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Sample records for metastable iron sulfide

  1. Impact of isostatic land uplift and artificial drainage on oxidation of brackish-water sediments rich in metastable iron sulfide

    NASA Astrophysics Data System (ADS)

    Boman, Anton; Fröjdö, Sören; Backlund, Krister; Åström, Mats E.

    2010-02-01

    This study examines the dynamics of sulfur and trace elements (As, Co, Mo, Ni, Ti and Zn) when brackish-water sediments, unusually rich in metastable iron sulfide (probably a mixture of mackinawite and greigite), are brought into the oxidation zone by postglacial isostatic land uplift and farmland drainage. When subaqueous sediments approach the sea level, metastable iron sulfide is oxidized in the upmost layers and pyrite preserved and even accumulated concomitantly trapping Co, Ni and Zn but not As and Mo. When the land uplift has brought the sediments above sea level and natural drainage thus is initiated, the pyrite is oxidized and Co, Ni and Zn are released and transported down the profile. If this setting remained undisturbed, the slightly oxidized sediment (unripe soil) would become covered by peat and thus protected from further oxidation and metal translocation. Often these sediments are, however, artificially drained resulting in extensive oxidation and fast soil-profile development. The soil is an acid sulfate (AS) soil, characterized by low pH (<4), extensive leaching of metals and an abundance of disseminated brownish Fe(III) precipitates. We suggest that the fast soil development is due to initial oxidation of metastable iron sulfide, followed by pyrite oxidation. Drain bottom sediment, which in terms of chemistry and S-isotopes resembled that of the surfacing sea bottom strata, acted during the sampling period as a sink for metals. The abundant preservation of metastable iron sulfide below the groundwater table, even long periods after uplift above the sea level, is a puzzling feature. We suggest that it is the net result of sulfur starvation, an abundance of Fe(II) and strongly reducing conditions.

  2. Iron Sulfide Minerals in Black Sea Sediments

    NASA Astrophysics Data System (ADS)

    Franke, Christine; Robin, Eric; Henkel, Susann; Courtin-Nomade, Alexandra; Bleil, Ulrich

    2010-05-01

    This study presents a mutidisciplinary geochemical and environmental magnetic approach, integrating advanced mineralogical techniques to better understand the physicochemical syn-sedimentary and post-depositional processes in the anoxic sediments from the northwestern Black Sea. The investigated gravity core GC 214 was retrieved in 2007 during RV METEOR cruise M72/1 west of the Crimean Peninsula in a water depth of 1686 mbsf. Geochemical analyses of the pore water and solid phase indicate non-steady state sedimentation. The oxygen-depleted water column conditions, anaerobic oxidation of methane (AOM), and related microbial-driven sulfate reduction favor a highly complex iron sulfide mineral assemblage in the sediment column. The detailed magnetic susceptibility and remanence measurements indicate an irregularly stratified depth profile showing intervals of particularly high values. Further environmental magnetic analyses of hysteresis loops depict strongly elevated coercivity values for those depth horizons, suggesting metastable ferrimagnetic greigite (Fe3S4) as the main magnetic carrier phase. Automated chemical classification (ACC), using electron dispersive spectrometer (EDS) attached to a JEOL 840 scanning electron microscope (SEM) on dispersed particle samples permitted the absolutequantification of the various present iron mineral phases with depth, identified as greigite (Fe3S4), pyrrhotite (Fe7S8), pyrite (FeS2), and monosulfides (FeS), such as troilite or markasite. The statistically stable ACC analyses were carried out on magnetic extracts and density separates to be able to calculate budgets between the different present iron sulfides. We also obtained excellent correlations between the different iron sulfide concentrations and the magnetic signal, which open the possibility to link the absolute particle concentrations to the magnetic signal. Additional synchrotron based micro-XRD analyses on polished sections yield inside into the details of the

  3. Corrosion of metastable iron alloys in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Wolf, Gerhard K.; Ferber, H.

    1983-05-01

    There exist some examples showing that metastable surface alloys can modify the corrision properties of a substrate in the same way as stable alloys do. In the present paper the corrosion behaviour of metastable surface alloys obtained by implanting gold, lead and mercury in iron was studied in aqueous solution of pH = 5.6. Potentiodynamic current density-potential curves were recorded of the implanted samples without further treatment and after isothermal annealing to temperatures up to 800°C. The results were compared with structural information on the alloys obtained by Turos et al. with α-backscattering and channeling experiments. Gold implantation turned out to enhance the active corrosion rate of iron, while lead and mercury had an impeding effect. The annealing experiments showed that the surface alloying facilitated the passivation of iron as long as the substitutional solid solution was "(meta)stable". After the breakdown at higher annealing temperatures leading to surface migration and clustering of the implanted elements a significant increase of the critical current density for passivation took place. This indicates passivation difficulties caused by the heterogeneous distribution of the "alloying" particles. In general the results suggest that substitutional metastable iron alloys cause in a systematic way corrosion inhibition or enhancement. However, their corrosion properties may change completely for non-substitutional distribution of the alloying elements as originating from annealing at higher temperatures.

  4. [Sulfide removal from wastewater by nanoscale iron].

    PubMed

    Xi, Hong-bo; Yang, Qi; Shang, Hai-tao; Hao, Chun-bo; Li, Zhi-ling

    2008-09-01

    Influencing factors, adsorption isotherm, adsorption kinetics and preliminary discussion on the mechanism of sulfide adsorption by nanoscale iron prepared in laboratory were studied using manual simulation sulfide wastewater. Experimental results indicate that the removal efficiency of S2- increases with increasing iron dosage and decreases with increasing initial S2- concentration and pH values. The removal efficiency of S2- is 100% when initial concentration is less than 100 mg x L(-1) and are 87.34%, 65.80% and 44.61% at pH 2, 7 and 13. The temperature at 25 degrees C favors the maximum adsorption of S2- with 19.17 mg x g(-1) of equilibrium adsorption quantity and the adsorption capacity decreas at higher or lower temperature. The adsorption data fit well to the Langmuir equation and the Freundlich equation. The sulfide adsorption follows the pseudo second order equation with the maximum initial sorption rate(h) is 1.575 3 mg x (g x mg)(-1) at 25 degrees C and the adsorption rate constant increases with the increasing of temperature. The activation energy(Ea) is 8.22 kJ x mol(-1). The mechanism of sulfide removal is being sorbed onto the iron nanoparticles via formation of surface compleses, FeOSH and iron sulfides (FeS, FeS2, FeSn).

  5. Iron sulfide minerals in Black Sea sediments

    NASA Astrophysics Data System (ADS)

    Franke, C.; Robin, E.; Henkel, S.; Kasten, S.; Bleil, U.

    2009-04-01

    This study presents an integrated geochemical, environmental magnetic, and electron microscopic approach to better understand the physicochemical processes in deep sea sediments from the northwestern Black Sea. The investigated gravity core GC 214 was retrieved in 2007 during RV Meteor cruise M72/1 west of the Crimean Peninsula in a water depth of 1686 mbsf. Geochemical analyses of the pore water and solid phase indicate non-steady state sedimentation. The oxygen-depleted water column conditions, anaerobic oxidation of methane (AOM) and related microbially-driven sulfate reduction favor a highly complex iron sulfide mineral assemblage in the sediment column. The detailed magnetic susceptibility and remanence measurements indicate an irregularly stratified depth profile showing intervals of particularly high values. Further environmental magnetic analyses depict strongly elevated coercivities for those depth horizons, suggesting greigite as one of the main magnetic carrier minerals. Automated chemical classification (ACC), using electron dispersive spectrometer (EDS) attached to a JEOL840 scanning electron microscope (SEM), on dispersed particle samples permitted the identification of greigite (Fe3S4) next to pyrrhotite (Fe7S8), pyrite (FeS2) and monosulfides (FeS), but also allowed for the absolute quantification of the various mineral phases. These analyses were carried out on magnetic extracts and density separates to be able to calculate budgets between the different present iron sulfides. We obtained excellent correlations between the different iron sulfide concentrations and the magnetic signal. Additional analyses on polished sections yield inside into the details of the sulfidization pathways along the depth profile of the sediment sequence and help to develop a more general process model for this particular geochemical (paleo-)environment. Keywords: Black Sea, iron sulfides, environmental magnetism, anaerobic oxidation of methane (AOM), scanning electron

  6. Iron-sulfide redox flow batteries

    DOEpatents

    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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  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. 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.

  15. IRON SULFIDES IN THE ENVIRONMENT: FORMATION, FATE, AND SIGNIFICANCE TO CONTAMINANT BEHAVIOR

    EPA Science Inventory

    This seminar will cover aspects of the geochemistry of iron sulfides, their formation in sedimentary and aquifer environments, and their roles in sequestering and releasing contaminants. A special emphasis will be placed on the interactions between iron sulfides and arsenic.

  16. 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...

  17. A new nanoscale metastable iron phase in carbon steels.

    PubMed

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

    2015-10-27

    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.

  18. 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

  19. A new nanoscale metastable iron phase in carbon steels

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

    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.

