, Cumrun

    2006-10-23

    We construct metastable configurations of branes and anti-branes wrapping 2-spheres inside local Calabi-Yau manifolds and study their large N duals. These duals are Calabi-Yau manifolds in which the wrapped 2-spheres have been replaced by 3-spheres with flux through them, and supersymmetry is spontaneously broken. The geometry of the non-supersymmetric vacuum is exactly calculable to all orders of the't Hooft parameter, and to the leading order in 1/N. The computation utilizes the same matrix model techniques that were used in the supersymmetric context. This provides a novel mechanism for breaking supersymmetry in the context of flux compactifications.

  11. Probing Metastability at the LHC

    SciTech Connect

    Clavelli, L.

    2010-02-10

    Current attempts to understand supersymmetry (susy) breaking are focused on the idea that we are not in the ground state of the universe but, instead, in a metastable state that will ultimately decay to an exactly susy ground state. It is interesting to ask how experiments at the Large Hadron Collider (LHC) will shed light on the properties of this future supersymmetric universe. In particular we ask how we can determine whether this final state has the possibility of supporting atoms and molecules in a susy background.

  12. Metal sulfide initiators for metal oxide sorbent regeneration

    DOEpatents

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

    1999-06-22

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

  13. Metal sulfide initiators for metal oxide sorbent regeneration

    DOEpatents

    Turk, Brian S.; Gupta, Raghubir P.

    1999-01-01

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

  14. Metal sulfide initiators for metal oxide sorbent regeneration

    DOEpatents

    Turk, Brian S.; Gupta, Raghubir P.

    2001-01-01

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

  15. Cadmium sulfide membranes

    DOEpatents

    Spanhel, Lubomir; Anderson, Marc A.

    1992-07-07

    A method is described for the creation of novel q-effect cadmium sulfide membranes. The membranes are made by first creating a dilute cadmium sulfide colloid in aqueous suspension and then removing the water and excess salts therefrom. The cadmium sulfide membrane thus produced is luminescent at room temperature and may have application in laser fabrication.

  16. Cadmium sulfide membranes

    DOEpatents

    Spanhel, Lubomir; Anderson, Marc A.

    1991-10-22

    A method is described for the creation of novel q-effect cadmium sulfide membranes. The membranes are made by first creating a dilute cadmium sulfide colloid in aqueous suspension and then removing the water and excess salts therefrom. The cadmium sulfide membrane thus produced is luminescent at room temperature and may have application in laser fabrication.

  17. Desensitization and recovery of metastable intermolecular composites

    DOEpatents

    Busse, James R.; Dye, Robert C.; Foley, Timothy J.; Higa, Kelvin T.; Jorgensen, Betty S.; Sanders, Victor E.; Son, Steven F.

    2010-09-07

    A method to substantially desensitize a metastable intermolecular composite material to electrostatic discharge and friction comprising mixing the composite material with an organic diluent and removing enough organic diluent from the mixture to form a mixture with a substantially putty-like consistency, as well as a concomitant method of recovering the metastable intermolecular composite material.

  18. Evolution of sulfide mineralization on Mars

    NASA Technical Reports Server (NTRS)

    Burns, Roger G.; Fisher, Duncan S.

    1990-01-01

    It has been previously suggested, on the basis of compositional and petrographic similarities noted between komatites, SNC meteorites, and the silicate portion of the Martian regolith fines, that iron-sulfide ore deposites may exist on Mars. This paper examines the possible locations of Archean-type sulfide and related ore deposits on Mars, their evolution, and the emplacement mechanisms for the ore deposit. The clues to these questions are deduced by applying to Mars the temporal patterns of ore distribution on earth and the experimental observations on sulfur solubility in basaltic melts.

  19. Formation of metastable phases by spinodal decomposition

    NASA Astrophysics Data System (ADS)

    Alert, Ricard; Tierno, Pietro; Casademunt, Jaume

    2016-10-01

    Metastable phases may be spontaneously formed from other metastable phases through nucleation. Here we demonstrate the spontaneous formation of a metastable phase from an unstable equilibrium by spinodal decomposition, which leads to a transient coexistence of stable and metastable phases. This phenomenon is generic within the recently introduced scenario of the landscape-inversion phase transitions, which we experimentally realize as a structural transition in a colloidal crystal. This transition exhibits a rich repertoire of new phase-ordering phenomena, including the coexistence of two equilibrium phases connected by two physically different interfaces. In addition, this scenario enables the control of sizes and lifetimes of metastable domains. Our findings open a new setting that broadens the fundamental understanding of phase-ordering kinetics, and yield new prospects of applications in materials science.

  20. Formation of metastable phases by spinodal decomposition

    PubMed Central

    Alert, Ricard; Tierno, Pietro; Casademunt, Jaume

    2016-01-01

    Metastable phases may be spontaneously formed from other metastable phases through nucleation. Here we demonstrate the spontaneous formation of a metastable phase from an unstable equilibrium by spinodal decomposition, which leads to a transient coexistence of stable and metastable phases. This phenomenon is generic within the recently introduced scenario of the landscape-inversion phase transitions, which we experimentally realize as a structural transition in a colloidal crystal. This transition exhibits a rich repertoire of new phase-ordering phenomena, including the coexistence of two equilibrium phases connected by two physically different interfaces. In addition, this scenario enables the control of sizes and lifetimes of metastable domains. Our findings open a new setting that broadens the fundamental understanding of phase-ordering kinetics, and yield new prospects of applications in materials science. PMID:27713406

  1. Metal sulfide for battery applications

    SciTech Connect

    Guidotti, R.A.

    1988-01-01

    A number of metal sulfides can be used in batteries as a cathode (reducible) material as part of an electrochemical couple to provide energy. There are a number of physical and chemical characteristics that can be evaluated for screening potential candidates for use in batteries. These include: cell potential vs. Li, thermal and chemical stability, electrical conductivity, allotropic form (phase), reaction kinetics during discharge, type of discharge mechanism, and material rechargeability. These are reviewed in general, with emphasis on sulfides of copper, iron, and molybdenum which are currently being used as cathodes in Li and Li-alloy batteries. The presence of impurities can adversely impact performance when naturally occurring sulfide minerals are used for battery applications. Sandia National Laboratories uses natural pyrite (FeS2) for its high-temperature, thermally activated Li(Si)/FeS2 batteries. The purification and processing procedures for the FeS2 involves both chemical and physical methods. Flotation was found to yield comparable results as HF leaching for removal of silica, but without the negative health and environmental concerns associated with this technique. 11 refs., 5 figs., 6 tabs.

  2. Vibrational, X-ray absorption, and Mössbauer spectra of sulfate minerals from the weathered massive sulfide deposit at Iron Mountain, California

    USGS Publications Warehouse

    Majzlan, Juraj; Alpers, Charles N.; Bender Koch, Christian; McCleskey, R. Blaine; Myneni, Satish B.C.; Neil, John M.

    2011-01-01

    The Iron Mountain Mine Superfund site in California is a prime example of an acid mine drainage (AMD) system with well developed assemblages of sulfate minerals typical for such settings. Here we present and discuss the vibrational (infrared), X-ray absorption, and M??ssbauer spectra of a number of these phases, augmented by spectra of a few synthetic sulfates related to the AMD phases. The minerals and related phases studied in this work are (in order of increasing Fe2O3/FeO): szomolnokite, rozenite, siderotil, halotrichite, r??merite, voltaite, copiapite, monoclinic Fe2(SO4)3, Fe2(SO4)3??5H2O, kornelite, coquimbite, Fe(SO4)(OH), jarosite and rhomboclase. Fourier transform infrared spectra in the region 750-4000cm-1 are presented for all studied phases. Position of the FTIR bands is discussed in terms of the vibrations of sulfate ions, hydroxyl groups, and water molecules. Sulfur K-edge X-ray absorption near-edge structure (XANES) spectra were collected for selected samples. The feature of greatest interest is a series of weak pre-edge peaks whose position is determined by the number of bridging oxygen atoms between Fe3+ octahedra and sulfate tetrahedra. M??ssbauer spectra of selected samples were obtained at room temperature and 80K for ferric minerals jarosite and rhomboclase and mixed ferric-ferrous minerals r??merite, voltaite, and copiapite. Values of Fe2+/[Fe2++Fe3+] determined by M??ssbauer spectroscopy agree well with those determined by wet chemical analysis. The data presented here can be used as standards in spectroscopic work where spectra of well-characterized compounds are required to identify complex mixtures of minerals and related phases. ?? 2011 Elsevier B.V.

  3. Vibrational, X-ray absorption, and Mössbauer spectra of sulfate minerals from the weathered massive sulfide deposit at Iron Mountain, California

    USGS Publications Warehouse

    Majzlan, Juraj; Alpers, Charles N.; Bender Koch, Christian; McCleskey, R. Blaine; Myneni, Satish B.C.; Neil, John M.

    2014-01-01

    The Iron Mountain Mine Superfund site in California is a prime example of an acid mine drainage (AMD) system with well developed assemblages of sulfate minerals typical for such settings. Here we present and discuss the vibrational (infrared), X-ray absorption, and Mössbauer spectra of a number of these phases, augmented by spectra of a few synthetic sulfates related to the AMD phases. The minerals and related phases studied in this work are (in order of increasing Fe2O3/FeO): szomolnokite, rozenite, siderotil, halotrichite, römerite, voltaite, copiapite, monoclinic Fe2(SO4)3, Fe2(SO4)3·5H2O, kornelite, coquimbite, Fe(SO4)(OH), jarosite and rhomboclase. Fourier transform infrared spectra in the region 750–4000 cm−1 are presented for all studied phases. Position of the FTIR bands is discussed in terms of the vibrations of sulfate ions, hydroxyl groups, and water molecules. Sulfur K-edge X-ray absorption near-edge structure (XANES) spectra were collected for selected samples. The feature of greatest interest is a series of weak pre-edge peaks whose position is determined by the number of bridging oxygen atoms between Fe3+ octahedra and sulfate tetrahedra. Mössbauer spectra of selected samples were obtained at room temperature and 80 K for ferric minerals jarosite and rhomboclase and mixed ferric–ferrous minerals römerite, voltaite, and copiapite. Values of Fe2+/[Fe2+ + Fe3+] determined by Mössbauer spectroscopy agree well with those determined by wet chemical analysis. The data presented here can be used as standards in spectroscopic work where spectra of well-characterized compounds are required to identify complex mixtures of minerals and related phases.

  4. Metastable Tight Knots in DNA

    NASA Astrophysics Data System (ADS)

    Dai, Liang; Renner, C. Benjamin; Doyle, Patrick

    2015-03-01

    Knotted structures can spontaneously occur in polymers such as DNA and proteins, and the formation of knots affects biological functions, mechanical strength and rheological properties. In this work, we calculate the equilibrium size distribution of trefoil knots in linear DNA using off-lattice simulations. We observe metastable knots on DNA, as predicted by Grosberg and Rabin. Furthermore, we extend their theory to incorporate the finite width of chains and show an agreement between our simulations and the modified theory for real chains. Our results suggest localized knots spontaneously occur in long DNA and the contour length in the knot ranges from 600 to 1800 nm. This research was supported by the National Research Foundation Singapore through the Singapore MIT Alliance for Research and Technology's research program in BioSystems and Micromechanics, the National Science Foundation (Grant No. 1335938).

  5. Atom lithography with metastable helium

    SciTech Connect

    Allred, Claire S.; Reeves, Jason; Corder, Christopher; Metcalf, Harold

    2010-02-15

    A bright metastable helium (He*) beam is collimated sequentially with the bichromatic force and three optical molasses velocity compression stages. Each He* atom in the beam has 20 eV of internal energy that can destroy a molecular resist assembled on a gold coated silicon wafer. Patterns in the resist are imprinted onto the gold layer with a standard selective etch. Patterning of the wafer with the He{sup *} was demonstrated with two methods. First, a mesh was used to protect parts of the wafer making an array of grid lines. Second, a standing wave of {lambda}=1083 nm light was used to channel and focus the He* atoms into lines separated by {lambda}/2. The patterns were measured with an atomic force microscope establishing an edge resolution of 80 nm. Our results are reliable and repeatable.

  6. Mitochondrial adaptations to utilize hydrogen sulfide for energy and signaling.

    PubMed

    Olson, Kenneth R

    2012-10-01

    Sulfur is a versatile molecule with oxidation states ranging from -2 to +6. From the beginning, sulfur has been inexorably entwined with the evolution of organisms. Reduced sulfur, prevalent in the prebiotic Earth and supplied from interstellar sources, was an integral component of early life as it could provide energy through oxidization, even in a weakly oxidizing environment, and it spontaneously reacted with iron to form iron-sulfur clusters that became the earliest biological catalysts and structural components of cells. The ability to cycle sulfur between reduced and oxidized states may have been key in the great endosymbiotic event that incorporated a sulfide-oxidizing α-protobacteria into a host sulfide-reducing Archea, resulting in the eukaryotic cell. As eukaryotes slowly adapted from a sulfidic and anoxic (euxinic) world to one that was highly oxidizing, numerous mechanisms developed to deal with increasing oxidants; namely, oxygen, and decreasing sulfide. Because there is rarely any reduced sulfur in the present-day environment, sulfur was historically ignored by biologists, except for an occasional report of sulfide toxicity. Twenty-five years ago, it became evident that the organisms in sulfide-rich environments could synthesize ATP from sulfide, 10 years later came the realization that animals might use sulfide as a signaling molecule, and only within the last 4 years did it become apparent that even mammals could derive energy from sulfide generated in the gastrointestinal tract. It has also become evident that, even in the present-day oxic environment, cells can exploit the redox chemistry of sulfide, most notably as a physiological transducer of oxygen availability. This review will examine how the legacy of sulfide metabolism has shaped natural selection and how some of these ancient biochemical pathways are still employed by modern-day eukaryotes. PMID:22430869

  7. Detection of sputtered metastable atoms by autoionization

    SciTech Connect

    Wucher, A.; Berthold, W.; Oechsner, H.; Franzreb, K.

    1994-03-01

    We report on a scheme for the detection of sputter-generated metastable atoms that is based on the resonant excitation of an autoionizing state by single-photon absorption from a tunable laser. Using this technique, sputtered silver atoms ejected in the metastable 4{ital d}{sup 9}5{ital s}{sup 2}{ital D}{sub 5/2} state with an excitation energy of 3.75 eV have been detected. This represents the highest excitation energy of sputtered metastable atoms observed so far.

  8. EFFECT OF BACTERIAL SULFATE REDUCTION ON IRON-CORROSION SCALES

    EPA Science Inventory

    Iron-sulfur geochemistry is important in many natural and engineered environments including drinking water systems. In the anaerobic environment beneath scales of corroding iron drinking water distribution system pipes, sulfate reducing bacteria (SRB) produce sulfide from natura...

  9. Metastability of a Supercompressed Fluid Monolayer

    PubMed Central

    Smith, Ethan C.; Crane, Jonathan M.; Laderas, Ted G.; Hall, Stephen B.

    2003-01-01

    Previous studies showed that monomolecular films of extracted calf surfactant collapse at the equilibrium spreading pressure during quasi-static compressions but become metastable at much higher surface pressures when compressed faster than a threshold rate. To determine the mechanism by which the films become metastable, we studied single-component films of 1-palmitoyl-2-oleoyl phosphatidylcholine (POPC). Initial experiments confirmed similar metastability of POPC if compressed above a threshold rate. Measurements at different surface pressures then showed that rates of collapse, although initially increasing above the equilibrium spreading pressure, reached a sharply defined maximum and then slowed considerably. When heated, rapidly compressed films recovered their ability to collapse with no discontinuous change in area, arguing that the metastability does not reflect transition of the POPC film to a new phase. These observations indicate that in several respects, the supercompression of POPC monolayers resembles the supercooling of three-dimensional liquids toward a glass transition. PMID:14581205

  10. Removal of sulfur fumes by metal sulfide sorbents.

    PubMed

    Chung, Jae Bin; Ziang, Zhidong; Chung, Jong Shik

    2002-07-01

    Removal of sulfur by a transition metal is studied at temperatures of 300-350 degrees C. Among various metal sulfides tested, only metal sulfides of iron, cobalt, and nickel can remove sulfur fumes as they are transformed into disulfides in the presence of sulfur vapor. The disulfide form can be regenerated into FeS, Co9S8, and Ni3S2, respectively, using hydrogen gas at 350-400 degrees C. These two reactions of deep sulfidation with sulfur and reduction with hydrogen can be utilized for the removal of sulfur fumes in a process stream and an emission gas.

  11. Iron catalyzed coal liquefaction process

    DOEpatents

    Garg, Diwakar; Givens, Edwin N.

    1983-01-01

    A process is described for the solvent refining of coal into a gas product, a liquid product and a normally solid dissolved product. Particulate coal and a unique co-catalyst system are suspended in a coal solvent and processed in a coal liquefaction reactor, preferably an ebullated bed reactor. The co-catalyst system comprises a combination of a stoichiometric excess of iron oxide and pyrite which reduce predominantly to active iron sulfide catalysts in the reaction zone. This catalyst system results in increased catalytic activity with attendant improved coal conversion and enhanced oil product distribution as well as reduced sulfide effluent. Iron oxide is used in a stoichiometric excess of that required to react with sulfur indigenous to the feed coal and that produced during reduction of the pyrite catalyst to iron sulfide.

  12. Metastable States of small-molecule solutions.

    PubMed

    He, Guangwen; Tan, Reginald B H; Kenis, Paul J A; Zukoski, Charles F

    2007-12-27

    Metastable states such as gels and glasses that are commonly seen in nanoparticle suspensions have found application in a wide range of products including toothpaste, hand cream, paints, and car tires. The equilibrium and metastable state behavior of nanoparticle suspensions are often described by simple fluid models where particles are treated as having hard cores and interacting with short-range attractions. Here we explore similar models to describe the presence of metastable states of small-molecule solutions. We have recently shown that the equilibrium solubilities of small hydrogen-bonding molecules and nanoparticles fall onto a corresponding-states solubility curve suggesting that with similar average strengths of attraction these molecules have similar solubilities. This observation implies that metastable states in small-molecule solutions may be found under conditions similar to those where metastable states are observed in nanoparticle and colloidal suspensions. Here we seek confirmation of this concept by exploring the existence of metastable states in solutions of small molecules.

  13. Iron clad wetlands: Soil iron-sulfur buffering determines coastal wetland response to salt water incursion

    NASA Astrophysics Data System (ADS)

    Schoepfer, Valerie A.; Bernhardt, Emily S.; Burgin, Amy J.

    2014-12-01

    Coastal freshwater wetland chemistry is rapidly changing due to increased frequency of salt water incursion, a consequence of global change. Seasonal salt water incursion introduces sulfate, which microbially reduces to sulfide. Sulfide binds with reduced iron, producing iron sulfide (FeS), recognizable in wetland soils by its characteristic black color. The objective of this study is to document iron and sulfate reduction rates, as well as product formation (acid volatile sulfide (AVS) and chromium reducible sulfide (CRS)) in a coastal freshwater wetland undergoing seasonal salt water incursion. Understanding iron and sulfur cycling, as well as their reduction products, allows us to calculate the degree of sulfidization (DOS), from which we can estimate how long soil iron will buffer against chemical effects of sea level rise. We show that soil chloride, a direct indicator of the degree of incursion, best predicted iron and sulfate reduction rates. Correlations between soil chloride and iron or sulfur reduction rates were strongest in the surface layer (0-3 cm), indicative of surface water incursion, rather than groundwater intrusion at our site. The interaction between soil moisture and extractable chloride was significantly related to increased AVS, whereas increased soil chloride was a stronger predictor of CRS. The current DOS in this coastal plains wetland is very low, resulting from high soil iron content and relatively small degree of salt water incursion. However, with time and continuous salt water exposure, iron will bind with incoming sulfur, creating FeS complexes, and DOS will increase.

  14. Iron and sulfur in the pre-biologic ocean

    NASA Technical Reports Server (NTRS)

    Walker, J. C.; Brimblecombe, P.

    1985-01-01

    Tentative geochemical cycles for the pre-biologic Earth are developed by comparing the relative fluxes of oxygen, dissolved iron, and sulfide to the atmosphere and ocean. The flux of iron is found to exceed both the oxygen and the sulfide fluxes. Because of the insolubility of iron oxides and sulfides the implication is that dissolved iron was fairly abundant and that oxygen and sulfide were rare in the atmosphere and ocean. Sulfate, produced by the oxidation of volcanogenic sulfur gases, was the most abundant sulfur species in the ocean, but its concentration was low by modern standards because of the absence of the river-borne flux of dissolved sulfate produced by oxidative weathering of the continents. These findings are consistent with the geologic record of the isotopic composition of sedimentary sulfates and sulfides. Except in restricted environments, the sulfur metabolism of the earliest organisms probably involved oxidized sulfur species not sulfide.

  15. Sulfide Mineralogy and Geochemistry

    NASA Astrophysics Data System (ADS)

    Dilles, John

    2007-02-01

    Reviews in Mineralogy and Geochemistry Series, Volume 61 David J. Vaughan, Editor Geochemical Society and Mineralogical Society of America; ISBN 0-939950-73-1 xiii + 714 pp.; 2006; $40. Sulfide minerals as a class represent important minor rock-forming minerals, but they are generally known as the chief sources of many economic metallic ores. In the past two decades, sulfide research has been extended to include important roles in environmental geology of sulfide weathering and resultant acid mine drainage, as well as in geomicrobiology in which bacteria make use of sulfides for metabolic energy sources. In the latter respect, sulfides played an important role in early evolution of life on Earth and in geochemical cycling of elements in the Earth's crust and hydrosphere.

  16. Optical Forces on Metastable Helium

    NASA Astrophysics Data System (ADS)

    Corder, Christopher Scott

    Optical forces using lasers allow precise control over the motion of atoms. The bichromatic optical force (BF) is unique in its large magnitude and velocity range, arising from the absorption and stimulated emission processes. These properties were used to transversely collimate a beam of metastable helium (He*) using the 23S - 23P transition. The collimation created a very bright beam of He*, allowing experiments of neutral atom lithography. The He* beam was used to pattern material surfaces using a resist-based lithography technique, where the pattern was determined by either mechanical or optical masks. The optical masks produced features with a separation of half the wavelength of the light used. Patterning was successfully demonstrated with both IR and UV optical masks. The etched pattern resolution was ˜ 100 nm and limited by the material surface. Further experiments were performed studying the ability of the bichromatic force to cool. The finite velocity range of the BF allows estimation of a characteristic cooling time which is independent of the excited state lifetime, only depending on the atomic mass and optical transition energy. Past experiments, including the helium collimation used for neutral atom lithography, have demonstrated that the BF can collimate and longitudinally slow atomic beams, but required long interaction times that included many spontaneous emission (SE) events. The effect of SE can be mitigated, and is predicted to not be necessary for BF cooling. Since the BF cooling time is not related to the excited state lifetime, a transition can be chosen such that the cooling time is shorter than the SE cycle time, allowing direct laser cooling on atoms and molecules that do not have cycling transitions. Experiments using the helium 2 3S-3P transition were chosen because the BF cooling time (285 ns) is on the order of the average SE cycle time (260 ns). Numerical simulations of the experimental system were run predicting compression of the

  17. Volcanogenic massive sulfide occurrence model: Chapter C in Mineral deposit models for resource assessment

    USGS Publications Warehouse

    Shanks, W.C. Pat; Koski, Randolph A.; Mosier, Dan L.; Schulz, Klaus J.; Morgan, Lisa A.; Slack, John F.; Ridley, W. Ian; Dusel-Bacon, Cynthia; Seal, Robert R., II; Piatak, Nadine M.; Shanks, W.C. Pat; Thurston, Roland

    2012-01-01

    An unusual feature of VMS deposits is the common association of stratiform "exhalative" deposits precipitated from hydrothermal fluids emanating into bottom waters. These deposits may extend well beyond the margins of massive sulfide and are typically composed of silica, iron, and manganese oxides, carbonates, sulfates, sulfides, and tourmaline.

  18. Incompatible Sets of Gradients and Metastability

    NASA Astrophysics Data System (ADS)

    Ball, J. M.; James, R. D.

    2015-12-01

    We give a mathematical analysis of a concept of metastability induced by incompatibility. The physical setting is a single parent phase, just about to undergo transformation to a product phase of lower energy density. Under certain conditions of incompatibility of the energy wells of this energy density, we show that the parent phase is metastable in a strong sense, namely it is a local minimizer of the free energy in an L 1 neighbourhood of its deformation. The reason behind this result is that, due to the incompatibility of the energy wells, a small nucleus of the product phase is necessarily accompanied by a stressed transition layer whose energetic cost exceeds the energy lowering capacity of the nucleus. We define and characterize incompatible sets of matrices, in terms of which the transition layer estimate at the heart of the proof of metastability is expressed. Finally we discuss connections with experiments and place this concept of metastability in the wider context of recent theoretical and experimental research on metastability and hysteresis.

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

    PubMed

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

    2016-07-15

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

  20. Metastability in the evolution of triple systems

    NASA Astrophysics Data System (ADS)

    Martynova, A. I.; Orlov, V. V.; Rubinov, A. V.

    2003-10-01

    The dynamical evolution of 15000 equal-mass triple systems with zero initial velocities (the free-fall three-body problem) is considered. The equations of motion are numerically integrated using regularization of binary and triple encounters. We find 170 triple systems which reach a state where the motions take place within a limited region of phase space during a long time. These regions are concentrated in the zones of regular motions in the vicinities of stable periodic orbits: the von Schubart orbit in the rectilinear problem, the Broucke orbit in the isosceles problem, and the `Eight' orbit. The classification of such metastable orbits is suggested. A change of the types is found during the dynamical evolution of some metastable systems. The triple system leaves the metastable regime after some time, and its evolution is finished by the escape of one body.

  1. Multistability with a Metastable Mixed State

    NASA Astrophysics Data System (ADS)

    Sneppen, Kim; Mitarai, Namiko

    2012-09-01

    Complex dynamical systems often show multiple metastable states. In macroevolution, such behavior is suggested by punctuated equilibrium and discrete geological epochs. In molecular biology, bistability is found in epigenetics and in the many mutually exclusive states that a human cell can take. Sociopolitical systems can be single-party regimes or a pluralism of balancing political fractions. To introduce multistability, we suggest a model system of D mutually exclusive microstates that battle for dominance in a large system. Assuming one common intermediate state, we obtain D+1 metastable macrostates for the system, one of which is a self-reinforced mixture of all D+1 microstates. Robustness of this metastable mixed state increases with diversity D.

  2. Metastable Detection Using Cold Solid Matrices

    NASA Astrophysics Data System (ADS)

    McConkey, William; Kedzierski, Wladek; Alsaiari, Fatimah

    2016-05-01

    Metastable particles produced in the interaction of electrons of carefully controlled energy with thermal gaseous target beams in a crossed beam set-up have been studied in the energy range from threshold to 300 eV. The e-beam is pulsed and the metastables produced drift to a solid nitrogen or rare gas detector held at 10 K. Here they form excimers which immediately radiate. The resultant photons are detected using a photomultiplier-filter combination. Time-of-flight techniques are used to separate these photons from prompt photons produced in the initial electron collision. With N2 as both target and detection matrix, the excimer emission is strongest in the green but still significant in the red spectral region. Excitation functions will be presented together with threshold measurements. These help to identify the metastable states being observed and the excitation mechanisms which are responsible. The authors thank NSERC and CFI (Canada) for financial support.

  3. Kinetic Trapping of Metastable Amino Acid Polymorphs

    PubMed Central

    2015-01-01

    Second harmonic generation (SHG) microscopy measurements indicate that inkjet-printed racemic solutions of amino acids can produce nanocrystals trapped in metastable polymorph forms upon rapid solvent evaporation. Polymorphism impacts the composition, distribution, and physico-kinetic properties of organic solids, with energetic arguments favoring the most stable polymorph. In this study, unfavored noncentrosymmetric crystal forms were observed by SHG microscopy. Polarization-dependent SHG measurement and synchrotron X-ray microdiffraction analysis of individual printed drops are consistent with formation of homochiral crystal production. Fundamentally, these results provide evidence supporting the ubiquity of Ostwald’s Rule of Stages, describing the hypothesized transitioning of crystals between metastable polymorphic forms in the early stages of crystal formation. Practically, the presence of homochiral metastable forms has implications on chiral resolution and on solid form preparations relying on rapid solvent evaporation. PMID:24451055

  4. Modeling the metastable dynamics of correlated structures

    PubMed Central

    Shakirov, Alexey M.; Tsibulsky, Sergey V.; Antipov, Andrey E.; Shchadilova, Yulia E.; Rubtsov, Alexey N.

    2015-01-01

    Metastable quantum dynamics of an asymmetric triangular cluster that is coupled to a reservoir is investigated. The dynamics is governed by bath-mediated transitions, which in part require a thermal activation process. The decay rate is controlled by tuning the excitation spectrum of the frustrated cluster. We use the master equation approach and construct transition operators in terms of many-body states. We analyze dynamics of observables and reveal metastability of an excited state and of a magnetically polarized ground state. PMID:25623327

  5. On the Destabilization of Metastable Solid He

    NASA Astrophysics Data System (ADS)

    Souris, F.; Qu, A.; Dupont-Roc, J.; Grucker, J.; Jacquier, Ph.

    2015-06-01

    Recently, a metastable state of solid He has been produced by locally lowering the density of the solid below the melting density using a focused acoustic wave pulse. An unexpected instability of the solid has been found about 4 bar below the melting line. This paper reports on experiments precisely localizing in time the instability birth within the acoustic pulse. It is found that, as expected, the instability always appears during a depression swing of the wave. However a metastability pressure limit does not emerge clearly. Total stress duration seems also to play a role in the instability triggering, suggesting a fatigue effect.

  6. Monitoring sulfide and sulfate-reducing bacteria

    SciTech Connect

    Tanner, R.S.

    1995-12-31

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

  7. Platinum metals in magmatic sulfide ores

    USGS Publications Warehouse

    Naldrett, A.J.; Duke, J.M.

    1980-01-01

    Platinum-group elements (PGE) are mined predominantly from deposits that have formed by the segregation of molten iron-nickel-copper sulfides from silicate magmas. The absolute concentrations of PGE in sulfides from different deposits vary over a range of five orders of magnitude, whereas those of other chalcophile elements vary by factors of only 2 to 100. However, the relative proportions of the different PGE in a given deposit are systematically related to the nature of the parent magma. The absolute and relative concentrations of PGE in magmatic sulfides are explained in terms of the degree of partial melting of mantle peridotite required to produce the parent magma and the processes of batch equilibration and fractional segregation of sulfides. The Republic of South Africa and the U.S.S.R. together possess more than 97 percent of the world PGE reserves, but significant undeveloped resources occur in North America. The Stillwater complex in Montana is perhaps the most important example. Copyright ?? 1980 AAAS.

  8. Optical production of metastable rare gases.

    SciTech Connect

    Young, L.; Yang, D.; Dunford, R.; Chemistry; Peking Univ.

    2002-01-01

    We have investigated a new scheme for excitation of the 5s, J = 2 metastable level of Kr (5s[3/2]J = 2) which can be readily extended to other rare gases. In the scheme, an ultraviolet (UV) lamp is used to create a population of Kr atoms in the 5s[3/2]J = 1 level in a gas cell. The excited atoms are then pumped to the 5p[3/2]J = 2 level, using 819 nm light from a Ti:sapphire laser, from which they decay to the metastable state with a branching ratio of 77%. We made two striking observations: (1) the laser power required to saturate the second step decreases markedly as a function of gas cell pressure, and (2) the UV photon flux is converted with very high efficiency (approx10%) to metastable atom flux. A Monte Carlo study of the scattering of UV photons in the cell reproduces the trends observed. The understanding achieved points to the design of a higher flux source of metastable atoms.

  9. Reheating metastable O'Raifeartaigh models

    SciTech Connect

    Fox, Patrick; Craig, Nathaniel J.; Fox, Patrick J.; Wacker, Jay G.

    2006-11-01

    In theories with multiple vacua, reheating to a temperature greater than the height of a barrier can stimulate transitions from a desirable metastable vacuum to a lower energy state. We discuss the constraints this places on various theories and demonstrate that in a class of supersymmetric models this transition does not occur even for arbitrarily high reheating temperature.

  10. Reheating Metastable O'Raifeartaigh Models

    SciTech Connect

    Craig, Nathaniel J.; Fox, Patrick J.; Wacker, Jay G.

    2006-12-05

    In theories with multiple vacua, reheating to a temperature greater than the height of a barrier can stimulate transitions from a desirable metastable vacuum to a lower energy state. We discuss the constraints this places on various theories and demonstrate that in a class of supersymmetric models this transition does not occur even for arbitrarily high reheating temperature.

  11. Reheating Metastable O'Raifeartaigh Models

    SciTech Connect

    Craig, Nathaniel J.; Fox, Patrick J.; Wacker, Jay G.; /SLAC /Stanford U., ITP

    2006-12-13

    In theories with multiple vacua, reheating to a temperature greater than the height of a barrier can stimulate transitions from a desirable metastable vacuum to a lower energy state. We discuss the constraints this places on various theories and demonstrate that in a class of supersymmetric models this transition does not occur even for arbitrarily high reheating temperature.

  12. Cellular folding pathway of a metastable serpin.

    PubMed

    Chandrasekhar, Kshama; Ke, Haiping; Wang, Ning; Goodwin, Theresa; Gierasch, Lila M; Gershenson, Anne; Hebert, Daniel N

    2016-06-01

    Although proteins generally fold to their thermodynamically most stable state, some metastable proteins populate higher free energy states. Conformational changes from metastable higher free energy states to lower free energy states with greater stability can then generate the work required to perform physiologically important functions. However, how metastable proteins fold to these higher free energy states in the cell and avoid more stable but inactive conformations is poorly understood. The serpin family of metastable protease inhibitors uses large conformational changes that are downhill in free energy to inhibit target proteases by pulling apart the protease active site. The serpin antithrombin III (ATIII) targets thrombin and other proteases involved in blood coagulation, and ATIII misfolding can thus lead to thrombosis and other diseases. ATIII has three disulfide bonds, two near the N terminus and one near the C terminus. Our studies of ATIII in-cell folding reveal a surprising, biased order of disulfide bond formation, with early formation of the C-terminal disulfide, before formation of the N-terminal disulfides, critical for folding to the active, metastable state. Early folding of the predominantly β-sheet ATIII domain in this two-domain protein constrains the reactive center loop (RCL), which contains the protease-binding site, ensuring that the RCL remains accessible. N-linked glycans and carbohydrate-binding molecular chaperones contribute to the efficient folding and secretion of functional ATIII. The inability of a number of disease-associated ATIII variants to navigate the folding reaction helps to explain their disease phenotypes. PMID:27222580

  13. Excitation of metastable argon and helium atoms by electron impact

    NASA Technical Reports Server (NTRS)

    Borst, W. L.

    1974-01-01

    Using a time-of-flight method, the excitation of argon and helium metastables by electron impact is investigated in the energy range from threshold to about 50 eV. The secondary-electron yields of the metastable detector used are reviewed in detail. The effect of metastable recoil is also discussed. Comparisons with data from other investigators are presented.

  14. Transformation of Reactive Iron Minerals in a Permeable Reactive Barrier (Biowall) Used to Treat TCE in Groundwater

    EPA Science Inventory

    Abstract: Iron and sulfur reducing conditions are generally created in permeable reactive barrier (PRB) systems constructed for groundwater treatment, which usually leads to formation of iron sulfide phases. Iron sulfides have been shown to play an important role in degrading ch...

  15. Synergistic stabilization of metastable Fe23B6 and γ-Fe in undercooled Fe83B17

    NASA Astrophysics Data System (ADS)

    Quirinale, D. G.; Rustan, G. E.; Kreyssig, A.; Goldman, A. I.