  20. Discrimination among iron sulfide species formed in microbial cultures.

    PubMed

    Popa, R; Kinkle, B K

    2000-10-01

    A quantitative method for the study of iron sulfides precipitated in liquid cultures of bacteria is described. This method can be used to quantify and discriminate among amorphous iron sulfide (FeS(amorph)), iron monosulfide minerals such as mackinawite or greigite (FeS(min)), and iron disulfide minerals such as pyrite or marcasite (FeS(2min)) formed in liquid cultures. Degradation of iron sulfides is performed using a modified Cr(2+) reduction method with reflux distillation. The basic steps of the method are: first, separation of FeS(amorph); second, elimination of interfering species of S such as colloidal sulfur (S(c) degrees ), thiosulphate (S(2)O(3)(2-)) and polysulfides (S(x)(2-)); third, separation of FeS(min); and fourth, separation of FeS(2min). The final product is H(2)S which is determined after trapping. The efficiency of recovery is 96-99% for FeS(amorph), 76-88% for FeS(min), and >97% for FeS(2min). This method has a high reproducibility if the experimental conditions are rigorously applied and only glass conduits are used. A well ventilated fume hood must be used because of the toxicity and volatility of several reagents and products. The advantage relative to previously described methods are better resolution for iron sulfide species and use of the same bottles for both incubation of cultures and acid degradation. The method can also be used for Fe/S stoichiometry with sub-sampling and Fe analysis.

  1. The rate characteristics of lithium iron sulfide

    NASA Astrophysics Data System (ADS)

    Kendrick, E.; Barker, J.; Bao, J.; Świątek, A.

    The electrochemical rate properties of Li 2FeS 2 synthesized via a low cost solid state method have been investigated. Apparent diffusion coefficients calculated from EVS and GITT measurements show rate limitations upon charge with distinct differences between the iron redox and sulfur redox regions. These differences between the iron and sulfur redox reactions are not mimicked upon discharge. The apparent diffusion coefficients are greater upon discharge than charge and this is reflected in the rate capabilities as measured by galvanostatic discharge and charge measurements.

  2. 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

  3. 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.

  4. 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.

  5. Behavior of iron aluminides in oxidizing and sulfidizing environments

    SciTech Connect

    Tortorelli, P.F.; DeVan, J.H.; DiStefano, J.R.

    1989-01-01

    To date, use of iron aluminides based on Fe/sub 3/Al (less than or equal to30 at. % Al) or FeAl (30--50 at. % Al) for structural applications has been limited by their low ductility and poor fracture toughness at room temperature and inadequate strength above 600/degree/C. However, in recent years, a renewed effort has been devoted to the development of ductile iron aluminides with increased strength, particularly in view of their good potential for use in hostile environments. While it is expected that such aluminides will be able to form oxide scales for corrosion protection in oxidizing high temperature environments, resistance to degradation in oxidizing salt or oxidizing/sulfidizing gas environments has not been adequately addressed as a function of compositional and microstructural changes. This paper reviews and extends results for iron aluminides exposed to an oxidizing/sulfidizing gas and presents the first data for corrosion of this class of materials by an aggressive oxidizing molten nitrate salt of 48.5NaNO/sub 3/--50.5KNO/sub 3/--1Na/sub 2/O/sub 2/. 14 refs., 11 figs.

  6. Spin-polarized metastable-atom deexcitation spectroscopy study of Xenon-adsorbed iron surfaces

    NASA Astrophysics Data System (ADS)

    Yamauchi, Yasushi; Kurahashi, Mitsunori; Suzuki, Taku; Sun, Xia; Wang, Zhongping

    2007-03-01

    The electron spin polarization at the interface between nonmagnetic and ferromagnetic medias is one of the essential factors that may alter the spin transport phenomena. To investigate fundamental aspects of induced spin polarization we have examined the adsorbate-covered magnetic surfaces by means of spin polarized metastable-atom deexcitation spectroscopy (SPMDS). Use of spin-polarized metastable helium atoms in triplet states moving at thermal energies gives rise to the ultimate surface sensitivity. Although Xenon can adsorb on surfaces at low temperatures by the van der Waals force, no electron exchange with surfaces, especially no spin interaction, is expected because of its closed shell structure. SPMDS spectra measured for Xenon-adsorbed iron surfaces show three prominent peaks that are the same as those previously reported for other surfaces by D. M. Oro, et al. [Phys. Rev. A 49 (1994) 4703]. Two peaks (^2P1/2, ^2P3/2) at higher kinetic energies exhibit clear spin asymmetries while the other low energy peak has no appreciable spin asymmetry. The spin asymmetries will be discussed on the basis of spin polarization and deexcitation processes of metastable atoms.

  7. 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

  8. 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

  9. 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

  10. 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

  11. 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

  12. Iron isotope fractionation in sulfides: constraints on mechanisms of sulfide formations in hydrothermal and magmatic systems.

    NASA Astrophysics Data System (ADS)

    Polyakov, Veniamin; Soultanov, Dilshod

    2010-05-01

    Data on non-traditional stable isotope fractionations (e.g., Fe, Cu) provide further insight into mechanisms of sulfide mineralization. Correct interpretation of these data is impossible without knowledge on equilibrium isotopic fractionation factors of sulfides. We present data on iron isotope fractionation factors (β-factors) of chalcopyrite (CuFeS2) and mackinawite (FeS). Iron β-factors for chalcopyrite were derived from synchrotron experimental data on inelastic nuclear resonant x-ray scattering (INRXS) [1] using the method described elsewhere [2,3]. The β-factors for mackinawite were found from the Moessbauer second-order Doppler shift data [4] by the method presented in [5]. The temperature dependence of the iron β-factors are fitted by following third-order polynomials: 103lnβcpy = 0.82560x - 0.01298x2 + 0.0005246x3 103lnβmcw = 0.2542x - 0.0001847x2 + 2.072×103x3 where x=106/T2 Using these data along with β-factors for pyrite and troilite [3,6], we compared iron isotope fractionation between pyrite and chalcopyrite in hydrothermal and magmatic conditions. Rouxel et al. [7] studied iron isotope of seafloor of hydrothermal vents in detail. They found that pyrite is enriched in light iron isotope relative to chalcopyrite in the case of black smoker Bio 9. This result evidences absence of iron isotope equilibrium between pyrite and chalcopyrite, because in equilibrium pyrite is enriched in heavy iron isotope (βpy > βcpy). Quantitatively, iron isotope fractionation between chalcolpyrite and pyrite is very close to equilibrium iron isotope fractionation between chalcolpyrite and FeS phase (mackinawite or troilite). This agrees the mechanism of pyrite formation through intermidient FeS phase if to assume isotopic equilibrium between the FeS phase and dissolved iron and no isotopic effect in the final stage of conversion FeS to FeS2 (pyrite). Another iron isotope fractionation was observed between pyrite and chalcopyrite in the case of the Cu-Au porphyry

  13. 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.

  14. Impact of iron sulfide transformation on trichloroethylene degradation

    SciTech Connect

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

    2010-05-04

    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{sub 2} could significantly slow down TCE degradation in both natural and engineered systems.

  15. Anoxic Iron Cycling Bacteria from an Iron Sulfide- and Nitrate-Rich Freshwater Environment

    PubMed Central

    Haaijer, Suzanne C. M.; Crienen, Gijs; Jetten, Mike S. M.; Op den Camp, Huub J. M.

    2012-01-01

    In this study, both culture-dependent and culture-independent methods were used to determine whether the iron sulfide mineral- and nitrate-rich freshwater nature reserve Het Zwart Water accommodates anoxic microbial iron cycling. Molecular analyses (16S rRNA gene clone library and fluorescence in situ hybridization, FISH) showed that sulfur-oxidizing denitrifiers dominated the microbial population. In addition, bacteria resembling the iron-oxidizing, nitrate-reducing Acidovorax strain BrG1 accounted for a major part of the microbial community in the groundwater of this ecosystem. Despite the apparent abundance of strain BrG1-like bacteria, iron-oxidizing nitrate reducers could not be isolated, likely due to the strictly autotrophic cultivation conditions adopted in our study. In contrast an iron-reducing Geobacter sp. was isolated from this environment while FISH and 16S rRNA gene clone library analyses did not reveal any Geobacter sp.-related sequences in the groundwater. Our findings indicate that iron-oxidizing nitrate reducers may be of importance to the redox cycling of iron in the groundwater of our study site and illustrate the necessity of employing both culture-dependent and independent methods in studies on microbial processes. PMID:22347219

  16. 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.

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

    USGS Publications Warehouse

    Picard, Aude A.; Gartman, Amy; Girguis, Peter R.

    2016-01-01

    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.

  18. Reductive immobilization of uranium(VI) by amorphous iron sulfide.

    PubMed

    Hua, Bin; Deng, Baolin

    2008-12-01

    Batch experiments were used to evaluate the reductive immobilization of hexavalent uranium (U(VI)) by synthesized, amorphous iron sulfide (FeS) in the anoxic environment. The tests were initiated by spiking 168.0 microM U(VI) to 0.18 g/L FeS suspensions under a CO2-free condition with pH varied from 5.99 to 10.17. The immobilization rate of U(VI) was determined by monitoring the changes of aqueous U(VI) concentration, and the reduction rate of U(VI) associated with FeS was determined by the difference between the total spiked U(VI) and the extractable amount of U(VI) by 25 mM NaHCO3 solution. The results showed that a rapid removal of U(VI) from the aqueous phase occurred within 1 h under all pH conditions accompanied by a simultaneous release of Fe(ll), whereas the reduction of U(VI) associated with FeS took hours to over a week for completion. The reduction rate was greatly increased with decreasing pH within the examined pH range. Product analysis by X-ray photoelectron spectroscopy showed the formation of U3O8/4O9/UO2, polysulfide, and ferric iron.

  19. 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.

  20. 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 ...

  1. 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

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

    NASA Astrophysics Data System (ADS)

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

    2013-01-01

    Rare-earth-iron mixed oxides with the rare earth/iron ratio=1 have either orthorhombic (o-REFeO3) or hexagonal (h-REFeO3) structure. h-REFeO3 is a metastable phase and the synthesis of h-REFeO3 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-REFeO3. 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-REFeO3 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 YbFeO3 had higher catalytic activity for C3H8 combustion than orthorhombic YbFeO3.

  3. Reductive Dechlorination of Trichloroethene by Zero-valent Iron Nanoparticles: Reactivity Enhancement through Sulfidation Treatment.

    PubMed

    Han, Yanlai; Yan, Weile

    2016-12-06

    Zero-valent iron nanoparticles (nZVI) synthesized in the presence of reduced sulfur compounds have been shown to degrade trichloroethene (TCE) at significantly higher rates. However, the applicability of sulfidation as a general means to enhance nZVI reactivity under different particle preparation conditions and the underlying cause for this enhancement effect are not well understood. In this study, the effects of sulfidation reagent, time point of sulfidation, and sulfur loading on the resultant particles were assessed through TCE degradation experiments. Up to 60-fold increase in TCE reaction rates was observed upon sulfidation treatment, with products being fully dechlorinated hydrocarbons. While the reactivity of these sulfur-treated nZVI (S-nZVI) was relatively unaffected by the sulfidation reagent (viz., sodium sulfide, dithionite, or thiosulfate) or the sequence of sulfidation relative to iron reduction, TCE reaction rates were found to depend strongly on sulfur to iron ratio. At a low sulfur loading, TCE degradation was accelerated with increasing sulfur dose. The rate constant reached a limiting value, however, as the sulfur to iron mole ratio was greater than 0.025. Different from previous propositions that iron sulfidation leads to more efficient TCE or tetrachloroethene (PCE) degradation by enabling depassivation of iron surface, affording catalytic pathways, or facilitating electron transfer, we show that the role of sulfur in nZVI lies essentially in its ability to poison hydrogen recombination, which drives surface reactions to favor reduction by atomic hydrogen. This implies that the reactivity of S-nZVI is contaminant-specific and is selective against the background reaction of water reduction. As the effect of sulfur manifests through surface processes, sulfidation represents a broadly applicable surface modification approach to modulate or increase the reactivity of nZVI for treating TCE and other related contaminants.

  4. 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.

  5. 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.

  6. 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...

  7. 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.

  8. Granular Microbial Habitats Built from Iron Sulfides: Alternative Microbial Lifestyles?

    NASA Astrophysics Data System (ADS)

    Schieber, J.

    2005-03-01

    Concentrically zoned pyrite grains grew as granular microbial colonies. They stayed in the surface layer during long history of reworking and accretion and consist of marcasite and pyrite cortices with sulfide mineralized microbial remains.

  9. Lithium/iron sulfide batteries for electric-vehicle propulsion and other applications

    NASA Astrophysics Data System (ADS)

    Barney, D. L.; Steunenberg, R. K.; Chilenskas, A. A.; Gay, E. C.; Battles, J. E.

    1983-09-01

    The development of lithium/iron sulfide batteries is described. The electrochemical and materials aspects of lithium alloy negative electrodes and iron sulfide positive electrodes, materials cell design, fabricated cells were examined. Alternatives to the present Li-Al and FeS electrodes which are expected to lead to higher specific energy and power investigations concerned with Li-Si, Li-Al-Si, Li-Al-Fe, are emphasized. Development work consisted of cell design improvements to increase lifetime and specific power and the fabrication of cells for testing.

  10. 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.

  11. Characterization of biological iron sulfide composites and its application in the treatment of cadmium-contaminated wastewater.

    PubMed

    Yang, Yang; Xie, Yifei; Li, Xudong

    2015-03-01

    A strain of sulfate reducing bacteria, which could generate biological iron sulfide composites, was applied for Cd (II) removal from wastewater. The influence of biological iron sulfide composites dosage, initial pH and temperature on the rate of Cd (II) removal from wastewater by biological iron sulfide composites were investigated. The microscopic morphological characteristics and elemental composition changes of the biological iron sulfide before and after treatment was compared, using scanning electron microscopy and energy-dispersive spectrometry, then the mechanism of Cd (II) removal was explored. The results showed that Cd (II) reduction rate increased with increase in dosage of biological iron sulfide composites and initial temperature. At 25 degrees C, pH 4.0, with dosage of sulfide and cadmium ions molar equal to 99.93% Cd (II) was removed from cadmium wastewater (100 mg l(-1)), and the residual concentration of cadmium reached Chinese Integrated Wastewater Discharge Standard (GB8978-1996). The present study revealed that bio- precipitation of FeS, the main component of biological iron sulfide composites, played leading role in the process of Cd (II) reduction. Therefore, it is prospective to apply biological iron sulfide composites in the emergency treatment of cadmium-contaminated wastewater.

  12. 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.

  13. Sulfate reduction and iron sulfide mineral formation in the southern East China Sea continental slope sediment

    NASA Astrophysics Data System (ADS)

    Lin, Saulwood; Huang, Kuo-Ming; Chen, Shin-Kuan

    2002-10-01

    Sulfate reduction rate, organic carbon and sulfide burial rate; organic carbon, carbonate carbon, and reactive iron contents; grain size; and sedimentation rate were determined in sediments of the southern East China Sea continental slope. The results show high sulfate reduction and pyrite sulfur burial rates in slope areas with high organic carbon and sedimentation rates. Unusually high rates of organic carbon deposition enhance sulfate reduction and pyrite sulfide burial in the region. Both sulfate reduction rates and pyrite sulfur burial rates increased linearly with increasing organic carbon burial rate, indicating that deposition of organic carbon on the slope is the primary controlling factor for pyrite formation. Abundant reactive iron indicated that iron is not limiting pyrite formation. Pyrite is the predominant sulfide mineral; however, acid volatile sulfide constituted up to 50% of total sulfide at some stations. Up to 240 μmol/g of pyrite sulfur and 5 mmol/m 2/day of sulfate reduction rates were found in the slope sediment. Sulfate reduction rate and pyrite sulfur did not decrease with increasing overlying water depth. High organic carbon burial rates enhanced the sulfate reduction rate and subsequently the rate of pyrite sulfur burial in the slope region. As a result, the southern East China Sea continental slope environment is an efficient pyrite sulfur burial environment.

  14. Sulfide, iron, manganese, and phosphate in the deep water of the Chesapeake Bay during anoxia

    NASA Astrophysics Data System (ADS)

    Gavis, Jerome; Grant, Virginia

    1986-10-01

    Concentrations of dissolved oxygen and sulfide, and of dissolved and particulate iron, manganese, and phosphate were measured as functions of salinity at a station in the Chesapeake Bay during stratification and deep water anoxia in spring and summer, 1981. The observed concentration/salinity profiles showed that oxygen was transported in a direction opposite to that of salt, while dissolved sulfide was transported in the same direction as salt through the anoxic water to be oxidized in oxygen consumption zones located below the steepest parts of the halocline. Both oxygen and sulfide were transported conservatively on 18 June. Their fluxes were 1·2 and 2 mol m -2 d -1, respectively. The oxygen flux was 30% of that stoichiometrically needed to oxidize the sulfide transported, suggesting that the oxygen consumption zone was advancing to shallower, less saline water, thus increasing the volume of anoxic water. Although oxygen was transported conservatively, sulfide was produced as it was transported through the anoxic water on 8 July. The anoxic water was supersaturated with respect to ferrous sulfide on 18 June, but most of the anoxic water was saturated on 8 July. Precipitation of ferrous sulfide had little effect on the sulfide flux on 18 June. The manganese(II) concentration/salinity profile exhibited a maximum in the oxygen consumption zone on 18 June. On 8 July the profile was independent of salinity at high salinities. Iron(II) and manganese(II) consumed little if any oxygen in the oxygen consumption zone. Soluble reactive phosphate was transported conservatively through the anoxic water on 18 June. It was produced as it was transported on 8 July. All of the phosphate was consumed in the oxygen consumption zones by sulfide oxidizing bacteria. On 18 June its flux, estimated to be 2·8 mmol m -2 d -1, was less than 10% of that required for bacterial oxidation of the sulfide reaching the oxygen consumption zone. The rest was oxidized chemically. The growth and

  15. Properties of iron sulfide, hydrosulfide, and mixed sulfide/hydrosulfide cluster anions through photoelectron spectroscopy and density functional theory calculations

    NASA Astrophysics Data System (ADS)

    Yin, Shi; Bernstein, Elliot R.