    2015-06-01

    Previous investigations of undercooled liquid Fe83B17 near the eutectic composition have found that metastable crystalline phases, such as Fe23B6, can be formed and persist down to ambient temperature even for rather modest cooling rates. Using time-resolved high-energy x-ray diffraction on electrostatically levitated samples of Fe83B17, we demonstrate that the Fe23B6 metastable phase and fcc γ-Fe grow coherently from the undercooled Fe83B17 liquid and effectively suppress the formation of the equilibrium Fe2B + bcc α-Fe phases. The stabilization of γ-Fe offers another opportunity for experimental investigations of magnetism in metastable fcc iron.

  16. Thioarsenates in sulfidic waters.

    PubMed

    Stauder, S; Raue, B; Sacher, F

    2005-08-15

    It has long been recognized that the formation of soluble arsenic sulfur complexes plays a key role for the mobility and toxicity of arsenic in sulfate-reducing environments. Knowledge of the exact arsenic species is essential to understand the behavior of arsenic in sulfidic aquifers and to develop remediation strategies. In the past, monomeric and trimeric thioarsenites were assumed to be the existing species in sulfidic systems. In this study, thioarsenates were identified by IC-ICP/MS in arsenite- and sulfide-containing solutions as well as in a reduced groundwater from a contaminated site. The unexpected finding of an oxidation of As(lll) to As(V) in thioarsenates in strongly reducing systems can be explained by the high affinity between As(Ill) and sulfur. In sulfide-containing solutions without oxidant, As(lll) therefore undergoes disproportionation to thioarsenates (As(V)) and elemental arsenic. It has previously been supposed that mobility as well as toxicity of arsenic increases if the redox state decreases. For sulfidic waters, the opposite is probably the case. Thus, the formation of thioarsenates could be used in connection with remediation strategies. Thioarsenates are highly sensitive to oxygen and pH. This is important for analytical procedures. A loss of soluble arsenic as well as a conversion to arsenite and arsenate may occur if water samples containing thioarsenates are analyzed with conventional methods.

  17. GEOCHEMISTRY OF SULFUR IN IRON CORROSION SCALES FOUND IN DRINKING WATER DISTRIBUTION SYSTEMS

    EPA Science Inventory

    Iron-sulfur geochemistry is important in many natural and engineered environments, including drinking water systems. In the anaerobic environment beneath scales of corroding iron drinking water distribution system pipes, sulfate reducing bacteria (SRB) produce sulfide from natu...

  18. Sulfidation of silver nanoparticles

    NASA Astrophysics Data System (ADS)

    Levard, C.; Michel, F. M.; Brown, G. E.

    2010-12-01

    Rapid development of nanotechnologies that exploit the properties of silver nanoparticles (Ag-NPs) raises questions concerning the impact of Ag on the environment. Ag-NPs are currently among the most widely used in the nanotechnology industry and the amount released into the environment is expected to increase along with production (1). When present in geochemical systems, Ag-NPs may undergo a variety of changes due to varying redox, pH, and chemical conditions. Expected changes range from surface modification (e.g., oxidation, sulfidation, chloridation etc.) to complete dissolution and re-precipitation. In this context, the focus of our work is on understanding the behavior of synthetic Ag-NPs with different particle sizes under varying conditions relevant to the environment. Sulfidation of Ag-NPs is of particular interest since it among the processes most likely to occur in aqueous systems, in particular under reducing conditions. Three sizes of Ag-NPs coated with polyvinyl pyrrolidone were produced using the polyol process (2) (7 ±1; 20 ±4, and 40 ±9 nm). Batch solutions containing the different Ag-NPs were subsequently reacted with Na2S solutions of different concentrations. The sulfidation process was followed step-wise for 24 hours and the corrosion products formed were characterized by electron microscopy (TEM/SEM), diffraction (XRD), and photo-electron spectroscopy (XPS). Surface charge (pHPZC) of the products formed during this process was also measured, as were changes in solubility and reactivity. Based on experimental observations we infer that the sulfidation process is the result of dissolution-precipitation and find that: (i) acanthite (Ag2S) is formed as a corrosion product; (ii) Ag-NPs aggregation increased with sulfidation rate; (iii) pHPZC increases with the rate of sulfidation; and (iv) the solubility of the corrosion products formed from sulfidation appears lower than that of non-sulfidated Ag-NPs. We observe size-dependent differences in

  19. Processing and applications of iron aluminides

    SciTech Connect

    Sikka, V.K.

    1994-09-01

    Iron aluminides are well known for their resistance to high- temperature sulfidizing and oxidizing environments. In order to take advantage of their excellent corrosion resistance, several methods for their processing have been identified. Issues with melting and processing are discussed detail. Effects of grain size and melting practice on low-temperature ductility are also presented. Many applications for iron aluminides are described.

  20. Metastable dynamics in heterogeneous neural fields

    PubMed Central

    Schwappach, Cordula; Hutt, Axel; beim Graben, Peter

    2015-01-01

    We present numerical simulations of metastable states in heterogeneous neural fields that are connected along heteroclinic orbits. Such trajectories are possible representations of transient neural activity as observed, for example, in the electroencephalogram. Based on previous theoretical findings on learning algorithms for neural fields, we directly construct synaptic weight kernels from Lotka-Volterra neural population dynamics without supervised training approaches. We deliver a MATLAB neural field toolbox validated by two examples of one- and two-dimensional neural fields. We demonstrate trial-to-trial variability and distributed representations in our simulations which might therefore be regarded as a proof-of-concept for more advanced neural field models of metastable dynamics in neurophysiological data. PMID:26175671

  1. Metastable structure of Li13Si4

    NASA Astrophysics Data System (ADS)

    Gruber, Thomas; Bahmann, Silvia; Kortus, Jens

    2016-04-01

    The Li13Si4 phase is one out of several crystalline lithium silicide phases, which is a potential electrode material for lithium ion batteries and contains a high theoretical specific capacity. By means of ab initio methods like density functional theory (DFT) many properties such as heat capacity or heat of formation can be calculated. These properties are based on the calculation of phonon frequencies, which contain information about the thermodynamical stability. The current unit cell of "Li13Si4" given in the ICSD database is unstable with respect to DFT calculations. We propose a modified unit cell that is stable in the calculations. The evolutionary algorithm EVO found a structure very similar to the ICSD one with both of them containing metastable lithium positions. Molecular dynamic simulations show a phase transition between both structures where these metastable lithium atoms move. This phase transition is achieved by a very fast one-dimensional lithium diffusion and stabilizes this phase.

  2. Universal metastability of sickle hemoglobin polymerization

    NASA Astrophysics Data System (ADS)

    Weng, Weijun

    Sickle hemoglobin (HbS) is a natural mutation of the normal hemoglobin (HbA) found in the red blood cells of human body. Polymerization of HbS occurs when the concentration of deoxyHbS exceeds a well-defined solubility, which is the underlying cause of the Sickle Cell Disease. It has long been assumed that thermodynamic equilibrium is reached when polymerization comes to an end. However, in this thesis we demonstrate that in confined volume as well as in bulk solution, HbS polymerization terminates prematurely, leaving the solution in a metastable state. A newly developed Reservoir method as well as modulated excitation method were adopted for the study. This discovery of universal metastability gives us new insights into understanding the mechanism of sickle cell disease.

  3. Metastable dynamics in heterogeneous neural fields.

    PubMed

    Schwappach, Cordula; Hutt, Axel; Beim Graben, Peter

    2015-01-01

    We present numerical simulations of metastable states in heterogeneous neural fields that are connected along heteroclinic orbits. Such trajectories are possible representations of transient neural activity as observed, for example, in the electroencephalogram. Based on previous theoretical findings on learning algorithms for neural fields, we directly construct synaptic weight kernels from Lotka-Volterra neural population dynamics without supervised training approaches. We deliver a MATLAB neural field toolbox validated by two examples of one- and two-dimensional neural fields. We demonstrate trial-to-trial variability and distributed representations in our simulations which might therefore be regarded as a proof-of-concept for more advanced neural field models of metastable dynamics in neurophysiological data. PMID:26175671

  4. SULFIDE METHOD PLUTONIUM SEPARATION

    DOEpatents

    Duffield, R.B.

    1958-08-12

    A process is described for the recovery of plutonium from neutron irradiated uranium solutions. Such a solution is first treated with a soluble sullide, causing precipitation of the plutoniunn and uraniunn values present, along with those impurities which form insoluble sulfides. The precipitate is then treated with a solution of carbonate ions, which will dissolve the uranium and plutonium present while the fission product sulfides remain unaffected. After separation from the residue, this solution may then be treated by any of the usual methods, such as formation of a lanthanum fluoride precipitate, to effect separation of plutoniunn from uranium.

  5. New metastable states in supercritical QED

    SciTech Connect

    Hirata, Y.S.; Minakata, H.

    1989-05-01

    It is shown that new metastable charge-neutral states exist in the supercritical phase of QED around a large-Z nucleus. They are the vibration modes of the induced electron cloud and therefore do not exist in the normal phase. Under the adiabatic approximation it is argued that the states mimic the stable particle states and may be responsible for the peak structure in e/sup +/e/sup -/ spectra found in heavy-ion-collision experiments.

  6. Optimized Markov state models for metastable systems

    NASA Astrophysics Data System (ADS)

    Guarnera, Enrico; Vanden-Eijnden, Eric

    2016-07-01

    A method is proposed to identify target states that optimize a metastability index amongst a set of trial states and use these target states as milestones (or core sets) to build Markov State Models (MSMs). If the optimized metastability index is small, this automatically guarantees the accuracy of the MSM, in the sense that the transitions between the target milestones is indeed approximately Markovian. The method is simple to implement and use, it does not require that the dynamics on the trial milestones be Markovian, and it also offers the possibility to partition the system's state-space by assigning every trial milestone to the target milestones it is most likely to visit next and to identify transition state regions. Here the method is tested on the Gly-Ala-Gly peptide, where it is shown to correctly identify the expected metastable states in the dihedral angle space of the molecule without a priori information about these states. It is also applied to analyze the folding landscape of the Beta3s mini-protein, where it is shown to identify the folded basin as a connecting hub between an helix-rich region, which is entropically stabilized, and a beta-rich region, which is energetically stabilized and acts as a kinetic trap.

  7. Detonation of Meta-stable Clusters

    SciTech Connect

    Kuhl, Allen; Kuhl, Allen L.; Fried, Laurence E.; Howard, W. Michael; Seizew, Michael R.; Bell, John B.; Beckner, Vincent; Grcar, Joseph F.

    2008-05-31

    We consider the energy accumulation in meta-stable clusters. This energy can be much larger than the typical chemical bond energy (~;;1 ev/atom). For example, polymeric nitrogen can accumulate 4 ev/atom in the N8 (fcc) structure, while helium can accumulate 9 ev/atom in the excited triplet state He2* . They release their energy by cluster fission: N8 -> 4N2 and He2* -> 2He. We study the locus of states in thermodynamic state space for the detonation of such meta-stable clusters. In particular, the equilibrium isentrope, starting at the Chapman-Jouguet state, and expanding down to 1 atmosphere was calculated with the Cheetah code. Large detonation pressures (3 and 16 Mbar), temperatures (12 and 34 kilo-K) and velocities (20 and 43 km/s) are a consequence of the large heats of detonation (6.6 and 50 kilo-cal/g) for nitrogen and helium clusters respectively. If such meta-stable clusters could be synthesized, they offer the potential for large increases in the energy density of materials.

  8. Stochastic basins of attraction for metastable states

    NASA Astrophysics Data System (ADS)

    Serdukova, Larissa; Zheng, Yayun; Duan, Jinqiao; Kurths, Jürgen

    2016-07-01

    Basin of attraction of a stable equilibrium point is an effective concept for stability analysis in deterministic systems; however, it does not contain information on the external perturbations that may affect it. Here we introduce the concept of stochastic basin of attraction (SBA) by incorporating a suitable probabilistic notion of basin. We define criteria for the size of the SBA based on the escape probability, which is one of the deterministic quantities that carry dynamical information and can be used to quantify dynamical behavior of the corresponding stochastic basin of attraction. SBA is an efficient tool to describe the metastable phenomena complementing the known exit time, escape probability, or relaxation time. Moreover, the geometric structure of SBA gives additional insight into the system's dynamical behavior, which is important for theoretical and practical reasons. This concept can be used not only in models with small noise intensity but also with noise whose amplitude is proportional or in general is a function of an order parameter. As an application of our main results, we analyze a three potential well system perturbed by two types of noise: Brownian motion and non-Gaussian α-stable Lévy motion. Our main conclusions are that the thermal fluctuations stabilize the metastable system with an asymmetric three-well potential but have the opposite effect for a symmetric one. For Lévy noise with larger jumps and lower jump frequencies ( α = 0.5 ) metastability is enhanced for both symmetric and asymmetric potentials.

  9. Stochastic basins of attraction for metastable states.

    PubMed

    Serdukova, Larissa; Zheng, Yayun; Duan, Jinqiao; Kurths, Jürgen

    2016-07-01

    Basin of attraction of a stable equilibrium point is an effective concept for stability analysis in deterministic systems; however, it does not contain information on the external perturbations that may affect it. Here we introduce the concept of stochastic basin of attraction (SBA) by incorporating a suitable probabilistic notion of basin. We define criteria for the size of the SBA based on the escape probability, which is one of the deterministic quantities that carry dynamical information and can be used to quantify dynamical behavior of the corresponding stochastic basin of attraction. SBA is an efficient tool to describe the metastable phenomena complementing the known exit time, escape probability, or relaxation time. Moreover, the geometric structure of SBA gives additional insight into the system's dynamical behavior, which is important for theoretical and practical reasons. This concept can be used not only in models with small noise intensity but also with noise whose amplitude is proportional or in general is a function of an order parameter. As an application of our main results, we analyze a three potential well system perturbed by two types of noise: Brownian motion and non-Gaussian α-stable Lévy motion. Our main conclusions are that the thermal fluctuations stabilize the metastable system with an asymmetric three-well potential but have the opposite effect for a symmetric one. For Lévy noise with larger jumps and lower jump frequencies ( α=0.5) metastability is enhanced for both symmetric and asymmetric potentials. PMID:27475077

  10. Metastable Equilibria Among Aqueous Organic Compounds

    NASA Astrophysics Data System (ADS)

    Shock, E.; Shipp, J.; Yang, Z.; Gould, I. R.

    2011-12-01

    Metastable equilibrium states exist when reactions among a subset of compounds in a chemical system are reversible even though other irreversible reactions exist in the same system. The existence of metastable equilibrium among organic compounds was initially detected by comparing ratios of organic acid concentrations reported for oil-field brines (Shock, 1988, Geology 16, 886-890; Shock, 1989, Geology 17, 572-573), and calculating the same ratios for likely oxidation states determined by mineral assemblages and mixtures of hydrocarbons in coexisting petroleum (Shock, 1994, in: The Role of Organic Acids in Geological Processes, Springer). This led to the notion of extending the concept of metastable equilibrium states to explicitly account for petroleum compositions (Helgeson et al., 1993, GCA, 57, 3295-3339), which eventually yielded the concept of hydrolytic disproportionation of kerogens to produce petroleum and CO2(g) (Helgeson et al., 2009, GCA, 73, 594-695). Experimental tests of metastable equilibrium among organic compounds began with the identification of reversible reactions between alkanes and alkenes that are dependent on the H2 fugacity of the experimental system (Seewald, 1994, Nature 370, 285-287). These were followed with a comprehensive series of long-term experiments leading to the hypothesis that reversible reactions include alkanes, alkenes, alcohol, aldehydes, ketones and carboxylic acids (e.g., Seewald, 2001, GCA 65, 1641-1664; 2003, Nature 426, 327-333; McCollom & Seewald, 2003, GCA 67, 3645-3664). We have conducted sets of hydrothermal organic transformation experiments that test the extent to which these reactions are indeed reversible using aromatic and cyclic compounds. Results demonstrate reversibility for reactions among dibenzyl ketone, 1,3-diphenyl-2-propanol, 1,3-diphenylpropene and 1,3-diphenylpropane, as well as among methylcyclohexanes, methylcyclohexenes, methylcyclohexanols, methylcyclohexanones and methylcyclohexadienes. The

  11. Zinc sulfide liquefaction catalyst

    DOEpatents

    Garg, Diwakar

    1984-01-01

    A process for the liquefaction of carbonaceous material, such as coal, is set forth wherein coal is liquefied in a catalytic solvent refining reaction wherein an activated zinc sulfide catalyst is utilized which is activated by hydrogenation in a coal derived process solvent in the absence of coal.

  12. Red soil as a regenerable sorbent for high temperature removal of hydrogen sulfide from coal gas.

    PubMed

    Ko, Tzu-Hsing; Chu, Hsin; Lin, Hsiao-Ping; Peng, Ching-Yu

    2006-08-25

    In this study, hydrogen sulfide (H(2)S) was removed from coal gas by red soil under high temperature in a fixed-bed reactor. Red soil powders were collected from the northern, center and southern of Taiwan. They were characterized by XRPD, porosity analysis and DCB chemical analysis. Results show that the greater sulfur content of LP red soils is attributed to the higher free iron oxides and suitable sulfidation temperature is around 773K. High temperature has a negative effect for use red soil as a desulfurization sorbent due to thermodynamic limitation in a reduction atmosphere. During 10 cycles of regeneration, after the first cycle the red soil remained stable with a breakthrough time between 31 and 36 min. Hydrogen adversely affects sulfidation reaction, whereas CO exhibits a positive effect due to a water-shift reaction. COS was formed during the sulfidation stage and this was attributed to the reaction of H(2)S and CO. Results of XRPD indicated that, hematite is the dominant active species in fresh red soil and iron sulfide (FeS) is a product of the reaction between hematite and hydrogen sulfide in red soils. The spinel phase FeAl(2)O(4) was found during regeneration, moreover, the amount of free iron oxides decreased after regeneration indicating the some of the free iron oxide formed a spinel phase, further reducting the overall desulfurization efficiency.

  13. Formation of Dimethyl Sulfide and Methanethiol in Anoxic Freshwater Sediments

    PubMed Central

    Lomans, B. P.; Smolders, A.; Intven, L. M.; Pol, A.; Op, De; Van Der Drift, C.

    1997-01-01

    Concentrations of volatile organic sulfur compounds (VOSC) were measured in water and sediment columns of ditches in a minerotrophic peatland in The Netherlands. VOSC, with methanethiol (4 to 40 nM) as the major compound, appeared to be mainly of sediment origin. Both VOSC and hydrogen sulfide concentrations decreased dramatically towards the water surface. High methanethiol and high dimethyl sulfide concentrations in the sediment and just above the sediment surface coincided with high concentrations of hydrogen sulfide (correlation factors, r = 0.91 and r = 0.81, respectively). Production and degradation of VOSC were studied in 32 sediment slurries collected from various freshwater systems in The Netherlands. Maximal endogenous methanethiol production rates of the sediments tested (up to 1.44 (mu)mol per liter of sediment slurry (middot) day(sup-1)) were determined after inhibition of methanogenic and sulfate-reducing populations in order to stop VOSC degradation. These experiments showed that the production and degradation of VOSC in sediments are well balanced. Statistical analysis revealed multiple relationships of methanethiol production rates with the combination of methane production rates (indicative of total anaerobic mineralization) and hydrogen sulfide concentrations (r = 0.90) or with the combination of methane production rates and the sulfate/iron ratios in the sediment (r = 0.82). These findings and the observed stimulation of methanethiol formation in sediment slurry incubations in which the hydrogen sulfide concentrations were artificially increased provided strong evidence that the anaerobic methylation of hydrogen sulfide is the main mechanism for VOSC formation in most freshwater systems. Methoxylated aromatic compounds are likely a major source of methyl groups for this methylation of hydrogen sulfide, since they are important degradation products of the abundant biopolymer lignin. Increased sulfate concentrations in several freshwater

  14. The interaction of the theophylline metastable phase with water vapor

    NASA Astrophysics Data System (ADS)

    Matvienko, A. A.; Boldyrev, V. V.; Sidel'Nikov, A. A.; Chizhik, S. A.

    2008-07-01

    The conditions of hydration of the stable and metastable theophylline phases were determined. Two-phase metastable phase/monohydrate and stable phase/monohydrate equilibrium pressures were measured at 25, 30, and 35°C. The metastable phase began to react with water vapor at lower relative humidities than the stable phase. Processes that occurred with the metastable and stable theophylline phases over various water pressure ranges were considered. The metastable phase exhibited an unusual behavior at 25°C and relative humidity 47%. At constant water vapor pressure and temperature, theophylline was initially hydrated and then lost water and again became anhydrous. Two consecutive processes occurred in the system, the formation of theophylline monohydrate from the metastable phase and its decomposition to the stable phase. The ratio between the rates of these processes determined the content of the monohydrate at the given time moment.

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

    PubMed

    Vera, Mario; Schippers, Axel; Sand, Wolfgang

    2013-09-01

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

  16. Complex magmatic sulfides from silicic ash flows of the Tintic Mountains, Utah: Origin, evolution, and significance for evolution of sulfur in silicic melts

    SciTech Connect

    Cannan, T.; Whitney, J.A. . Dept. of Geology); Keith, J.D. . Dept. of Geology)

    1992-01-01

    Complex magmatic sulfides are found within a variety of phenocrystal phases within latitic ash-flows of the Tintic Mts., Utah. Crystallization temperatures for pyroxenes and iron-titanium oxides are above 900 C. The sulfides appear to have originated as a Fe-Cu-Ni monosulfide. The consistency in composition and rounded nature suggests formation as an immiscible sulfide liquid. During quenching, the sulfide separated into pyrrhotite with a partial rim of chalcopyrite and a small amount of nickel sulfide. Nearly all sulfides not contained within phenocrysts degas during eruption. The pyrrhotite breaks down first to form magnetite. The chalcopyrite is the most resistant to degassing and will remain after the pyrrhotite has disappeared. During this process, arsenic is concentrated near the outer margins of the grain. The abundance of the sulfide suggests that the amount of sulfur released during degassing is at least equal to that available from sulfur dissolved in the silicic melt. In magmas which have extensively degassed prior to eruption only chalcopyrite or nickel sulfide may survive. Such may have been the case at Mt. Pinatubo where only these phases are observed. The immiscible sulfide melt and resulting sulfides may have formed when a more iron rich mafic melt intruded into the silicic chamber causing magma mixing, reduction of the sulfur solubility, and separation of the sulfide phase. These sulfide phases may be important sources of heavy elements for the subsequent formation of ore deposits.

  17. Noise signatures of metastable resistivity states in ferromagnetic insulating manganite

    SciTech Connect

    Przybytek, J.; Fink-Finowicki, J.; Puźniak, R.; Markovich, V.; Jung, G.

    2015-07-28

    Pronounced noise signatures enabling one to discriminate metastable resistivity states in La{sub 0.86}Ca{sub 0.14}MnO{sub 3} single crystals have been observed. The normalized noise spectra for metastable resisitivity differ both in shape and magnitude, indicating that the metastable state is associated with transition of the electronic system into another local minimum of the potential landscape. Such scenario is consistent with freezing of the electronic system into a Coulomb glass state.

  18. Transient Cognitive Dynamics, Metastability, and Decision Making

    PubMed Central

    Rabinovich, Mikhail I.; Huerta, Ramón; Varona, Pablo; Afraimovich, Valentin S.

    2008-01-01

    The idea that cognitive activity can be understood using nonlinear dynamics has been intensively discussed at length for the last 15 years. One of the popular points of view is that metastable states play a key role in the execution of cognitive functions. Experimental and modeling studies suggest that most of these functions are the result of transient activity of large-scale brain networks in the presence of noise. Such transients may consist of a sequential switching between different metastable cognitive states. The main problem faced when using dynamical theory to describe transient cognitive processes is the fundamental contradiction between reproducibility and flexibility of transient behavior. In this paper, we propose a theoretical description of transient cognitive dynamics based on the interaction of functionally dependent metastable cognitive states. The mathematical image of such transient activity is a stable heteroclinic channel, i.e., a set of trajectories in the vicinity of a heteroclinic skeleton that consists of saddles and unstable separatrices that connect their surroundings. We suggest a basic mathematical model, a strongly dissipative dynamical system, and formulate the conditions for the robustness and reproducibility of cognitive transients that satisfy the competing requirements for stability and flexibility. Based on this approach, we describe here an effective solution for the problem of sequential decision making, represented as a fixed time game: a player takes sequential actions in a changing noisy environment so as to maximize a cumulative reward. As we predict and verify in computer simulations, noise plays an important role in optimizing the gain. PMID:18452000

  19. Stability and metastability of bromine clathrate polymorphs.

    PubMed

    Nguyen, Andrew H; Molinero, Valeria

    2013-05-23

    Clathrate hydrates are crystals in which water forms a network of fully hydrogen-bonded polyhedral cages that contain small guests. Clathrate hydrates occur mostly in two cubic crystal polymorphs, sI and sII. Bromine is one of two guests that yield a hydrate with the tetragonal structure (TS), the topological dual of the Frank-Kasper σ phase. There has been a long-standing disagreement on whether bromine hydrate also forms metastable sI and sII crystals. To date there are no data on the thermodynamic range of stability (e.g., the melting temperatures) of the metastable polymorphs. Here we use molecular dynamics simulations with the coarse-grained model of water mW to (i) investigate the thermodynamic stability of the empty and guest-filled the sI, sII, TS, and HS-I hydrate polymorphs, (ii) develop a coarse-grained model of bromine compatible with mW water, and (iii) evaluate the stability of the bromine hydrate polymorphs. The mW model predicts the same relative energy of the empty clathrate polymorphs and the same phase diagram as a function of water-guest interaction than the fully atomistic TIP4P water model. There is a narrow region in water-guest parameter space for which TS is marginally more stable than sI or sII. We parametrize a coarse-grained model of bromine compatible with mW water and use it to determine the order of stability of the bromine hydrate polymorphs. The melting temperatures of the bromine hydrate polymorphs predicted by the coarse-grained model are 281 ± 1 K for TS, 279 ± 1 K for sII, and 276 ± 1 K for sI. The closeness of the melting temperatures supports the plausibility of formation of metastable sII and sI bromine hydrates.

  20. Enhanced Mantle Conductivity from Sulfides beneath the Sierra Nevada?

    NASA Astrophysics Data System (ADS)

    Park, S. K.

    2002-12-01

    -Shtrikman models provide similar estimates. The idea that a discontinous, volumetrically small component can alter substantially the bulk conductivity of a rock is counterintuitive. If this hypothesis is true, then the interconnected basaltic melt forms the bridge between the patches of sulfide melt. Laboratory studies are needed to confirm this hypothesis, however. Measurements of sulfide melt at elevated pressures and temperatures are needed, as are measurements of mixed basalt-matrix-sulfide systems. Ducea, M.N., and S.K. Park, 2000. Enhanced mantle conductivity from sulfide minerals, southern Sierra Nevada, California, Geophys. Res. Lett., 27, 2405-2408. Holzheid, A., Schmitz, M.D., and T.L. Grove, Textural equilibria of iron sulfide liquids in partially molten silicate aggregates and their relevance to core formation scenarios, J. Geophys. Res., 105, 13555-13567, 2000. Park, S.K., B. Hirasuna, G.R. Jiracek, and C.L. Kinn, Magnetotelluric evidence of lithospheric mantle thinning beneath the southern Sierra Nevada, J. Geophys. Res., 101, 16241-16255, 1996.

  1. Iron Test

    MedlinePlus

    ... detect and help diagnose iron deficiency or iron overload. In people with anemia , these tests can help ... also be ordered when iron deficiency or iron overload is suspected. Early iron deficiency often goes unnoticed. ...

  2. Metastable feshbach molecules in high rotational states.

    PubMed

    Knoop, S; Mark, M; Ferlaino, F; Danzl, J G; Kraemer, T; Nägerl, H-C; Grimm, R

    2008-02-29

    We experimentally demonstrate Cs2 Feshbach molecules well above the dissociation threshold, which are stable against spontaneous decay on the time scale of 1 s. An optically trapped sample of ultracold dimers is prepared in a high rotational state and magnetically tuned into a region with a negative binding energy. The metastable character of these molecules arises from the large centrifugal barrier in combination with negligible coupling to states with low rotational angular momentum. A sharp onset of dissociation with increasing magnetic field is mediated by a crossing with a lower rotational dimer state and facilitates dissociation on demand with a well-defined energy. PMID:18352621

  3. Noise-induced metastability in biochemical networks.

    PubMed

    Biancalani, Tommaso; Rogers, Tim; McKane, Alan J

    2012-07-01

    Intracellular biochemical reactions exhibit a rich dynamical phenomenology which cannot be explained within the framework of mean-field rate equations and additive noise. Here, we show that the presence of metastable states and radically different time scales are general features of a broad class of autocatalytic reaction networks, and that this fact may be exploited to gain analytical results. The latter point is demonstrated by a treatment of the paradigmatic Togashi-Kaneko reaction, which has resisted theoretical analysis for the last decade.

  4. Metastability in spin-polarized Fermi gases.

    PubMed

    Liao, Y A; Revelle, M; Paprotta, T; Rittner, A S C; Li, Wenhui; Partridge, G B; Hulet, R G

    2011-09-30

    We study the role of particle transport and evaporation on the phase separation of an ultracold, spin-polarized atomic Fermi gas. We show that the previously observed deformation of the superfluid paired core is a result of evaporative depolarization of the superfluid due to a combination of enhanced evaporation at the center of the trap and the inhibition of spin transport at the normal-superfluid phase boundary. These factors contribute to a nonequilibrium jump in the chemical potentials at the phase boundary. Once formed, the deformed state is highly metastable, persisting for times of up to 2 s. PMID:22107209

  5. Review of Abiotic Degradation of Chlorinated Solvents by Reactive Iron Minerals

    EPA Science Inventory

    Abiotic degradation of chlorinated solvents by reactive iron minerals such as iron sulfides, magnetite, green rust, and other Fe(II)-containing minerals has been observed in both laboratory and field conditions. These reactive iron minerals typically form under iron and sulfate ...

  6. Metastable phase formation in undercooled liquid lead alloys

    NASA Technical Reports Server (NTRS)

    Fecht, Hans J.

    1991-01-01

    During non-equilibrium processes metastable phases are formed instead of stable phases due to the operation of various kinetic or structural constraints. By removing the most effective nucleation sites for the stable phase using emulsified droplet samples, stable phase formation can be prohibited in a broad range of undercooling and the phase space available in the metastable regime can be mapped out. With this method the thermodynamic properties of the undercooled liquid and the metastable phase boundaries corresponding to reversible metastable (solid + liquid) phase equilibria are examined from experimental data. The analysis reveals important implications for the nucleation kinetics and the choice of the kinetically most favored solidification path.

  7. Electrochemical behavior of silver sulfide

    SciTech Connect

    Drouven, B.U.E.

    1982-01-01

    The electrochemical behavior of silver sulfide in sulfuric acid as well as in nitric acid was studied using electrodes made from synthetic silver sulfide. The primary techniques used were potentiostatic, potentiodynamic, galvanostatic and corrosion cell experiments. The cathodic reaction of silver sulfide produces silver and hydrogen sulfide. This reaction mechanism is a sequential two step charge transfer involving a single electron in each step. Silver ions are produced from silver sulfide upon applying an anodic potential. The dissolution rate of silver sulfide can be so high that the formation of silver sulfate occurs which partially covers the silver sulfide surface and inhibits a further rate increase. The sulfur from the silver sulfide will be oxidized at low overpotentials to elemental sulfur; at high overpotentials, the oxidation to sulfate or bisulfate is observed. The results suggest that the catalysis of chalcopyrite by the addition of silver ions is caused by the formation and subsequent dissolution of silver sulfide leaving a porous layer behind. The understanding of the reaction mechanism of silver sulfide dissolution and its optimization will significantly improve the economic evaluation of industrial processes using the catalyzed leaching of chalcopyrite. The present knowledge of the catalysis indicates that other ions may be substituted for silver ions which would increase the feasibility of hydrometallurgical processes.

  8. Geothermal hydrogen sulfide removal

    SciTech Connect

    Urban, P.

    1981-04-01

    UOP Sulfox technology successfully removed 500 ppM hydrogen sulfide from simulated mixed phase geothermal waters. The Sulfox process involves air oxidation of hydrogen sulfide using a fixed catalyst bed. The catalyst activity remained stable throughout the life of the program. The product stream composition was selected by controlling pH; low pH favored elemental sulfur, while high pH favored water soluble sulfate and thiosulfate. Operation with liquid water present assured full catalytic activity. Dissolved salts reduced catalyst activity somewhat. Application of Sulfox technology to geothermal waters resulted in a straightforward process. There were no requirements for auxiliary processes such as a chemical plant. Application of the process to various types of geothermal waters is discussed and plans for a field test pilot plant and a schedule for commercialization are outlined.

  9. [The balneotherapeutic components of sulfide-containing mineral waters].

    PubMed

    Khutoryansky, V A; Gorshkov, A G

    2015-01-01

    It has been suggested in an early study that sulfanes may serve as a source of sulfur contained in hydrogen sulfide sources. We have performed derivatization of sulfanes, known to be present in the "Novonukutskaya" mineral water. The presence of polysulfanes in balneotherapeutic sulfide waters was confirmed by the HPLC-UV and chromato-mass spectrometric techniques. Derivatization of inorganic polysulfides was achieved by using the reaction with methyl iodide. It was shown that polysulfanes contained in the examined samples were metastable and disintegrated into So and H2S. Almost all molecular zero-valent sulfur was present in the form of S8. The application of HPLC allowed to determine the equilibrium concentration of molecular sulfur. The presence of the above compounds in therapeutic sulfide waters raises the question of the mechanism of their curative action. The authors hypothesize that it may be related to the high therapeutic potency of the substances obtained by steam distillation from the "Novonukutskaya" mineral water. PMID:26841531

  10. Metastable Metal Hydrides for Hydrogen Storage

    DOE PAGESBeta

    Graetz, Jason

    2012-01-01

    The possibility of using hydrogen as a reliable energy carrier for both stationary and mobile applications has gained renewed interest in recent years due to improvements in high temperature fuel cells and a reduction in hydrogen production costs. However, a number of challenges remain and new media are needed that are capable of safely storing hydrogen with high gravimetric and volumetric densities. Metal hydrides and complex metal hydrides offer some hope of overcoming these challenges; however, many of the high capacity “reversible” hydrides exhibit a large endothermic decomposition enthalpy making it difficult to release the hydrogen at low temperatures. Onmore » the other hand, the metastable hydrides are characterized by a low reaction enthalpy and a decomposition reaction that is thermodynamically favorable under ambient conditions. The rapid, low temperature hydrogen evolution rates that can be achieved with these materials offer much promise for mobile PEM fuel cell applications. However, a critical challenge exists to develop new methods to regenerate these hydrides directly from the reactants and hydrogen gas. This spotlight paper presents an overview of some of the metastable metal hydrides for hydrogen storage and a few new approaches being investigated to address the key challenges associated with these materials.« less

  11. Removal of sulfide, sulfate and sulfite ions by electro coagulation.

    PubMed

    Murugananthan, M; Raju, G Bhaskar; Prabhakar, S

    2004-06-18

    The removal of various species of sulfur from beamhouse of tannery wastewater and also from synthetic samples was studied by electro-flotation technique. Consumable anodes of iron and aluminum and insoluble anode of titanium were tested as anodes. It was found that iron and aluminum anodes were effective for the removal of suspended solids, sulfide, sulfite and sulfate. Progress of simultaneous coagulation of suspended solids during electro-flotation was measured using particle size analysis. Coagulation was found to be essential for effective flotation of suspended solids. Metal ions generated in situ by electrolytic oxidation of anode were found to react with dissolved sulfide ions. Metal sulfides thus formed as colloidal suspension were coagulated and floated simultaneously by hydrogen bubbles generated from cathode. Simultaneous occurrence of precipitation, coagulation and flotation was observed during electro-flotation. X-ray diffraction studies were conducted to identify the nature of sulfide phase formed during electrolytic precipitation. The effect of pH, current density and initial concentration of pollutants was studied and the results are discussed. The removal of sulfite and sulfate ions is explained by zeta-potential measurements. PMID:15177743

  12. Micelle Mediated Trace Level Sulfide Quantification through Cloud Point Extraction

    PubMed Central

    Devaramani, Samrat; Malingappa, Pandurangappa

    2012-01-01

    A simple cloud point extraction protocol has been proposed for the quantification of sulfide at trace level. The method is based on the reduction of iron (III) to iron (II) by the sulfide and the subsequent complexation of metal ion with nitroso-R salt in alkaline medium. The resulting green-colored complex was extracted through cloud point formation using cationic surfactant, that is, cetylpyridinium chloride, and the obtained surfactant phase was homogenized by ethanol before its absorbance measurement at 710 nm. The reaction variables like metal ion, ligand, surfactant concentration, and medium pH on the cloud point extraction of the metal-ligand complex have been optimized. The interference effect of the common anions and cations was studied. The proposed method has been successfully applied to quantify the trace level sulfide in the leachate samples of the landfill and water samples from bore wells and ponds. The validity of the proposed method has been studied by spiking the samples with known quantities of sulfide as well as comparing with the results obtained by the standard method. PMID:22619597

  13. Removal of sulfide, sulfate and sulfite ions by electro coagulation.

    PubMed

    Murugananthan, M; Raju, G Bhaskar; Prabhakar, S

    2004-06-18

    The removal of various species of sulfur from beamhouse of tannery wastewater and also from synthetic samples was studied by electro-flotation technique. Consumable anodes of iron and aluminum and insoluble anode of titanium were tested as anodes. It was found that iron and aluminum anodes were effective for the removal of suspended solids, sulfide, sulfite and sulfate. Progress of simultaneous coagulation of suspended solids during electro-flotation was measured using particle size analysis. Coagulation was found to be essential for effective flotation of suspended solids. Metal ions generated in situ by electrolytic oxidation of anode were found to react with dissolved sulfide ions. Metal sulfides thus formed as colloidal suspension were coagulated and floated simultaneously by hydrogen bubbles generated from cathode. Simultaneous occurrence of precipitation, coagulation and flotation was observed during electro-flotation. X-ray diffraction studies were conducted to identify the nature of sulfide phase formed during electrolytic precipitation. The effect of pH, current density and initial concentration of pollutants was studied and the results are discussed. The removal of sulfite and sulfate ions is explained by zeta-potential measurements.

  14. Sulfidization of lepidocrocite and its effect on uranium phase distribution and reduction

    NASA Astrophysics Data System (ADS)

    Alexandratos, Vasso G.; Behrends, Thilo; Van Cappellen, Philippe

    2014-10-01

    Sulfidization of iron oxyhydroxides can be accompanied by a release of adsorbed uranium, thus enhancing the mobility of uranium in systems undergoing a shift in redox conditions. We investigated the phase distribution and redox state of uranium in batch experiments, in which lepidocrocite with adsorbed U(VI) was reacted with sulfide. The amount of added sulfide was varied in the experiments performed, at pH 8 and ionic strength of 0.1 M. Sulfide, when not added in excess, was removed from solution within less than 1 h of reaction time. Consumption of dissolved sulfide was accompanied by reduction of Fe(III) and formation of iron sulfide. Each addition of sulfide led to an instantaneous release of uranium into solution. This release is most likely caused by the exchange of hydroxide groups at the lepidocrocite surface by thiol groups which have a lower tendency to bind uranium. Along with the consumption of dissolved sulfide, part of the released uranium became reassociated with the solid phase. This can be explained by a reversal of the ligand exchange process at the solid surfaces. However, steady state concentrations of dissolved uranium remained higher than before sulfide addition, indicating that the product of lepidocrocite sulfidization has a lower affinity for uranium than the starting material. Reduction of U(VI) also contributed to the transfer of dissolved uranium back to the solid phase. X-ray absorption spectroscopy revealed that reduction of U(VI) occurred in all experiments. The extent of U(VI) reduction depended on sulfide addition, however, formation of UO2 occurred within a period of 48 h only when sulfide was added in excess. This suggests that the presence of dissolved sulfide is a prerequisite for fast reduction of U(VI) and formation of UO2. This would imply that the fast reaction of lepidocrocite with sulfide outcompetes reduction of U(VI) and, by this, kinetically inhibits the thermodynamically more favorable reduction of U(VI) to uraninite

  15. Chemical dosing for sulfide control in Australia: An industry survey.

    PubMed

    Ganigue, Ramon; Gutierrez, Oriol; Rootsey, Ray; Yuan, Zhiguo

    2011-12-01

    Controlling sulfide (H(2)S) production and emission in sewer systems is critical due to the corrosion and malodour problems that sulfide causes. Chemical dosing is one of the most commonly used measures to mitigate these problems. Many chemicals have been reported to be effective for sulfide control, but the extent of success varies between chemicals and is also dependent on how they are applied. This industry survey aims to summarise the current practice in Australia with the view to assist the water industry to further improve their practices and to identify new research questions. Results showed that dosing is mainly undertaken in pressure mains. Magnesium hydroxide, sodium hydroxide and nitrate are the most commonly used chemicals for sewers with low flows. In comparison, iron salts are preferentially used for sulfide control in large systems. The use of oxygen injection has declined dramatically in the past few years. Chemical dosing is mainly conducted at wet wells and pumping stations, except for oxygen, which is injected into the pipe. The dosing rates are normally linked to the control mechanisms of the chemicals and the dosing locations, with constant or profiled dosing rates usually applied. Finally, key opportunities for improvement are the use of mathematical models for the selection of chemicals and dosing locations, on-line dynamic control of the dosing rates and the development of more cost-effective chemicals for sulfide control.

  16. Conversion of ammonia into hydrogen and nitrogen by reaction with a sulfided catalyst

    DOEpatents

    Matthews, Charles W.

    1977-01-01

    A method is provided for removing ammonia from the sour water stream of a coal gasification process. The basic steps comprise stripping the ammonia from the sour water; heating the stripped ammonia to a temperature from between 400.degree. to 1,000.degree. F; passing the gaseous ammonia through a reactor containing a sulfided catalyst to produce elemental hydrogen and nitrogen; and scrubbing the reaction product to obtain an ammonia-free gas. The residual equilibrium ammonia produced by the reactor is recycled into the stripper. The ammonia-free gas may be advantageously treated in a Claus process to recover elemental sulfur. Iron sulfide or cobalt molybdenum sulfide catalysts are used.

  17. Effect of anions on selective solubilization of zinc and copper in bacterial leaching of sulfide ores.

    PubMed

    Harahuc, L; Lizama, H M; Suzuki, I

    2000-07-20

    Bacterial leaching of sulfide ores using Thiobacillus ferrooxidans, Thiobacillus thiooxidans, or a combination of the two was studied at various concentrations of specific anions. Selective zinc and copper solubilization was obtained by inhibiting iron oxidation without affecting sulfur/sulfide oxidation. Phosphate reduced iron solubilization from a pyrite (FeS(2))-sphalerite (ZnS) mixture without significantly affecting zinc solubilization. Copper leaching from a chalcopyrite (CuFeS(2))-sphalerite mixture was stimulated by phosphate, whereas chloride accelerated zinc extraction. In a complex sulfide ore containing pyrite, chalcopyrite, and sphalerite, both phosphate and chloride reduced iron solubilization and increased copper extraction, whereas only chloride stimulated zinc extraction. Maximum leaching obtained was 100% zinc and 50% copper. Time-course studies of copper and zinc solubilization suggest the possibility of selective metal recovery following treatment with specific anions. PMID:10861398

  18. Iron monosulfide as a scavenger for dissolved hexavalent chromium and cadmium.

    PubMed

    Jo, S; Lee, J Y; Kong, S H; Choi, J; Park, J W

    2008-09-01

    Iron sulfide minerals are common components of soil/sedimentary environments. Reactions near the surfaces of iron sulfides play important roles in metal retention, mobility, and bioavailability. A series of batch experiments was conducted to study the removal of aqueous chromium and cadmium by iron monosulfide. Hexavalent chromium was reduced to Cr(III) by iron monosulfide with simultaneous precipitation of chromium and iron oxyhydroxide. In contrast to chromium, the primary retention mechanism of cadmium by iron monosulfide was lattice exchange. Surface adsorption to iron monosulfide and precipitation with sulfide on the iron monosulfide surface also contributed to the removal of aqueous cadmium. New phases of both chromium and cadmium were confirmed with transmission electron microscopy. The solution pH was an important factor in this research; it can change particle surface charge and metal species, hence affecting the removal of chromium, but not cadmium. Ferrous ions without FeS exhibited less Cr(VI) removal than with FeS, which might be owing to sulfides from FeS and the existence of the solid phase. Iron monosulfide exhibited higher removal efficiency for chromium and cadmium than zero valent iron and other iron oxide minerals, and the synergistic effect of ferrous iron and sulfide appeared to cause this result.

  19. Nitrate-dependent iron oxidation limits iron transport in anoxic ocean regions

    NASA Astrophysics Data System (ADS)

    Scholz, Florian; Löscher, Carolin R.; Fiskal, Annika; Sommer, Stefan; Hensen, Christian; Lomnitz, Ulrike; Wuttig, Kathrin; Göttlicher, Jörg; Kossel, Elke; Steininger, Ralph; Canfield, Donald E.

    2016-11-01

    Iron is an essential element for life on Earth and limits primary production in large parts of the ocean. Oxygen-free continental margin sediments represent an important source of bioavailable iron to the ocean, yet little of the iron released from the seabed reaches the productive sea surface. Even in the anoxic water of oxygen minimum zones, where iron solubility should be enhanced, most of the iron is rapidly re-precipitated. To constrain the mechanism(s) of iron removal in anoxic ocean regions we explored the sediment and water in the oxygen minimum zone off Peru. During our sampling campaign the water column featured two distinct redox boundaries separating oxic from nitrate-reducing (i.e., nitrogenous) water and nitrogenous from weakly sulfidic water. The sulfidic water mass in contact with the shelf sediment contained elevated iron concentrations >300 nM. At the boundary between sulfidic and nitrogenous conditions, iron concentrations dropped sharply to <20 nM coincident with a maximum in particulate iron concentration. Within the iron gradient, we found an increased expression of the key functional marker gene for nitrate reduction (narG). Part of this upregulation was related to the activity of known iron-oxidizing bacteria. Collectively, our data suggest that iron oxidation and removal is induced by nitrate-reducing microbes, either enzymatically through anaerobic iron oxidation or by providing nitrite for an abiotic reaction. Given the important role that iron plays in nitrogen fixation, photosynthesis and respiration, nitrate-dependent iron oxidation likely represents a key-link between the marine biogeochemical cycles of nitrogen, oxygen and carbon.

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

    USGS Publications Warehouse

    Goldhaber, M.B.

    1983-01-01

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

  1. Metastable isomers - A new class of interstellar molecules

    NASA Technical Reports Server (NTRS)

    Green, S.; Herbst, E.

    1979-01-01

    The abundances of a variety of metastable isomers of small organic molecules, analogous to HNC/HCN, in dense interstellar clouds are considered. These metastable species, some of which are thought to exist as intermediates in laboratory organic chemical reactions, are of considerable interest to chemists. Current ideas of gas-phase, ion-molecule chemistry are utilized to demonstrate that such metastable species should often be present in dense clouds in sufficient abundance to be observed. Unfortunately, the spectral constants of metastable isomers have rarely been determined in the laboratory, and quantum chemical calculations of a varying degree of accuracy must be utilized; results are included of some new quantum chemical calculations. The interstellar chemistry and expected microwave spectra of a representative sample of possibly important interstellar metastable isomers are discussed.

  2. Hydrogen sulfide intoxication.

    PubMed

    Guidotti, Tee L

    2015-01-01

    Hydrogen sulfide (H2S) is a hazard primarily in the oil and gas industry, agriculture, sewage and animal waste handling, construction (asphalt operations and disturbing marshy terrain), and other settings where organic material decomposes under reducing conditions, and in geothermal operations. It is an insoluble gas, heavier than air, with a very low odor threshold and high toxicity, driven by concentration more than duration of exposure. Toxicity presents in a unique, reliable, and characteristic toxidrome consisting, in ascending order of exposure, of mucosal irritation, especially of the eye ("gas eye"), olfactory paralysis (not to be confused with olfactory fatigue), sudden but reversible loss of consciousness ("knockdown"), pulmonary edema (with an unusually favorable prognosis), and death (probably with apnea contributing). The risk of chronic neurcognitive changes is controversial, with the best evidence at high exposure levels and after knockdowns, which are frequently accompanied by head injury or oxygen deprivation. Treatment cannot be initiated promptly in the prehospital phase, and currently rests primarily on supportive care, hyperbaric oxygen, and nitrite administration. The mechanism of action for sublethal neurotoxicity and knockdown is clearly not inhibition of cytochrome oxidase c, as generally assumed, although this may play a role in overwhelming exposures. High levels of endogenous sulfide are found in the brain, presumably relating to the function of hydrogen sulfide as a gaseous neurotransmitter and immunomodulator. Prevention requires control of exposure and rigorous training to stop doomed rescue attempts attempted without self-contained breathing apparatus, especially in confined spaces, and in sudden release in the oil and gas sector, which result in multiple avoidable deaths. PMID:26563786

  3. Sulfidization of Witwatersrand black sands: From enigma to myth

    SciTech Connect

    Reimer, T.O. ); Mossman, D.J. )

    1990-05-01

    Reassessment of the nature and distribution of iron-titanium oxide minerals vs. pyrite in several South African Archean arenaceous sequences and conglomerates shows that in rocks of the Swaziland, Pongola, and Witwatersrand Supergroups, (1) pyrite of allogenic and/or authigenic origin is the predominant heavy mineral; (2) iron-titanium oxides generally take the form of very fine grained, dispersed retile-leucoxene replacements after earlier black-sand minerals; (3) iron-titanium oxides constitute 1%-6% of the total heavy minerals; and (4) the phenomenon of sulfidization of iron-titanium oxide minerals is evident only on a very local scale. Exceptions to points 1 and 3 occur in conglomerates of the Dominion Group, which were derived from a largely pegmatitic terrain. The lack of macroscopically visible iron-titanium oxide minerals in the Witwatersrand conglomerates is a result of a combination of two factors. First, recycling of older sedimentary material was critical to the genesis of the conglomerates; older sedimentary material was critical to the genesis of the conglomerates; about 60% of the source area consisted of arenaceous sequences. Iron-titanium mineral grains from this source had been altered to rutile-leucoxene prior to erosion, and thus did not contribute fresh iron-titanium minerals to the conglomerates. Second, those minerals derived from the remaining 40% of the source area were altered and decomposed to rutile-leucoxene in the Witwatersrand conglomerates. Furthermore, much of the resulting finely dispersed material helped to form brannerite, an important titanium sink. There is no need to invoke widespread sulfidization of black sands to sands to account for the supposed lack of iron-titanium minerals and abundance of pyrite in the Witwatersrand conglomerates and ores.

  4. Metastable Atom Detection Using Solid N2

    NASA Astrophysics Data System (ADS)

    McConkey, William; Kedzierski, Wladek; Lukic, Dragan

    2014-05-01

    Over the years our laboratory has been a center for the use of rare-gas matrices at temperatures below 70K in the detection and study of low energy atomic and molecular metastable particles [see Kedzierski et al., Can J Phys, 91, 1044, (2013) for Refs]. Recently we have extended this work to study the use of a solid nitrogen matrix at temperatures below 35K as a detector of O(1S) atoms. This proves to be at least as sensitive as any rare gas matrix though the lifetime of the excimer formed in the matrix is somewhat longer (~ 20 μs) than what is observed in a Xe matrix for example. The detailed performance of the detector as a function of temperature and other parameters will be presented at the conference. The authors thank NSERC and CFI, (Canada), for financial support.

  5. Electrostatic trapping of metastable NH molecules

    SciTech Connect

    Hoekstra, Steven; Metsaelae, Markus; Zieger, Peter C.; Scharfenberg, Ludwig; Gilijamse, Joop J.; Meijer, Gerard; Meerakker, Sebastiaan Y. T. van de

    2007-12-15

    We report on the Stark deceleration and electrostatic trapping of {sup 14}NH (a{sup 1}{delta}) radicals. In the trap, the molecules are excited on the spin-forbidden A{sup 3}{pi}<-a{sup 1}{delta} transition and detected via their subsequent fluorescence to the X{sup 3}{sigma}{sup -} ground state. The 1/e trapping time is 1.4{+-}0.1 s, from which a lower limit of 2.7 s for the radiative lifetime of the a{sup 1}{delta}, v=0, J=2 state is deduced. The spectral profile of the molecules in the trapping field is measured to probe their spatial distribution. Electrostatic trapping of metastable NH followed by optical pumping of the trapped molecules to the electronic ground state is an important step toward accumulation of these radicals in a magnetic trap.

  6. Simulation of metastable CL-20 cluster structures

    NASA Astrophysics Data System (ADS)

    Degtyarenko, N. N.; Katin, K. P.; Maslov, M. M.

    2014-07-01

    Ensembles of C6H6N12O12 (CL-20) clusters with different types of intercluster bonds have been studied theoretically. The stability of such cluster has been investigated and the heights of potential barriers preventing their decomposition or isomerization have been determined by means of quantum-mechanical calculations based on the density functional theory and nonorthogonal tight-binding model. From the analysis of molecular dynamics data and potential energy hypersurface of these metastable configurations, it has been established that dimers and tetramers of CL-20 clusters are characterized by sufficiently high kinetic stability, which suggests the theoretical possibility of creation of high-energy covalent crystals on their basis.

  7. Metastable orientational order of colloidal discoids

    PubMed Central

    Hsiao, Lilian C.; Schultz, Benjamin A.; Glaser, Jens; Engel, Michael; Szakasits, Megan E.; Glotzer, Sharon C.; Solomon, Michael J.

    2015-01-01

    The interplay between phase separation and kinetic arrest is important in supramolecular self-assembly, but their effects on emergent orientational order are not well understood when anisotropic building blocks are used. Contrary to the typical progression from disorder to order in isotropic systems, here we report that colloidal oblate discoids initially self-assemble into short, metastable strands with orientational order—regardless of the final structure. The model discoids are suspended in a refractive index and density-matched solvent. Then, we use confocal microscopy experiments and Monte Carlo simulations spanning a broad range of volume fractions and attraction strengths to show that disordered clusters form near coexistence boundaries, whereas oriented strands persist with strong attractions. We rationalize this unusual observation in light of the interaction anisotropy imparted by the discoids. These findings may guide self-assembly for anisotropic systems in which orientational order is desired, such as when tailored mechanical properties are sought. PMID:26443082

  8. Metastable cosmic strings in realistic models

    SciTech Connect

    Holman, R.; Hsu, S.; Vachaspati, T.; Watkins, R. |

    1992-11-01

    The stability of the electroweak Z-string is investigated at high temperatures. The results show that, while finite temperature corrections can improve the stability of the Z-string, their effect is not strong enough to stabilize the Z-string in the standard electroweak model. Consequently, the Z-string will be unstable even under the conditions present during the electroweak phase transition. Phenomenologically viable models based on the gauge group SU(2){sub L} {times} SU(2) {sub R} {times} U(1){sub B-L} are then considered, and it is shown that metastable strings exist and are stable to small perturbations for a large region of the parameter space for these models. It is also shown that these strings are superconducting with bosonic charge carriers. The string superconductivity may be able to stabilize segments and loops against dynamical contraction. Possible implications of these strings for cosmology are discussed.

  9. Metastable cosmic strings in realistic models

    SciTech Connect

    Holman, R. . Dept. of Physics); Hsu, S. . Lyman Lab. of Physics); Vachaspati, T. . Dept. of Physics and Astronomy); Watkins, R. Fermi National Accelerator Lab., Batavia, IL )

    1992-01-01

    The stability of the electroweak Z-string is investigated at high temperatures. The results show that, while finite temperature corrections can improve the stability of the Z-string, their effect is not strong enough to stabilize the Z-string in the standard electroweak model. Consequently, the Z-string will be unstable even under the conditions present during the electroweak phase transition. Phenomenologically viable models based on the gauge group SU(2)[sub L] [times] SU(2) [sub R] [times] U(1)[sub B-L] are then considered, and it is shown that metastable strings exist and are stable to small perturbations for a large region of the parameter space for these models. It is also shown that these strings are superconducting with bosonic charge carriers. The string superconductivity may be able to stabilize segments and loops against dynamical contraction. Possible implications of these strings for cosmology are discussed.

  10. The role of FeS(aq) molecular clusters in microbial redox cycling and iron mineralization.

    NASA Astrophysics Data System (ADS)

    Druschel, G.; Oduro, H.; Sperling, J.; Johnson, C.

    2008-12-01

    Iron sulfide molecular clusters, FeS(aq), are a group of polynuclear Fe-S complexes varying in size between a few and a few hundred molecules that occur in many environments and are critical parts of cycling between soluble iron and iron sulfide minerals. These clusters react uniquely with voltammetric Au-amalgam electrodes, and the signal for these molecules has now been observed in many terrestrial and marine aquatic settings. FeS(aq) clusters form when aqueous sulfide and iron(II) interact, but the source of those ions can come from abiotic or microbial sulfate and iron reduction or from the abiotic non-oxidative dissolution of iron sulfide minerals. Formation of iron sulfide minerals, principally mackinawite as the first solid nanocrystalline phase in many settings, is necessarily preceeded by formation and evolution of these molecular clusters as mineralization proceeds, and the clusters have been suggested to additionally be part of the pyritization process (Rickard and Luther, 1997; Luther and Rickard, 2005). In several systems, we have also observed FeS(aq) clusters to be the link between Fe-S mineral dissolution and oxidation of iron and sulfide, with important implications for changes to the overall oxidation pathway. Microorganisms can clearly be involved in the formation of FeS(aq) through iron and sulfate reduction, but it is not clear to date if organisms can utilize these clusters either as metabolic components or as anabolic 'building blocks' for enzyme production. Cycling of iron in the Fe-S system linked to FeS(aq) would clearly be a critical part of understanding iron isotope dynamics preserved in iron sulfide minerals. We will review ongoing work towards understanding the role of FeS(aq) in iron cycling and isotope fractionation as well as the measurement and characterization of this key class of iron complexes using environmental voltammetry.

  11. Selective removal of either metastable species from a mixed 3P 0,2 rare-gas metastable beam

    NASA Technical Reports Server (NTRS)

    Dunning, F. B.; Cook, T. B.; West, W. P.; Stebbings, R. F.

    1975-01-01

    A tunable CW laser has been used to selectively remove either of the two metastable species, 3P 0,2, which are initially present in a neon metastable beam. The method is applicable to other rare gases and provides the opportunity for separate investigation of effects due to atoms in either the 3P 0 or 3P 2 state.

  12. Iron Chelation

    MedlinePlus

    ... iron overload and need treatment. What is iron overload? Iron chelation therapy is used when you have ... may want to perform: How quickly does iron overload happen? This is different for each person. It ...

  13. Field method for sulfide determination

    SciTech Connect

    Wilson, B L; Schwarser, R R; Chukwuenye, C O

    1982-01-01

    A simple and rapid method was developed for determining the total sulfide concentration in water in the field. Direct measurements were made using a silver/sulfide ion selective electrode in conjunction with a double junction reference electrode connected to an Orion Model 407A/F Specific Ion Meter. The method also made use of a sulfide anti-oxidant buffer (SAOB II) which consists of ascorbic acid, sodium hydroxide, and disodium EDTA. Preweighed sodium sulfide crystals were sealed in air tight plastic volumetric flasks which were used in standardization process in the field. Field standards were prepared by adding SAOB II to the flask containing the sulfide crystals and diluting it to the mark with deionized deaerated water. Serial dilutions of the standards were used to prepare standards of lower concentrations. Concentrations as low as 6 ppB were obtained on lake samples with a reproducibility better than +- 10%.

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

    PubMed

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

    1981-01-01

    Samples of natural pyrites and sphalerites were subjected to the action of the mineral medium 9K with 1 g of Fe3+ per litre in the presence and in the absence of Thiobacillus ferrooxidans, and incubated at 28 degrees C under the stationary conditions for 30 days. The chemical composition of the solutions was studied after leaching as well as changes of the surfaces of monoliths. The deepest etching of surfaces with the formation of crusts and films of jarosite, limonite and goslarite occurs upon the combined action of bacteria and Fe3+ in regions of a fine-zonal structure enriched with an isomorphous arsenic admixture which are characterized by a defective weak structure. The pyrite and sphalerite from Charmitan with a higher arsenic and iron content were leached more than the pyrite and sphalerite from Kurgashincan. This was also corroborated by chemical analyses of leaching solutions and by monometric studies of crushed sulfide samples. PMID:7219212

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

    PubMed

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

    1981-01-01

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

  16. Synergistic stabilization of metastable Fe{sub 23}B{sub 6} and γ-Fe in undercooled Fe{sub 83}B{sub 17}

    SciTech Connect

    Quirinale, D. G.; Rustan, G. E.; Kreyssig, A.; Goldman, A. I.

    2015-06-15

    Previous investigations of undercooled liquid Fe{sub 83}B{sub 17} near the eutectic composition have found that metastable crystalline phases, such as Fe{sub 23}B{sub 6}, can be formed and persist down to ambient temperature even for rather modest cooling rates. Using time-resolved high-energy x-ray diffraction on electrostatically levitated samples of Fe{sub 83}B{sub 17}, we demonstrate that the Fe{sub 23}B{sub 6} metastable phase and fcc γ-Fe grow coherently from the undercooled Fe{sub 83}B{sub 17} liquid and effectively suppress the formation of the equilibrium Fe{sub 2}B + bcc α-Fe phases. The stabilization of γ-Fe offers another opportunity for experimental investigations of magnetism in metastable fcc iron.

  17. Room-temperature synthesis, hydrothermal recrystallization, and properties of metastable stoichiometric FeSe.

    PubMed

    Nitsche, F; Goltz, T; Klauss, H-H; Isaeva, A; Müller, U; Schnelle, W; Simon, P; Doert, Th; Ruck, M

    2012-07-01

    Room-temperature precipitation from aqueous solutions yields the hitherto unknown metastable stoichiometric iron selenide (ms-FeSe) with tetragonal anti-PbO type structure. Samples with improved crystallinity are obtained by diffusion-controlled precipitation or hydrothermal recrystallization. The relations of ms-FeSe to superconducting β-FeSe(1-x) and other neighbor phases of the iron-selenium system are established by high-temperature X-ray diffraction, DSC/TG/MS (differential scanning calorimetry/thermogravimetry/mass spectroscopy), (57)Fe Mössbauer spectroscopy, magnetization measurements, and transmission electron microscopy. Above 300 °C, ms-FeSe decomposes irreversibly to β-FeSe(1-x) and Fe(7)Se(8). The structural parameters of ms-FeSe (P4/nmm, a = 377.90(1) pm, c = 551.11(3) pm, Z = 2), obtained by Rietveld refinement, differ significantly from literature data for β-FeSe(1-x). The Mössbauer spectrum rules out interstitial iron atoms or additional phases. Magnetization data suggest canted antiferromagnetism below T(N) = 50 K. Stoichiometric non-superconducting ms-FeSe can be regarded as the true "parent" compound for the "11" iron-chalcogenide superconductors and may serve as starting point for new chemical modifications.

  18. Enhancement of stability in systems with metastable states

    SciTech Connect

    Spagnolo, B.; Augello, G.; Pizzolato, N.; Valenti, D.; Fiasconaro, A.

    2007-12-06

    The investigation of noise-induced phenomena in far from equilibrium systems is one of the approach used to understand the behaviour of physical and biological complex systems. Metastability is a generic feature of many nonlinear systems, and the problem of the lifetime of metastable states involves fundamental aspects of nonequilibrium statistical mechanics. The enhancement of the life-time of metastable states through the noise enhanced stability effect and the role played by the resonant activation phenomenon will be discussed in models of interdisciplinary physics: (i) Ising model (ii) Josephson junction; (iii) stochastic FitzHugh-Nagumo model; (iv) a population dynamics model, and (v) a market model with stochastic volatility.

  19. Dissociation-excitation reactions of argon metastables with carbon dioxide.

    NASA Technical Reports Server (NTRS)

    Starr, W. L.

    1971-01-01

    Results of a study showing that a metastable argon-carbon dioxide reaction results in dissociation of carbon dioxide and electronic excitation of one of the products, carbon monoxide or oxygen. A flow system using a 2450-MHz discharge was used to produce metastable argon atoms. Metastable argon in the afterglow was confirmed by adding nitrogen to the afterglow. Without addition of carbon dioxide no argon line emission, or any other emission, is observed from the reaction zone. Absence of argon line emission produced by recombination indicates the absence of charged species.

  20. Polymorphism and Formation Mechanism of Nanobipods in Manganese Sulfide Nanocrystals Induced by Temperature or Pressure

    SciTech Connect

    Yang, Xinyi; Wang, Yingnan; Wang, Kai; Sui, Yongming; Zhang, Meiguang; Li, Bing; Ma, Yanming; Liu, Bingbing; Zou, Guangtian; Zou, Bo

    2012-03-15

    Manganese sulfide (MnS) nanocrystals (NCs) with three different phases were synthesized by one-pot solvent thermal approach. The crystal structures and morphologies were investigated using powder X-ray diffraction, transmission electron microscopy, and high-resolution transmission electron microscopy. We found that the crystal structure and morphology of MnS NCs could be controlled by simply varying the reaction temperature. The detailed growth process of MnS nanobipods, including the zinc blende (ZB)-core formation and wurtzite (WZ)-arms growth, provides direct experimental evidence for the polymorphism model. Furthermore, we have studied the stability of metastable ZB- and WZ-MnS NCs under high pressure and found that ZB-nanoparticles and ZB/WZ-nanobipods are stable below their critical pressure, 5.3 and 2.9 GPa, respectively. When pressures exceed the critical point, all these metastable MnS NCs directly convert to the stable rock salt MnS.

  1. Volcanogenic Massive Sulfide Deposit Density

    USGS Publications Warehouse

    Mosier, Dan L.; Singer, Donald A.; Berger, Vladimir I.

    2007-01-01

    A mineral-deposit density model for volcanogenic massive sulfide deposits was constructed from 38 well-explored control areas from around the world. Control areas contain at least one exposed volcanogenic massive sulfide deposit. The control areas used in this study contain 150 kuroko, 14 Urals, and 25 Cyprus massive sulfide subtypes of volcanogenic massive sulfide deposits. For each control area, extent of permissive rock, number of exposed volcanogenic massive sulfide deposits, map scale, deposit age, and deposit density were determined. The frequency distribution of deposit densities in these 38 control areas provides probabilistic estimates of the number of deposits for tracts that are permissive for volcanogenic massive sulfide deposits-90 percent of the control areas have densities of 100 or more deposits per 100,000 square kilometers, 50 percent of the control areas have densities of 700 or more deposits per 100,000 square kilometers, and 10 percent of the control areas have densities of 3,700 or more deposits per 100,000 square kilometers. Both map scale and the size of the control area are shown to be predictors of deposit density. Probabilistic estimates of the number of volcanogenic massive sulfide deposits can be made by conditioning the estimates on sizes of permissive area. The model constructed for this study provides a powerful tool for estimating the number of undiscovered volcanogenic massive sulfide deposits when conducting resource assessments. The value of these deposit densities is due to the consistency of these models with the grade and tonnage and the descriptive models. Mineral-deposit density models combined with grade and tonnage models allow reasonable estimates of the number, size, and grades of volcanogenic massive sulfide deposits to be made.

  2. Iron control in west Texas sour-gas wells provides sustained production increases

    SciTech Connect

    Walker, M.L.; Dill, W.R.; Besler, M.R.; McFatridge, D.G. )

    1991-05-01

    Permian Basin operators have recorded sustained production increases in oil wells by preventing precipitation of iron sulfide and other sulfur-containing species. This improvement has resulted largely from cleaning out tubing before acidizing and from preventing the precipitation of ferrous sulfide and the formation of elemental sulfur by simultaneous use of iron chelants and sulfide-control agents. Previously used methods gave only temporary production increases that terminated when iron dissolved by the stimulation acid reprecipitated in the pay zone and damage the formation after the stimulation acid was spent. This paper describes a method to optimize iron sulfide control, methods to minimize reprecipitation, and case histories from the Permian Basin that show improved methods to control iron in sour-well environments.

  3. Use of ferric sulfate: acid media for the desulfurization of model compounds of coal. [Dibenzothiophene, diphenyl sulfide, di-n-butyl sulfide

    SciTech Connect

    Clary, L.R.; Vermeulen, T.; Lynn, S.

    1980-12-01

    The objective of this work has been to investigate the ability of ferric sulfate-acid leach systems to oxidize the sulfur in model compounds of coal. Ferric iron-acid leach systems have been shown to be quite effective at removal of inorganic sulfur in coal. In this study, the oxidative effect of ferric iron in acid-leach systems was studied using dibenzothiophene, diphenyl sulfide, and di-n-butyl sulfide as models of organic sulfur groups in coal. Nitrogen and oxygen, as well as various transition metal catalysts and oxidants, were utilized in this investigation. Dibenzothiophene was found to be quite refractory to oxidation, except in the case where metavanadate was added, where it appears that 40% oxidation to sulfone could have occurred per hour at 150/sup 0/C and mild oxygen pressure. Diphenyl sulfide was selectively oxidized to sulfoxide and sulfone in an iron and oxygen system. Approximately 15% conversion to sulfone occurred per hour under these conditions. Some of the di-n-butyl sulfide was cracked to 1-butene and 1-butanethiol under similar conditions. Zinc chloride and ferric iron were used at 200/sup 0/C in an attempt to desulfonate dibenzothiophene sulfone, diphenyl sulfone, and di-n-butyl sulfone. Di-n-butyl sulfone was completely desulfurized on one hour and fragmented to oxidized parafins, while dibenzothiophene sulfone and diphenyl sulfone were unaffected. These results suggest that an iron-acid leach process could only selectively oxidize aryl sulfides under mild conditions, representing only 20% of the organic sulfur in coal (8% of the total sulfur). Removal through desulfonation once selective sulfur oxidation had occurred was only demonstrated for alkyl sulfones, with severe oxidation of the fragmented paraffins also occurring in one hour.

  4. Kinetic studies of sulfide mineral oxidation and xanthate adsorption

    NASA Astrophysics Data System (ADS)

    Mendiratta, Neeraj K.

    2000-10-01

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

  5. A novel method for improving cerussite sulfidization

    NASA Astrophysics Data System (ADS)

    Feng, Qi-cheng; Wen, Shu-ming; Zhao, Wen-juan; Cao, Qin-bo; Lü, Chao

    2016-06-01

    Evaluation of flotation behavior, solution measurements, and surface analyses were performed to investigate the effects of chloride ion addition on the sulfidization of cerussite in this study. Micro-flotation tests indicate that the addition of chloride ions prior to sulfidization can significantly increase the flotation recovery of cerussite, which is attributed to the formation of more lead sulfide species on the mineral surface. Solution measurement results suggest that the addition of chloride ions prior to sulfidization induces the transformation of more sulfide ions from pulp solution onto the mineral surface by the formation of more lead sulfide species. X-ray diffraction and energy-dispersive spectroscopy indicate that more lead sulfide species form on the mineral surface when chloride ions are added prior to sulfidization. These results demonstrate that the addition of chloride ions prior to sulfidization can significantly improve the sulfidization of cerussite, thereby enhancing the flotation performance.