    2016-10-01

    A new magnetic-bottle time-of-flight photoelectron spectroscopy (PES) apparatus is constructed in our laboratory. The PES spectra of iron sulfide, hydrosulfide, and mixed sulfide/hydrosulfide [FeSm(SH)n-; m, n = 0-3, 0 < (m + n) ≤ 3] cluster anions, obtained at 2.331 eV (532 nm) and 3.492 eV (355 nm) photon energies, are reported. The electronic structure and bonding properties of these clusters are additionally investigated at different levels of density functional theory. The most probable structures and ground state spin multiplicity for these cluster anions are tentatively assigned by comparing their theoretical first vertical detachment energies (VDEs) with their respective experiment values. The behavior of S and (SH) as ligands in these iron sulfide, hydrosulfide, and mixed sulfide/hydrosulfide cluster anions is investigated and compared. The experimental first VDEs for Fe(SH)1-3- cluster anions are lower than those found for their respective FeS1-3- cluster anions. The experimental first VDEs for FeS1-3- clusters are observed to increase for the first two S atoms bound to Fe-; however, due to the formation of an S-S bond for the FeS3- cluster, its first VDE is found to be ˜0.41 eV lower than the first VDE for the FeS2- cluster. The first VDEs of Fe(SH)1-3- cluster anions are observed to increase with the increasing numbers of SH groups. The calculated partial charges of the Fe atom for ground state FeS1-3- and Fe(SH)1-3- clusters are apparently related to and correlated with their determined first VDEs. The higher first VDE is correlated with a higher, more positive partial charge for the Fe atom of these cluster anions. Iron sulfide/hydrosulfide mixed cluster anions are also explored in this work: the first VDE for FeS(SH)- is lower than that for FeS2-, but higher than that for Fe(SH)2-; the first VDEs for FeS2(SH)- and FeS(SH)2- are close to that for FeS3-, but higher than that for Fe(SH)3-. The first VDEs of general iron sulfide, hydrosulfide, and

  16. Properties of iron sulfide, hydrosulfide, and mixed sulfide/hydrosulfide cluster anions through photoelectron spectroscopy and density functional theory calculations.

    PubMed

    Yin, Shi; Bernstein, Elliot R

    2016-10-21

    A new magnetic-bottle time-of-flight photoelectron spectroscopy (PES) apparatus is constructed in our laboratory. The PES spectra of iron sulfide, hydrosulfide, and mixed sulfide/hydrosulfide [FeSm(SH)n(-); m, n = 0-3, 0 < (m + n) ≤ 3] cluster anions, obtained at 2.331 eV (532 nm) and 3.492 eV (355 nm) photon energies, are reported. The electronic structure and bonding properties of these clusters are additionally investigated at different levels of density functional theory. The most probable structures and ground state spin multiplicity for these cluster anions are tentatively assigned by comparing their theoretical first vertical detachment energies (VDEs) with their respective experiment values. The behavior of S and (SH) as ligands in these iron sulfide, hydrosulfide, and mixed sulfide/hydrosulfide cluster anions is investigated and compared. The experimental first VDEs for Fe(SH)1-3(-) cluster anions are lower than those found for their respective FeS1-3(-) cluster anions. The experimental first VDEs for FeS1-3(-) clusters are observed to increase for the first two S atoms bound to Fe(-); however, due to the formation of an S-S bond for the FeS3(-) cluster, its first VDE is found to be ∼0.41 eV lower than the first VDE for the FeS2(-) cluster. The first VDEs of Fe(SH)1-3(-) cluster anions are observed to increase with the increasing numbers of SH groups. The calculated partial charges of the Fe atom for ground state FeS1-3(-) and Fe(SH)1-3(-) clusters are apparently related to and correlated with their determined first VDEs. The higher first VDE is correlated with a higher, more positive partial charge for the Fe atom of these cluster anions. Iron sulfide/hydrosulfide mixed cluster anions are also explored in this work: the first VDE for FeS(SH)(-) is lower than that for FeS2(-), but higher than that for Fe(SH)2(-); the first VDEs for FeS2(SH)(-) and FeS(SH)2(-) are close to that for FeS3(-), but higher than that for Fe(SH)3(-). The first VDEs of general

  17. 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.

  18. Reductive dechlorination of chlorinated solvents by zero-valent iron, iron oxide and iron sulfide minerals

    SciTech Connect

    Sivavec, T.M.; Horney, D.P.

    1996-10-01

    The degradation of chlorinated solvents by reduction at the surface of zero-valent metals and bimetallic systems has emerged as an important approach to the in-situ remediation of ground water. Reduction by iron metal was studied in batch and column systems to develop a mechanistic understanding of the reaction chemistry and to determine the factors that affect dechlorination rate and long term performance in field applications.

  19. 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.

  20. 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

  1. Mechanism study on the sulfidation of ZnO with sulfur and iron oxide at high temperature

    PubMed Central

    Han, Junwei; Liu, Wei; Zhang, Tianfu; Xue, Kai; Li, Wenhua; Jiao, Fen; Qin, Wenqing

    2017-01-01

    The mechanism of ZnO sulfidation with sulfur and iron oxide at high temperatures was studied. The thermodynamic analysis, sulfidation behavior of zinc, phase transformations, morphology changes, and surface properties were investigated by HSC 5.0 combined with FactSage 7.0, ICP, XRD, optical microscopy coupled with SEM-EDS, and XPS. The results indicate that increasing temperature and adding iron oxide can not only improve the sulfidation of ZnO but also promote the formation and growth of ZnS crystals. Fe2O3 captured the sulfur in the initial sulfidation process as iron sulfides, which then acted as the sulfurizing agent in the late period, thus reducing sulfur escape at high temperatures. The addition of carbon can not only enhance the sulfidation but increase sulfur utilization rate and eliminate the generation of SO2. The surfaces of marmatite and synthetic zinc sulfides contain high oxygen due to oxidation and oxygen adsorption. Hydroxyl easily absorbs on the surface of iron-bearing zinc sulfide (Zn1−xFexS). The oxidation of synthetic Zn1−xFexS is easier than marmatite in air. PMID:28186156

  2. Mechanism study on the sulfidation of ZnO with sulfur and iron oxide at high temperature

    NASA Astrophysics Data System (ADS)

    Han, Junwei; Liu, Wei; Zhang, Tianfu; Xue, Kai; Li, Wenhua; Jiao, Fen; Qin, Wenqing

    2017-02-01

    The mechanism of ZnO sulfidation with sulfur and iron oxide at high temperatures was studied. The thermodynamic analysis, sulfidation behavior of zinc, phase transformations, morphology changes, and surface properties were investigated by HSC 5.0 combined with FactSage 7.0, ICP, XRD, optical microscopy coupled with SEM-EDS, and XPS. The results indicate that increasing temperature and adding iron oxide can not only improve the sulfidation of ZnO but also promote the formation and growth of ZnS crystals. Fe2O3 captured the sulfur in the initial sulfidation process as iron sulfides, which then acted as the sulfurizing agent in the late period, thus reducing sulfur escape at high temperatures. The addition of carbon can not only enhance the sulfidation but increase sulfur utilization rate and eliminate the generation of SO2. The surfaces of marmatite and synthetic zinc sulfides contain high oxygen due to oxidation and oxygen adsorption. Hydroxyl easily absorbs on the surface of iron-bearing zinc sulfide (Zn1‑xFexS). The oxidation of synthetic Zn1‑xFexS is easier than marmatite in air.

  3. 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.

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

    PubMed

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

    2014-05-15

    Sulfate-reducing bacteria (SRB) can produce iron sulfide (FeS) solids with mineralogical characteristics that may be beneficial for a variety of biogeochemical applications, such as long-term immobilization of uranium. In this study, the growth and metabolism of Desulfovibrio vulgaris, one of the best-studied SRB species, were comprehensively monitored in batch studies, and the biogenic FeS solids were characterized by X-ray diffraction. Controlling the pH by varying the initial pH, the iron-to-sulfate ratio, or the electron donor - affected the growth of D. vulgaris and strongly influenced the formation and growth of FeS solids. In particular, lower pH (from initial conditions or a decrease caused by less sulfate reduction, FeS precipitation, or using pyruvate as the electron donor) produced larger-sized mackinawite (Fe1+xS). Greater accumulation of free sulfide, from more sulfate reduction by D. vulgaris, also led to larger-sized mackinawite and particularly stimulated mackinawite transformation to greigite (Fe3S4) when the free sulfide concentration was 29.3mM. Furthermore, sufficient free Fe(2+) led to the additional formation of vivianite [Fe3(PO4)2·8(H2O)]. Thus, microbially relevant conditions (initial pH, choice of electron donor, and excess or deficiency of sulfide) are tools to generate biogenic FeS solids of different characteristics.

  5. 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)

  6. 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

  7. 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.

  8. 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.

  9. 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.

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

    PubMed

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

    2014-05-23

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

  11. 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.

  12. Lithium/iron sulfide cell development for electric-vehicle propulsion

    NASA Astrophysics Data System (ADS)

    Gay, E. C.; Miller, W. E.; Kolba, V. M.; Shimotake, H.

    The status of a program to develop a lithium/iron sulfide battery for electric vehicle propulsion is reviewed. The cells consist of a lithium-aluminum negative electrode, an FeS positive electrode, and molten LiCl-KCl electrolyte. The melting point of the electrolyte (352 C) requires a cell operating temperature in the range 400-500 C. The cells have met the performance goal of 80 W-hr/kg at the 4 hr discharge rate and 60 W/kg at 50% discharge. The most promising cell designs for high specific energy over long cyclic periods have been identified.

  13. 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.