  6. Metastable Polymerization of Sickle Hemoglobin in Droplets

    PubMed Central

    Aprelev, Alexey; Weng, Weijun; Zakharov, Mikhail; Rotter, Maria; Yosmanovich, Donna; Kwong, Suzanna; Briehl, Robin W.; Ferrone, Frank A.

    2007-01-01

    Sickle cell disease arises from a genetic mutation of one amino acid in each of the two hemoglobin β chains, leading to the polymerization of hemoglobin in the red cell upon deoxygenation, and is characterized by vascular crises and tissue damage due to the obstruction of small vessels by sickled cells. It has been an untested assumption that, in red cells that sickle, the growing polymer mass would consume monomers until the thermodynamically well-described monomer solubility was reached. By photolyzing droplets of sickle hemoglobin suspended in oil we find that polymerization does not exhaust the available store of monomers, but stops prematurely, leaving the solutions in a supersaturated, metastable state typically 20% above solubility at 37°C, though the particular values depend on the details of the experiment. We propose that polymer growth stops because the growing ends reach the droplet edge, whereas new polymer formation is thwarted by long nucleation times, since the hemoglobin concentration is lowered by depletion of monomers into the polymers that have formed. This finding suggests a new aspect to the pathophysiology of sickle cell disease, namely, that cells deoxygenated in the microcirculation are not merely undeformable, but will actively wedge themselves tightly against the walls of the microvasculature by a ratchet-like mechanism driven by the supersaturated solution. PMID:17493634

  7. Multistage Zeeman deceleration of metastable neon

    SciTech Connect

    Wiederkehr, Alex W.; Motsch, Michael; Hogan, Stephen D.; Andrist, Markus; Schmutz, Hansjuerg; Lambillotte, Bruno; Agner, Josef A.; Merkt, Frederic

    2011-12-07

    A supersonic beam of metastable neon atoms has been decelerated by exploiting the interaction between the magnetic moment of the atoms and time-dependent inhomogeneous magnetic fields in a multistage Zeeman decelerator. Using 91 deceleration solenoids, the atoms were decelerated from an initial velocity of 580 m/s to final velocities as low as 105 m/s, corresponding to a removal of more than 95% of their initial kinetic energy. The phase-space distribution of the cold, decelerated atoms was characterized by time-of-flight and imaging measurements, from which a temperature of 10 mK was obtained in the moving frame of the decelerated sample. In combination with particle-trajectory simulations, these measurements allowed the phase-space acceptance of the decelerator to be quantified. The degree of isotope separation that can be achieved by multistage Zeeman deceleration was also studied by performing experiments with pulse sequences generated for {sup 20}Ne and {sup 22}Ne.

  8. Propagation studies of metastable intermolecular composites (MIC).

    SciTech Connect

    Son, S. F.; Busse, J. R.; Asay, B. W.; Peterson, P. D.; Mang, J. T.; Bockmon, B.; Pantoya, M.

    2002-01-01

    Thermite materials are attractive energetic materials because the reactions are highly exothermic, have high energy densities, and high temperatures of combustion. However, the application of thermite materials has been limited because of the relative slow release of energy compared to other energetic materials. Engineered nano-scale composite energetic materials, such as Al/MoO{sub 3}, show promise for additional energetic material applications because they can react very rapidly. The composite material studied in this work consists of tailored, ultra-fine grain (30-200 nm diameter) aluminum particles that dramatically increase energy release rates of these thermite materials. These reactant clusters of fuel and oxidizer particles are in nearly atomic scale proximity to each other but are constrained from reaction until triggered. Despite the growing importance of nano-scale energetic materials, even the most basic combustion characteristics of these materials have not been thoroughly studied. This paper reports initial studies of the ignition and combustion of metastable intermolecular composites (MIC) materials. The goals were lo obtain an improved understanding of flame propagation mechanisms and combustion behaviors associated with nano-structured energetic materials. Information on issues such as reaction rate and behavior as a function of composition (mixture ratio), initial static charge, and particle size are essential and will allow scientists to design applications incorporating the benefits of these compounds. The materials have been characterized, specifically focusing on particle size, shape, distribution and morphology.

  9. Towards a Theory of Metastability in Open Quantum Dynamics.

    PubMed

    Macieszczak, Katarzyna; Guţă, Mădălin; Lesanovsky, Igor; Garrahan, Juan P

    2016-06-17

    By generalizing concepts from classical stochastic dynamics, we establish the basis for a theory of metastability in Markovian open quantum systems. Partial relaxation into long-lived metastable states-distinct from the asymptotic stationary state-is a manifestation of a separation of time scales due to a splitting in the spectrum of the generator of the dynamics. We show here how to exploit this spectral structure to obtain a low dimensional approximation to the dynamics in terms of motion in a manifold of metastable states constructed from the low-lying eigenmatrices of the generator. We argue that the metastable manifold is in general composed of disjoint states, noiseless subsystems, and decoherence-free subspaces.

  10. Rates and mechanisms of metastable deactivation over surfaces

    NASA Astrophysics Data System (ADS)

    Rawlins, W. T.; Marinelli, W. J.; Woodward, A. M.; Kaufman, D.; Upschulte, B. L.

    1991-02-01

    The objective of this project was to investigate mechanisms of energy disposal in the quenching of rare gas and molecular metastable species upon collisions with practical surfaces representative of plasma reactors. An apparatus was designed and constructed to generate a molecular beam of selected metastable species (He*, Ar*, N2*) and impinge the beam on clean or gas-dosed surfaces in an ultra high vacuum (UHV) chamber. The metastables were generated in a discharge-flow reactor, sampled and skimmed into a molecular beam, and directed into the UHV target chamber via two-stage differential pumping. A hemispherical, retarding potential electron energy analyzer was used to measure production rates and energy distributions of electrons ejected from the surface via the Penning ionization and Auger neutralization quenching mechanisms. The absence of significant electron ejection from metastable impingement is quite unexpected in light of previous investigations of this process for polished, high-purity, oriented single crystals.

  11. Slow metastable atomic hydrogen beam by optical pumping

    NASA Astrophysics Data System (ADS)

    Harvey, K. C.

    1982-05-01

    A beam source of atomic hydrogen is described which produces metastable atoms in the 2S1/2 state by optical pumping. A beam flux of 1016 atoms/s is generated in the ground state. The atoms in the beam pass in front of a lamp producing Lyman-β (1026 Å) radiation, where some of them are excited to the 3P level and cascade with a branching ratio of 12% to the 2S1/2 state. The number of metastable atoms produced is measured by quenching them with an electric field and detecting the emitted Lyman-α (1216 Å) radiation. Beams of 106 metastable atoms/s were obtained. Using the Bethe-Lamb theory for the quenching process, a metastable beam effective temperature of 100 K was measured.

  12. The Importance of Kinetic Metastability: Some Common Everyday Examples

    ERIC Educational Resources Information Center

    Jensen, William B.

    2015-01-01

    The importance of kinetic metastability is illustrated in detail using several common household products and recommendations are made for how this important and widespread, but often neglected, phenomenon can be more effectively presented in the introductory chemistry textbook.

  13. Metastable states in the Cd-As system

    SciTech Connect

    Nipan, G.D.; Grinberg, Ya.Kh.; Lazarev, V.B.

    1988-03-01

    Attempts to explain the appearance of metastable states in the system Cd-As have thus far been based only on thermographic experiments. In this work paths for metastable crystallization of cadmium arsenides in the phase space p-T-x are studied. The metastable diagrams were constructed using fragment of p-T and T-x projections of the p-T-x phase diagram. Thermodynamic analysis shows that metastable states of two types can be expected in the system Cd-As: (I) crystallization of Ca/sub 3/As/sub 2/ and arsenic instead of the equilibrium crystallization of CdAs/sub 2/; (II) crystallization of CdAs and arsenic or Cd/sub 3/As/sub 2/ instead of the formation of CdAs/sub 2/.

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

    NASA Astrophysics Data System (ADS)

    Nyström, Elsa; Alakangas, Lena

    2015-04-01

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

  15. Apparatus for use in sulfide chemiluminescence detection

    DOEpatents

    Spurlin, S.R.; Yeung, E.S.

    1987-01-06

    A method is described for chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction and a specifically designed chemiluminescence detection cell for the reaction. 4 figs.

  16. Apparatus for use in sulfide chemiluminescence detection

    DOEpatents

    Spurlin, Stanford R.; Yeung, Edward S.

    1987-01-01

    A method of chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction and a specifically designed chemiluminescence detection cell for the reaction.

  17. Discovery of a metastable Al20Sm4 phase

    DOE PAGESBeta

    Ye, Z.; Zhang, F.; Sun, Y.; Mendelev, M. I.; Ott, R. T.; Park, E.; Besser, M. F.; Kramer, M. J.; Ding, Z.; Wang, C. -Z.; et al

    2015-03-09

    In this study, we present an efficient genetic algorithm, integrated with experimental diffraction data, to solve a nanoscale metastable Al20Sm4 phase that evolves during crystallization of an amorphous magnetron sputtered Al90Sm10 alloy. The excellent match between calculated and experimental X-ray diffraction patterns confirms an accurate description of this metastable phase. Molecular dynamic simulations of crystal growth from the liquid phase predict the formation of disordered defects in the devitrified crystal.

  18. Selective Sulfidation of Lead Smelter Slag with Sulfur

    NASA Astrophysics Data System (ADS)

    Han, Junwei; Liu, Wei; Wang, Dawei; Jiao, Fen; Qin, Wenqing

    2016-02-01

    The selective sulfidation of lead smelter slag with sulfur was studied. The effects of temperature, sulfur dosage, carbon, and Na salts additions were investigated based on thermodynamic calculation. The results indicated that more than 96 pct of zinc in the slag could be converted into sulfides. Increasing temperature, sulfur dosage, or Na salts dosage was conducive to the sulfidation of the zinc oxides in the slag. High temperature and excess Na salts would result in the more consumption of carbon and sulfur. Carbon addition not only promoted the selective sulfidation but reduced the sulfur dosage and eliminated the generation of SO2. Iron oxides had a buffering role on the sulfur efficient utilization. The transformation of sphalerite to wurtzite was feasible under reducing condition at high temperature, especially above 1273 K (1000 °C). The growth of ZnS particles largely depended upon the roasting temperature. They were significantly increased when the temperature was above 1273 K (1000 °C), which was attributed to the formation of a liquid phase.

  19. Sulfide-mediated dehydrative glycosylation.

    PubMed

    Nguyen, H M; Chen, Y; Duron, S G; Gin, D Y

    2001-09-12

    The development of a new method for glycosylation with 1-hydroxy glycosyl donors employing dialkyl sulfonium reagents is described. The process employs the reagent combination of a dialkyl sulfide and triflic anhydride to effect anomeric bond constructions. This controlled dehydrative coupling of various C(1)-hemiacetal glycosyl donors and nucleophilic acceptors proceeds by way of a sulfide-to-sulfoxide oxidation process in which triflic anhydride serves as the oxidant.

  20. Chemical Bonding in Sulfide Minerals

    SciTech Connect

    Vaughan, David J.; Rosso, Kevin M.

    2006-08-01

    An understanding of chemical bonding and electronic structure in sulfide minerals is central to any attempt at understanding their crystal structures, stabilities and physical properties. It is also an essential precursor to understanding reactivity through modeling surface structure at the molecular scale. In recent decades, there have been remarkable advances in first principles (ab initio) methods for the quantitative calculation of electronic structure. These advances have been made possible by the very rapid development of high performance computers. Several review volumes that chart the applications of these developments in mineralogy and geochemistry are available (Tossell and Vaughan, 1992; Cygan and Kubicki, 2001). An important feature of the sulfide minerals is the diversity of their electronic structures, as evidenced by their electrical and magnetic properties (see Pearce et al. 2006, this volume). Thus, sulfide minerals range from insulators through semiconductors to metals, and exhibit every type of magnetic behavior. This has presented problems for those attempting to develop bonding models for sulfides, and also led to certain misconceptions regarding the kinds of models that may be appropriate. In this chapter, chemical bonding and electronic structure models for sulfides are reviewed with emphasis on more recent developments. Although the fully ab initio quantitative methods are now capable of a remarkable degree of sophistication in terms of agreement with experiment and potential to interpret and predict behavior with varying conditions, both qualitative and more simplistic quantitative approaches will also be briefly discussed. This is because we believe that the insights which they provide are still helpful to those studying sulfide minerals. In addition to the application of electronic structure models and calculations to solid sulfides, work on sulfide mineral surfaces (Rosso and Vaughan 2006a,b) and solution complexes and clusters (Rickard

  1. Mars surface weathering products and spectral analogs: Palagonites and synthetic iron minerals

    NASA Technical Reports Server (NTRS)

    Golden, D. C.; Ming, D. W.; Morris, R. V.; Lauer, H. V., Jr.

    1992-01-01

    There are several hypotheses regarding the formation of Martian surface fines. These surface fines are thought to be products of weathering processes occurring on Mars. Four major weathering environments of igneous rocks on Mars have been proposed; (1) impact induced hydrothermal alterations; (2) subpermafrost igneous intrusion; (3) solid-gas surface reactions; and (4) subaerial igneous intrusion over permafrost. Although one or more of these processes may be important on the Martian surface, one factor in common for all these processes is the reaction of solid or molten basalt with water (solid, liquid, or gas). These proposed processes, with the exception of solid-gas surface reactions, are transient processes. The most likely product of transient hydrothermal processes are layer silicates, zeolites, hydrous iron oxides and palagonites. The long-term instability of hydrous clay minerals under present Martian conditions has been predicted; however, the persistence of such minerals due to slow kinetics of dehydration, or entrapment in permafrost, where the activity of water is high, can not be excluded. Anhydrous oxides of iron (e.g., hematite and maghemite) are thought to be stable under present Martian surface conditions. Oxidative weathering of sulfide minerals associated with Martian basalts has been proposed. Weathering of sulfide minerals leads to a potentially acidic permafrost and the formation of Fe(3) oxides and sulfates. Weathering of basalts under acidic conditions may lead to the formation of kaolinite through metastable halloysite and metahalloysite. Kaolinite, if present, is thought to be a thermodynamically stable phase at the Martian surface. Fine materials on Mars are important in that they influence the surface spectral properties; these fines are globally distributed on Mars by the dust storms and this fraction will have the highest surface area which should act as a sink for most of the absorbed volatiles near the surface of Mars. Therefore

  2. Sulfidization of lacustrine glacial clay upon Holocene marine transgression (Arkona Basin, Baltic Sea)

    NASA Astrophysics Data System (ADS)

    Holmkvist, Lars; Kamyshny, Alexey; Brüchert, Volker; Ferdelman, Timothy G.; Jørgensen, Bo Barker

    2014-10-01

    Towards the end of the last deglaciation more than 13,500 years ago the southern Baltic Sea was a freshwater lake, the Baltic Ice Lake, for several thousand years during which iron-rich, organic-poor clay was deposited. The modern brackish-marine stage started about 8600 years ago with the deposition of organic-rich mud, which is today characterized by high rates of sulfate reduction and high concentrations of free sulfide. We studied the iron-sulfur diagenesis in gravity cores from the Arkona Basin, SW Baltic Sea, to track the progressing sulfidization front in the buried Ice Lake sediment. The geochemical zonation was unusual as the sulfate concentration dropped steeply by two thirds below which it increased again due to a deep sulfate reservoir. The reservoir had been established during the early Holocene marine period as sulfate and other seawater ions diffused down into the lake sediment for several thousand years. Sulfur isotope analyses confirmed its origin as seawater sulfate, while its oxygen isotope composition indicated a microbially catalyzed equilibration with ambient interstitial water, decoupled from net sulfate reduction. Today, hydrogen sulfide diffuses from the marine mud down into the lake sediment where a black band with high magnetic susceptibility and high iron monosulfide, greigite and elemental sulfur content shows progressing sulfidization of the large pool of solid-phase reactive iron. Dissolved iron from the deep Ice Lake sediment diffuses up to the sulfide front and provides a small supplement to the solid Fe(III) pool as a sulfide sink. Pyrite formation at the sulfidization front may involve surface-bound zero-valent sulfur while, above the front, polysulfides are in equilibrium with the system hydrogen sulfide - polysulfide - rhombic sulfur and may not be important for further pyrite formation. The Holocene iron-sulfur diagenesis observed in the Arkona Basin represents an important transitional state for post-glacial transgressions

  3. Use of bauxite residue (red mud) as a low cost sorbent for sulfide removal in polluted water remediation.

    PubMed

    Sheng, Yanqing; Sun, Qiyao; Sun, Ruichuan; Burke, Ian T; Mortimer, Robert J G

    2016-01-01

    Sulfide is an important pollutant in aqueous systems. Sulfide removal from polluted waters is required prior to discharge. Red mud (RM) is a solid waste of bauxite processing that is rich in reactive iron oxides and consequently has the potential to be used to remove sulfide from aqueous systems. A series of experiments was undertaken using raw and sintered RM to remove sulfide from waters. RM was highly efficient at sulfide removal (average 75% sulfide removal at initial concentration of ∼5 mg L(-1), with 500 mg L(-1) RM addition) due to both physical adsorption (high specific area) and chemical reaction (with amorphous Fe). Sintered RM, which has a lower surface area and lower mineral reactivity, was much less efficient at removing sulfide (∼20% removal under equivalent experimental conditions). Furthermore, concomitant metal release from raw RM was lower than for sintered RM during the sulfide removal process. The results showed that raw RM is a potentially suitable material for sulfide removal from polluted waters and consequently could be used as a low cost alternative treatment in certain engineering applications. PMID:27438240

  4. The Corrosion Behavior of Carbon Steel in Sulfide Aqueous Media at 30°C

    NASA Astrophysics Data System (ADS)

    El Mendili, Yassine; Abdelouas, Abdesselam; Bardeau, Jean-François

    2014-04-01

    In this paper, we studied the effect of sulfide ions on the corrosion behavior of carbon steel to simulate the geological disposal of high-level radioactive waste. In geological storage conditions, sulfidogenic environment was sustained by sulfate-reducing bacteria. Corrosion tests were conducted in systems in a controlled atmosphere of 5% H2/N2. Batch experiments were conducted at 30°C for 1 month with steel coupons immersed in Na2S solutions. The structural characterization of the corrosion products was investigated by scanning electron microscope/energy dispersive x-ray spectroscopy, confocal micro-Raman spectrometry, and x-ray diffraction. In the absence of sulfide ion, a magnetite (Fe3O4) corrosion product layer was formed on steel surface while in the presence of sulfide ions we observed the formation of a poorly crystallized irons sulfide at low-sulfide concentration (1 mg/L) and a solid adherent pyrrhotite layer at higher sulfide concentration (5-15 mg/L). The strong drop in steel corrosion rate with sulfide concentration was revealed and related to the formation of well-crystallized pyrrhotite.

  5. Reaction of Hydrogen Sulfide with Oxygen in the Presence ofSulfite

    SciTech Connect

    Weres, Oleh; Tsao, Leon

    1983-01-01

    Commonly, abatement of hydrogen sulfide emissions from a geothermal powerplant requires that hydrogen sulfide dissolved in the cooling water be eliminated by chemical reaction. Oxidation by atmospheric oxygen is the preferred reaction, but requires a suitable catalyst. Nickel is the most potent and thereby cheapest catalyst for this purpose. One Mg/L nickel in the cooling water would allow 99% removal of hydrogen sulfide to be attained. A major drawback of catalytic air oxidation is that colloidal sulfur is a major reaction product; this causes rapid sludge accumulation and deposition of sulfur scale. The authors studied the kinetics and product distribution of the reaction of hydrogen sulfide with oxygen, catalyzed by nickel. Adding sodium sulfite to the solution completely suppresses formation of colloidal sulfur by converting it to thiosulfate. The oxidation reaction is an autocatalytic, free radical chain reaction. A rate expression for this reaction and a detailed reaction mechanism were developed. Nickel catalyzes the chain initiation step, and polysulfidoradical ions propagate the chains. Several complexes of iron and cobalt were also studied. Iron citrate and iron N-hydroxyEDT are the most effective iron based catalysts. Uncomplexed cobalt is as effective as nickel, but forms a precipitate of cobalt oxysulfide and is too expensive for practical use.

  6. Reaction of hydrogen sulfide with oxygen in the presence of sulfite

    SciTech Connect

    Weres, O.; Tsao, L.

    1983-01-14

    Commonly, abatement of hydrogen sulfide emission from a geothermal powerplant requires that hydrogen sulfide dissolved in the cooling water be eliminated by chemical reaction. Oxidation by atmospheric oxygen is the preferred reaction, but requires a suitable catalyst. Nickel is the most potent and thereby cheapest catalyst for this purpose. One mg/L nickel in the cooling water would allow 99% removal of hydrogen sulfide to be attained. A major drawback of catalytic air oxidation is that colloidal sulfur is a major reaction product; this causes rapid sludge accumulation and deposition of sulfur scale. We studied the kinetics and product distribution of the reaction of hydrogen sulfide with oxygen, catalyzed by nickel. Adding sodium sulfite to the solution completely suppresses formation of colloidal sulfur by converting it to thiosulfate. The oxidation reaction is an autocatalytic, free radical chain reaction. A rate expression for this reaction and a detailed reaction mechanism were developed. Nickel catalyzes the chain initiation step, and polysulfidoradical ions propagate the chains. Several complexes of iron and cobalt were also studied. Iron citrate and iron N-hydroxyEDTA are the most effective iron based catalysts. Uncomplexed cobalt is as effective as nickel, but forms a precipitate of cobalt oxysulfide and is too expensive for practical use. 33 figures, 9 tables.

  7. The reactions of cobalt, iron and nickel in SO-2 atmospheres: Similarities and differences

    NASA Technical Reports Server (NTRS)

    Jacobson, N. S.; Worrell, W. L.

    1984-01-01

    The reactions of cobalt, iron and nickel in SO2 atmospheres are reviewed and compared. A mixed oxide-sulfide product layer is observed in all cases. Cobalt and nickel exhibits similar behavior. The observed rates are near the sulfidation rates, and the reaction rate is strongly influenced by the outward diffusion of metal through an interconnected sulfide network. A continuous interconnected sulfide is not observed in the oxide-sulfide scales formed on iron, and the reaction rates are more difficult to summarize. The differences and similarities among the three metals are explained in terms of the absence of scale-gas equilibrium and the ratio of the metal diffusivity in the corresponding oxide and sulfide.

  8. The reactions of cobalt, iron and nickel in SO2 atmospheres Similarities and differences

    NASA Technical Reports Server (NTRS)

    Jacobson, N. S.; Worrell, W. L.

    1985-01-01

    The reactions of cobalt, iron and nickel in SO2 atmospheres are reviewed and compared. A mixed oxide-sulfide product layer is observed in all cases. Cobalt and nickel exhibit similar behavior. The observed rates are near the sulfidation rates, and the reaction rate is strongly influenced by the outward diffusion of metal through an interconnected sulfide network. A continuous interconnected sulfide is not observed in the oxide-sulfide scales formed on iron, and the reaction rates are more difficult to summarize. The differences and similarities among the three metals are explained in terms of the absence of scale-gas equilibrium and the ratio of the metal diffusivity in the corresponding oxide and sulfide.

  9. Quench-Condensed Microalloyed Particles: a Microscopic View of Solid Solubility and Metastability

    NASA Astrophysics Data System (ADS)

    Lamberti, Vincent Edward

    Solid solubility and metastability in noble-metal and iron-silver alloys have been studied from the perspective of microalloyed particles. Samples were obtained through a novel, gram-scale technique that consisted of cocondensation of two elemental metal vapors with a large excess of inert gas on the reaction surface of a rotating cryostat at 77 K. This technique permitted greater control of both particle size and composition than conventional gas aggregation methods. The chemical and physical characteristics of the microalloys have been elaborated through chemical analysis, x-ray diffraction, electron microscopy, temperature-programmed mass spectrometry, EXAFS, XPS and Moessbauer spectroscopy. Electron microscopy indicated the microstructures of copper-gold and copper-silver microalloys prepared in sulfur hexafluoride to consist of discrete collections of crystallites suspended in amorphous "baths". The average dimensions of the crystallites were <100 A, while the aggregates spanned hundreds of nanometers. The microstructures of both systems were metastable. The EXAFS of a copper-silver microalloy showed it to be stiffer, as well as more disordered, than a homometallic copper product. The EXAFS also showed no detectable Cu-Ag contacts, but suggested the existence (through a "missing-atom" effect) of a large number of disordered copper sites. Moessbauer spectra of an iron -silver microalloy prepared in xenon revealed the presence of a superparamagnetic alloy phase characterized by a blocking temperature of approximately 45 K. Cocondensations of iron vapor with excess sulfur hexafluoride produced ultrafine (dimensions ~ 100 A), amorphous particles that were decorated with a -CF_{2^-} polymer. The formation of the polymer was attributed to reaction of the iron with the matrix and adventitious organic compounds--that is, to activation of S-F and C-H bonds. Matrix isolation experiments indicated that, although inert in their ground-state configuration, photoexcited (4p

  10. Metastable NAT in Ice-Clouds

    NASA Astrophysics Data System (ADS)

    Weiss, Fabian; Kubel, Frank; Gálvez, Óscar; Hoelzel, Markus; Parker, Stewart F.; Iannarelli, Riccardo; Rossi, Michel J.; Grothe, Hinrich

    2015-04-01

    Polar Stratospheric Clouds and Cirrus Clouds contain, besides pure water ice, a rather large fraction of various hydrates. These are very important for the formation of the cloud, which is a yet not well understood process. We recently solved the structure of a metastable NAT phase (alpha-NAT), we believe to not only be present, but playing a major role in the formation of clouds. On the basis of previous work on this phase by Grothe et al. [1], we enhanced the production of alpha-NAT to the point, where we could produce enough sample to do neutron diffraction. This enabled us to solve the structure. Our quantum mechanical calculations, using this newly found structure, show a large affinity towards water-ice. With this in mind, we interlaced our results with the experiments of R. Iannarelli [2] to derive a new 3-step NAT-formation mechanism in ice-clouds, which could explain some of the observed kinetics better than the mechanism postulated in Zondlo et al. [3]. 1. Grothe, H., Tizek, H., Waller, D. & Stokes, D. The crystallization kinetics and morphology of nitric acid trihydrate. Phys. Chem. Chem. Phys., 8, 2232-2239 (2006) 2. Iannarelli, R. Multidiagnostic Observations on HCl and HNO3 Hydrate Films in the Temperature Range 170-205K: A Kinetic Study. PhD Thesis 21791, ETH Zürich, (2013). 3. Zondlo, M.A., Hudson, P.K., Prenni A.J. & Tolbert, M.A. Chemistry and microphysics of polar stratospheric clouds and Cirrus clouds. Ann. Rev. Phys. Chem., 51, 473-499 (2000).

  11. A field investigation of the relationship between zinc and acid volatile sulfide concentrations in freshwater sediments

    USGS Publications Warehouse

    Ankley, Gerald T.; Liber, Karsten; Call, Daniel J.; Markee, Thomas P.; Canfield, Timothy J.; Ingersoll, Christopher G.

    1996-01-01

    Understanding relationships between cationic metals such as cadmium, copper, nickel, lead and zinc, and amorphous iron sulfides, measured as acid volatile sulfide (AVS), is key to predicting metal bioavailability and toxicity insediments. The objective of the present study was to assess seasonal and spatial variations of AVS in freshwater sediments contaminated with zinc. Sediments were sampled from three streams with varying levels of zinc contamination at two different times, March and June of 1995, representing cold- and warm-weather situations. Interstitial (pore) water concentrations of zinc, and solid phase concentrations of AVS and zinc were measured in surficial and deep sediment horizons. Toxicity tests (10-d) with the amphipodHyalella azteca were conducted using intact cores. Sediment zinc concentrations from six sites within the primary test stream differed by about five-fold, and also varied seasonally. Acid volatile sulfide concentrations were generally lower than those of zinc, and pore water zinc concentrations typically were elevated. There was a positive correlation between solid-phase AVS and zinc concentrations, suggesting that the system was dominated by zinc, as opposed to iron sulfides. In contrast to expectations arising from some studies of seasonal variations of AVS in iron-dominated systems, AVS concentrations were smaller in June than in March. However, this was likely due to a major storm event and associated sediment scouring before the June sampling, rather than to seasonal processes related to variations in temperature and dissolved oxygen. Based upon an indirect analysis of depth variations in AVS, there was some indication that zinc sulfide might be less prone to oxidation than iron sulfide. There was a strong correlation between toxicity of the sediment samples toH. azteca and interstitial water concentrations of zinc; however, the possible contribution of other contaminants to sediment toxicity cannot be dismissed.

  12. Wet oxidation of oil-bearing sulfide wastes

    SciTech Connect

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

    1991-01-01

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

  13. Extended Neural Metastability in an Embodied Model of Sensorimotor Coupling

    PubMed Central

    Aguilera, Miguel; Bedia, Manuel G.; Barandiaran, Xabier E.

    2016-01-01

    The hypothesis that brain organization is based on mechanisms of metastable synchronization in neural assemblies has been popularized during the last decades of neuroscientific research. Nevertheless, the role of body and environment for understanding the functioning of metastable assemblies is frequently dismissed. The main goal of this paper is to investigate the contribution of sensorimotor coupling to neural and behavioral metastability using a minimal computational model of plastic neural ensembles embedded in a robotic agent in a behavioral preference task. Our hypothesis is that, under some conditions, the metastability of the system is not restricted to the brain but extends to the system composed by the interaction of brain, body and environment. We test this idea, comparing an agent in continuous interaction with its environment in a task demanding behavioral flexibility with an equivalent model from the point of view of “internalist neuroscience.” A statistical characterization of our model and tools from information theory allow us to show how (1) the bidirectional coupling between agent and environment brings the system closer to a regime of criticality and triggers the emergence of additional metastable states which are not found in the brain in isolation but extended to the whole system of sensorimotor interaction, (2) the synaptic plasticity of the agent is fundamental to sustain open structures in the neural controller of the agent flexibly engaging and disengaging different behavioral patterns that sustain sensorimotor metastable states, and (3) these extended metastable states emerge when the agent generates an asymmetrical circular loop of causal interaction with its environment, in which the agent responds to variability of the environment at fast timescales while acting over the environment at slow timescales, suggesting the constitution of the agent as an autonomous entity actively modulating its sensorimotor coupling with the world. We

  14. Atomic layer deposition of metastable β-Fe₂O₃ via isomorphic epitaxy for photoassisted water oxidation.

    PubMed

    Emery, Jonathan D; Schlepütz, Christian M; Guo, Peijun; Riha, Shannon C; Chang, Robert P H; Martinson, Alex B F

    2014-12-24

    We report the growth and photoelectrochemical (PEC) characterization of the uncommon bibyite phase of iron(III) oxide (β-Fe2O3) epitaxially stabilized via atomic layer deposition on an conductive, transparent, and isomorphic template (Sn-doped In2O3). As a photoanode, unoptimized β-Fe2O3 ultrathin films perform similarly to their ubiquitous α-phase (hematite) counterpart, but reveal a more ideal bandgap (1.8 eV), a ∼0.1 V improved photocurrent onset potential, and longer wavelength (>600 nm) spectral response. Stable operation under basic water oxidation justifies further exploration of this atypical phase and motivates the investigation of other unexplored metastable phases as new PEC materials.

  15. Arsenic Repartitioning during Biogenic Sulfidization and Transformation of Ferrihydrite

    SciTech Connect

    Kocar, B.; Borch, T; Fendorf, S

    2010-01-01

    Iron (hydr)oxides are strong sorbents of arsenic (As) that undergo reductive dissolution and transformation upon reaction with dissolved sulfide. Here we examine the transformation and dissolution of As-bearing ferrihydrite and subsequent As repartitioning amongst secondary phases during biotic sulfate reduction. Columns initially containing As(V)-ferrihydrite coated sand, inoculated with the sulfate reducing bacteria Desulfovibrio vulgaris (Hildenborough), were eluted with artificial groundwater containing sulfate and lactate. Rapid and consistent sulfate reduction coupled with lactate oxidation is observed at low As(V) loading (10% of the adsorption maximum). The dominant Fe solid phase transformation products at low As loading include amorphous FeS within the zone of sulfate reduction (near the inlet of the column) and magnetite downstream where Fe(II){sub (aq)} concentrations increase; As is displaced from the zone of sulfidogenesis and Fe(III){sub (s)} depletion. At high As(V) loading (50% of the adsorption maximum), sulfate reduction and lactate oxidation are initially slow but gradually increase over time, and all As(V) is reduced to As(III) by the end of experimentation. With the higher As loading, green rust(s), as opposed to magnetite, is a dominant Fe solid phase product. Independent of loading, As is strongly associated with magnetite and residual ferrihydrite, while being excluded from green rust and iron sulfide. Our observations illustrate that sulfidogenesis occurring in proximity with Fe (hydr)oxides induce Fe solid phase transformation and changes in As partitioning; formation of As sulfide minerals, in particular, is inhibited by reactive Fe(III) or Fe(II) either through sulfide oxidation or complexation.

  16. Arsenic repartitioning during biogenic sulfidization and transformation of ferrihydrite

    SciTech Connect

    Kocar, Benjamin D.; Borch, Thomas; Fendorf, Scott

    2012-04-30

    Iron (hydr)oxides are strong sorbents of arsenic (As) that undergo reductive dissolution and transformation upon reaction with dissolved sulfide. Here we examine the transformation and dissolution of As-bearing ferrihydrite and subsequent As repartitioning amongst secondary phases during biotic sulfate reduction. Columns initially containing As(V)-ferrihydrite coated sand, inoculated with the sulfate reducing bacteria Desulfovibrio vulgaris (Hildenborough), were eluted with artificial groundwater containing sulfate and lactate. Rapid and consistent sulfate reduction coupled with lactate oxidation is observed at low As(V) loading (10% of the adsorption maximum). The dominant Fe solid phase transformation products at low As loading include amorphous FeS within the zone of sulfate reduction (near the inlet of the column) and magnetite downstream where Fe(II)(aq) concentrations increase; As is displaced from the zone of sulfidogenesis and Fe(III)(s) depletion. At high As(V) loading (50% of the adsorption maximum), sulfate reduction and lactate oxidation are initially slow but gradually increase over time, and all As(V) is reduced to As(III) by the end of experimentation. With the higher As loading, green rust(s), as opposed to magnetite, is a dominant Fe solid phase product. Independent of loading, As is strongly associated with magnetite and residual ferrihydrite, while being excluded from green rust and iron sulfide. Our observations illustrate that sulfidogenesis occurring in proximity with Fe (hydr)oxides induce Fe solid phase transformation and changes in As partitioning; formation of As sulfide minerals, in particular, is inhibited by reactive Fe(III) or Fe(II) either through sulfide oxidation or complexation.