  14. Iron-sulfide-bearing chimneys as potential catalytic energy traps at life's emergence.

    PubMed

    Mielke, Randall E; Robinson, Kirtland J; White, Lauren M; McGlynn, Shawn E; McEachern, Kavan; Bhartia, Rohit; Kanik, Isik; Russell, Michael J

    2011-12-01

    The concept that life emerged where alkaline hydrogen-bearing submarine hot springs exhaled into the most ancient acidulous ocean was used as a working hypothesis to investigate the nature of precipitate membranes. Alkaline solutions at 25-70°C and pH between 8 and 12, bearing HS(-)±silicate, were injected slowly into visi-jars containing ferrous chloride to partially simulate the early ocean on this or any other wet and icy, geologically active rocky world. Dependent on pH and sulfide content, fine tubular chimneys and geodal bubbles were generated with semipermeable walls 4-100 μm thick that comprised radial platelets of nanometric mackinawite [FeS]±ferrous hydroxide [∼Fe(OH)(2)], accompanied by silica and, at the higher temperature, greigite [Fe(3)S(4)]. Within the chimney walls, these platelets define a myriad of micropores. The interior walls of the chimneys host iron sulfide framboids, while, in cases where the alkaline solution has a pH>11 or relatively low sulfide content, their exteriors exhibit radial flanges with a spacing of ∼4 μm that comprise microdendrites of ferrous hydroxide. We speculate that this pattern results from outward and inward radial flow through the chimney walls. The outer Fe(OH)(2) flanges perhaps precipitate where the highly alkaline flow meets the ambient ferrous iron-bearing fluid, while the intervening troughs signal where the acidulous iron-bearing solutions could gain access to the sulfidic and alkaline interior of the chimneys, thereby leading to the precipitation of the framboids. Addition of soluble pentameric peptides enhances membrane durability and accentuates the crenulations on the chimney exteriors. These dynamic patterns may have implications for acid-base catalysis and the natural proton motive force acting through the matrix of the porous inorganic membrane. Thus, within such membranes, steep redox and pH gradients would bear across the nanometric platelets and separate the two counter-flowing solutions

  15. 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

  16. Synthesis and Electrochemical Lithium Storage Behavior of Carbon Nanotubes Filled with Iron Sulfide Nanoparticles

    PubMed Central

    Yu, Wan‐Jing; Zhang, Lili; Hou, Peng‐Xiang; Li, Feng; Cheng, Hui‐Ming

    2016-01-01

    Carbon nanotubes (CNTs) filled with iron sulfide nanoparticles (NPs) are prepared by inserting sulfur and ferrocene into the hollow core of CNTs followed by heat treatment. It is found that pyrrhotite‐11T iron sulfide (Fe‐S) NPs with an average size of ≈15 nm are encapsulated in the tubular cavity of the CNTs (Fe‐S@CNTs), and each particle is a single crystal. When used as the anode material of lithium‐ion batteries, the Fe‐S@CNT material exhibits excellent electrochemical lithium storage performance in terms of high reversible capacity, good cyclic stability, and desirable rate capability. In situ transmission electron microscopy studies show that the CNTs not only play an essential role in accommodating the volume expansion of the Fe‐S NPs but also provide a fast transport path for Li ions. The results demonstrate that CNTs act as a unique nanocontainer and reactor that permit the loading and formation of electrochemically active materials with desirable electrochemical lithium storage performance. CNTs with their superior structural stability and Li‐ion transfer kinetics are responsible for the improved rate capability and cycling performance of Fe‐S NPs in CNTs. PMID:27840800

  17. 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.

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

    DOE PAGES

    Toso, Daniel B.; Javed, Muhammad Mohsin; Czornyj, Elizabeth; ...

    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

  19. 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

    2016-04-05

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

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

    NASA Astrophysics Data System (ADS)

    Sun, Fenglong

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

  1. Influence of iron sulfides on abiotic oxidation of UO2 by nitrite and dissolved oxygen in natural sediments.

    PubMed

    Carpenter, Julian; Bi, Yuqiang; Hayes, Kim F

    2015-01-20

    Iron sulfide precipitates formed under sulfate reducing conditions may buffer U(IV) insoluble solid phases from reoxidation after oxidants re-enter the reducing zone. In this study, sediment column experiments were performed to quantify the effect of biogenic mackinawite on U(IV) stability in the presence of nitrite or dissolved oxygen (DO). Two columns, packed with sediment from an abandoned U contaminated mill tailings site near Rifle, CO, were biostimulated for 62 days with an electron donor (3 mM acetate) in the presence (BRS+) and absence (BRS−) of 7 mM sulfate. The bioreduced sediment was supplemented with synthetic uraninite (UO2(s)), sterilized by gamma-irradiation, and then subjected to a sequential oxidation by nitrite and DO. Biogenic iron sulfides produced in the BRS+ column, mostly as mackinawite, inhibited U(IV) reoxidation and mobilization by both nitrite and oxygen. Most of the influent nitrite (0.53 mM) exited the columns without oxidizing UO2, while a small amount of nitrite was consumed by iron sulfides precipitates. An additional 10-day supply of 0.25 mM DO influent resulted in the release of about 10% and 49% of total U in BRS+ and BRS– columns, respectively. Influent DO was effectively consumed by biogenic iron sulfides in the BRS+ column, while DO and a large U spike were detected after only a brief period in the effluent in the BRS– column.

  2. Iron(III) [bond] Salen complexes as enzyme models: mechanistic study of oxo(salen)iron complexes oxygenation of organic sulfides.

    PubMed

    Sivasubramanian, Veluchamy Kamaraj; Ganesan, Muniyandi; Rajagopal, Seenivasan; Ramaraj, Ramasamy

    2002-03-08

    The oxidation of a series of para-substituted phenyl methyl sulfides was carried out with several oxo(salen)iron (salen = N,N'-bis(salicylidine)ethylenediaminato) complexes in acetonitrile. The oxo complex [O=Fe(IV)(salen)](*+), generated from an iron(III) [bond] salen complex and iodosylbenzene, effectively oxidizes the organic sulfides to the corresponding sulfoxides. The formation of [O [double bond] Fe(IV)(salen)](*+) as the active oxidant is supported by resonance Raman studies. The kinetic data indicate that the reaction is first-order in the oxidant and fractional-order with respect to sulfide. The observed saturation kinetics of the reaction and spectral data indicate that the substrate binds to the oxidant before the rate-controlling step. The rate constant (k) values for the product formation step determined using Michaelis-Menten kinetics correlate well with Hammett sigma constants, giving reaction constant (rho) values in the range of -0.65 to -1.54 for different oxo(salen)iron complexes. The log k values observed in the oxidation of each aryl methyl sulfide by substituted oxo(salen)iron complexes also correlate with Hammett sigma constants, giving positive rho values. The substituent effect, UV-vis absorption, and EPR spectral studies indicate oxygen atom transfer from the oxidant to the substrate in the rate-determining step.

  3. 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

  4. 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.

  5. Organic sulfur compounds resulting from the interaction of iron sulfide, hydrogen sulfide and carbon dioxide in an anaerobic aqueous environment.

    PubMed

    Heinen, W; Lauwers, A M

    1996-04-01

    The reaction of iron sulfide (FeS) with H2S in water, in presence of CO2 under anaerobic conditions was found to yield H2 and a variety of organic sulfur compounds, mainly thiols and small amounts of CS2 and dimethyldisulfide. The same compounds were produced when H2S was replaced by HCl, in the H2S-generating system FeS/HCl/CO2. The identification of the products was confirmed by GC-MS analyses and the incorporation of H2 in the organic sulfur compounds was demonstrated by experiments in which all hydrogen compounds were replaced by deuterium compounds. Generation of H2 and the synthesis of thiols were both dependent upon the relative abundance of FeS and HCl or H2S, i.e. the FeS/HCl- or FeS/H2S-proportions. Whether thiols or CS2 were formed as the main products depended also on the FeS/HCl-ratio: All conditions which create a H2 deficiency were found to initiate a proportional increase in the amount of CS2. The quantities of H2 and thiols generated depended on temperature: the production of H2 was significantly accelerated from 50 degrees C onward and thiol synthesis above 75 degrees C. The yield of thiols increased with the amount of FeS and HCl (H2S), given a certain FeS/HCl-ratio and a surplus of CO2. A deficiency of CO2 results in lower thiol synthesis. The end product, pyrite (FeS2), was found to appear as a silvery granular layer floating on the aqueous surface. The identity of the thiols was confirmed by mass spectrometry, and the reduction of CO2 demonstrated by the determination of deuterium incorporation with DCl and D2O. The described reactions can principally proceed under the conditions comparable to those obtaining around submarine hydrothermal vents, or the global situation about 4 billion years ago, before the dawn of life, and could replace the need for a reducing atmosphere on the primitive earth.

  6. 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.

  7. 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

    2016-09-09

    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.

  8. 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.

  9. 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.

  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. 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.

  12. 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.

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

    PubMed

    Deng, Dongyang; Lin, Lian-Shin

    2017-05-01

    This study evaluated the technical feasibility of packed-bed sulfidogenic bioreactors dosed with ferrous chloride for continuous wastewater treatment over a 450-day period. In phase I, the bioreactors were operated under different combinations of carbon, iron, and sulfate mass loads without sludge recycling to identify optimal treatment conditions. A COD/sulfate mass ratio of 2 and a Fe/S molar ratio of 1 yielded the best treatment performance with COD oxidation rate of 786 ± 82 mg/(L⋅d), which resulted in 84 ± 9% COD removal, 94 ± 6% sulfate reduction, and good iron retention (99 ± 1%) under favorable pH conditions (6.2-7.0). In phase II, the bioreactors were operated under this chemical load combination over a 62-day period, during which 7 events of sludge collection, oxidation, and recycling were performed. The collected sludge materials contained both inorganic and organic matter with FeS and FeS2 as the main inorganic constituents. In each event, the sludge materials were oxidized in an oxidizing basin before recycling to mix with the wastewater influent. Sludge recycling yielded enhanced COD removal (90 ± 6% vs. 75 ± 7%), and better effluent quality in terms of pH (6.8 ± 0.1 vs. 6.5 ± 0.2), iron (0.7 ± 0.5 vs. 1.9 ± 1.7 mg/L), and sulfide-S (0.3 ± 0.1 vs. 0.4 ± 0.1 mg/L) removal compared to the baseline operation without sludge recycling during phase II. This process exhibited treatment stability with reasonable variations, and fairly consistent sludge content over long periods of operation under a range of COD/sulfate and Fe/S ratios without sludge recycling. The bioreactors were found to absorb recycling-induced changes efficiently without causing elevated suspended solids in the effluents.

  14. 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.

  15. 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.

  16. 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).

  17. Iron Sulfides and Sulfur Species Produced at (001) Hematite Surfaces in the Presence of Sulfate-Reducing Bacteria

    SciTech Connect

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

    2001-01-01

    In the presence of sulfate-reducing bacteria (Desulfovibrio desulfuricans) hematite (a-Fe2O3) dissolution is affected and hydrogen sulfide, the product of sulfate reduction is released. As a consequence, ferrous ions are free to react with excess H2S to form insoluble iron sulfides. X-ray photoelectron spectra indicate binding energies consistent with the iron sulfides having a pyrrhotite structure (Fe2p3/2 708.4 eV; S2p3/2 161.5 eV). Other sulfur species identified at the surface include sulfate, sulfite and polysulfides. X-ray diffraction suggests an unidentifiable crystal structure at the hematite surface develops within 3 months, HRTEM confirms the presence of a hexagonal structure again suggesting the formation of pyrrhotite. The identification of pyrrhotite is inconsistent with previous reports in which mackinawite and greigite were products of biological sulfate reduction (Rickard 1969; Herbert et al 1998). The apparent differences in stoiciometries may be related to the availability of Fe2+(aq.) at the mineral surface through respiratory iron reduction by subsurface bacteria. The significance of pyrrhotite and polysulfide production in relation to the S- and Fe-cycles and to trace metal bioavailability is discussed.

  18. Remediation of hexavalent chromium spiked soil by using synthesized iron sulfide particles.

    PubMed

    Li, Yujie; Wang, Wanyu; Zhou, Liqiang; Liu, Yuanyuan; Mirza, Zakaria A; Lin, Xiang

    2017-02-01

    Carboxymethyl cellulose (CMC) stabilized microscale iron sulfide (FeS) particles were synthesized and applied to remediate hexavalent chromium (Cr(VI)) spiked soil. The effects of parameters including dosage of FeS particles, soil moisture, and natural organic matter (NOM) in soil were investigated with comparison to iron sulfate (FeSO4). The results show that the stabilized FeS particles can reduce Cr(VI) and immobilize Cr in soil quickly and efficiently. The soil moisture ranging from 40% to 70% and NOM in soil had no significant effects on Cr(VI) remediation by FeS particles. When molar ratio of FeS to Cr(VI) was 1.5:1, about 98% of Cr(VI) in soil was reduced by FeS particles in 3 d and Cr(VI) concentration decreased from 1407 mg kg(-1) to 16 mg kg(-1). The total Cr and Cr(VI) in Toxicity Characteristic Leaching Procedure (TCLP) leachate were reduced by 98.4% and 99.4%, respectively. In FeS particles-treated soil, the exchangeable Cr fraction was mainly converted to Fe-Mn oxides bound fraction because of the precipitation of Cr(III)-Fe(III) hydroxides. The physiologically based extraction test (PBET) bioaccessibility of Cr was decreased from 58.67% to 6.98%. Compared to FeSO4, the high Cr(VI) removal and Cr immobilization efficiency makes prepared FeS particles a great potential in field application of Cr(VI) contaminated soil remediation.

  19. 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...

  20. Creep cavitation in iron - I. Sulfides and carbides as nucleation sites

    SciTech Connect

    George, E.P.; Li, P.L.; Pope, D.P.

    1987-10-01

    The nucleation of creep cavities in iron containing controlled additions of C, P and S has been studied using slow strain rate tensile tests (epsilon = 1.1 x 10/sup -6/ and 4.4 x 10/sup -5/s/sup -1/)at temperatures between 500 and 800/sup 0/C. The test materials all had the same 100 ..mu..m grain size and showed approximately the same UTS at 700/sup 0/C. When failure occurred by grain boundary cavitation a ductility minimum was found at 700/sup 0/C and the ductility (% RA) was less than about 40%. The cavitation process depends strongly on the S content: if the S content is above the solubility limit, cavities nucleate easily on grain boundary sulfides and the ductility is very low. In this S regime additions of P can improve the ductility, but the mechanism of this improvement has not been identified. If the S content is well below the solubility limit (about 1 wt ppm), the material is always very ductile, even though there are many small (--0.1 ..mu..m dia.) oxide particles on the grain boundaries that are potential nucleation sites. Carbides were never seen to nucleate cavities, even when the C concentration is as high as 4 times the solubility limit at 700/sup 0/C. Auger analyses of the grain boundary facets of one of the brittle alloys showed that both S and C segregate to the grain boundaries.

  1. 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.

  2. 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.

  3. 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

  4. pH-dependent degradation of p-nitrophenol by sulfidated nanoscale zerovalent iron under aerobic or anoxic conditions.

    PubMed

    Tang, Jing; Tang, Lin; Feng, Haopeng; Zeng, Guangming; Dong, Haoran; Zhang, Chang; Huang, Binbin; Deng, Yaocheng; Wang, Jiajia; Zhou, Yaoyu

    2016-12-15

    Sulfidated nanoscale zerovalent iron (S-NZVI) is attracting considerable attention due to its easy production and high reactivity to pollutants. We studied the reactivity of optimized S-NZVI (Fe/S molar ratio 6.9), comparing with pristine nanoscale zerovalent iron (NZVI), at various pH solutions (6.77-9.11) towards p-nitrophenol (PNP) under aerobic and anoxic conditions. Studies showed that the optimized extent of sulfidation could utterly enhance PNP degradation compared to NZVI. Batch experiments indicated that in anoxic S-NZVI systems the degradation rate constant increased with increasing pH up to 7.60, and then declined. However, in aerobic S-NZVI, and in anoxic or aerobic NZVI systems, it decreased as pH increased. It was manifested that anoxic S-NZVI systems preferred to weaker alkaline solutions, whereas aerobic S-NZVI systems performed better in acidic solutions. The highest TOC removal efficiency of PNP (17.59%) was achieved in the aerobic S-NZVI system at pH 6.77, revealing that oxygen improved the degradation of PNP by excessive amounts of hydroxyl radicals in slightly acidic conditions, and the TOC removal efficiency was supposed to be further improved in moderate acidic solutions. Acetic acid, a nontoxic ring opening by-product, confirms that the S-NZVI system could be a promising process for industrial wastewater containing sulfide ions.

  5. 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

  6. 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.

  7. Energy of the Isolated Metastable Iron-Nickel FCC Nanocluster with a Carbon Atom in the Tetragonal Interstice

    NASA Astrophysics Data System (ADS)

    Bondarenko, Natalya V.; Nedolya, Anatoliy V.

    2017-02-01

    The energy of the isolated iron-nickel nanocluster was calculated by molecular mechanics method using Lennard-Jones potential. The cluster included a carbon atom that drifted from an inside octahedral interstice to a tetrahedral interstice in direction and after that in <222> direction to the surface. In addition, one of 14 iron atoms was replaced by a nickel atom, the position of which was changing during simulation.

  8. 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

  9. Atomic Layer Deposition of Iron Sulfide and Its Application as a Catalyst in the Hydrogenation of Azobenzenes.

    PubMed

    Shao, Youdong; Guo, Zheng; Li, Hao; Su, Yantao; Wang, Xinwei

    2017-03-13

    The atomic layer deposition (ALD) of iron sulfide (FeSx ) is reported for the first time. The deposition process employs bis(N,N'-di-tert-butylacetamidinato)iron(II) and H2 S as the reactants and produces fairly pure, smooth, and well-crystallized FeSx thin films following an ideal self-limiting ALD growth behavior. The FeSx films can be uniformly and conformally deposited into deep narrow trenches with aspect ratios as high as 10:1, which highlights the broad applicability of this ALD process for engineering the surface of complex 3D nanostructures in general. Highly uniform nanoscale FeSx coatings on porous γ-Al2 O3 powder were also prepared. This compound shows excellent catalytic activity and selectivity in the hydrogenation of azo compounds under mild reaction conditions, demonstrating the promise of ALD FeSx as a catalyst for organic reactions.

  10. 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

    2015-05-05

    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.

  11. 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.

  12. 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 ...

  13. Energy of the Isolated Metastable Iron-Nickel FCC Nanocluster with a Carbon Atom in the Tetragonal Interstice.

    PubMed

    Bondarenko, Natalya V; Nedolya, Anatoliy V

    2017-12-01

    The energy of the isolated iron-nickel nanocluster was calculated by molecular mechanics method using Lennard-Jones potential. The cluster included a carbon atom that drifted from an inside octahedral interstice to a tetrahedral interstice in [Formula: see text] direction and after that in <222> direction to the surface. In addition, one of 14 iron atoms was replaced by a nickel atom, the position of which was changing during simulation.The energy of the nanocluster was estimated at the different interatomic distances. As a result of simulation, the optimal interatomic distances of Fe-Ni-C nanocluster was chosen for the simulation, in which height of the potential barrier was maximal and face-centered cubic (FCC) nanocluster was the most stable.It is shown that there were three main positions of a nickel atom that significantly affected nanocluster's energy.The calculation results indicated that position of the carbon atom in the octahedral interstice was more energetically favorable than tetrahedral interstice in the case of FCC nanocluster. On the other side, the potential barrier was smaller in the direction [Formula: see text] than in the direction <022>.This indicates that there are two ways for carbon atom to drift to the surface of the nanocluster.