  17. Arsenic repartitioning during biogenic sulfidization and transformation of ferrihydrite

    NASA Astrophysics Data System (ADS)

    Kocar, Benjamin D.; Borch, Thomas; Fendorf, Scott

    2010-02-01

    Iron (hydr)oxides are strong sorbents of arsenic (As) that undergo reductive dissolution and transformation upon reaction with dissolved sulfide. Here we examine the transformation and dissolution of As-bearing ferrihydrite and subsequent As repartitioning amongst secondary phases during biotic sulfate reduction. Columns initially containing As(V)-ferrihydrite coated sand, inoculated with the sulfate reducing bacteria Desulfovibrio vulgaris (Hildenborough), were eluted with artificial groundwater containing sulfate and lactate. Rapid and consistent sulfate reduction coupled with lactate oxidation is observed at low As(V) loading (10% of the adsorption maximum). The dominant Fe solid phase transformation products at low As loading include amorphous FeS within the zone of sulfate reduction (near the inlet of the column) and magnetite downstream where Fe(II) (aq) concentrations increase; As is displaced from the zone of sulfidogenesis and Fe(III) (s) depletion. At high As(V) loading (50% of the adsorption maximum), sulfate reduction and lactate oxidation are initially slow but gradually increase over time, and all As(V) is reduced to As(III) by the end of experimentation. With the higher As loading, green rust(s), as opposed to magnetite, is a dominant Fe solid phase product. Independent of loading, As is strongly associated with magnetite and residual ferrihydrite, while being excluded from green rust and iron sulfide. Our observations illustrate that sulfidogenesis occurring in proximity with Fe (hydr)oxides induce Fe solid phase transformation and changes in As partitioning; formation of As sulfide minerals, in particular, is inhibited by reactive Fe(III) or Fe(II) either through sulfide oxidation or complexation.

  18. Structure of as-deposited and heat-treated iron-zinc coatings from chloride bath

    SciTech Connect

    Drewien, C.A.; Goldstein, J.I.; Marder, A.R.

    1993-09-01

    The iron content, phase constitution, and microstructure of electrodeposited iron-zinc alloy (EZA) coatings, deposited from chloride baths, is described for as-deposited and heat-treated conditions of coatings containing bulk iron contents of 6, 8, 10, and 13 w/o. The observed influence of current density upon iron content, which in turn influences the phase constitution and microstructure of the coatings, is reported. The microstructure, composed of non-equilibrium phases that have nanometer grain sizes, is illustrated and described with respect to iron content, crystallography, and morphology. As-deposited {eta} phase coatings undergo transformations through a sequence of metastable phases when heated. The sequence of phase transformations varies with iron content, but the mechanisms of phase transformation from the as-deposited eta phase to the metastable G phase was found to be similar in 6, 8, and 10 w/o Fe coatings. Microstructural, compositional, and crystallographic changes associated with this phase transformation are discussed.

  19. New spectrophotometric methods for the determinations of hydrogen sulfide present in the samples of lake water, industrial effluents, tender coconut, sugarcane juice and egg

    NASA Astrophysics Data System (ADS)

    Shyla, B.; Nagendrappa, G.

    2012-10-01

    The new methods are working on the principle that iron(III) is reduced to iron(II) by hydrogen sulfide, catechol and p-toluidine the system 1/hydrogen sulfide the system 2, in acidic medium followed by the reduced iron forming complex with 1,10-phenanthroline with λmax 510 nm. The other two methods are based on redox reactions between electrolytically generated manganese(III) sulfate taken in excess and hydrogen sulfide followed by the unreacted oxidant oxidizing diphenylamine λmax 570 the system 3/barium diphenylamine sulphonate λmax 540 nm, the system 4. The increase/decrease in the color intensity of the dye products of the systems 1 and 2 or 3 and 4 are proportional to the concentration of hydrogen sulfide with its quantification range 0.035-1.40 μg ml-1/0.14-1.40 μg ml-1.

  20. New spectrophotometric methods for the determinations of hydrogen sulfide present in the samples of lake water, industrial effluents, tender coconut, sugarcane juice and egg.

    PubMed

    Shyla, B; Nagendrappa, G

    2012-10-01

    The new methods are working on the principle that iron(III) is reduced to iron(II) by hydrogen sulfide, catechol and p-toluidine the system 1/hydrogen sulfide the system 2, in acidic medium followed by the reduced iron forming complex with 1,10-phenanthroline with λ(max) 510 nm. The other two methods are based on redox reactions between electrolytically generated manganese(III) sulfate taken in excess and hydrogen sulfide followed by the unreacted oxidant oxidizing diphenylamine λ(max) 570 the system 3/barium diphenylamine sulphonate λ(max) 540 nm, the system 4. The increase/decrease in the color intensity of the dye products of the systems 1 and 2 or 3 and 4 are proportional to the concentration of hydrogen sulfide with its quantification range 0.035-1.40 μg ml(-1)/0.14-1.40 μg ml(-1).

  1. Reactivity of Sulfide Mineral Surfaces

    SciTech Connect

    Rosso, Kevin M.; Vaughan, David J.

    2006-08-01

    In the preceding chapter, the fundamental nature of sulfide mineral surfaces has been discussed, and the understanding we have of the ways in which the surface differs from a simple truncation of the bulk crystal structure reviewed. This naturally leads on to considering our understanding of sulfide surface chemistry, in the sense of how sulfide surfaces interact and react, particularly with gases and liquids. As noted elsewhere in this volume, research on sulfide mineral surfaces and surface reactivity is a relatively recent concern of mineralogists and geochemists, partly prompted by the availability of new imaging and spectroscopic methods, powerful computers and new computer algorithms. There has been a significantly longer history of sulfide mineral surface research associated with technologists working with, or within, the mining industry. Here, electrochemical methods, sometimes combined with analytical and spectroscopic techniques, have been used to probe surface chemistry. The motivation for this work has been to gain a better understanding of the controls of leaching reactions used to dissolve out metals from ores, or to understand the chemistry of the froth flotation systems used in concentrating the valuable (usually sulfide) minerals prior to metal extraction. The need for improved metal extraction technologies is still a major motivation for research on sulfide surfaces, but in the last couple of decades, new concerns have become important drivers for such work. In particular, much greater awareness of the negative environmental impact of acid and toxic metal-bearing waters derived from breakdown of sulfide minerals at former mining operations has prompted research on oxidation reactions, and on sorption of metals at sulfide surfaces. At the interface between fundamental geochemistry and industrial chemistry, the role of sulfide substrates in catalysis, and in the self-assembly and functionalization of organic molecules, has become an area of

  2. Deposition of Biogenic Iron Minerals in a Methane Oxidizing Microbial Mat

    PubMed Central

    Wrede, Christoph; Dreier, Anne; Heller, Christina; Reitner, Joachim; Hoppert, Michael

    2013-01-01

    The syntrophic community between anaerobic methanotrophic archaea and sulfate reducing bacteria forms thick, black layers within multi-layered microbial mats in chimney-like carbonate concretions of methane seeps located in the Black Sea Crimean shelf. The microbial consortium conducts anaerobic oxidation of methane, which leads to the formation of mainly two biomineral by-products, calcium carbonates and iron sulfides, building up these chimneys. Iron sulfides are generated by the microbial reduction of oxidized sulfur compounds in the microbial mats. Here we show that sulfate reducing bacteria deposit biogenic iron sulfides extra- and intracellularly, the latter in magnetosome-like chains. These chains appear to be stable after cell lysis and tend to attach to cell debris within the microbial mat. The particles may be important nuclei for larger iron sulfide mineral aggregates. PMID:23843725

  3. Stable and Metastable Equilibria in the Pb-Cd System

    NASA Astrophysics Data System (ADS)

    Chuang, Ying-Yu; Paik, J.-S.; Zhang, C.; Perepezko, J. H.; Chang, Y. A.

    2013-07-01

    Thermodynamic and phase diagram data in the Pb-Cd system are reevaluated. A substitutional solution model is used for the liquid and fcc and hcp phases. The stable and metastable equilibria of this system are calculated using the thermodynamic equations derived from equilibrium data. Besides the well-established eutectic reaction at 521 K (248 °C), one stable monotectic reaction at 548 K (275 °C) is found due to the existence of a stable liquid miscibility gap. The stable monotectic reaction has been missed in all previous evaluations. Experimental verifications of the stable and metastable phase equilibria are provided using droplet samples and undercooled liquid alloys. A differential thermal analysis (DTA) method is applied to determine the phase reaction temperatures using both traditional heating and cooling processes and a specially designed cycling process. Additional microstructural evidence is used to elucidate the nature of the phase reactions. The refined thermodynamic descriptions are based upon both the thermochemical and phase diagram stable and metastable data. The agreement between the calculated and experimental data is good. All experimental stable and metastable results are well explained by the new Pb-Cd phase diagram calculations within the experimental accuracy limits. Combined experimental and thermodynamic modeling procedures developed for determining the stable and metastable phase equilibria yield a highly reliable overall phase diagram assessment and a quantitative basis for the interpretation of non-equilibrium solidification processing.

  4. Assaying the catalytic potential of transition metal sulfides for abiotic carbon fixation

    NASA Astrophysics Data System (ADS)

    Cody, G. D.; Boctor, N. Z.; Brandes, J. A.; Filley, T. R.; Hazen, R. M.; Yoder, H. S.

    2004-05-01

    A suite of nickel, cobalt, iron, copper, and zinc containing sulfides are assayed for the promotion of a model carbon fixation reaction with relevance to local reducing environments of the early Earth. The assay tests the promotion of hydrocarboxylation (the Koch reaction) wherein a carboxylic acid is synthesized via carbonyl insertion at a metal-sulfide-bound alkyl group. The experimental conditions are chosen for optimal assay, i.e., high reactant concentrations and pressures (200 MPa) to enhance chemisorption, and high temperature (250°C) to enhance reaction kinetics. All of the metal sulfides studied, with the exception CuS, promote hydrocarboxylation. Two other significant reactions involve the catalytic reduction of CO to form a surface-bound methyl group, detected after nucleophilic attack by nonane thiol to form methyl nonyl sulfide, and the formation of dinonyl sulfide via a similar reaction. Estimation of the catalytic turnover frequencies for each of the metal sulfides with respect to each of the primary reactions reveals that NiS, Ni 3S 2, and CoS perform comparably to commonly employed industrial catalysts. A positive correlation between the yield of primary product to NiS and Ni 3S 2 surface areas provides strong evidence that the reactions are surface catalytic in these cases. The sulfides FeS and Fe (1-x)S are unique in that they exhibit evidence of extensive dissolution, thus, complicating interpretation regarding heterogeneous vs. homogeneous catalysis. With the exception of CuS, each of the metal sulfides promotes reactions that mimic key intermediate steps manifest in the mechanistic details of an important autotrophic enzyme, acetyl-CoA synthase. The relatively high temperatures chosen for assaying purposes, however, are incompatible with the accumulation of thioesters. The results of this study support the hypothesis that transition metal sulfides may have provided useful catalytic functionality for geochemical carbon fixation in a prebiotic

  5. Catalytic oxidation of aqueous hydrogen sulfide in the presence of sulfite

    SciTech Connect

    Weres, O.; Tsao, L.; Chhatre, R.M.

    1985-06-01

    Nickel sulfate catalyzes the reaction of hydrogen sulfide with oxygen in aqueous solution. This reaction was studied, and an empirical rate expression and a reaction mechanism were deduced. The rate of oxidation is independent of oxygen concentration and pH over the range investigated. The reaction rate is one half order in nickel, and it changes from second to first order in sulfide with increasing concentration. The oxidation reaction is an autocatalytic, free radical chain reaction. Nickel catalyzes the chain initiation step, and polysulfido radical ions propagate the chains. Colloidal sulfur is a major, frequently undesirable reaction product. Sodium sulfite suppresses formation of colloidal sulfur by converting it to thiosulfate. Cobalt is an equally potent catalyst, but a colloidal dispersion of cobalt oxysulfide is produced. Iron compounds are much weaker catalysts; iron citrate and iron HEDTA (n-hydroxyethylenediaminetriacetic acid) were among those tested. 24 references, 15 figures, 3 tables.

  6. Sulfide Stability of Planetary Basalts

    NASA Technical Reports Server (NTRS)

    Caiazza, C. M.; Righter, K.; Gibson, E. K., Jr.; Chesley, J. T.; Ruiz, J.

    2004-01-01

    The isotopic system, 187Re 187Os, can be used to determine the role of crust and mantle in magma genesis. In order to apply the system to natural samples, we must understand variations in Re/Os concentrations. It is thought that low [Os] and [Re] in basalts can be attributed to sulfide (FeS) saturation, as Re behaves incompatibly to high degrees of evolution until sulfide saturation occurs [1]. Previous work has shown that lunar basalts are sulfide under-saturated, and mid-ocean ridge, ocean-island and Martian (shergottites) basalts are saturated [2,3]. However, little is known about arc basalts. In this study, basaltic rocks were analyzed across the Trans-Mexican Volcanic Belt.

  7. A Reaction Involving Oxygen and Metal Sulfides.

    ERIC Educational Resources Information Center

    Hill, William D. Jr.

    1986-01-01

    Describes a procedure for oxygen generation by thermal decomposition of potassium chlorate in presence of manganese dioxide, reacted with various sulfides. Provides a table of sample product yields for various sulfides. (JM)

  8. Long-Lived Metastable bcc Phase during Ordering of Micelles

    NASA Astrophysics Data System (ADS)

    Bang, Joona; Lodge, Timothy P.

    2005-03-01

    We report a metastable bcc phase that intervenes between a disordered micellar suspension and an fcc crystal in a block copolymer solution. A symmetric poly(styrene-b-isoprene) diblock copolymer in the isoprene-selective solvent squalane at a volume fraction of 0.20 was investigated using small angle x-ray scattering and rheology. Upon heating, the metastable bcc phase nucleates first, and then transforms over the course of hours to the stable fcc phase. At still higher temperatures the fcc phase transforms to an equilibrium bcc phase. The metastability of the bcc phase was confirmed by oscillatory shear and annealing using small angle x-ray scattering. These results constitute an interesting experimental manifestation of Ostwald's step rule, and also support recent theory and simulation results whereby bcc nucleates more readily from a melt of spheres.

  9. Degenerate Bose-Fermi Mixture of Metastable Atoms

    SciTech Connect

    McNamara, J. M.; Jeltes, T.; Tychkov, A. S.; Hogervorst, W.; Vassen, W.

    2006-08-25

    We report the observation of simultaneous quantum degeneracy in a dilute gaseous Bose-Fermi mixture of metastable atoms. Sympathetic cooling of helium-3 (fermion) by helium-4 (boson), both in the lowest triplet state, allows us to produce ensembles containing more than 10{sup 6} atoms of each isotope at temperatures below 1 {mu}K, and achieve a fermionic degeneracy parameter of T/T{sub F}=0.45. Because of their high internal energy, the detection of individual metastable atoms with subnanosecond time resolution is possible, permitting the study of bosonic and fermionic quantum gases with unprecedented precision. This may lead to metastable helium becoming the mainstay of quantum atom optics.

  10. An efficient magneto-optical trap of metastable krypton atoms.

    PubMed

    Cheng, C-F; Jiang, W; Yang, G-M; Sun, Y-R; Pan, H; Gao, Y; Liu, A-W; Hu, S-M

    2010-12-01

    We report a magneto-optical trap of metastable krypton atoms with a trap loading rate of 3×10(11) atoms/s and a trap capture efficiency of 3×10(-5). The system starts with an atomic beam of metastable krypton produced in a liquid-nitrogen cooled, radio-frequency driven discharge. The metastable beam flux emerging from the discharge is 1.5×10(14) atoms/s/sr. The flux in the forward direction is enhanced by a factor of 156 with transverse laser cooling. The atoms are then slowed inside a Zeeman slower before captured by a magneto-optic trap. The trap efficiency can be further improved, possibly to the 10(-2) level, by gas recirculation. Such an atom trap is useful in trace analysis applications where available sample size is limited.

  11. Argon metastable production in argon-helium microplasmas

    NASA Astrophysics Data System (ADS)

    Hoskinson, Alan R.; Gregorío, José; Hopwood, Jeffrey; Galbally-Kinney, Kristin; Davis, Steven J.; Rawlins, Wilson T.

    2016-06-01

    Microwave resonator-driven microplasmas are a promising technology for generating the high density of rare-gas metastable states required for optically pumped rare gas laser systems. We measure the density of argon 1s5 states (Paschen notation) in argon-helium plasmas between 100 Torr and atmospheric pressure using diode laser absorption. The metastable state density is observed to rise with helium mole fraction at lower pressures but to instead fall slightly when tested near atmospheric pressure. A 0-D model of the discharge suggests that these distinct behaviors result from the discharge being diffusion-controlled at lower pressures, but with losses occurring primarily through dissociative recombination at high pressures. In all cases, the argon metastable density falls sharply when the neutral argon gas fraction is reduced below approximately 2%.

  12. Metastable Aluminum Atoms Floating on the Surface of Helium Nanodroplets.

    PubMed

    Jeffs, Jay; Besley, Nicholas A; Stace, Anthony J; Sarma, Gautam; Cunningham, Ethan M; Boatwright, Adrian; Yang, Shengfu; Ellis, Andrew M

    2015-06-12

    Metal atoms have proved to be sensitive probes of the properties of superfluid helium nanodroplets. To date, all experiments on the doping of helium droplets have concentrated on the attachment of metal atoms in their ground electronic states. Here we report the first examples of metal atoms in excited states becoming attached to helium nanodroplets. The atoms in question are aluminum, and they have been generated by laser ablation in a metastable quartet state, which attaches to and remains on the surface of helium droplets. Evidence for a surface location comes from electronic spectra, which consist of very narrow absorption profiles that show very small spectral shifts. Supporting ab initio calculations show there to be an energy incentive for a metastable Al atom to remain on the surface of a helium droplet rather than move to the interior. The results suggest that helium droplets may provide a method for the capture and transport of metastable excited atomic and molecular species.

  13. Metastable Lennard-Jones fluids. III. Bulk viscosity.

    PubMed

    Baidakov, Vladimir G; Protsenko, Sergey P

    2014-09-21

    The method of equilibrium molecular-dynamics simulation in combination with the Green-Kubo formula has been used to calculate the bulk viscosity of a Lennard-Jones fluid. Calculations have been made at temperatures 0.4 ≤ k(B)T/ɛ ≤ 2.0 and densities 0.0075 ≤ ρσ(3) ≤ 1.2 at 116 stable and 106 metastable states of liquid and gas. The depth of penetration into the region of metastable states was limited by spontaneous nucleation. In the region of stable states the data obtained are compared with the results of previous investigations. It has been established that the system transition across the lines of liquid-gas and liquid-crystal phase equilibrium and penetration into the metastable regions of liquid and gas are connected with increasing bulk viscosity. The behavior of bulk viscosity close to the spinodal of a superheated liquid and supersaturated vapor is discussed. PMID:25240360

  14. Classification of knotted tori in 2-metastable dimension

    SciTech Connect

    Cencelj, Matija; Repovs, Dusan; Skopenkov, Mihail B

    2012-11-30

    This paper is devoted to the classical Knotting Problem: for a given manifold N and number m describe the set of isotopy classes of embeddings N{yields}S{sup m}. We study the specific case of knotted tori, that is, the embeddings S{sup p} Multiplication-Sign S{sup q}{yields}S{sup m}. The classification of knotted tori up to isotopy in the metastable dimension range m {>=} p + 3/2q + 2, p{<=}q, was given by Haefliger, Zeeman and A. Skopenkov. We consider the dimensions below the metastable range and give an explicit criterion for the finiteness of this set of isotopy classes in the 2-metastable dimension. Bibliography: 35 titles.

  15. Visible light responsive systems based on metastable-state photoacids

    NASA Astrophysics Data System (ADS)

    Liao, Yi

    2015-09-01

    Proton transfer is one of the most fundamental processes in nature. Metastable-state photoacids can reversibly generate a large proton concentration under visible light with moderate intensity. which provides a general approach to control various proton transfer processes. Several applications of mPAHs have been demonstrated recently including control of acid-catalyzed reactions, volume-change of hydrogels, polymer conductivity, bacteria killing, odorant release, and color change of materials. They have also been utilized to control supramolecular assemblies, molecular switches, microbial fuel cells and cationic sensors. In this talk, the mechanism, structure design, and applications of metastable-state photoacids are introduced. Recent development of different types of metastable-state photoacids is presented. Challenges and future work are also discussed.

  16. Metastable Lennard-Jones fluids. III. Bulk viscosity.

    PubMed

    Baidakov, Vladimir G; Protsenko, Sergey P

    2014-09-21

    The method of equilibrium molecular-dynamics simulation in combination with the Green-Kubo formula has been used to calculate the bulk viscosity of a Lennard-Jones fluid. Calculations have been made at temperatures 0.4 ≤ k(B)T/ɛ ≤ 2.0 and densities 0.0075 ≤ ρσ(3) ≤ 1.2 at 116 stable and 106 metastable states of liquid and gas. The depth of penetration into the region of metastable states was limited by spontaneous nucleation. In the region of stable states the data obtained are compared with the results of previous investigations. It has been established that the system transition across the lines of liquid-gas and liquid-crystal phase equilibrium and penetration into the metastable regions of liquid and gas are connected with increasing bulk viscosity. The behavior of bulk viscosity close to the spinodal of a superheated liquid and supersaturated vapor is discussed.

  17. Dissolved sulfide distributions in the water column and sediment pore waters of the Santa Barbara Basin

    USGS Publications Warehouse

    Kuwabara, J.S.; VanGeen, A.; McCorkle, D.C.; Bernhard, J.M.

    1999-01-01

    Dissolved sulfide concentrations in the water column and in sediment pore waters were measured by square-wave voltammetry (nanomolar detection limit) during three cruises to the Santa Barbara Basin in February 1995, November-December 1995, and April 1997. In the water column, sulfide concentrations measured outside the basin averaged 3 ?? 1 nM (n = 28) in the 0 to 600 m depth range. Inside the basin, dissolved sulfides increased to reach values of up to 15 nM at depths >400 m. A suite of box cores and multicores collected at four sites along the northeastern flank of the basin showed considerable range in surficial (400 ??M at 10 cm. Decreases in water-column nitrate below the sill depth indicate nitrate consumption (-55 to -137 ??mole m-2 h-1) similar to nearby Santa Monica Basin. Peaks in pore-water iron concentrations were generally observed between 2 and 5 cm depth with shallowest peaks at the 590 m site. These observations, including observations of the benthic microfauna, suggest that the extent to which the sulfide flux, sustained by elevated pore-water concentrations, reaches the water column may be modulated by the abundance of sulfide-oxidizing bacteria in addition to iron redox and precipitation reactions.

  18. Energetic Metastable Oxygen and Nitrogen Atoms in the Terrestrial Atmosphere

    NASA Technical Reports Server (NTRS)

    Kharchenko, Vasili; Dalgarno, A.

    2005-01-01

    This report summarizes our research performed under NASA Grant NAG5-11857. The three-year grant have been supported by the Geospace Sciences SR&T program. We have investigated the energetic metastable oxygen and nitrogen atoms in the terrestrial stratosphere, mesosphere and thermosphere. Hot atoms in the atmosphere are produced by solar radiation, the solar wind and various ionic reactions. Nascent hot atoms arise in ground and excited electronic states, and their translational energies are larger by two - three orders of magnitude than the thermal energies of the ambient gas. The relaxation kinetics of hot atoms determines the rate of atmospheric heating, the intensities of aeronomic reactions, and the rate of atom escape from the planet. Modeling of the non-Maxwellian energy distributions of metastable oxygen and nitrogen atoms have been focused on the determination of their impact on the energetics and chemistry of the terrestrial atmosphere between 25 and 250 km . At this altitudes, we have calculated the energy distribution functions of metastable O and N atoms and computed non-equilibrium rates of important aeronomic reactions, such as destruction of the water molecules by O(1D) atoms and production of highly excited nitric oxide molecules. In the upper atmosphere, the metastable O(lD) and N(2D) play important role in formation of the upward atomic fluxes. We have computed the upward fluxes of the metastable and ground state oxygen atoms in the upper atmosphere above 250 km. The accurate distributions of the metastable atoms have been evaluated for the day and night-time conditions.

  19. Metal-sulfide melt non-interconnectivity in silicates, even at high pressure, high temperature, and high melt fractions

    SciTech Connect

    Minarik, W.G.; Ryerson, F.J.

    1996-01-01

    The authors have investigated the textural microstructure of iron-nickel-sulfur melts in contact with olivine, pyroxene, and the modified-spinel polymorph of olivine. The experiments were conducted at 1,500 C and pressures ranging from 1 to 17 GPa. For compositions more metal-rich than the monosulfide, including the eutectic composition, the metal sulfide melt has a dihedral angle greater than 60{degree} and does not form an interconnected grain-edge fluid. Increasing pressure does not measurably alter the dihedral angles. Textural evolution results in coarsening of the sulfide melt pockets, resulting in large pockets surrounded by many silicate grains and separated from one another by melt-free grain edges. Chemical communication between these large pockets is limited to lattice and grain-boundary diffusion. Due to the large interfacial energy between sulfide melt and silicates, sulfide melts are unable to separate from solid silicate via grain-boundary percolation and remain stranded in isolated melt pockets. Sulfide melt in excess of the critical melt fraction (5--25%) will develop a transient interconnectivity as sulfide collects into larger melt pockets and interconnectivity is pinched off. Efficient separation of core-forming sulfide melts from silicate requires either melting of the silicate matrix or a very large fraction of metal-sulfide melt (perhaps as large as 40%).

  20. Origin of photoinduced metastable defects in amorphous chalcogenides

    NASA Astrophysics Data System (ADS)

    Shimakawa, K.; Inami, S.; Kato, T.; Elliott, S. R.

    1992-10-01

    Prolonged exposure to band-gap light decreases the photoconductivity of annealed films of amorphous chalcogenides (As2S3, As3S7, AsS, As2Se3, GeS2, GeSe2, and GeSe). This can be attributed to photoinduced metastable defects, which could act as additional trapping and/or recombination centers. These metastable centers are removed by annealing near the glass transition temperature. The kinetics of the temporal change of photocurrent during illumination are discussed in a model of defect-conserved bond switching.

  1. Metastable states of plasma particles close to a charged surface

    SciTech Connect

    Shavlov, A. V.; Dzhumandzhi, V. A.

    2015-09-15

    The free energy of the plasma particles and the charged surface that form an electroneutral system is calculated on the basis of the Poisson-Boltzmann equation. It is shown that, owing to correlation of light plasma particles near the charged surface and close to heavy particles of high charge, there can be metastable states in plasma. The corresponding phase charts of metastable states of the separate components of plasma, and plasma as a whole, are constructed. These charts depend on temperature, the charge magnitude, the size of the particles, and the share of the charge of the light carriers out of the total charge of the plasma particles.

  2. Selective crystallization of metastable phase of acetaminophen by ultrasonic irradiation

    NASA Astrophysics Data System (ADS)

    Mori, Yoichiro; Maruyama, Mihoko; Takahashi, Yoshinori; Ikeda, Kenji; Fukukita, Suguru; Yoshikawa, Hiroshi Y.; Okada, Shino; Adachi, Hiroaki; Sugiyama, Shigeru; Takano, Kazufumi; Murakami, Satoshi; Matsumura, Hiroyoshi; Inoue, Tsuyoshi; Yoshimura, Masashi; Mori, Yusuke

    2015-06-01

    A new method for selective crystallization of the metastable phase (form II) of acetaminophen is described. To obtain form II, we prepared a highly supersaturated solution (σI = 3.7) and then applied ultrasonic irradiation at different frequencies. Without ultrasonic irradiation, spontaneous crystallization did not occur within one month in the highly supersaturated condition (σI = 3.7). When ultrasonic irradiation at 28 kHz was applied, form II preferentially crystallized. Therefore, we conclude that ultrasonic irradiation can be an effective technique for selectively crystallizing the metastable phase.

  3. Strong attraction between charged spheres due to metastable ionized states

    PubMed

    Messina; Holm; Kremer

    2000-07-24

    We report a mechanism which can lead to long-range attractions between like-charged spherical macroions, stemming from the existence of metastable ionized states. We show that the ground state of a single highly charged colloid plus a few excess counterions is overcharged. For the case of two highly charged macroions in their neutralizing divalent counterion solution we demonstrate that, in the regime of strong Coulomb coupling, the counterion clouds are very likely to be unevenly distributed, leading to one overcharged and one undercharged macroion. This long-living metastable configuration in turn leads to a long-range Coulomb attraction.

  4. Selective detection of singlet gerade metastable states of N2

    NASA Astrophysics Data System (ADS)

    Kedzierski, W.; McConkey, J. W.

    2016-07-01

    Metastable N2 molecules produced by electron impact on N2 are detected using a unique solid nitrogen matrix detector. The time-of-flight system is shown to be selectively sensitive to a1Πg and 1Σg+ or 1Γg metastable species. The latter species had been identified theoretically previously but was detected experimentally for the first time in the present investigation. Their identification and excitation as a function of electron energy from threshold to 300 eV are presented. Comparison is made with the data obtained by other techniques.

  5. Metastable bcc phase formation in the Nb-Cr system

    SciTech Connect

    Thoma, D.J.; Schwarz, R.B.; Perepezko, J.H.; Plantz, D.H.

    1993-08-01

    Extended metastable bcc solid solutions of Nb-Xat.%Cr (X = 35, 50, 57, 77, 82, and 94) were synthesized by two-anvil splat-quenching. In addition, bcc (Nb-67at.%Cr) was prepared by mechanically alloying mixtures of niobium and chromium powders. The lattice parameters were measured by X-ray diffraction and the Young`s moduli were measured by low-load microindentation. The composition dependence of the lattice parameters and elastic moduli show a positive deviation with respect to a rule of mixtures. During continuous heating at 15C/min., the metastable precursor bcc phases decomposed at temperatures above 750C to uniformly refined microstructures.

  6. 30 CFR 250.604 - Hydrogen sulfide.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 30 Mineral Resources 2 2010-07-01 2010-07-01 false Hydrogen sulfide. 250.604 Section 250.604... OPERATIONS IN THE OUTER CONTINENTAL SHELF Oil and Gas Well-Workover Operations § 250.604 Hydrogen sulfide. When a well-workover operation is conducted in zones known to contain hydrogen sulfide (H2S) or...

  7. 30 CFR 250.504 - Hydrogen sulfide.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 30 Mineral Resources 2 2010-07-01 2010-07-01 false Hydrogen sulfide. 250.504 Section 250.504... OPERATIONS IN THE OUTER CONTINENTAL SHELF Oil and Gas Well-Completion Operations § 250.504 Hydrogen sulfide. When a well-completion operation is conducted in zones known to contain hydrogen sulfide (H2S) or...

  8. 30 CFR 250.808 - Hydrogen sulfide.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 30 Mineral Resources 2 2010-07-01 2010-07-01 false Hydrogen sulfide. 250.808 Section 250.808... OPERATIONS IN THE OUTER CONTINENTAL SHELF Oil and Gas Production Safety Systems § 250.808 Hydrogen sulfide. Production operations in zones known to contain hydrogen sulfide (H2S) or in zones where the presence of...

  9. 30 CFR 250.808 - Hydrogen sulfide.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 30 Mineral Resources 2 2012-07-01 2012-07-01 false Hydrogen sulfide. 250.808 Section 250.808 Mineral Resources BUREAU OF SAFETY AND ENVIRONMENTAL ENFORCEMENT, DEPARTMENT OF THE INTERIOR OFFSHORE OIL... § 250.808 Hydrogen sulfide. Production operations in zones known to contain hydrogen sulfide (H2S) or...

  10. 30 CFR 250.604 - Hydrogen sulfide.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 30 Mineral Resources 2 2011-07-01 2011-07-01 false Hydrogen sulfide. 250.604 Section 250.604...-Workover Operations § 250.604 Hydrogen sulfide. When a well-workover operation is conducted in zones known to contain hydrogen sulfide (H2S) or in zones where the presence of H2S is unknown (as defined...

  11. 30 CFR 250.504 - Hydrogen sulfide.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 30 Mineral Resources 2 2011-07-01 2011-07-01 false Hydrogen sulfide. 250.504 Section 250.504...-Completion Operations § 250.504 Hydrogen sulfide. When a well-completion operation is conducted in zones known to contain hydrogen sulfide (H2S) or in zones where the presence of H2S is unknown (as defined...

  12. 30 CFR 250.808 - Hydrogen sulfide.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 30 Mineral Resources 2 2014-07-01 2014-07-01 false Hydrogen sulfide. 250.808 Section 250.808 Mineral Resources BUREAU OF SAFETY AND ENVIRONMENTAL ENFORCEMENT, DEPARTMENT OF THE INTERIOR OFFSHORE OIL... § 250.808 Hydrogen sulfide. Production operations in zones known to contain hydrogen sulfide (H2S) or...

  13. 30 CFR 250.808 - Hydrogen sulfide.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 30 Mineral Resources 2 2013-07-01 2013-07-01 false Hydrogen sulfide. 250.808 Section 250.808 Mineral Resources BUREAU OF SAFETY AND ENVIRONMENTAL ENFORCEMENT, DEPARTMENT OF THE INTERIOR OFFSHORE OIL... § 250.808 Hydrogen sulfide. Production operations in zones known to contain hydrogen sulfide (H2S) or...

  14. Iron deficiency.

    PubMed

    Scrimshaw, N S

    1991-10-01

    The world's leading nutritional problem is iron deficiency. 66% of children and women aged 15-44 years in developing countries have it. Further, 10-20% of women of childbearing age in developed countries are anemic. Iron deficiency is identified with often irreversible impairment of a child's learning ability. It is also associated with low capacity for adults to work which reduces productivity. In addition, it impairs the immune system which reduces the body's ability to fight infection. Iron deficiency also lowers the metabolic rate and the body temperature when exposed to cold. Hemoglobin contains nearly 73% of the body's iron. This iron is always being recycled as more red blood cells are made. The rest of the needed iron does important tasks for the body, such as binds to molecules that are reservoirs of oxygen for muscle cells. This iron comes from our diet, especially meat. Even though some plants, such as spinach, are high in iron, the body can only absorb 1.4-7% of the iron in plants whereas it can absorb 20% of the iron in red meat. In many developing countries, the common vegetarian diets contribute to high rates of iron deficiency. Parasitic diseases and abnormal uterine bleeding also promote iron deficiency. Iron therapy in anemic children can often, but not always, improve behavior and cognitive performance. Iron deficiency during pregnancy often contributes to maternal and perinatal mortality. Yet treatment, if given to a child in time, can lead to normal growth and hinder infections. However, excess iron can be damaging. Too much supplemental iron in a malnourished child promotes fatal infections since the excess iron is available for the pathogens use. Many countries do not have an effective system for diagnosing, treating, and preventing iron deficiency. Therefore a concerted international effort is needed to eliminate iron deficiency in the world.

  15. Understanding the Factors Affecting the Formation of Carbonyl Iron Electrodes in Rechargeable Alkaline Iron Batteries

    SciTech Connect

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

    2012-01-01

    Rechargeable iron-based alkaline batteries such as iron - air and nickel - iron batteries are attractive for large-scale electrical energy storage because iron is inexpensive, globally-abundant and environmentally-friendly. Further, the iron electrode is known for its robustness to repeated charge/discharge cycling. During manufacturing these batteries are charged and discharged 20 to 50 times during which the discharge capacity of the iron electrode increases gradually and attains a stable value. This process of achieving stable capacity is called formation. In this study we have focused our efforts on understanding the effect of electrode design on formation. We have investigated the role of wetting agent, pore-former additive, and sulfide additive on the formation of carbonyl iron electrodes. The wetting agent increased the rate of formation while the pore-former additive increased the final capacity. Sodium sulfide added to the electrolyte worked as a de-passivation agent and increased the final discharge capacity. We have proposed a phenomenological model for the formation process that predicts the rate of formation and final discharge capacity given the design parameters for the electrode. The understanding gained here will be useful in reducing the time lost in formation and in maximizing the utilization of the iron electrode. (C) 2012 The Electrochemical Society. [DOI: 10.1149/2.021301jes] All rights reserved.