  14. 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.

  15. 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.

  16. 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

  17. 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...

  18. 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.

  19. Cronstedtite and iron sulfide mineralogy of CM-type carbonaceous chondrites from cryogenic Moessbauer spectra

    NASA Technical Reports Server (NTRS)

    Fisher, Duncan S.; Burns, Roger G.

    1993-01-01

    Determinations of oxidation states and the crystal chemistry of iron-bearing minerals in CM meteorites by Moessbauer spectroscopy are complicated by thermally-induced electron hopping in cronstedtite and by ill-defined contributions from the hydrous iron sulphide phase believed to be tochilinite. Moessbauer spectral measurements at 30 K of several cronstedtite and tochilinite specimens have enabled modal proportions of these minerals, as well as Fe(3+)/Fe(2+) ratios, to be determined quantitatively for a suite of CM-type carbonaceous chondrites that included Murchison, Murray, Cold Bokkeveld, ALH 83100, and LEW 90500.

  20. 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

  1. 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.

  2. Iron Sulfide Attenuates the Methanogenic Toxicity of Elemental Copper and Zinc Oxide Nanoparticles and their Soluble Metal Ion Analogs

    PubMed Central

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

    2016-01-01

    Elemental copper (Cu0) 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 Cu0 and ZnO NPs and their soluble salt analogs. The toxicity attenuation capacity of fine (25–75 µm) and coarse (500 to 1200 µm) preparations of FeS (FeS-f and FeS-c respectively) was tested in the presence of highly inhibitory concentrations of CuCl2, ZnCl2 Cu0 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/Cu0 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 excesses of FeS to highly attenuate Cu and Zn toxicity. Overall, this study provides evidence that FeS attenuates the toxicity caused by Cu0 and ZnO NPs and their soluble ion analogs to methanogens. PMID:26803736

  3. 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...

  4. 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.

  5. Milankovitch orbital cycles encoded by diagenetic iron sulfides in Neogene sediments, Stirone River section, Northern Apennines, Italy

    NASA Astrophysics Data System (ADS)

    Gunderson, K. L.; Kodama, K. P.; Anastasio, D. J.; Pazzaglia, F. J.

    2009-12-01

    component with a mean coercivity of 23 mT. We interpret the high coercivity component to represent magnetic iron-sulfides, which have been previously recognized in the Stirone section (Mary et al, 1993). A biplot of SIRM/MS versus 40mT ARM/ 100mT ARM suggests greigite is possibly the dominant magnetic iron sulfide and is responsible for encoding Milankovitch orbital cycles in the Stirone section.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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

  13. Ferric iron uptake genes are differentially expressed in the presence of copper sulfides in Acidithiobacillus ferrooxidans strain LR.

    PubMed

    Ferraz, Lúcio F C; Verde, Leandro C L; Vicentini, Renato; Felício, Ana P; Ribeiro, Marcelo L; Alexandrino, Fabiana; Novo, Maria T M; Garcia, Oswaldo; Rigden, Daniel J; Ottoboni, Laura M M

    2011-03-01

    Acidithiobacillus ferrooxidans is one of the most widely used microorganisms in bioleaching operations to recover copper from low-grade copper sulfide ores. This work aimed to investigate the relative expression of genes related to the iron uptake system when A. ferrooxidans LR was maintained in contact with chalcopyrite or bornite as the sole energy source. Real-time quantitative PCR analysis revealed that the presence of bornite had no effect on the expression of seven genes related to the siderophore-mediated Fe(III) uptake system, while in the presence of chalcopyrite the expression of the genes was up-regulated. Bioinformatic analysis of the genomic region where these genes were found revealed the existence of three new putative DNA-binding sequences for the ferric iron uptake transcriptional regulator (Fur). Electrophoretic mobility shift assays demonstrated that a purified A. ferrooxidans His-tagged Fur protein was able to bind in vitro to each of these putative Fur boxes, suggesting that Fur regulated the expression of these genes. The expression of fur and two known Fur-regulated genes, mntH and dsrK, was also investigated in the presence of chalcopyrite. While the expression of fur and mntH was up-regulated, the expression of dsrK was down-regulated. The low amount of ferrous iron in the medium was probably responsible for the up-regulation of fur and the genes related to the siderophore-mediated Fe(III) uptake system when A. ferrooxidans LR was kept in the presence of chalcopyrite. A homology model of the A. ferrooxidans Fur was constructed and revealed that the putative DNA-binding surface presents conserved positively charged residues, supporting a previously suggested mode of interaction with DNA. The up-regulation of fur and the siderophore-mediated Fe(III) uptake genes, and the down-regulation of dsrK suggest that in the presence of chalcopyrite Fur acts as a transcription inducer and repressor.

  14. Pathways of ferrous iron mineral formation upon sulfidation of lepidocrocite surfaces

    NASA Astrophysics Data System (ADS)

    Hellige, Katrin; Pollok, Kilian; Larese-Casanova, Philip; Behrends, Thilo; Peiffer, Stefan

    2012-03-01

    The interaction between S(-II) and ferric oxides exerts a major control for the sulphur and iron cycle and in particular for the carbon and electron flow in many aquatic systems. It is regarded to be a key reaction leading ultimately to pyrite formation, the pathways still remaining unresolved. We have studied the reaction between lepidocrocite (γ-FeOOH, 21-42 mmol L-1) and dissolved S(-II) (3-9 mmol L-1) in batch experiments at pH 7 in a glove box using TEM, XRD, Mössbauer spectroscopy, and wet chemistry extraction to explore the nanocrystalline products forming at different time steps in close contact to the lepidocrocite surface. S(0) and acid extractable Fe(II) (Fe(II)HCl) were the main products detected by wet chemistry extraction. The reaction could be divided into three steps: a rapid (<15 min) consumption of dissolved S(-II), formation of S(0) and the build-up of an Fe(II)HCl pool. Then in the absence of dissolved S(-II) concentrations of S(0) and Fe(II)HCl increased only slightly. TEM measurements revealed the occurrence of a mackinawite rim covering the lepidocrocite crystals and being separated from the lepidocrocite surface by an interfacial magnetite layer that can be regarded as a steady state product of the interaction between lepidocrocite and mackinawite. A significant fraction of Fe(II) was formed in excess to FeS within the first 2 h. The amount of this fraction increased with decreasing ratio between dissolved S(-II) concentration and the concentration of surface sites, which we attributed to a kinetic decoupling of S(-II) oxidation and Fe(II) detachment from the lepidocrocite surface. At low ratios, S(-II) seems to transfer electrons to lepidocrocite faster then stoichiometric amounts of FeS could. After 2 days Fe(II)HCl and S(0) started to decrease resulting in pyrite formation accompanied by traces of magnetite. TEM measurements indicated that mackinawite completely dissolved and precipitation of pyrite occurred dislocated from the

  15. 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.

  16. Caloranaerobacter ferrireducens sp. nov., an anaerobic, thermophilic, iron (III)-reducing bacterium isolated from deep-sea hydrothermal sulfide deposits.

    PubMed

    Zeng, Xiang; Zhang, Zhao; Li, Xi; Jebbar, Mohamed; Alain, Karine; Shao, Zongze

    2015-06-01

    A thermophilic, anaerobic, iron-reducing bacterium (strain DY22619T) was isolated from a sulfide sample collected from an East Pacific Ocean hydrothermal field at a depth of 2901 m. Cells were Gram-stain-negative, motile rods (2-10 µm in length, 0.5 µm in width) with multiple peritrichous flagella. The strain grew at 40-70 °C inclusive (optimum 60 °C), at pH 4.5-8.5 inclusive (optimum pH 7.0) and with sea salts concentrations of 1-10 % (w/v) (optimum 3 % sea salts) and NaCl concentrations of 1.5-5.0 % (w/v) (optimum 2.5 % NaCl). Under optimal growth conditions, the generation time was around 55 min. The isolate was an obligate chemoorganoheterotroph, utilizing complex organic compounds, amino acids, carbohydrates and organic acids including peptone, tryptone, beef extract, yeast extract, alanine, glutamate, methionine, threonine, fructose, mannose, galactose, glucose, palatinose, rhamnose, turanose, gentiobiose, xylose, sorbose, pyruvate, tartaric acid, α-ketobutyric acid, α-ketovaleric acid, galacturonic acid and glucosaminic acid. Strain DY22619T was strictly anaerobic and facultatively dependent on various forms of Fe(III) as an electron acceptor: insoluble forms and soluble forms. It did not reduce sulfite, sulfate, thiosulfate or nitrate. The genomic DNA G+C content was 29.0 mol%. Phylogenetic 16S rRNA gene sequence analyses revealed that the closest relative of strain DY22619T was Caloranaerobacter azorensis MV1087T, sharing 97.41 % 16S rRNA gene sequence similarity. On the basis of physiological distinctness and phylogenetic distance, the isolate is considered to represent a novel species of the genus Caloranaerobacter, for which the name Caloranaerobacterhttp://dx.doi.org/10.1601/nm.4081ferrireducens sp. nov. is proposed. The type strain is DY22619T ( = JCM 19467T = DSM 27799T = MCCC1A06455T).