  16. Fluidized Bed Selective Oxidation-Sulfation Roasting of Nickel Sulfide Concentrate: Part I. Oxidation Roasting

    NASA Astrophysics Data System (ADS)

    Yu, Dawei; Utigard, Torstein A.; Barati, Mansoor

    2014-04-01

    Two-stage oxidation-sulfation roasting of nickel sulfide concentrate in fluidized bed was investigated to generate water-soluble metal sulfates as an alternative process to smelting of the sulfide concentrate for the recovery of valuable metals. The first stage, i.e., oxidation roasting, was employed to preferentially oxidize the iron before performing sulfation roasting. A batch fluidized bed roaster was constructed for roasting tests. Roasting products from various roasting temperatures and different roasting times were analyzed by SEM/EDS, EPMA, XRD, and ICP-OES to investigate the oxidation roasting behavior of the nickel concentrate as a function of temperature and time.

  17. p-Chlorophenyl methyl sulfide

    Integrated Risk Information System (IRIS)

    p - Chlorophenyl methyl sulfide ; CASRN 123 - 09 - 1 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for N

  18. Transition metal sulfide loaded catalyst

    DOEpatents

    Maroni, V.A.; Iton, L.E.; Pasterczyk, J.W.; Winterer, M.; Krause, T.R.

    1994-04-26

    A zeolite-based catalyst is described for activation and conversion of methane. A zeolite support includes a transition metal (Mo, Cr or W) sulfide disposed within the micropores of the zeolite. The catalyst allows activation and conversion of methane to C[sub 2]+ hydrocarbons in a reducing atmosphere, thereby avoiding formation of oxides of carbon.

  19. Transition metal sulfide loaded catalyst

    DOEpatents

    Maroni, Victor A.; Iton, Lennox E.; Pasterczyk, James W.; Winterer, Markus; Krause, Theodore R.

    1994-01-01

    A zeolite based catalyst for activation and conversion of methane. A zeolite support includes a transition metal (Mo, Cr or W) sulfide disposed within the micropores of the zeolite. The catalyst allows activation and conversion of methane to C.sub.2 + hydrocarbons in a reducing atmosphere, thereby avoiding formation of oxides of carbon.

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

    USGS Publications Warehouse

    Sobron, Pablo; Alpers, Charles N.

    2013-01-01

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

  1. Cyclic cosmology, conformal symmetry and the metastability of the Higgs

    NASA Astrophysics Data System (ADS)

    Bars, Itzhak; Steinhardt, Paul J.; Turok, Neil

    2013-10-01

    Recent measurements at the LHC suggest that the current Higgs vacuum could be metastable with a modest barrier (height ( GeV)4) separating it from a ground state with negative vacuum density of order the Planck scale. We note that metastability is problematic for standard bang cosmology but is essential for cyclic cosmology in order to end one cycle, bounce, and begin the next. In this Letter, motivated by the approximate scaling symmetry of the standard model of particle physics and the primordial large-scale structure of the universe, we use our recent formulation of the Weyl-invariant version of the standard model coupled to gravity to track the evolution of the Higgs in a regularly bouncing cosmology. We find a band of solutions in which the Higgs field escapes from the metastable phase during each big crunch, passes through the bang into an expanding phase, and returns to the metastable vacuum, cycle after cycle after cycle. We show that, due to the effect of the Higgs, the infinitely cycling universe is geodesically complete, in contrast to inflation.

  2. Global segregation of cortical activity and metastable dynamics

    PubMed Central

    Stratton, Peter; Wiles, Janet

    2015-01-01

    Cortical activity exhibits persistent metastable dynamics. Assemblies of neurons transiently couple (integrate) and decouple (segregate) at multiple spatiotemporal scales; both integration and segregation are required to support metastability. Integration of distant brain regions can be achieved through long range excitatory projections, but the mechanism supporting long range segregation is not clear. We argue that the thalamocortical matrix connections, which project diffusely from the thalamus to the cortex and have long been thought to support cortical gain control, play an equally-important role in cortical segregation. We present a computational model of the diffuse thalamocortical loop, called the competitive cross-coupling (CXC) spiking network. Simulations of the model show how different levels of tonic input from the brainstem to the thalamus could control dynamical complexity in the cortex, directing transitions between sleep, wakefulness and high attention or vigilance. The model also explains how mutually-exclusive activity could arise across large portions of the cortex, such as between the default-mode and task-positive networks. It is robust to noise but does not require noise to autonomously generate metastability. We conclude that the long range segregation observed in brain activity and required for global metastable dynamics could be provided by the thalamocortical matrix, and is strongly modulated by brainstem input to the thalamus. PMID:26379514

  3. Metastable Oxygen Production by Electron-Impact of Oxygen

    NASA Astrophysics Data System (ADS)

    Hein, Jeffrey; Johnson, Paul; Kanik, Isik; Malone, Charles

    2014-05-01

    Electron-impact excitation processes involving atomic and molecular oxygen are important in atmospheric interactions. The production of long-lived metastable O(1S) and O(1D) through electron impact of atomic O and molecular O2 play a significant role in the dynamics of oxygen-containing atmospheres (Earth, Europa, Io). Emissions from metastable O (1S --> 1D) produce the well-recognized green light from terrestrial aurora. Electron-impact excitation to 1S and 1D are sensitive channels for determining energy partitioning and dynamics from space weather. Electron-impact excitation cross sections determined through fundamental experimental studies are necessary for modeling of natural phenomena and observation data. The detection of metastable states in laboratory experiments requires a novel approach, since typical detection techniques (e.g., fluorescence by radiative de-excitation) cannot be performed due to the long-lived nature of the excited species. In this work, metastable O is produced through electron impact, and is incident on a cryogenically cooled rare gas matrix. The excimer production and subsequent rapid radiative de-excitation provides measurable signal that is directly related to the originating electron-impact excitation process.

  4. Global segregation of cortical activity and metastable dynamics.

    PubMed

    Stratton, Peter; Wiles, Janet

    2015-01-01

    Cortical activity exhibits persistent metastable dynamics. Assemblies of neurons transiently couple (integrate) and decouple (segregate) at multiple spatiotemporal scales; both integration and segregation are required to support metastability. Integration of distant brain regions can be achieved through long range excitatory projections, but the mechanism supporting long range segregation is not clear. We argue that the thalamocortical matrix connections, which project diffusely from the thalamus to the cortex and have long been thought to support cortical gain control, play an equally-important role in cortical segregation. We present a computational model of the diffuse thalamocortical loop, called the competitive cross-coupling (CXC) spiking network. Simulations of the model show how different levels of tonic input from the brainstem to the thalamus could control dynamical complexity in the cortex, directing transitions between sleep, wakefulness and high attention or vigilance. The model also explains how mutually-exclusive activity could arise across large portions of the cortex, such as between the default-mode and task-positive networks. It is robust to noise but does not require noise to autonomously generate metastability. We conclude that the long range segregation observed in brain activity and required for global metastable dynamics could be provided by the thalamocortical matrix, and is strongly modulated by brainstem input to the thalamus.

  5. Metastable atom probe for measuring electron beam density profiles

    NASA Technical Reports Server (NTRS)

    Lockhart, J. M.; Zorn, J. C.

    1972-01-01

    Metastable atom probe was developed for measuring current density in electron beam as function of two arbitrary coordinates, with spatial resolution better than 0.5 mm. Probe shows effects of space charge, magnetic fields, and other factors which influence electron current density, but operates with such low beam densities that introduced perturbation is very small.

  6. Searching for high magnetization density in bulk Fe: the new metastable Fe₆ phase.

    PubMed

    Umemoto, Koichiro; Himmetoglu, Burak; Wang, Jian-Ping; Wentzcovitch, Renata M; Cococcioni, Matteo

    2015-01-14

    We report the discovery of a new allotrope of iron by first principles calculations. This phase has Pmn2(1) symmetry, a six-atom unit cell (hence the name Fe6), and the highest magnetization density (Ms) among all the known crystalline phases of iron. Obtained from the structural optimizations of the Fe3C-cementite crystal upon carbon removal, Pmn2(1) Fe6 is shown to result from the stabilization of a ferromagnetic FCC phase, further strained along the Bain path. Although metastable from 0 to 50 GPa, the new phase is more stable at low pressures than the other well-known HCP and FCC allotropes and smoothly transforms into the FCC phase under compression. If stabilized to room temperature, for example, by interstitial impurities, Fe6 could become the basis material for high Ms rare-earth-free permament magnets and high-impact applications such as light-weight electric engine rotors or high-density recording media. The new phase could also be key to explaining the enigmatic high Ms of Fe16N2, which is currently attracting intense research activity.

  7. Searching for high magnetization density in bulk Fe: the new metastable Fe-6 phase

    SciTech Connect

    Umemoto, K; Himmetoglu, B; Wang, JP; Wentzcovitch, RM; Cococcioni, M

    2014-11-26

    We report the discovery of a new allotrope of iron by first principles calculations. This phase has Pmn2(1) symmetry, a six-atom unit cell (hence the name Fe-6), and the highest magnetization density (M-s) among all the known crystalline phases of iron. Obtained from the structural optimizations of the Fe3C-cementite crystal upon carbon removal, Pmn2(1) Fe-6 is shown to result from the stabilization of a ferromagnetic FCC phase, further strained along the Bain path. Although metastable from 0 to 50 GPa, the new phase is more stable at low pressures than the other well-known HCP and FCC allotropes and smoothly transforms into the FCC phase under compression. If stabilized to room temperature, for example, by interstitial impurities, Fe-6 could become the basis material for high M-s rare-earth-free permament magnets and high-impact applications such as light-weight electric engine rotors or high-density recording media. The new phase could also be key to explaining the enigmatic high M-s of Fe16N2, which is currently attracting intense research activity.

  8. Chemical influences on trace metal-sulfide interactions in anoxic sediments

    SciTech Connect

    Morse, J.W.; Luther, G.W. III

    1999-10-01

    Interactions of trace metals with sulfide in anoxic environments are important in determining their chemical form and potential toxicity to organisms. In recent years, a considerable body of observational data has accumulated that indicates very different behavior for various trace metals in sulfidic sediments. These differences in behavior cannot be entirely attributed to thermodynamic relationships, but also reflect differences in ligand exchange reaction kinetics, and redox reaction pathways. Pb, Zn, and Cd, which are generally pyritized to only a few percent of the reactive fraction, have faster water exchange reaction kinetics than Fe{sup 2+}, resulting in MeS phases precipitating prior to FeS formation and subsequent pyrite formation, whereas, Co and Ni, which have slower H{sub 2}O exchange kinetics than Fe{sup 2+}, are incorporated into pyrite. Although Hg and Cu have faster reaction kinetics than Fe{sup 2+}, both are incorporated into pyrite or leached from the pyrite fraction with nitric acid. Hg undergoes significant chloride complexation, which can retard reaction with sulfide, but can also replace Fe in FeS to form HgS, which can only be dissolved in the pyrite fraction. Cu{sup 2+} is reduced by sulfide and forms a variety of sulfides with and without Fe that can only be dissolved with nitric acid. Mn{sup 2+} does not form a MnS phase easily and is incorporated into pyrite at high iron degrees of pyritization (DOP). Oxyanions of Mo and As are first reduced by sulfide. These reduced forms may then react with sulfides resulting in incorporation into pyrite. However, the oxyanion of Cr is reduced to Cr{sup 3+}, which is kinetically inert to reaction with sulfide and, therefore, not incorporated into pyrite.

  9. Nucleation of metastable aragonite CaCO3 in seawater

    DOE PAGESBeta

    Sun, Wenhao; Jayaraman, Saivenkataraman; Chen, Wei; Persson, Kristin A.; Ceder, Gerbrand

    2015-03-04

    Predicting the conditions in which a compound adopts a metastable structure when it crystallizes out of solution is an unsolved and fundamental problem in materials synthesis, and one which, if understood and harnessed, could enable the rational design of synthesis pathways toward or away from metastable structures. Crystallization of metastable phases is particularly accessible via low-temperature solution-based routes, such as chimie douce and hydrothermal synthesis, but although the chemistry of the solution plays a crucial role in governing which polymorph forms, how it does so is poorly understood. Here, we demonstrate an ab initio technique to quantify thermodynamic parameters ofmore » surfaces and bulks in equilibrium with an aqueous environment, enabling the calculation of nucleation barriers of competing polymorphs as a function of solution chemistry, thereby predicting the solution conditions governing polymorph selection. We apply this approach to resolve the long-standing “calcite–aragonite problem”––the observation that calcium carbonate precipitates as the metastable aragonite polymorph in marine environments, rather than the stable phase calcite––which is of tremendous relevance to biomineralization, carbon sequestration, paleogeochemistry, and the vulnerability of marine life to ocean acidification. We identify a direct relationship between the calcite surface energy and solution Mg–Ca ion concentrations, showing that the calcite nucleation barrier surpasses that of metastable aragonite in solutions with Mg:Ca ratios consistent with modern seawater, allowing aragonite to dominate the kinetics of nucleation. Our ability to quantify how solution parameters distinguish between polymorphs marks an important step toward the ab initio prediction of materials synthesis pathways in solution.« less

  10. Nucleation of metastable aragonite CaCO3 in seawater

    PubMed Central

    Sun, Wenhao; Jayaraman, Saivenkataraman; Chen, Wei; Persson, Kristin A.; Ceder, Gerbrand

    2015-01-01

    Predicting the conditions in which a compound adopts a metastable structure when it crystallizes out of solution is an unsolved and fundamental problem in materials synthesis, and one which, if understood and harnessed, could enable the rational design of synthesis pathways toward or away from metastable structures. Crystallization of metastable phases is particularly accessible via low-temperature solution-based routes, such as chimie douce and hydrothermal synthesis, but although the chemistry of the solution plays a crucial role in governing which polymorph forms, how it does so is poorly understood. Here, we demonstrate an ab initio technique to quantify thermodynamic parameters of surfaces and bulks in equilibrium with an aqueous environment, enabling the calculation of nucleation barriers of competing polymorphs as a function of solution chemistry, thereby predicting the solution conditions governing polymorph selection. We apply this approach to resolve the long-standing “calcite–aragonite problem”––the observation that calcium carbonate precipitates as the metastable aragonite polymorph in marine environments, rather than the stable phase calcite––which is of tremendous relevance to biomineralization, carbon sequestration, paleogeochemistry, and the vulnerability of marine life to ocean acidification. We identify a direct relationship between the calcite surface energy and solution Mg–Ca ion concentrations, showing that the calcite nucleation barrier surpasses that of metastable aragonite in solutions with Mg:Ca ratios consistent with modern seawater, allowing aragonite to dominate the kinetics of nucleation. Our ability to quantify how solution parameters distinguish between polymorphs marks an important step toward the ab initio prediction of materials synthesis pathways in solution. PMID:25739963

  11. Argon metastable dynamics and lifetimes in a direct current microdischarge

    SciTech Connect

    Stefanović, Ilija; Kuschel, Thomas; Schröter, Sandra; Böke, Marc

    2014-09-21

    In this paper we study the properties of a pulsed dc microdischarge with the continuous flow of argon. Argon metastable lifetimes are measured by tunable diode laser absorption spectroscopy (TDLAS) and are compared with calculated values which yield information about excitation and de-excitation processes. By increasing the gas flow-rate about 5 times from 10 to 50 sccm, the Ar{sup m} lifetime increases from 1 to 5 μs due to the reduction of metastable quenching with gas impurities. Optical emission spectroscopy reveals nitrogen and water molecules as the main gas impurities. The estimated N₂ density [N₂]=0.1% is too low to explain the measured metastable lifetimes. Water impurity was found to be the main de-excitation source of argon metastable atoms due to high quenching coefficients. The water impurity level of [H₂O]=0.15% to 1% is sufficient to bring calculated metastable lifetimes in line with experiments. The maximum value of water content in the discharge compared to the argon atoms is estimated to approximately 6%, due to the large surface to volume ratio of the microdischarge. The current pulse releases the water molecules from the electrode surface and they are either re-adsorbed in the time between 0.4 ms for [H₂O]=1% and 2.6 ms for [H₂O]=0.15% or pumped out of the discharge with the speed equal to the gas flow-rate. Depending on its partial pressure, the water impurity re-adsorption time is of the order of magnitude or less then the argon gas residence time.

  12. Optical features of nanosize iron and molybdenum sulfide clusters

    SciTech Connect

    Wilcoxon, J.P.; Samara, G.; Newcomer, P.

    1995-01-01

    In the bulk state FeS{sub 2} and MoS{sub 2} are optically opaque, narrow bandgap semiconductors and MoS{sub 2} have bandgaps that with no optical applications. We demonstrate that nanosize FeS{sub 2} can be adjusted to the visible and even UV region of the spectrum by control of the cluster size. This opens up a host of applications of these materials as inexpensive solar photocatalysts. We demonstrate that the band-gap of both materials shifts to the blue with decreasing size but ceases shifting when a size of {approximately}3 nm (in the case of MoS{sub 2}) is attained. We interpret this observation as a change from bulk quantum confinement of the hole-electron pair of a tiny semiconductor to a set of discrete molecular-like transitions more characteristic of a whopper molecule. Room temperature photoemission studies of these clusters demonstrate that, while photoemission shifts to the blue with increasing bandgap for large clusters, small clusters have photoemission exclusively from trapped sub-bandgap surface states. Chemical modification of the surface to introduce hole or electron traps can result in either an enhancement or a decrease in the photoluminescence. In addition, we report our results concerning chemical purification and preliminary surface characterization of MoS{sub 2} clusters by chromatography.

  13. 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.

  14. Iron Meteorite

    NASA Astrophysics Data System (ADS)

    Murdin, P.

    2000-11-01

    A meteorite composed mainly of nickel-iron, with traces of other metals; also referred to simply as an iron, and formerly known as a siderite. Irons account for over 6% of all known meteorite specimens. They are the easiest type to identify, being heavy, magnetic and rust-colored; their metallic sheen tarnishes quickly on the Earth's surface, but otherwise irons show better resistance to weatheri...

  15. Iron active electrode and method of making same

    DOEpatents

    Jackovitz, John F.; Seidel, Joseph; Pantier, Earl A.

    1982-10-26

    An iron active electrode and method of preparing same in which iron sulfate is calcined in an oxidizing atmosphere at a temperature in the range of from about 600.degree. C. to about 850.degree. C. for a time sufficient to produce an iron oxide with a trace amount of sulfate. The calcined material is loaded into an electrically conductive support and then heated in a reducing atmosphere at an elevated temperature to produce activated iron having a trace amount of sulfide which is formed into an electrode plate.

  16. Environmental implications of the use of sulfidic back-bay sediments for dune reconstruction - Lessons learned post Hurricane Sandy.

    PubMed

    Plumlee, Geoffrey S; Benzel, William M; Hoefen, Todd M; Hageman, Philip L; Morman, Suzette A; Reilly, Timothy J; Adams, Monique; Berry, Cyrus J; Fischer, Jeffrey M; Fisher, Irene

    2016-06-30

    Some barrier-island dunes damaged or destroyed by Hurricane Sandy's storm surges in October 2012 have been reconstructed using sediments dredged from back bays. These sand-, clay-, and iron sulfide-rich sediments were used to make berm-like cores for the reconstructed dunes, which were then covered by beach sand. In November 2013, we sampled and analyzed partially weathered materials collected from the cores of reconstructed dunes. There are generally low levels of metal toxicants in the reconstructed dune materials. However oxidation of reactive iron sulfides by percolating rainwater produces acid-sulfate pore waters, which evaporate during dry periods to produce efflorescent gypsum and sodium jarosite salts. The results suggest use of sulfidic sediments in dune reconstruction has both drawbacks (e.g., potential to generate acid runoff from dune cores following rainfall, enhanced corrosion of steel bulwarks) and possible benefits (e.g., efflorescent salts may enhance structural integrity). PMID:27210565

  17. Sulfide smelting using Ausmelt technology

    NASA Astrophysics Data System (ADS)

    Mounsey, Edward N.; Robilliard, Ken R.

    1994-08-01

    Over the past decade, Ausmelt has been developing the top submerged lancing process for the smelting of sulfidic ores to recover such metals as copper, lead, silver, tin, antimony, and nickel as well as for separation of minor elements such as arsenic, antimony, and bismuth. Development has taken place in Ausmelt's pilot plant in Dandenong, near Melbourne, Australia. A number of projects have proceeded to commercial-scale operation. This paper reviews developments at both the pilot and commercial scales.

  18. Auger electron spectroscopic study of mechanism of sulfide-accelerated corrosion of copper-nickel alloy in seawater

    NASA Astrophysics Data System (ADS)

    Schrader, Malcolm E.

    The mechanism of sulfide-induced accelerated corrosion of 90-10 copper-nickel(iron) alloy is investigated. Samples of the alloy are exposed to flowing (2.4 m/s) seawater, with and without 0 01 mg/l sulfide, for various periods of time. The resulting surfaces are examined by means of Auger electron spectroscopy coupled with inert-ion-homoardment. A detailed depth profile is thereby obtained of concentrations in the surface region of a total of nine elements. The results are consistent with the hypothesis that iron hydroxide segregates at the surface to form a protective gelatinous layer against the normal chloride-induced corrosion process. Trace sulfide interferes with formation of a good protective layer and leaves the iron hydroxide vulnerable to ultimate partial or complete debonding. When the alloy is first exposed to "pure" seawater for a prolonged period of time, however, subsequent exposure to sulfide is no longer deleterious. This is apparently due to a layer of copper-nickel salt that slowly forms over the iron hydroxide.

  19. How Mercury can be the most reduced terrestrial planet and still store iron in its mantle

    NASA Astrophysics Data System (ADS)

    Malavergne, Valérie; Cordier, Patrick; Righter, Kevin; Brunet, Fabrice; Zanda, Brigitte; Addad, Ahmed; Smith, Thomas; Bureau, Hélène; Surblé, Suzy; Raepsaet, Caroline; Charon, Emeline; Hewins, Roger H.

    2014-05-01

    Mercury is notorious as the most reduced planet with the highest metal/silicate ratio, yet paradoxically data from the MESSENGER spacecraft show that its iron-poor crust is high in sulfur (up to ˜6 wt%, ˜80× Earth crust abundance) present mainly as Ca-rich sulfides on its surface. These particularities are simply impossible on the other terrestrial planets. In order to understand the role played by sulfur during the formation of Mercury, we investigated the phase relationships in Mercurian analogs of enstatite chondrite-like composition experimentally under conditions relevant to differentiation of Mercury (˜1 GPa and 1300-2000 °C). Our results show that Mg-rich and Ca-rich sulfides, which both contain Fe, crystallize successively from reduced silicate melts upon cooling below 1550 °C. As the iron concentration in the reduced silicates stays very low (≪1 wt%), these sulfides represent new host phases for both iron and sulfur in the run products. Extrapolated to Mercury, these results show that Mg-rich sulfide crystallization provides the first viable and fundamental means for retaining iron as well as sulfur in the mantle during differentiation, while sulfides richer in Ca would crystallize at shallower levels. The distribution of iron in the differentiating mantle of Mercury was mainly determined by its partitioning between metal (or troilite) and Mg-Fe-Ca-rich sulfides rather than by its partitioning between metal (or troilite) and silicates. Moreover, the primitive mantle might also be boosted in Fe by a reaction at the core mantle boundary (CMB) between Mg-rich sulfides of the mantle and FeS-rich outer core materials to produce (Fe, Mg)S. The stability of Mg-Fe-Ca-rich sulfides over a large range of depths up to the surface of Mercury would be consistent with sulfur, calcium and iron abundances measured by MESSENGER.

  20. Chemical dissolution of sulfide minerals

    USGS Publications Warehouse

    Chao, T.T.; Sanzolone, R.F.

    1977-01-01

    Chemical dissolution treatments involving the use of aqua regia, 4 N HNO3, H2O2-ascorbic acid, oxalic acid, KClO3+HCl, and KClO3+HCl followed by 4 N HNO3 were applied to specimens of nine common sulfide minerals (galena, chalcopyrite, cinnabar, molybdenite, orpiment, pyrite, stibnite, sphalerite, and tetrahedrite) mixed individually with a clay loam soil. The resultant decrease in the total sulfur content of the mixture, as determined by using the Leco induction furnace, was used to evaluate the effectiveness of each chemical treatment. A combination of KClO3+HCl followed by 4 N HNO3 boiling gently for 20 min has been shown to be very effective in dissolving all the sulfide minerals. This treatment is recommended to dissolve metals residing in sulfide minerals admixed with secondary weathering products, as one step in a fractionation scheme whereby metals in soluble and adsorbed forms, and those associated with organic materials and secondary oxides, are first removed by other chemical extractants.

  1. Sulfide-Driven Microbial Electrosynthesis

    SciTech Connect

    Gong, YM; Ebrahim, A; Feist, AM; Embree, M; Zhang, T; Lovley, D; Zengler, K

    2013-01-01

    Microbial electrosynthesis, the conversion of carbon dioxide to organic molecules using electricity, has recently been demonstrated for acetogenic microorganisms, such as Sporomusa ovata. The energy for reduction of carbon dioxide originates from the hydrolysis of water on the anode, requiring a sufficiently low potential. Here we evaluate the use of sulfide as an electron source for microbial electrosynthesis. Abiotically oxidation of sulfide on the anode yields two electrons. The oxidation product, elemental sulfur, can be further oxidized to sulfate by Desulfobulbus propionicus, generating six additional electrons in the process. The eight electrons generated from the combined abiotic and biotic steps were used to reduce carbon dioxide to acetate on a graphite cathode by Sporomusa ovata at a rate of 24.8 mmol/day.m(2). Using a strain of Desulfuromonas as biocatalyst on the anode resulted in an acetate production rate of 49.9 mmol/day.m(2), with a Coulombic efficiency of over 90%. These results demonstrate that sulfide can serve effectively as an alternative electron donor for microbial electrosynthesis.

  2. Studies of two-center three-electron S...S bonds in [n-Pr{sub 2}S...Sn-Pr{sub 2}]{sup +} and [i-Pr{sub 2}S...Si-Pr{sub 2}]{sup +}: Thermochemistry of adduct formation and MS/MS metastable and collision-induced dissociation spectra of the adducts

    SciTech Connect

    James, M.A.; Illies, A.J.

    1996-09-26

    Gas-phase ion-molecule association reactions of n-propyl sulfide radical cation ([n-Pr{sub 2}S]{sup +}) with n-propyl sulfide (n-Pr{sub 2}S) were studied by equilibrium methods in CO{sub 2} bath gas to investigate the bond energy of the 2c-3e bond. The 2c-3e S...S bond enthalpy in [n-Pr{sub 2}S...Sn-Pr{sub 2}]{sup +} was determined to be 119 kJ/mol at 507 K. This results in a scaled S...S bond energy of 123 kJ/mol. The S...S bond enthalpy in the i-propyl sulfide dimer cation ([i-Pr{sub 2}S...Si-Pr{sub 2}]{sup +}) could not be determined due to a fragmentation reaction, the loss of an i-propyl group. MS/MS metastable and collision-induced dissociation experiments were carried out to determine metastable fragmentation pathways and to aid in structure analysis. The results are consistent with association products containing 2c-3e bonds; statistical unimolecular metastable fragmentation of the association adduct, [i-Pr{sub 2}S...Si-Pr{sub 2}]{sup +}, confirms the loss of the i-propyl group, which prevented the equilibrium experiments. 21 refs., 11 figs., 1 tab.

  3. Sulfide capacity of CaO-CaF2-SiO2 slags

    NASA Astrophysics Data System (ADS)

    Susaki, Katsujiro; Maeda, Masafumi; Sano, Nobuo

    1990-02-01

    The sulfide capacity C S 2- = (pct S2-) · ( P O 2/ P S 2)1/2) of CaO-CaF2-SiO2 slags saturated with CaO, 3CaO · SiO2 or 2CaOSiO2 was determined at 1200 °C, 1250 °C, 1300 °C, and 1350 °C by equilibrating molten slag, molten silver, and CO-CO2 gas mixtures. Higher sulfide capacities were obtained for CaO-saturated slags. A drastic decrease was observed in those values when the ratio pct CaO/pct SiO2 is less than 2. The sulfur partition between carbon-saturated iron melts and presently investigated slags was calculated by using the sulfide capacities obtained and the activity coefficient of sulfur in carbon-saturated iron, which was also experimentally determined. For slags saturated with CaO, partitions of sulfur as high as 10,000 were obtained at 1300 °C and 1350 °C. Correlations between the sulfide capacity and other basicity indexes such as carbonate capacity and theoretical optical basicity were also discussed.

  4. Cooperative photoinduced metastable phase control in strained manganite films

    NASA Astrophysics Data System (ADS)

    Zhang, Jingdi; Tan, Xuelian; Liu, Mengkun; Teitelbaum, S. W.; Post, K. W.; Jin, Feng; Nelson, K. A.; Basov, D. N.; Wu, Wenbin; Averitt, R. D.

    2016-09-01

    A major challenge in condensed-matter physics is active control of quantum phases. Dynamic control with pulsed electromagnetic fields can overcome energetic barriers, enabling access to transient or metastable states that are not thermally accessible. Here we demonstrate strain-engineered tuning of La2/3Ca1/3MnO3 into an emergent charge-ordered insulating phase with extreme photo-susceptibility, where even a single optical pulse can initiate a transition to a long-lived metastable hidden metallic phase. Comprehensive single-shot pulsed excitation measurements demonstrate that the transition is cooperative and ultrafast, requiring a critical absorbed photon density to activate local charge excitations that mediate magnetic-lattice coupling that, in turn, stabilize the metallic phase. These results reveal that strain engineering can tune emergent functionality towards proximal macroscopic states to enable dynamic ultrafast optical phase switching and control.

  5. Homonuclear ionizing collisions of laser-cooled metastable helium atoms

    SciTech Connect

    Stas, R. J. W.; McNamara, J. M.; Hogervorst, W.; Vassen, W.

    2006-03-15

    We present a theoretical and experimental investigation of homonuclear ionizing collisions of laser-cooled metastable (2 {sup 3}S{sub 1}) helium atoms, considering both the fermionic {sup 3}He and bosonic {sup 4}He isotopes. The theoretical description combines quantum threshold behavior, Wigner's spin-conservation rule, and quantum-statistical symmetry requirements in a single-channel model, complementing a more complete close-coupling theory that has been reported for collisions of metastable {sup 4}He atoms. The model is supported with measurements (in the absence of light fields) of ionization rates in magneto-optically trapped samples that contain about 3x10{sup 8} atoms of a single isotope. The ionization rates are determined from measurements of trap loss due to light-assisted collisions combined with comparative measurements of the ion production rate in the absence and presence of trapping light. Theory and experiment show good agreement.

  6. Geometric phases causing lifetime modifications of metastable states of hydrogen

    NASA Astrophysics Data System (ADS)

    Trappe, Martin-Isbjörn; Augenstein, Peter; DeKieviet, Maarten; Gasenzer, Thomas; Nachtmann, Otto

    2016-04-01

    Externally applied electromagnetic fields in general have an influence on the width of atomic spectral lines. The decay rates of atomic states can also be affected by the geometry of an applied field configuration giving rise to an imaginary geometric phase. A specific chiral electromagnetic field configuration is presented which geometrically modifies the lifetimes of metastable states of hydrogen. We propose to extract the relevant observables in a realistic longitudinal atomic beam spin-echo apparatus which allows the initial and final fluxes of the metastable atoms to be compared with each other interferometrically. A geometry-induced change in lifetimes at the 5%-level is found, an effect large enough to be observed in an available experiment.

  7. Dependence of stability of metastable superconductors on copper fraction

    SciTech Connect

    Elrod, S. A.; Lue, J. W.; Miller, J. R.; Dresner, L.

    1980-12-01

    The stability of composite superconductors operating in the metastable regime depends upon such factors as matrix resistivity, cooled surface dimensions, fraction of critical current, and volume fraction of stabilizer. By assuming constant thermophysical properties, we developed analytic expressions for the energy and voltage of the minimum propagating zone (MPZ). With other factors held constant, these expressions have been used to predict composite superconductor stability as a function of copper fraction: lower copper fractions lead to higher MPZ energies. MPZ voltages have been measured for three NbTi/Cu composites having different copper fractions and different critical current densities for several magnetic fields and transport currents. Experimental MPZ voltages have been used to calculate an effective heat transfer coefficient, which is subsequently used to calculate the MPZ energy. The experimental MPZ energies support the theoretical expectation that lower copper fractions lead to higher stability in the metastable regime.

  8. Metastable Amyloid Phases and their Conversion to Mature Fibrils

    NASA Astrophysics Data System (ADS)

    Muschol, Martin; Miti, Tatiana; Mulaj, Mentor; Schmit, Jeremy

    Self-assembly of proteins into amyloid fibrils plays a key role in both functional biological responses and pathogenic disorders which include Alzheimer's disease and type II diabetes. Amyloid fibril assembly frequently generates compact oligomeric and curvilinear polymeric intermediates which are implicated to be toxic to cells. Yet, the relation between these early-stage oligomeric aggregates and late-stage rigid fibrils, which are the hallmark structure of amyloid plaques, has remained unclear. Our measurements indicate that lysozyme amyloid oligomers and their curvilinear fibrils only form after crossing a salt and protein concentration dependent threshold. These oligomeric aggregates are structurally distinct from rigid fibrils and are metastable against nucleation and growth of rigid fibrils. Our experimental transition boundaries match well with colloidal model predictions accounting for salt-modulated charge repulsion. We also report our preliminary findings on the mechanism by which these metastable oligomeric phases are converted into stable amyloid fibrils.

  9. Cooperative photoinduced metastable phase control in strained manganite films.

    PubMed

    Zhang, Jingdi; Tan, Xuelian; Liu, Mengkun; Teitelbaum, S W; Post, K W; Jin, Feng; Nelson, K A; Basov, D N; Wu, Wenbin; Averitt, R D

    2016-09-01

    A major challenge in condensed-matter physics is active control of quantum phases. Dynamic control with pulsed electromagnetic fields can overcome energetic barriers, enabling access to transient or metastable states that are not thermally accessible. Here we demonstrate strain-engineered tuning of La2/3Ca1/3MnO3 into an emergent charge-ordered insulating phase with extreme photo-susceptibility, where even a single optical pulse can initiate a transition to a long-lived metastable hidden metallic phase. Comprehensive single-shot pulsed excitation measurements demonstrate that the transition is cooperative and ultrafast, requiring a critical absorbed photon density to activate local charge excitations that mediate magnetic-lattice coupling that, in turn, stabilize the metallic phase. These results reveal that strain engineering can tune emergent functionality towards proximal macroscopic states to enable dynamic ultrafast optical phase switching and control. PMID:27400387

  10. Evidence that dimethyl sulfide facilitates a tritrophic mutualism between marine primary producers and top predators

    PubMed Central

    Savoca, Matthew S.; Nevitt, Gabrielle A.

    2014-01-01

    Tritrophic mutualistic interactions have been best studied in plant–insect systems. During these interactions, plants release volatiles in response to herbivore damage, which, in turn, facilitates predation on primary consumers or benefits the primary producer by providing nutrients. Here we explore a similar interaction in the Southern Ocean food web, where soluble iron limits primary productivity. Dimethyl sulfide has been studied in the context of global climate regulation and is an established foraging cue for marine top predators. We present evidence that procellariiform seabird species that use dimethyl sulfide as a foraging cue selectively forage on phytoplankton grazers. Their contribution of beneficial iron recycled to marine phytoplankton via excretion suggests a chemically mediated link between marine top predators and oceanic primary production. PMID:24591607

  11. Evidence that dimethyl sulfide facilitates a tritrophic mutualism between marine primary producers and top predators.

    PubMed

    Savoca, Matthew S; Nevitt, Gabrielle A

    2014-03-18

    Tritrophic mutualistic interactions have been best studied in plant-insect systems. During these interactions, plants release volatiles in response to herbivore damage, which, in turn, facilitates predation on primary consumers or benefits the primary producer by providing nutrients. Here we explore a similar interaction in the Southern Ocean food web, where soluble iron limits primary productivity. Dimethyl sulfide has been studied in the context of global climate regulation and is an established foraging cue for marine top predators. We present evidence that procellariiform seabird species that use dimethyl sulfide as a foraging cue selectively forage on phytoplankton grazers. Their contribution of beneficial iron recycled to marine phytoplankton via excretion suggests a chemically mediated link between marine top predators and oceanic primary production.

  12. 30 CFR 250.604 - Hydrogen sulfide.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 30 Mineral Resources 2 2014-07-01 2014-07-01 false Hydrogen sulfide. 250.604 Section 250.604... § 250.604 Hydrogen sulfide. When a well-workover operation is conducted in zones known to contain hydrogen sulfide (H2S) or in zones where the presence of H2S is unknown (as defined in § 250.490 of...

  13. 30 CFR 250.504 - Hydrogen sulfide.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 30 Mineral Resources 2 2014-07-01 2014-07-01 false Hydrogen sulfide. 250.504 Section 250.504... § 250.504 Hydrogen sulfide. When a well-completion operation is conducted in zones known to contain hydrogen sulfide (H2S) or in zones where the presence of H2S is unknown (as defined in § 250.490 of...

  14. 30 CFR 250.604 - Hydrogen sulfide.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 30 Mineral Resources 2 2013-07-01 2013-07-01 false Hydrogen sulfide. 250.604 Section 250.604... § 250.604 Hydrogen sulfide. When a well-workover operation is conducted in zones known to contain hydrogen sulfide (H2S) or in zones where the presence of H2S is unknown (as defined in § 250.490 of...

  15. 30 CFR 250.504 - Hydrogen sulfide.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 30 Mineral Resources 2 2012-07-01 2012-07-01 false Hydrogen sulfide. 250.504 Section 250.504... § 250.504 Hydrogen sulfide. When a well-completion operation is conducted in zones known to contain hydrogen sulfide (H2S) or in zones where the presence of H2S is unknown (as defined in § 250.490 of...

  16. 30 CFR 250.604 - Hydrogen sulfide.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 30 Mineral Resources 2 2012-07-01 2012-07-01 false Hydrogen sulfide. 250.604 Section 250.604... § 250.604 Hydrogen sulfide. When a well-workover operation is conducted in zones known to contain hydrogen sulfide (H2S) or in zones where the presence of H2S is unknown (as defined in § 250.490 of...

  17. 30 CFR 250.504 - Hydrogen sulfide.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 30 Mineral Resources 2 2013-07-01 2013-07-01 false Hydrogen sulfide. 250.504 Section 250.504... § 250.504 Hydrogen sulfide. When a well-completion operation is conducted in zones known to contain hydrogen sulfide (H2S) or in zones where the presence of H2S is unknown (as defined in § 250.490 of...

  18. Breaking of a metastable string at finite temperature

    SciTech Connect

    Monin, A.; Voloshin, M. B.

    2008-12-15

    We consider the phase transition of a string with tension {epsilon}{sub 1} to a string with a smaller tension {epsilon}{sub 2} at finite temperature. For sufficiently small temperatures the transition proceeds through thermally catalyzed quantum tunneling, and we calculate in arbitrary number of dimensions the thermal catalysis factor. At {epsilon}{sub 2}=0 the found formula for the decay rate also describes a breakup of a metastable string into two pieces.

  19. Deexcitation mechanisms in metastable He-surface collisions

    NASA Astrophysics Data System (ADS)

    Conrad, H.; Ertl, G.; Küppers, J.; Sesselman, W.; Haberland, H.

    1980-11-01

    Electron emission caused by impact of metastable He atoms on surfaces can either proceed by a two-stage resonance ionization + Auger neutralisation (RI + AN) or by a one-stage Auger deexcitation (AD or Penning ionization) mechanism. The RI + AN mechanism will dominate with clean transition metal surfaces and may be suppressed for example by lowering the local work function as demonstrated for K and Cs adlayers.

  20. Fundamental Mvssbauer Parameters of Hydrous Iron Sulfates

    NASA Technical Reports Server (NTRS)

    Rothstein, Y.; Dyar, M. D.; Schaefer, M. W.; Lane, M. D.; Bishop, J. L.

    2005-01-01

    Hydrous iron sulfates, which form as alteration products of sulfides, are rare on Earth. On Mars, the low temperature and pH found in the martian permafrost create ideal conditions for the formation of this group of minerals [1], which includes such phases as coquimbite (Fe2(SO4) 9H2O) and amarantite (FeSO4(OH) 3H2O). Viking, Mars Pathfinder, MER and OMEGA data [e.g., [2

  1. Metastable growth of pure wurtzite InGaAs microstructures.

    PubMed

    Ng, Kar Wei; Ko, Wai Son; Lu, Fanglu; Chang-Hasnain, Connie J

    2014-08-13

    III-V compound semiconductors can exist in two major crystal phases, namely, zincblende (ZB) and wurtzite (WZ). While ZB is thermodynamically favorable in conventional III-V epitaxy, the pure WZ phase can be stable in nanowires with diameters smaller than certain critical values. However, thin nanowires are more vulnerable to surface recombination, and this can ultimately limit their performances as practical devices. In this work, we study a metastable growth mechanism that can yield purely WZ-phased InGaAs microstructures on silicon. InGaAs nucleates as sharp nanoneedles and expand along both axial and radial directions simultaneously in a core-shell fashion. While the base can scale from tens of nanometers to over a micron, the tip can remain sharp over the entire growth. The sharpness maintains a high local surface-to-volume ratio, favoring hexagonal lattice to grow axially. These unique features lead to the formation of microsized pure WZ InGaAs structures on silicon. To verify that the WZ microstructures are truly metastable, we demonstrate, for the first time, the in situ transformation from WZ to the energy-favorable ZB phase inside a transmission electron microscope. This unconventional core-shell growth mechanism can potentially be applied to other III-V materials systems, enabling the effective utilization of the extraordinary properties of the metastable wurtzite crystals.

  2. Thermal beam of metastable krypton atoms produced by optical excitation

    SciTech Connect

    Ding, Y.; Hu, S.-M.; Bailey, K.; Davis, A. M.; Dunford, R. W.; Lu, Z.-T.; O'Connor, T. P.; Young, L.

    2007-02-15

    A room-temperature beam of krypton atoms in the metastable 5s[3/2]{sub 2} level is demonstrated via an optical excitation method. A Kr-discharge lamp is used to produce vacuum ultraviolet photons at 124 nm for the first-step excitation from the ground level 4p{sup 6} {sup 1}S{sub 0} to the 5s[3/2]{sub 1} level. An 819 nm Ti:sapphire laser is used for the second-step excitation from 5s[3/2]{sub 1} to 5s[3/2]{sub 2} followed by a spontaneous decay to the 5s[3/2]{sub 2} metastable level. A metastable atomic beam with an angular flux density of 3x10{sup 14} s{sup -1} sr{sup -1} is achieved at the total gas flow rate of 0.01 cm{sup 3}/s at STP (or 3x10{sup 17} at./s). The dependences of the flux on the gas flow rate, laser power, and lamp parameters are investigated.

  3. Detecting vapour bubbles in simulations of metastable water.

    PubMed

    González, Miguel A; Menzl, Georg; Aragones, Juan L; Geiger, Philipp; Caupin, Frederic; Abascal, Jose L F; Dellago, Christoph; Valeriani, Chantal

    2014-11-14

    The investigation of cavitation in metastable liquids with molecular simulations requires an appropriate definition of the volume of the vapour bubble forming within the metastable liquid phase. Commonly used approaches for bubble detection exhibit two significant flaws: first, when applied to water they often identify the voids within the hydrogen bond network as bubbles thus masking the signature of emerging bubbles and, second, they lack thermodynamic consistency. Here, we present two grid-based methods, the M-method and the V-method, to detect bubbles in metastable water specifically designed to address these shortcomings. The M-method incorporates information about neighbouring grid cells to distinguish between liquid- and vapour-like cells, which allows for a very sensitive detection of small bubbles and high spatial resolution of the detected bubbles. The V-method is calibrated such that its estimates for the bubble volume correspond to the average change in system volume and are thus thermodynamically consistent. Both methods are computationally inexpensive such that they can be used in molecular dynamics and Monte Carlo simulations of cavitation. We illustrate them by computing the free energy barrier and the size of the critical bubble for cavitation in water at negative pressure. PMID:25399176

  4. Study on the metastable zone width of ketoprofen.

    PubMed

    Lu, Ying Hong; Ching, Chi Bun

    2006-05-01

    With increasing awareness for the need of pure enantiomer drugs, strong emphasis has been focused on the research of chiral drug separation. Compared with other separation methods, crystallization is a simple and economical method, and the metastable zone width (MSZW) is a very important factor for the entire crystallization process. In this paper, the effects of the metastable zones of (R,S)- and (S)-ketoprofen and a 0.94 mole fraction of (S)-ketoprofen in order to enhance the MSZW were studied. Four main factors were studied, namely, temperature, cooling rate, stirring rate, and volume ratio of mixed solvent (water/ethanol). Through the L9 fractional experiment design, it was observed that all samples' MSZWs would increase with an increase in cooling rate and decrease with an increase in the ethanol volume ratio and temperature. The ethanol ratio may have the strongest effect on the process and can greatly enhance the metastable zone, and the other three factors influence the MSZW only slightly. In conclusion, the these four factors for enhancing MSZW have been optimized: water-to-ethanol volume ratio, 1:0.6; temperature, 20 degrees C; stirring rate, 700 rpm; and cooling rate, 12.0 degrees C/h. All of these results will be helpful for the following chiral separation of ketoprofen by crystallization. PMID:16521089

  5. Metastable Oxygen Production by Electron-Impact of Oxygen

    NASA Astrophysics Data System (ADS)

    Hein, J. D.; Malone, C. P.; Johnson, P. V.; Kanik, I.

    2014-12-01

    Electron-impact excitation processes involving atomic and molecular oxygen are important in atmospheric interactions. The production of long-lived metastable O(1S) and O(1D) through electron impact of oxygen-containing molecules plays a significant role in the dynamics of planetary atmospheres (Earth, Mars, Europa, Io, Enceladus) and cometary bodies (Hale-Bopp). The electron-impact excitation channels to O(1S) and O(1D) are important for determining energy partitioning and dynamics. To reliably model natural phenomena and interpret observational data, the accurate determination of underlying collision processes (cross sections, dissociation dynamics) through fundamental experimental studies is essential. The detection of metastable species in laboratory experiments requires a novel approach. Typical radiative de-excitation detection techniques cannot be performed due to the long-lived nature of excited species, and conventional particle detectors are insensitive to the low internal energies O(1S) and O(1D). We have recently constructed an apparatus to detect and characterize metastable oxygen production by electron impact using the "rare gas conversion technique." Recent results will be presented, including absolute excitation functions for target gases O2, CO, CO2, and N2O. This work was performed at the Jet Propulsion Laboratory (JPL), California Institute of Technology, under a contract with the National Aeronautics and Space Administration (NASA). Financial support through NASA's OPR, PATM, and MFRP programs, as well as the NASA Postdoctoral Program (NPP) are gratefully acknowledged.

  6. Metastable pitting of carbon steel under potentiostatic control

    SciTech Connect

    Cheng, Y.F.; Luo, J.L.

    1999-03-01

    The metastable pitting of A516-70 carbon steel was studied under potentiostatic control in solutions containing chloride ions. It was shown that there were different current fluctuation patterns and spectral slopes, that is, roll-off slopes, in passivity, general corrosion, and metastable pitting. Pits were often covered by a deposit which played an important role in the current fluctuation, with a quick current rise followed by a slow drop. There was a transitional potential (about 0 mV vs Ag/AgCl electrode) below which the metastable pitting initiation rate increased with the potential, because more sites would be activated. Above the transitional potential, the decay of the pitting occurrence rate with increased potential was due to the elimination of available pit sites. When the applied potential was between {minus}50 and 100 mV, pit growth kinetics was controlled by the potential drop through the deposit over the pit mouth. The potential dependence of repassivation time was mainly due to the effect of applied potential on the deposit over the pit mouth. There seemed to be good agreement between the calculated pit size and the measured values by optical microphotography. The assumption of hemispherical pit geometry was reasonable in calculating the pit radii.

  7. Detecting vapour bubbles in simulations of metastable water

    SciTech Connect

    González, Miguel A.; Abascal, Jose L. F.; Valeriani, Chantal E-mail: cvaleriani@quim.ucm.es; Menzl, Georg; Geiger, Philipp; Dellago, Christoph E-mail: cvaleriani@quim.ucm.es; Aragones, Juan L.; Caupin, Frederic

    2014-11-14

    The investigation of cavitation in metastable liquids with molecular simulations requires an appropriate definition of the volume of the vapour bubble forming within the metastable liquid phase. Commonly used approaches for bubble detection exhibit two significant flaws: first, when applied to water they often identify the voids within the hydrogen bond network as bubbles thus masking the signature of emerging bubbles and, second, they lack thermodynamic consistency. Here, we present two grid-based methods, the M-method and the V-method, to detect bubbles in metastable water specifically designed to address these shortcomings. The M-method incorporates information about neighbouring grid cells to distinguish between liquid- and vapour-like cells, which allows for a very sensitive detection of small bubbles and high spatial resolution of the detected bubbles. The V-method is calibrated such that its estimates for the bubble volume correspond to the average change in system volume and are thus thermodynamically consistent. Both methods are computationally inexpensive such that they can be used in molecular dynamics and Monte Carlo simulations of cavitation. We illustrate them by computing the free energy barrier and the size of the critical bubble for cavitation in water at negative pressure.

  8. Detecting vapour bubbles in simulations of metastable water.

    PubMed

    González, Miguel A; Menzl, Georg; Aragones, Juan L; Geiger, Philipp; Caupin, Frederic; Abascal, Jose L F; Dellago, Christoph; Valeriani, Chantal

    2014-11-14

    The investigation of cavitation in metastable liquids with molecular simulations requires an appropriate definition of the volume of the vapour bubble forming within the metastable liquid phase. Commonly used approaches for bubble detection exhibit two significant flaws: first, when applied to water they often identify the voids within the hydrogen bond network as bubbles thus masking the signature of emerging bubbles and, second, they lack thermodynamic consistency. Here, we present two grid-based methods, the M-method and the V-method, to detect bubbles in metastable water specifically designed to address these shortcomings. The M-method incorporates information about neighbouring grid cells to distinguish between liquid- and vapour-like cells, which allows for a very sensitive detection of small bubbles and high spatial resolution of the detected bubbles. The V-method is calibrated such that its estimates for the bubble volume correspond to the average change in system volume and are thus thermodynamically consistent. Both methods are computationally inexpensive such that they can be used in molecular dynamics and Monte Carlo simulations of cavitation. We illustrate them by computing the free energy barrier and the size of the critical bubble for cavitation in water at negative pressure.

  9. Detecting vapour bubbles in simulations of metastable water

    NASA Astrophysics Data System (ADS)

    González, Miguel A.; Menzl, Georg; Aragones, Juan L.; Geiger, Philipp; Caupin, Frederic; Abascal, Jose L. F.; Dellago, Christoph; Valeriani, Chantal

    2014-11-01

    The investigation of cavitation in metastable liquids with molecular simulations requires an appropriate definition of the volume of the vapour bubble forming within the metastable liquid phase. Commonly used approaches for bubble detection exhibit two significant flaws: first, when applied to water they often identify the voids within the hydrogen bond network as bubbles thus masking the signature of emerging bubbles and, second, they lack thermodynamic consistency. Here, we present two grid-based methods, the M-method and the V-method, to detect bubbles in metastable water specifically designed to address these shortcomings. The M-method incorporates information about neighbouring grid cells to distinguish between liquid- and vapour-like cells, which allows for a very sensitive detection of small bubbles and high spatial resolution of the detected bubbles. The V-method is calibrated such that its estimates for the bubble volume correspond to the average change in system volume and are thus thermodynamically consistent. Both methods are computationally inexpensive such that they can be used in molecular dynamics and Monte Carlo simulations of cavitation. We illustrate them by computing the free energy barrier and the size of the critical bubble for cavitation in water at negative pressure.

  10. Metastable charged sparticles and the cosmological {sup 7}Li problem

    SciTech Connect

    Cyburt, Richard H.; Ellis, John; Luo, Feng; Fields, Brian D.; Olive, Keith A.; Spanos, Vassilis C. E-mail: John.Ellis@cern.ch E-mail: feng.luo@kcl.ac.uk E-mail: spanos@inp.demokritos.gr

    2012-12-01

    We consider the effects of metastable charged sparticles on Big-Bang Nucleosynthesis (BBN), including bound-state reaction rates and chemical effects. We make a new analysis of the bound states of negatively-charged massive particles with the light nuclei most prominent in BBN, and present a new code to track their abundances, paying particular attention to that of {sup 7}Li. Assuming, as an example, that the gravitino is the lightest supersymmetric particle (LSP), and that the lighter stau slepton, τ-tilde {sub 1}, is the metastable next-to-lightest sparticle within the constrained minimal supersymmetric extension of the Standard Model (CMSSM), we analyze the possible effects on the standard BBN abundances of τ-tilde {sub 1} bound states and decays for representative values of the gravitino mass. Taking into account the constraint on the CMSSM parameter space imposed by the discovery of the Higgs boson at the LHC, we delineate regions in which the fit to the measured light-element abundances is as good as in standard BBN. We also identify regions of the CMSSM parameter space in which the bound state properties, chemistry and decays of metastable charged sparticles can solve the cosmological {sup 7}Li problem.

  11. Stable, Metastable, and Kinetically Trapped Amyloid Aggregate Phases

    PubMed Central

    2015-01-01

    Self-assembly of proteins into amyloid fibrils plays a key role in a multitude of human disorders that range from Alzheimer’s disease to type II diabetes. Compact oligomeric species, observed early during amyloid formation, are reported as the molecular entities responsible for the toxic effects of amyloid self-assembly. However, the relation between early-stage oligomeric aggregates and late-stage rigid fibrils, which are the hallmark structure of amyloid plaques, has remained unclear. We show that these different structures occupy well-defined regions in a peculiar phase diagram. Lysozyme amyloid oligomers and their curvilinear fibrils only form after they cross a salt and protein concentration-dependent threshold. We also determine a boundary for the onset of amyloid oligomer precipitation. The oligomeric aggregates are structurally distinct from rigid fibrils and are metastable against nucleation and growth of rigid fibrils. These experimentally determined boundaries match well with colloidal model predictions that account for salt-modulated charge repulsion. The model also incorporates the metastable and kinetic character of oligomer phases. Similarities and differences of amyloid oligomer assembly to metastable liquid–liquid phase separation of proteins and to surfactant aggregation are discussed. PMID:25469942

  12. Metastable charge-transfer state of californium(iii) compounds.

    PubMed

    Liu, Guokui; Cary, Samantha K; Albrecht-Schmitt, Thomas E

    2015-06-28

    Among a series of anomalous physical and chemical properties of Cf(iii) compounds revealed by recent investigations, the present work addresses the characteristics of the optical spectra of An(HDPA)3·H2O (An = Am, Cm, and Cf), especially the broadband photoluminescence from Cf(HDPA)3·H2O induced by ligand-to-metal charge transfer (CT). As a result of strong ion-ligand interactions and the relative ease of reducing Cf(iii) to Cf(ii), a CT transition occurs at low energy (<3 eV) via the formation of a metastable Cf(ii) state. It is shown that the systematic trend in CT transitions of the lanthanide series is not paralleled by actinide elements lighter than Cf(iii), and californium represents a turning point in the periodicity of the actinide series. Analyses and modeling of the temperature-dependent luminescence dynamics indicate that the metastable Cf(ii) charge-transfer state undergoes radiative and non-radiative relaxations. Broadening of the CT transition arises from strong vibronic coupling and hole-charge interactions in the valence band. The non-radiative relaxation of the metastable CT state results from a competition between phonon-relaxation and thermal tunneling that populates the excited states of Cf(iii).

  13. Changes in Iron, Sulfur, and Arsenic Speciation Associated with Bacterial Sulfate Reduction in Ferrihydrite-Rich Systems

    SciTech Connect

    Saalfield, S.; Bostick, B

    2009-01-01

    Biologically mediated redox processes have been shown to affect the mobility of iron oxide-bound arsenic in reducing aquifers. This work investigates how dissimilatory sulfate reduction and secondary iron reduction affect sulfur, iron, and arsenic speciation. Incubation experiments were conducted with As(III/V)-bearing ferrihydrite in carbonate-buffered artificial groundwater enriched with lactate (10 mM) and sulfate (0.08-10 mM) and inoculated with Desulfovibrio vulgaris (ATCC 7757, formerly D. desulfuricans), which reduces sulfate but not iron or arsenic. Sulfidization of ferrihydrite led to formation of magnetite, elemental sulfur, and trace iron sulfides. Observed reaction rates imply that the majority of sulfide is recycled to sulfate, promoting microbial sulfate reduction in low-sulfate systems. Despite dramatic changes in Fe and S speciation, and minimal formation of Fe or As sulfides, most As remained in the solid phase. Arsenic was not solubilized in As(V)-loaded incubations, which experienced slow As reduction by sulfide, whereas As(III)-loaded incubations showed limited and transient As release associated with iron remineralization. This suggests that As(III) production is critical to As release under reducing conditions, with sulfate reduction alone unlikely to release As. These data also suggest that bacterial reduction of As(V) is necessary for As sequestration in sulfides, even where sulfate reduction is active.

  14. Occurrence of selenium in sulfides from some sedimentary rocks of the western United States

    USGS Publications Warehouse

    Coleman, Robert G.; Delevaux, Maryse

    1956-01-01

    Investigations of the minor- and trace-element content of sulfides associated with uranium ore deposits from sandstone-type deposits have shown that selenium commonly substitutes for sulfur. The Morrison formation and Entrada sandstone of Jurassic age and the Wind River formation of Eocene age seem to be seleniferous stratigraphic zones; sulfides deposited within these formations generally contain abnormal amounts of selenium. The selenium content of the pyrite, marcasite, and chalcocite is much greater than that reported in previously published data. Under the prevailing temperatures and pressures of formation of the Colorado Plateau uranium deposits the maximum amount of Se substituting for S in the pyrite structure was found to be 3 percent by weight. Ferroselite, the iron selenide (FeSe2), was found in two deposits on the Colorado Plateau and it was also established that galena (PbS) forms an isomorphous series with clausthalite (PbSe) in nature. During oxidation of the selenium-bearing sulfides and selenides in the Colorado Plateau and Wyoming, the selenium forms pinkish crusts of either monoclinic or hexagonal native selenium intergrown with soluble sulfates, suggesting that under "normal" oxidizing conditions native selenium is more stable than selenites or selenates. The above-normal selenium content of these sulfides from sedimentary rocks of Mesozoic and Tertiary age is significant. The high selenium in these sulfides is related to periods of volcanic and intrusive activity penecontemporaneous with the formation of the containing sediments.

  15. Sulfide Oxidation by a Noncanonical Pathway in Red Blood Cells Generates Thiosulfate and Polysulfides*

    PubMed Central

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

    2015-01-01

    A cardioprotectant at low concentrations, H2S is a toxin at high concentrations and inhibits cytochrome c oxidase. A conundrum in H2S homeostasis is its fate in red blood cells (RBCs), which produce H2S but lack the canonical mitochondrial sulfide oxidation pathway for its clearance. The sheer abundance of RBCs in circulation enhances the metabolic significance of their clearance strategy for H2S, necessary to avoid systemic toxicity. In this study, we demonstrate that H2S generation by RBCs is catalyzed by mercaptopyruvate sulfurtransferase. Furthermore, we have discovered the locus of sulfide oxidation in RBCs and describe a new role for an old protein, hemoglobin, which in the ferric or methemoglobin state binds H2S and oxidizes it to a mixture of thiosulfate and hydropolysulfides. Our study reveals a previously undescribed route for the biogenesis of hydropolysulfides, which are increasingly considered important for H2S-based signaling, but their origin in mammalian cells is unknown. An NADPH/flavoprotein oxidoreductase system restores polysulfide-carrying hemoglobin derivatives to ferrous hemoglobin, thus completing the methemoglobin-dependent sulfide oxidation cycle. Methemoglobin-dependent sulfide oxidation in mammals is complex and has similarities to chemistry reported for the dissolution of iron oxides in sulfidic waters and during bioleaching of metal sulfides. The catalytic oxidation of H2S by hemoglobin explains how RBCs maintain low steady-state H2S levels in circulation, and suggests that additional hemeproteins might be involved in sulfide homeostasis in other tissues. PMID:25688092

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

    where pH remains neutral. The "low-acid" oxidation of sulfides with nitrate as an electron acceptor has been demonstrated at the laboratory scale. In 90-day microcosm respirometry experiments, we exposed a mixture of pulverized quartz and pyrite -rich ore to natural, high-nitrate groundwater and inoculated the microcosms with a culture of aerobic and anaerobic nitrate-dependent iron and sulfur-oxidising microorganisms, which were enriched from ore, groundwater and activated waste water. Incubations were performed under both oxic and anoxic conditions, in addition to abiotic controls. Initial results show that oxidation of the sulfides under nitrate-rich and microbially enhanced conditions does produce less acid than the same material under oxic conditions, and to some degree can match the models as long as oxygen ingress can be controlled. These results are the focus of further research into how this process can be enhanced and whether it can be applied in the field. Nitrate-driven oxidation of sulfides could potentially be used as a new approach to reduce acid generation and leaching of contaminants from waste dumps, in a passive or actively managed process designed to deplete and/or ameliorate (i.e. through surface passivation) the mineralogical hazard. Developing our understanding of biological aspects of these processes may also allow testing of longer-term "bio-caps" for various tailings and dump materials.

  17. Dissolved sulfide in groundwater with elevated arsenic concentrations at Winthrop, Maine

    NASA Astrophysics Data System (ADS)

    He, Y.; Zheng, Y.; Zheng, Y.; Locke, D. C.; Simpson, J. H.; Stute, M.

    2001-12-01

    Although sulfur is a biogeochemically significant element because of its strong influence on and response to redox conditions, there are relatively few reliable data sets of trace levels of dissolved sulfide \\(less than1 uM \\) in groundwaters This circumstance results from the relatively high detection limit \\(˜ 1uM \\) of methylene blue colorimetry and the general lack of sensitive methods for field analysis. We were motivated to investigate trace levels of dissolved sulfide because highly insoluble sulfide precipitates of many elements such as As and Fe represent important removal pathways for these metals in reducing groundwaters. Using differential pulse cathodic stripping voltammetry \\(DPCSV\\) capable of detecting 4 nM of dissolved sulfide, we observed that at a site in Winthrop, Maine, groundwater sulfide concentrations ranged from less than 4 nM to ˜ 2000 nM for about a dozen multi-level observation wells under a landfill cap and less than 4 nM to ˜ 7300 nM from several nearby monitoring wells outside the landfill. Sulfide concentrations generally increased when oxygen reduction potential \\(ORP\\) values became more negative. Determination of sulfide should be carried out within 1 hr of sample collection. Samples taken by two methods, \\(1\\) PTFE syringes with luer-lock valves and \\(2\\) BOD bottles show a rapid decline of sulfide following sampling, with up to 90% and 60% losses, respectively, after 24 hrs of storage at 4 ° C. Despite the three orders of magnitude range of dissolved sulfide, arsenic and iron concentrations were all elevated in observational wells installed in a roughly 25 m by 20 m rectangle under the landfill cap, suggesting that As remains mobile under mildly sulfate-reducing conditions. In one well outside of the landfill area, with extremely negative ORP \\(-321 mV\\) and ˜ 7300 nM of dissolved sulfide, groundwater was very low in dissolved As, Fe, and sulfate, suggesting that precipitation of arsenopyrite could be a

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

    NASA Astrophysics Data System (ADS)

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

    2012-04-01

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

  19. Normal and abnormal evolution of argon metastable density in high-density plasmas

    SciTech Connect

    Seo, B. H.; Kim, J. H.; You, S. J.

    2015-05-15

    A controversial problem on the evolution of Ar metastable density as a function of electron density (increasing trend versus decreasing trend) was resolved by discovering the anomalous evolution of the argon metastable density with increasing electron density (discharge power), including both trends of the metastable density [Daltrini et al., Appl. Phys. Lett. 92, 061504 (2008)]. Later, by virtue of an adequate physical explanation based on a simple global model, both evolutions of the metastable density were comprehensively understood as part of the abnormal evolution occurring at low- and high-density regimes, respectively, and thus the physics behind the metastable evolution has seemed to be clearly disclosed. In this study, however, a remarkable result for the metastable density behavior with increasing electron density was observed: even in the same electron density regime, there are both normal and abnormal evolutions of metastable-state density with electron density depending on the measurement position: The metastable density increases with increasing electron density at a position far from the inductively coupled plasma antenna but decreases at a position close to the antenna. The effect of electron temperature, which is spatially nonuniform in the plasma, on the electron population and depopulation processes of Argon metastable atoms with increasing electron density is a clue to understanding the results. The calculated results of the global model, including multistep ionization for the argon metastable state and measured electron temperature, are in a good agreement with the experimental results.

  20. Electrostatic levitation studies of supercooled liquids and metastable solid phases

    NASA Astrophysics Data System (ADS)

    Rustan, Gustav Errol

    A new laboratory has been developed at Iowa State University (ISU) to be used for the study of high temperature liquids and solids, with particular focus on the supercooling of liquids and their metastable solidification products. This new laboratory employs the electrostatic levitation (ESL) technique, in which a charged sample is suspended between a set of electrodes to achieve non-contact handling. Owing to the elimination of a crucible, high temperature processing of samples can be achieved with reduced levels of contamination and heterogeneous nucleation. Because of the reduction in heterogeneous nucleation, samples can be supercooled well below their equilibrium melting temperature, opening the door to a wide range of measurements on supercooled liquids. Measurements methods have been implemented for the characterization of thermophysical properties such as: volume/density, ratio of specific heat to total hemispherical emissivity, surface tension, viscosity, electrical resistivity, and magnetic susceptibility. For measurements of electrical resistivity and magnetic susceptibility, a new method has been developed at ISU based on the tunnel diode oscillator (TDO) technique. The TDO technique uses the negative differential resistance of a tunnel diode to drive an LC tank circuit into self-sustained oscillation at the resonant LC frequency. The LC tank is inductively coupled to the samples under study, and changes in the electrical resistivity or magnetic susceptibility of the sample are manifested as changes in the resonant frequency. By measuring the frequency shifts of the TDO, insights can be made into changes in the material's electrical and magnetic properties. This method has been validated by performing resistivity measurements on a sample of high purity Zr, and by performing measurements on the ferromagnetic transition in a low-carbon steel ball bearing. In addition to the development of the laboratory and its supporting instrumentation, an effort has

  1. Lithium-cupric sulfide cell

    SciTech Connect

    Cuesta, A.J.; Bump, D.D.

    1980-01-01

    Lithium cells have become the primary power source for cardiac pacemakers due to their reliability and longevity at low current drain rates. A lithium-cupric sulfide cell was developed which makes maximum use of the shape of a pacemaker's battery compartment. The cell has a stable voltage throughout 90% of its lifetime. It then drops to a second stable voltage before depletion. The voltage drop creates a small decrease in pacemaker rate, which alerts the physician to replace the pacemaker. No loss of capacity due to self-discharge as been seen to date, and cells have proven to be safe under extreme conditions. 2 refs.

  2. Molybdenum sulfide/carbide catalysts

    DOEpatents

    Alonso, Gabriel; Chianelli, Russell R.; Fuentes, Sergio; Torres, Brenda

    2007-05-29

    The present invention provides methods of synthesizing molybdenum disulfide (MoS.sub.2) and carbon-containing molybdenum disulfide (MoS.sub.2-xC.sub.x) catalysts that exhibit improved catalytic activity for hydrotreating reactions involving hydrodesulfurization, hydrodenitrogenation, and hydrogenation. The present invention also concerns the resulting catalysts. Furthermore, the invention concerns the promotion of these catalysts with Co, Ni, Fe, and/or Ru sulfides to create catalysts with greater activity, for hydrotreating reactions, than conventional catalysts such as cobalt molybdate on alumina support.

  3. Preparation of amorphous sulfide sieves

    DOEpatents

    Siadati, Mohammad H.; Alonso, Gabriel; Chianelli, Russell R.

    2006-11-07

    The present invention involves methods and compositions for synthesizing catalysts/porous materials. In some embodiments, the resulting materials are amorphous sulfide sieves that can be mass-produced for a variety of uses. In some embodiments, methods of the invention concern any suitable precursor (such as thiomolybdate salt) that is exposed to a high pressure pre-compaction, if need be. For instance, in some cases the final bulk shape (but highly porous) may be same as the original bulk shape. The compacted/uncompacted precursor is then subjected to an open-flow hot isostatic pressing, which causes the precursor to decompose and convert to a highly porous material/catalyst.

  4. Iron isotopes in an Archean ocean analogue

    NASA Astrophysics Data System (ADS)

    Busigny, Vincent; Planavsky, Noah J.; Jézéquel, Didier; Crowe, Sean; Louvat, Pascale; Moureau, Julien; Viollier, Eric; Lyons, Timothy W.

    2014-05-01

    Iron isotopes have been extensively used to trace the history of microbial metabolisms and the redox evolution of the oceans. Archean sedimentary rocks display greater variability in iron isotope ratios and more markedly negative values than those deposited in the Proterozoic and Phanerozoic. This increased variability has been linked to changes in either water column iron cycling or the extent of benthic microbial iron reduction through time. We tested these contrasting scenarios through a detailed study of anoxic and ferruginous Lac Pavin (France), which can serve as a modern analogue of the Archean ocean. A depth-profile in the water column of Lac Pavin shows a remarkable increase in dissolved Fe concentration (0.1-1200 μM) and δ56Fe values (-2.14‰ to +0.31‰) across the oxic-anoxic boundary to the lake bottom. The largest Fe isotope variability is found at the redox boundary and is related to partial oxidation of dissolved ferrous iron, leaving the residual Fe enriched in light isotopes. The analysis of four sediment cores collected along a lateral profile (one in the oxic layer, one at the redox boundary, one in the anoxic zone, and one at the bottom of the lake) indicates that bulk sediments, porewaters, and reactive Fe mostly have δ56Fe values near 0.0 ± 0.2‰, similar to detrital iron. In contrast, pyrite δ56Fe values in sub-chemocline cores (60, 65, and 92 m) are highly variable and show significant deviations from the detrital iron isotope composition (δ56Fepyrite between -1.51‰ and +0.09‰; average -0.93‰). Importantly, the pyrite δ56Fe values mirror the δ56Fe of dissolved iron at the redox boundary—where near quantitative sulfate and sulfide drawdown occurs—suggesting limited iron isotope fractionation during iron sulfide formation. This finding has important implications for the Archean environment. Specifically, this work suggests that in a ferruginous system, most of the Fe isotope variability observed in sedimentary pyrites can

  5. Synthesis and optical properties of sulfide nanoparticles prepared in dimethylsulfoxide.

    PubMed

    Li, Yuebin; Ma, Lun; Zhang, Xing; Joly, Alan G; Liu, Zuli; Chen, Wei

    2008-11-01

    Many methods have been reported for the formation of sulfide nanoparticles by the reaction of metallic salts with sulfide chemical sources in aqueous solutions or organic solvents. Here, we report the formation of sulfide nanoparticles in dimethylsulfoxide (DMSO) by boiling metallic salts without sulfide sources. The sulfide sources are generated from the boiling of DMSO and react with metallic salts to form sulfide nanoparticles. In this method DMSO functions as a solvent and a sulfide source as well as a stabilizer for the formation of the nanoparticles. The recipe is simple and economical making sulfide nanoparticles formed in this way readily available for many potential applications.

  6. 40 CFR 425.03 - Sulfide analytical methods and applicability.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... Provisions § 425.03 Sulfide analytical methods and applicability. (a) The potassium ferricyanide titration... the potassium ferricyanide titration method for the determination of sulfide in wastewaters...

  7. 40 CFR 425.03 - Sulfide analytical methods and applicability.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... Provisions § 425.03 Sulfide analytical methods and applicability. (a) The potassium ferricyanide titration... the potassium ferricyanide titration method for the determination of sulfide in wastewaters...

  8. 40 CFR 425.03 - Sulfide analytical methods and applicability.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... Provisions § 425.03 Sulfide analytical methods and applicability. (a) The potassium ferricyanide titration... the potassium ferricyanide titration method for the determination of sulfide in wastewaters...

  9. Synthesis and Optical Properties of Sulfide Nanoparticles Prepared in Dimethylsulfoxide

    SciTech Connect

    Li, Yuebin; Ma, Lun; Zhang, Xing; Joly, Alan G.; Liu, Zuli; Chen, Wei

    2008-11-01

    Many methods have been reported for the formation of sulfide nanoparticles by the reaction of metallic salts with sulfide chemical sources in aqueous solutions or organic solvents. Here, we report the formation of sulfide nanoparticles in dimethylsulfoxide (DMSO) by boiling metallic salts without sulfide sources. The sulfide sources are generated from the boiling of DMSO and react with metallic salts to form sulfide nanoparticles. In this method DMSO functions as a solvent and a sulfide source as well as a stabilizer for the formation of the nanoparticles. The recipe is simple and economical making sulfide nanoparticles formed in this way readily available for many potential applications.

  10. Variation in sulfide tolerance of photosystem II in phylogenetically diverse cyanobacteria from sulfidic habitats

    NASA Technical Reports Server (NTRS)

    Miller, Scott R.; Bebout, Brad M.

    2004-01-01

    Physiological and molecular phylogenetic approaches were used to investigate variation among 12 cyanobacterial strains in their tolerance of sulfide, an inhibitor of oxygenic photosynthesis. Cyanobacteria from sulfidic habitats were found to be phylogenetically diverse and exhibited an approximately 50-fold variation in photosystem II performance in the presence of sulfide. Whereas the degree of tolerance was positively correlated with sulfide levels in the environment, a strain's phenotype could not be predicted from the tolerance of its closest relatives. These observations suggest that sulfide tolerance is a dynamic trait primarily shaped by environmental variation. Despite differences in absolute tolerance, similarities among strains in the effects of sulfide on chlorophyll fluorescence induction indicated a common mode of toxicity. Based on similarities with treatments known to disrupt the oxygen-evolving complex, it was concluded that sulfide toxicity resulted from inhibition of the donor side of photosystem II.

  11. Ammonia and hydrogen sulfide removal using biochar

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Reducing ammonia and hydrogen sulfide emissions from livestock facilities is an important issue for many communities and livestock producers. Ammonia has been regarded as odorous, precursor for particulate matter (PM), and contributed to livestock mortality. Hydrogen sulfide is highly toxic at elev...

  12. Sulfide oxidation under chemolithoautotrophic denitrifying conditions.

    PubMed

    Cardoso, Ricardo Beristain; Sierra-Alvarez, Reyes; Rowlette, Pieter; Flores, Elias Razo; Gómez, Jorge; Field, Jim A

    2006-12-20

    Chemolithoautotrophic denitrifying microorganisms oxidize reduced inorganic sulfur compounds coupled to the reduction of nitrate as an electron acceptor. These denitrifiers can be applied to the removal of nitrogen and/or sulfur contamination from wastewater, groundwater, and gaseous streams. This study investigated the physiology and kinetics of chemolithotrophic denitrification by an enrichment culture utilizing hydrogen sulfide, elemental sulfur, or thiosulfate as electron donor. Complete oxidation of sulfide to sulfate was observed when nitrate was supplemented at concentrations equal or exceeding the stoichiometric requirement. In contrast, sulfide was only partially oxidized to elemental sulfur when nitrate concentrations were limiting. Sulfide was found to inhibit chemolithotrophic sulfoxidation, decreasing rates by approximately 21-fold when the sulfide concentration increased from 2.5 to 10.0 mM, respectively. Addition of low levels of acetate (0.5 mM) enhanced denitrification and sulfate formation, suggesting that acetate was utilized as a carbon source by chemolithotrophic denitrifiers. The results of this study indicate the potential of chemolithotrophic denitrification for the removal of hydrogen sulfide. The sulfide/nitrate ratio can be used to control the fate of sulfide oxidation to either elemental sulfur or sulfate.

  13. 30 CFR 250.808 - Hydrogen sulfide.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 30 Mineral Resources 2 2011-07-01 2011-07-01 false Hydrogen sulfide. 250.808 Section 250.808 Mineral Resources BUREAU OF OCEAN ENERGY MANAGEMENT, REGULATION, AND ENFORCEMENT, DEPARTMENT OF THE... Safety Systems § 250.808 Hydrogen sulfide. Production operations in zones known to contain...

  14. Iron refractory iron deficiency anemia

    PubMed Central

    De Falco, Luigia; Sanchez, Mayka; Silvestri, Laura; Kannengiesser, Caroline; Muckenthaler, Martina U.; Iolascon, Achille; Gouya, Laurent; Camaschella, Clara; Beaumont, Carole

    2013-01-01

    Iron refractory iron deficiency anemia is a hereditary recessive anemia due to a defect in the TMPRSS6 gene encoding Matriptase-2. This protein is a transmembrane serine protease that plays an essential role in down-regulating hepcidin, the key regulator of iron homeostasis. Hallmarks of this disease are microcytic hypochromic anemia, low transferrin saturation and normal/high serum hepcidin values. The anemia appears in the post-natal period, although in some cases it is only diagnosed in adulthood. The disease is refractory to oral iron treatment but shows a slow response to intravenous iron injections and partial correction of the anemia. To date, 40 different Matriptase-2 mutations have been reported, affecting all the functional domains of the large ectodomain of the protein. In vitro experiments on transfected cells suggest that Matriptase-2 cleaves Hemojuvelin, a major regulator of hepcidin expression and that this function is altered in this genetic form of anemia. In contrast to the low/undetectable hepcidin levels observed in acquired iron deficiency, in patients with Matriptase-2 deficiency, serum hepcidin is inappropriately high for the low iron status and accounts for the absent/delayed response to oral iron treatment. A challenge for the clinicians and pediatricians is the recognition of the disorder among iron deficiency and other microcytic anemias commonly found in pediatric patients. The current treatment of iron refractory iron deficiency anemia is based on parenteral iron administration; in the future, manipulation of the hepcidin pathway with the aim of suppressing it might become an alternative therapeutic approach. PMID:23729726

  15. Weathering of sulfides on Mars

    NASA Technical Reports Server (NTRS)

    Burns, Roger G.; Fisher, Duncan S.

    1987-01-01

    Pyrrhotite-pentlandite assemblages in mafic and ultramafic igneous rocks may have contributed significantly to the chemical weathering reactions that produce degradation products in the Martian regolith. By analogy and terrestrial processes, a model is proposed whereby supergene alteration of these primary Fe-Ni sulfides on Mars has generated secondary sulfides (e.g., pyrite) below the water table and produced acidic groundwater containing high concentrations of dissolved Fe, Ni, and sulfate ions. The low pH solutions also initiated weathering reactions of igneous feldspars and ferromagnesian silicates to form clay silicate and ferric oxyhydroxide phases. Near-surface oxidation and hydrolysis of ferric sulfato-and hydroxo-complex ions and sols formed gossan above the water table consisting of poorly crystalline hydrated ferric sulfates (e.g., jarosite), oxides (ferrihydrite, goethite), and silica (opal). Underlying groundwater, now permafrost contains hydroxo sulfato complexes of Fe, Al, Mg, Ni, which may be stabilized in frozen acidic solutions beneath the surface of Mars. Sublimation of permafrost may replenish colloidal ferric oxides, sulfates, and phyllosilicates during dust storms on Mars.

  16. Percutaneous absorption of selenium sulfide

    SciTech Connect

    Farley, J.; Skelly, E.M.; Weber, C.B.

    1986-01-01

    The purpose of this study was to determine selenium levels in the urine of Tinea patients before and after overnight application of a 2.5% selenium sulfide lotion. Selenium was measured by atomic absorption spectroscopy (AAS). Hydride generation and carbon rod atomization were studied. It was concluded from this study that selenium is absorbed through intact skin. Selenium is then excreted, at least partially, in urine, for at least a week following treatment. The data show that absorption and excretion of selenium vary on an individual basis. Selenium levels in urine following a single application of selenium sulfide lotion do not indicate that toxic amounts of selenium are being absorbed. Repeated treatments with SeS/sub 2/ result in selenium concentrations in urine which are significantly higher than normal. Significant matrix effects are observed in the carbon rod atomization of urine samples for selenium determinations, even in the presence of a matrix modifier such as nickel. The method of standard additions is required to obtain accurate results in the direct determination of selenium in urine by carbon rod AAS.

  17. Hydrogen sulfide pollution in wastewater treatment facilities

    SciTech Connect

    AlDhowalia, K.H. )

    1987-01-01

    The hydrogen sulfide (H{sub 2}S) found in wastewater collection systems and wastewater treatment facilities results from the bacterial reduction of the sulfate ion (SO{sub 4}). Hydrogen sulfide is a gas that occurs both in the sewer atmosphere and as a dissolved gas in the wastewater. When raw wastewater first enters the wastewater treatment facility by gravity most of the hydrogen sulfide is in the gaseous phase and will escape into the atmosphere at the inlet structures. Also some of the dissolved hydrogen sulfide will be released at points of turbulance such as at drops in flow, flumes, or aeration chambers. Several factors can cause excessive hydrogen sulfide concentrations in a sewerage system. These include septic sewage, long flow times in the sewerage system, high temperatures, flat sewer grades, and poor ventilation. These factors are discussed in this paper.

  18. Dissociation of CH4 by electron impact: Production of metastable hydrogen and carbon fragments

    NASA Technical Reports Server (NTRS)

    Finn, T. G.; Carnahan, B. L.; Zipf, E. C.

    1974-01-01

    Metastable fragments produced by electron impact excitation of CH4 have been investigated for incident electron energies from threshold to 300 eV. Only metastable hydrogen and carbon atoms were observed. Onset energies for the production of metastable hydrogen atoms were observed at electron impact energies of 22.0 + or - .5 eV, 25.5 + or - .6 eV, 36.7 + or - .6 eV and 66 + or - 3 eV, and at 26.6 + or - .6 eV for the production of metastable carbon atoms. Most of the fragments appear to have been formed in high-lying Rydberg states. The total metastable hydrogen cross section reaches a maximum value of approximately 1 X 10 to the minus 18th power sq cm at 100 eV. At the same energy, the metastable carbon cross section is 2 x 10 to the minus 19th power sq cm.

  19. Metastable Eutectic Equilibrium in Natural Environments: Recent Developments and Research Opportunities

    NASA Technical Reports Server (NTRS)

    Rietmeijer, Fans J. M.; Nuth, Joseph A., II; Jablonska, Mariola; Karner, James M.

    2000-01-01

    Chemical ordering at metastable eutectics was recognized in non-equilibrium gas-to- solid condensation experiments to constrain 'silicate' dust formation in O-rich circumstellar environments. The predictable metastable eutectic behavior successfully predicted the observed ferromagnesiosilica, compositions of circumstellar dust, presolar and solar nebula grains in the matrix of the collected aggregate IDPs. Many of the experimentally determined metastable eutectic solids match the fundamental building blocks of common rock-forming layer silicates: this could have implications for the origin of Life. The physical conditions conducive to metastable eutectic behavior, i.e. high temperature and (ultra)fast quenching, lead to unique amorphous, typically nano- to micrometer-sized, materials. The new paradigm of metastable eutectic behavior opens the door to new and exciting research opportunities in uncovering the many implications of these unique amorphous and typically nano- to micrometer-sized, metastable eutectic materials.

  20. Metastable Eutectic Equilibrium in Natural Environments: Recent Development and Research Opportunities

    NASA Technical Reports Server (NTRS)

    Rietmeijer, Frans J. M.; Nuth, Joseph A., III; Jablonska, Mariola; Karner, James M.

    2000-01-01

    Chemical ordering at metastable eutectics was recognized in non-equilibrium gas-to- solid condensation experiments to constrain 'silicate' dust formation in O-rich circumstellar environments. The predictable metastable eutectic behavior successfully predicted the observed ferromagnesiosilica compositions of circumstellar dust presolar and solar nebula grains in the matrix of the collected aggregate IDPs (Interplanetary Dust Particles). Many of the experimentally determined metastable eutectic solids match the fundamental building blocks of common rock-forming layer silicates: this could have implications for the origin of Life. The physical conditions conducive to metastable eutectic behavior, i.e. high temperature and (ultra) fast quenching, lead to unique amorphous, typically nano- to micrometer-sized, materials. The new paradigm of metastable eutectic behavior opens the door to new and exciting research opportunities in uncovering the many implications of these unique amorphous, and typically nano-to micrometer-sized, metastable eutectic materials.

  1. The synthesis of cadmium sulfide nanoplatelets using a novel continuous flow sonochemical reactor

    DOE PAGESBeta

    Palanisamy, Barath; Paul, Brian; Chang, Chih -hung

    2015-01-21

    A continuous flow sonochemical reactor was developed capable of producing metastable cadmium sulfide (CdS) nanoplatelets with thicknesses at or below 10 nm. The continuous flow sonochemical reactor included the passive in-line micromixing of reagents prior to sonochemical reaction. Synthesis results were compared with those from reactors involving batch conventional heating and batch ultrasound-induced heating. The continuous sonochemical synthesis was found to result in high aspect ratio hexagonal platelets of CdS possessing cubic crystal structures with thicknesses well below 10 nm. The unique shape and crystal structure of the nanoplatelets are suggestive of high localized temperatures within the sonochemical process. Asmore » a result, the particle size uniformity and product throughput are much higher for the continuous sonochemical process in comparison to the batch sonochemical process and conventional synthesis processes.« less

  2. The synthesis of cadmium sulfide nanoplatelets using a novel continuous flow sonochemical reactor

    SciTech Connect

    Palanisamy, Barath; Paul, Brian; Chang, Chih -hung

    2015-01-21

    A continuous flow sonochemical reactor was developed capable of producing metastable cadmium sulfide (CdS) nanoplatelets with thicknesses at or below 10 nm. The continuous flow sonochemical reactor included the passive in-line micromixing of reagents prior to sonochemical reaction. Synthesis results were compared with those from reactors involving batch conventional heating and batch ultrasound-induced heating. The continuous sonochemical synthesis was found to result in high aspect ratio hexagonal platelets of CdS possessing cubic crystal structures with thicknesses well below 10 nm. The unique shape and crystal structure of the nanoplatelets are suggestive of high localized temperatures within the sonochemical process. As a result, the particle size uniformity and product throughput are much higher for the continuous sonochemical process in comparison to the batch sonochemical process and conventional synthesis processes.

  3. "Amorphous nickel sulfide" is hydrated nanocrystalline nis with a core-shell structure.

    PubMed

    Huang, Shanshan; Harris, Kenneth D M; Lopez-Capel, Elisa; Manning, David A C; Rickard, David

    2009-12-21

    The application of a range of experimental techniques shows that "amorphous nickel sulfide" (the material precipitated from aqueous solutions of Ni(II) salts and S(II-) under ambient conditions) is actually a hydrated nanoparticulate material with an approximate formula NiS.1.5H(2)O. The particles comprise a crystalline, anhydrous core (diameter ca. 1-3 nm) with the millerite (NiS) structure, surrounded by a hydrated shell phase. The materials prepared under acidic conditions (pH = 3 and 5) transform with age to form polydymite (Ni(3)S(4)) and heazlewoodite (Ni(3)S(2)), while materials prepared at pH = 7 and 9 do not undergo this transformation. At pH = 12, the preparation procedure yields NiAs-type NiS as a metastable phase.

  4. Metastable gamma-Iron Nickel Nanostructures for Magnetic Refrigeration Near Room Temperature

    NASA Astrophysics Data System (ADS)

    Ucar, Huseyin

    The observation of a giant magnetocaloric effect in Gd5Ge 1.9Si2Fe0.1 has stimulated the magnetocaloric research in the last two decades. However, the high price of Gd and its proclivity to corrosion of these compounds have prevented their commercial use. To reduce raw materials cost, transition metal-based alloys are investigated to replace rare earth-based materials. Environmental considerations, substitution for scarce and strategic elements, and cost considerations all speak to potential contributions of these new materials to sustainability. Efforts in improving the refrigeration capacity (RC) of refrigerants mainly rely on broadening the magnetic entropy change. One promising technique is to couple two phases of magnetic materials with desirable properties. Second is the investigation of nanoparticle synthesis routes, with ball milling being the most widely used one. The motivation for the nanoparticles synthesis is rooted in their inherent tendency to have distributed exchange coupling, which will broaden the magnetic entropy curve. As proven with the cost analysis, the focus is believed to shift from improving the RC of refrigerants toward finding the most economically advantageous magnetic refrigerant with the highest performance. Mechanically alloyed Fe70Ni30 and Fe72Ni 28 alloys were characterized in terms of their structural and magnetic properties. Previous studies showed that single phase FCC gamma-FeNi alloys with 26-30 at. % Ni have Curie temperatures, TC, near room temperature. Having TC near room temperatures along with large magnetization makes gamma-FeNi alloys attractive for room temperature magnetocaloric cooling technologies. To obtain a single gamma-phase, particles were solution annealed in the gamma-phase field and water quenched. The preferential oxidation of Fe during ball milling was used as a means to tune the TC of the alloy. Refrigeration capacities, RCFWHM, of the Fe70Ni30 and the Fe72Ni28 alloys were calculated to be 470 J/kg and 250 J/kg at 5 T, with peak temperatures 363 K and 333 K, respectively. The RCFW H M for the Fe70Ni30 is higher than the previously reported Nanoperm (Fe70Ni 30)89Zr7B4 type alloy and on the same order of magnitude with other Fe-based alloys. The maximum magnetic entropy change values observed for the Fe70Ni30 and the Fe 72Ni28 are 0.65 and 0.5 Jkg--1K --1, respectively, at a field of 5 T. These are smaller than those of rare earth magnetic refrigerants showing first order transformation behavior. The larger RCFW H M value results mainly from the width of the magnetic entropy curve in these types of materials. In a follow up study, nanocrystalline powders of (Fe70Ni 30)100--xMox (x=1 to x=4) were produced by high energy (SPEX) mechanical alloying. Increasing the Mo content was found to stabilize the FCC phase in mechanically alloyed nanopowders. The TC of the alloys was lowered with Mo additions, without decreasing the Refrigeration Capacity (RC), due to the additional temperature broadening of the magnetic entropy change. Based on the previous study on the role of disorder, the additional temperature broadening was attributed to the increased positional disorder introduced by the Mo additions into the gammaFeNi system. Alloy with (Fe70Ni 30)96Mo4 composition was observed to have RCFW H M of 432 J/kg at 5T which is comparable to other prominent magnetic refrigerants operating near room temperatures. The economic viability of these rare-earth-free alloys, along with respectable magnetocaloric properties and potential for scalable production, make them good candidates for magnetic refrigeration applications.

  5. Light induced metastable state of silver nitroprusside probed by Raman spectroscopy

    SciTech Connect

    Ghalsasi, Pallavi; Ghalsasi, Prasanna; Thomas, A.; Muthu, D. V. S.; Sood, A. K.

    2015-06-24

    Low temperature Raman spectroscopic measurements on silver nitroprusside (AgNP), Ag{sub 2}[Fe(CN){sub 5}NO] powders display reversible features of a partially converted metastable state. The results are compared with similarly observed metastable state in case of sodium nitroprusside (NaNP) and the differences have been discussed in terms of possible resistance to metastable state formation offered by silver atoms on the basis of hard soft acid base (HSAB) theory.

  6. Metastable hydronium ions in UV-irradiated ice

    SciTech Connect

    Moon, Eui-Seong; Kang, Heon

    2012-11-28

    We show that the irradiation of UV light (10-11 eV) onto an ice film produces metastable hydronium (H{sub 3}O{sup +}) ions in the ice at low temperatures (53-140 K). Evidence of the presence of metastable hydronium ions was obtained by experiments involving adsorption of methylamine onto UV-irradiated ice films and hydrogen-deuterium (H/D) isotopic exchange reaction. The methylamine adsorption experiments showed that photogenerated H{sub 3}O{sup +} species transferred a proton to the methylamine arriving at the ice surface, thus producing the methyl ammonium ion, which was detected by low energy sputtering method. The H{sub 3}O{sup +} species induced the H/D exchange of water, which was monitored through the detection of water isotopomers on the surface by using the Cs{sup +} reactive ion scattering method. Thermal and temporal stabilities of H{sub 3}O{sup +} and its proton migration activity were examined. The lifetime of the hydronium ions in the amorphized ice was greater than 1 h at {approx}53 K and decreased to {approx}5 min at 140 K. Interestingly, a small portion of hydronium ions survived for an extraordinarily long time in the ice, even at 140 K. The average migration distance of protons released from H{sub 3}O{sup +} in the ice was estimated to be about two water molecules at {approx}54 K and about six molecules at 100 K. These results indicate that UV-generated hydronium ions can be efficiently stabilized in low-temperature ice. Such metastable hydronium ions may play a significant role in the acid-base chemistry of ice particles in interstellar clouds.

  7. Metastable hydronium ions in UV-irradiated ice.

    PubMed

    Moon, Eui-Seong; Kang, Heon

    2012-11-28

    We show that the irradiation of UV light (10-11 eV) onto an ice film produces metastable hydronium (H(3)O(+)) ions in the ice at low temperatures (53-140 K). Evidence of the presence of metastable hydronium ions was obtained by experiments involving adsorption of methylamine onto UV-irradiated ice films and hydrogen-deuterium (H∕D) isotopic exchange reaction. The methylamine adsorption experiments showed that photogenerated H(3)O(+) species transferred a proton to the methylamine arriving at the ice surface, thus producing the methyl ammonium ion, which was detected by low energy sputtering method. The H(3)O(+) species induced the H∕D exchange of water, which was monitored through the detection of water isotopomers on the surface by using the Cs(+) reactive ion scattering method. Thermal and temporal stabilities of H(3)O(+) and its proton migration activity were examined. The lifetime of the hydronium ions in the amorphized ice was greater than 1 h at ∼53 K and decreased to ∼5 min at 140 K. Interestingly, a small portion of hydronium ions survived for an extraordinarily long time in the ice, even at 140 K. The average migration distance of protons released from H(3)O(+) in the ice was estimated to be about two water molecules at ∼54 K and about six molecules at 100 K. These results indicate that UV-generated hydronium ions can be efficiently stabilized in low-temperature ice. Such metastable hydronium ions may play a significant role in the acid-base chemistry of ice particles in interstellar clouds.

  8. Metastable hydronium ions in UV-irradiated ice

    NASA Astrophysics Data System (ADS)

    Moon, Eui-Seong; Kang, Heon

    2012-11-01

    We show that the irradiation of UV light (10-11 eV) onto an ice film produces metastable hydronium (H3O+) ions in the ice at low temperatures (53-140 K). Evidence of the presence of metastable hydronium ions was obtained by experiments involving adsorption of methylamine onto UV-irradiated ice films and hydrogen-deuterium (H/D) isotopic exchange reaction. The methylamine adsorption experiments showed that photogenerated H3O+ species transferred a proton to the methylamine arriving at the ice surface, thus producing the methyl ammonium ion, which was detected by low energy sputtering method. The H3O+ species induced the H/D exchange of water, which was monitored through the detection of water isotopomers on the surface by using the Cs+ reactive ion scattering method. Thermal and temporal stabilities of H3O+ and its proton migration activity were examined. The lifetime of the hydronium ions in the amorphized ice was greater than 1 h at ˜53 K and decreased to ˜5 min at 140 K. Interestingly, a small portion of hydronium ions survived for an extraordinarily long time in the ice, even at 140 K. The average migration distance of protons released from H3O+ in the ice was estimated to be about two water molecules at ˜54 K and about six molecules at 100 K. These results indicate that UV-generated hydronium ions can be efficiently stabilized in low-temperature ice. Such metastable hydronium ions may play a significant role in the acid-base chemistry of ice particles in interstellar clouds.

  9. Metastable Features of Economic Networks and Responses to Exogenous Shocks

    PubMed Central

    Hosseiny, Ali; Bahrami, Mohammad; Palestrini, Antonio; Gallegati, Mauro

    2016-01-01

    It is well known that a network structure plays an important role in addressing a collective behavior. In this paper we study a network of firms and corporations for addressing metastable features in an Ising based model. In our model we observe that if in a recession the government imposes a demand shock to stimulate the network, metastable features shape its response. Actually we find that there exists a minimum bound where any demand shock with a size below it is unable to trigger the market out of recession. We then investigate the impact of network characteristics on this minimum bound. We surprisingly observe that in a Watts-Strogatz network, although the minimum bound depends on the average of the degrees, when translated into the language of economics, such a bound is independent of the average degrees. This bound is about 0.44ΔGDP, where ΔGDP is the gap of GDP between recession and expansion. We examine our suggestions for the cases of the United States and the European Union in the recent recession, and compare them with the imposed stimulations. While the stimulation in the US has been above our threshold, in the EU it has been far below our threshold. Beside providing a minimum bound for a successful stimulation, our study on the metastable features suggests that in the time of crisis there is a “golden time passage” in which the minimum bound for successful stimulation can be much lower. Hence, our study strongly suggests stimulations to arise within this time passage. PMID:27706166

  10. Photoionization of Fe7+ from the ground and metastable states

    NASA Astrophysics Data System (ADS)

    Tayal, S. S.; Zatsarinny, O.

    2015-01-01

    The B -spline Breit-Pauli R -matrix method is used to investigate the photoionization of Fe7 + from the ground and metastable states in the energy region from ionization thresholds to 172 eV. The present calculations were designed to resolve the large discrepancies between recent measurements and available theoretical results. The multiconfiguration Hartree-Fock method in connection with B -spline expansions is employed for an accurate representation of the initial- and final-state wave functions. The close-coupling expansion includes 99 fine-structure levels of the residual Fe8 + ion in the energy region up to 3 s23 p54 s states. It includes levels of the 3 s23 p6,3 s23 p53 d ,3 s23 p54 s , and 3 s 3 p63 d configurations and some levels of the 3 s23 p43 d2 configuration which lie in the energy region under investigation. The present photoionization cross sections in the length and velocity formulations exhibit excellent agreement. The present photoionization cross sections agree well with the Breit-Pauli R -matrix calculation by Sossah et al. and the TOPbase data in the magnitude of the background nonresonant cross sections but show somewhat richer resonance structures, which qualitatively agree with the measurements. The calculated cross sections, however, are several times lower than the measured cross sections, depending upon the photon energy. The cross sections for photoionization of metastable states were found to have approximately the same magnitude as the cross sections for photoionization of the ground state, thereby the presence of metastable states in the ion beam may not be the reason for the enhancement of the measured cross sections.

  11. Hydrogen attack - Influence of hydrogen sulfide. [on carbon steel

    NASA Technical Reports Server (NTRS)

    Eliezer, D.; Nelson, H. G.

    1978-01-01

    An experimental study is conducted on 12.5-mm-thick SAE 1020 steel (plain carbon steel) plate to assess hydrogen attack at room temperature after specimen exposure at 525 C to hydrogen and a blend of hydrogen sulfide and hydrogen at a pressure of 3.5 MN/sq m for exposure times up to 240 hr. The results are discussed in terms of tensile properties, fissure formation, and surface scales. It is shown that hydrogen attack from a high-purity hydrogen environment is severe, with the formation of numerous methane fissures and bubbles along with a significant reduction in the room-temperature tensile yield and ultimate strengths. However, no hydrogen attack is observed in the hydrogen/hydrogen sulfide blend environment, i.e. no fissure or bubble formation occurred and the room-temperature tensile properties remained unchanged. It is suggested that the observed porous discontinuous scale of FeS acts as a barrier to hydrogen entry, thus reducing its effective equilibrium solubility in the iron lattice. Therefore, hydrogen attack should not occur in pressure-vessel steels used in many coal gasification processes.

  12. Hydrogen Sulfide Chemical Biology: Pathophysiological roles and detection

    PubMed Central

    Kolluru, Gopi K; Shen, Xinggui; Bir, Shyamal C.; Kevil, Christopher G.

    2014-01-01

    Hydrogen sulfide (H2S) is the most recent endogenous gasotransmitter that has been reported to serve many physiological and pathological functions in different tissues. Studies over the past decade have revealed that H2S can be synthesized through numerous pathways and its bioavailability regulated through its conversion into different biochemical forms. H2S exerts its biological effects in various manners including redox regulation of protein and small molecular weight thiols, polysulfides, thiosulfate/sulfite, iron-sulfur cluster proteins, and anti-oxidant properties that affect multiple cellular and molecular responses. However, precise measurement of H2S bioavailability and its associated biochemical and pathophysiological roles remains less well understood. In this review, we discuss recent understanding of H2S chemical biology, its relationship to tissue pathophysiological responses and possible therapeutic uses. PMID:23850632

  13. Shear-induced metastable states of end-grafted polystyrene

    SciTech Connect

    Sasa, Leslie A.; Yearley, Eric J.; Jablin, Michael S.; Majewski, Jaroslaw; Hjelm, Rex P.; Gilbertson, Robert D.; Lavine, Adrienne S.

    2011-08-15

    The in situ molecular scale response of end-grafted polystyrene to shear against a deuterated polystyrene melt was investigated with neutron reflectometry. The derived grafted polystyrene density profiles showed that the grafted polystyrene was retained on the quartz wafer during the measurements. The profiles suggested that the end-grafted polystyrene response to shear results in a series of metastable states, rather than equilibrium states assumed in the current theory. Except for some possible extension and/or contraction of the grafted polystyrene with shear, there was no obvious correlation between the grafted polymer structure and the shear thinning behavior observed in these samples.

  14. Origin of metastable knots in single flexible chains.

    PubMed

    Dai, Liang; Renner, C Benjamin; Doyle, Patrick S

    2015-01-23

    Recent theoretical progress has explained the physics of knotting of semiflexible polymers, yet knotting of flexible polymers is relatively unexplored. We herein develop a new theory for the size distribution of knots on a flexible polymer and the existence of metastable knots. We show the free energy of a flexible molecule in a tube can be mapped to quantitatively reproduce the free energy distribution of a knot on a flexible chain. The size distribution of knots on flexible chains is expected to be universal and might be observed at a macroscopic scale, such as a string of hard balls. PMID:25659023

  15. Investigating the Metastability of Clathrate Hydrates for Energy Storage

    SciTech Connect

    Koh, Carolyn Ann

    2014-11-18

    Important breakthrough discoveries have been achieved from the DOE award on the key processes controlling the synthesis and structure-property relations of clathrate hydrates, which are critical to the development of clathrate hydrates as energy storage materials. Key achievements include: (i) the discovery of key clathrate hydrate building blocks (stable and metastable) leading to clathrate hydrate nucleation and growth; (ii) development of a rapid clathrate hydrate synthesis route via a seeding mechanism; (iii) synthesis-structure relations of H2 + CH4/CO2 binary hydrates to control thermodynamic requirements for energy storage and sequestration applications; (iv) discovery of a new metastable phase present during clathrate hydrate structural transitions. The success of our research to-date is demonstrated by the significant papers we have published in high impact journals, including Science, Angewandte Chemie, J. Am. Chem. Soc. Intellectual Merits of Project Accomplishments: The intellectual merits of the project accomplishments are significant and transformative, in which the fundamental coupled computational and experimental program has provided new and critical understanding on the key processes controlling the nucleation, growth, and thermodynamics of clathrate hydrates containing hydrogen, methane, carbon dioxide, and other guest molecules for energy storage. Key examples of the intellectual merits of the accomplishments include: the first discovery of the nucleation pathways and dominant stable and metastable structures leading to clathrate hydrate formation; the discovery and experimental confirmation of new metastable clathrate hydrate structures; the development of new synthesis methods for controlling clathrate hydrate formation and enclathration of molecular hydrogen. Broader Impacts of Project Accomplishments: The molecular investigations performed in this project on the synthesis (nucleation & growth)-structure-stability relations of clathrate

  16. Anomalous slowing down in the metastable liquid of hard spheres

    NASA Astrophysics Data System (ADS)

    Dzugutov, M.

    2002-03-01

    It is demonstrated that a straightforward extension of the Arrhenius law accurately describes diffusion in the thermodynamically stable liquid of hard spheres. A sharp negative deviation from this behavior is observed as the liquid is compressed beyond its stability limit. This dynamical anomaly can be compared with the nonlinear slowing down characteristic of the supercooled dynamics regime in liquids with continuous interaction. It is suggested that the observed dynamical transition is caused by long-time decomposition of the configuration space. This interpretation is corroborated by the observation of characteristic anomalies in the geometry of a particle trajectory in the metastable domain.

  17. Measurement of a metastability-exchange cross section in krypton

    SciTech Connect

    Brechignac, C.; Vetter, R.

    1980-08-01

    The metastability-exchange cross section between (/sup 3/P/sub 2/)Kr atoms and (/sup 1/S/sub 0/)Kr atoms is measured by means of a two-laser saturated-absorption experiment performed on the lambda=557-nm transition. A study of velocity changes occurring in pure /sup 86/Kr and in (/sup 86/Kr--/sup 78/Kr) discharges leads to a value for the cross section Q75=(plus-or-minus10) A/sup 2/.

  18. Light-induced metastable structural changes in hydrogenated amorphous silicon

    SciTech Connect

    Fritzsche, H.

    1996-09-01

    Light-induced defects (LID) in hydrogenated amorphous silicon (a-Si:H) and its alloys limit the ultimate efficiency of solar panels made with these materials. This paper reviews a variety of attempts to find the origin of and to eliminate the processes that give rise to LIDs. These attempts include novel deposition processes and the reduction of impurities. Material improvements achieved over the past decade are associated more with the material`s microstructure than with eliminating LIDs. We conclude that metastable LIDs are a natural by-product of structural changes which are generally associated with non-radiative electron-hole recombination in amorphous semiconductors.

  19. Measurement of Metastable Lifetimes of Highly-Charged Ions

    NASA Technical Reports Server (NTRS)

    Smith, Steven J.; Chutjian, A.; Lozano, J.

    2002-01-01

    The present work is part of a series of measurements of metastable lifetimes of highly-charged ions (HCIs) which contribute to optical absorption, emission and energy balance in the Interstellar Medium (ISM), stellar atmospheres, etc. Measurements were carried out using the 14-GHz electron cyclotron resonance ion source (ECRIS) at the JPL HCI facility. The ECR provides useful currents of charge states such as C(sup(1-6)+), Mg(sup(1-6)+) and Fe(sup(1-17)+). In this work the HCI beam is focused into a Kingdon electrostatic ion trap for measuring lifetimes via optical decays.

  20. Assessing a candidate IIA dual to metastable supersymmetry-breaking

    NASA Astrophysics Data System (ADS)

    Giecold, Gregory; Goi, Enrico; Orsi, Francesco

    2012-02-01

    We analyze the space of linearized non-supersymmetric deformations around a IIA solution found by Cvetič, Gibbons, Lü and Pope (CGLP) in hep-th/0101096. We impose boundary conditions aimed at singling out among those perturbations the ones describing the backreaction of anti-D2 branes on the CGLP background. The corresponding supergravity solution is a would-be dual to a metastable supersymmetry-breaking state. However, it turns out that this candidate bulk solution is inevitably riddled with IR divergences of its flux densities and action, whose physical meaning and implications for models of string cosmology call for further investigation.