  17. 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.

  18. 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.

  19. 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

  20. Stabilities of thiomolybdate complexes of iron; implications for retention of essential trace elements (Fe, Cu, Mo) in sulfidic waters.

    PubMed

    Helz, George R; Erickson, Britt E; Vorlicek, Trent P

    2014-06-01

    In aquatic ecosystems, availabilities of Fe, Mo and Cu potentially limit rates of critical biological processes, including nitrogen fixation, nitrate assimilation and N2O decomposition. During long periods in Earth's history when large parts of the ocean were sulfidic, what prevented these elements' quantitative loss from marine habitats as insoluble sulfide phases? They must have been retained by formation of soluble complexes. Identities of the key ligands are poorly known but probably include thioanions. Here, the first determinations of stability constants for Fe(2+)-[MoS4](2-) complexes in aqueous solution are reported based on measurements of pyrrhotite (hexagonal FeS) solubility under mildly alkaline conditions. Two linear complexes, [FeO(OH)MoS4](3-) and [(Fe2S2)(MoS4)2](4-), best explain the observed solubility variations. Complexes that would be consistent with cuboid cluster structures were less successful, implying that such clusters probably are minor or absent in aqueous solution under the conditions studied. The new data, together with prior data on stabilities of Cu(+)-[MoS4](2-) complexes, are used to explore computationally how competition of Fe(2+) and Cu(+) for [MoS4](2-), as well as competition of [MoS4](2-) and HS(-) for both metals would be resolved in solutions representative of sulfidic natural waters. Thiomolybdate complexes will be most important at sulfide concentrations near the [MoO4](2-)-[MoS4](2-) equivalence point. At lower sulfide concentrations, thiomolybdates are insufficiently stable to be competitive ligands in natural waters and at higher sulfide concentrations HS(-) ligands out-compete thiomolybdates.

  1. S K-edge X-ray absorption studies of tetranuclear iron-sulfur clusters: mu-sulfide bonding and its contribution to electron delocalization.

    PubMed

    Glaser, T; Rose, K; Shadle, S E; Hedman, B; Hodgson, K O; Solomon, E I

    2001-01-24

    X-ray absorption spectroscopy (XAS) at the sulfur ( approximately 2470 eV) and chlorine ( approximately 2822 eV) K-edges has been applied to a series of 4Fe-4S model complexes. These are compared to 2Fe-2S model complexes to obtain insight into the localized ground state in the mixed-valence dimer versus the delocalized ground state in the mixed-valence tetramer. The preedges of hypothetical delocalized mixed-valence dimers [Fe(2)S(2)](+) are estimated using trends from experimental data and density functional calculations, for comparison to the delocalized mixed-valence tetramer [Fe(4)S(4)](2+). The differences between these two mixed-valence sites are due to the change of the sulfide-bridging mode from micro(2) to micro(3). The terminal chloride and thiolate ligands are used as spectator ligands for the electron density of the iron center. From the intensity of the preedge, the covalency of the terminal ligands is found to increase in the tetramer as compared to the dimer. This is associated with a higher effective nuclear charge on the iron in the tetramer (derived from the energies of the preedge). The micro(3)-bridging sulfide in the tetramer has a reduced covalency per bond (39%) as compared to the micro(2)-bridging sulfide in the dimer (51%). A simple perturbation model is used to derive a quadratic dependence of the superexchange coupling constant J on the covalency of the metal ions with the bridging ligands. This relationship is used to estimate the superexchange contribution in the tetramer (J = -156 cm(-)(1)) as compared to the mixed-valence dimer (J = -360 cm(-)(1)). These results, combined with estimates for the double exchange and the vibronic coupling contributions of the dimer sub-site of the tetramer, lead to a delocalized S(t) = (9)/(2) spin ground state for the mixed-valence dimer in the tetramer. Thus, the decrease in the covalency, hence the superexchange pathway associated with changing the bridging mode of the sulfides from micro(2) to micro

  2. Ligand-free highly effective iron/copper co-catalyzed formation of dimeric aryl ethers or sulfides.

    PubMed

    Qu, Xiaoming; Li, Tingyi; Zhu, Yan; Sun, Peng; Yang, Hailong; Mao, Jincheng

    2011-07-21

    Highly selective coupling of diiodoarenes with phenols or phenthiols can be performed by using a low-cost, benign character and readily available Fe/Cu catalytic system in the absence of ligands. It is noteworthy that the desired dimeric aryl ethers or sulfides could be obtained in high yields by coupling between diiodoarenes and phenols, or diphenols with aryl iodides.

  3. The Metastable Brain

    PubMed Central

    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

  4. Polarization of metastable 129Xe

    NASA Astrophysics Data System (ADS)

    Xia, Tian; Morgan, Steven; Jau, Yuan-Yu; Happer, William

    2008-05-01

    We have measured atomic polarization of metastable 129Xe in a pyrex cell by optical pumping, while metastability exchange optical pumping of 3He is routinely done. The atomic polarization of metastable Xe is on the order of 10%. Metastable xenon is created by electrodeless rf discharge. The hyperfine transition of metastable 129Xe is observed by microwave excitation. Atomic polarization can be demonstrated by comparison of the intensities of the transitions between different Zeeman sublevels, while pumping a specific optical transition of metastable Xe with circularly polarized light. This work offers insight into attempts to polarize 129Xe nuclei by metastability exchange optical pumping.

  5. 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

  6. In-situ Measurements of Sedimentary Graphites and Sulfides in Early Archean (>3.7 Ga) Banded Iron-Formations from West Greenland: Biological and Atmospheric Influences

    NASA Astrophysics Data System (ADS)

    Mojzsis, S. J.

    2001-05-01

    Stable isotopes of carbon [13C, 12C] and sulfur [32S, 33S, 34S and 36S] are used as tracers for igneous, hydrothermal and biological processes on Earth. Carbon and sulfur are abundant in marine systems and they have been utilized as biomarkers in ancient sediments. Kinetic isotope fractionations between inorganic and bioorganic carbon and sulfur during metabolic cycling results in a marked enrichment of the light isotope in the biological component by several percent. Graphitic inclusions from early Archean banded iron-formations are isotopically light [range δ 13CVPDB = -20 to -50‰ ]; these results are consistent with a biological origin. Bacterial sulfate reduction has been linked to the range of over 150‰ in δ 34S from sulfate and sulfide in the rock record. Mass-dependent sulfur isotope fractionations, commonly expressed as δ 34SCDT values for sulfur-containing minerals, exhibit a small range centered at ~0‰ for terrestrial igneous [0+/-5‰ ] and hydrothermal [0+/-10‰ ] systems. Atmospheric chemical reactions on the low pO2 early Earth are implicated in non-mass-dependent sulfur isotope anomalies [expressed as: Δ 33S=δ 33S-0.520δ 34S] reported from whole-rock analyses of sulfur-containing phases in Precambrian sediments. Only atmospheric processes in planetary environments, and nucleosynthetic, spallation or ion-molecule reactions in the stellar or near-stellar environment, appear capable of producing non-mass-dependent isotope fractionations. To explore how sulfur signatures are preserved in early Archean BIFs new techniques have been developed to obtain precise 32S, 33S and 34S measurements in situ of sulfide grains from sedimentary rocks ranging in age from early Archean [ ~3.83 Ga] to Proterozoic [ ~1.8 Ga]. High-precision simultaneous measurements of multiple sulfur isotopes enable Δ 33S to be evaluated at the sub-grain scale [<30 μm ]. These results may then be compared with previous carbon isotope measurements from the same rocks. How

  7. 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 ...

  8. Selenium Sulfide

    MedlinePlus

    Selenium sulfide, an anti-infective agent, relieves itching and flaking of the scalp and removes the dry, ... Selenium sulfide comes in a lotion and is usually applied as a shampoo. As a shampoo, selenium ...

  9. 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.

  10. Metastable nematic hedgehogs

    NASA Astrophysics Data System (ADS)

    Rosso, Riccardo; Virga, Epifanio G.

    1996-07-01

    For nematic liquid crystals, we study the local stability of a radial hedgehog against biaxial perturbations. Our analysis employs the Landau - de Gennes functional to describe the free energy stored in a ball, whose radius is a parameter of the model. We find that a radial hedgehog may be either unstable or metastable, depending on the values of the elastic constants. For unstable hedgehogs, we give an explicit expression for the radius of the ball within which the instability manifests itself: it can be interpreted as the size of the biaxial core of the defect; it is of the same order of magnitude as the radius of the disclination ring predicted by Penzenstadler and Trebin's model. The metastable hedgehogs predicted by our model are the major novelty of the paper. They tell us that we may also expect truly uniaxial point defects, whose core contains no biaxial structure.

  11. Metastable dark energy

    NASA Astrophysics Data System (ADS)

    Landim, Ricardo G.; Abdalla, Elcio

    2017-01-01

    We build a model of metastable dark energy, in which the observed vacuum energy is the value of the scalar potential at the false vacuum. The scalar potential is given by a sum of even self-interactions up to order six. The deviation from the Minkowski vacuum is due to a term suppressed by the Planck scale. The decay time of the metastable vacuum can easily accommodate a mean life time compatible with the age of the universe. The metastable dark energy is also embedded into a model with SU(2)R symmetry. The dark energy doublet and the dark matter doublet naturally interact with each other. A three-body decay of the dark energy particle into (cold and warm) dark matter can be as long as large fraction of the age of the universe, if the mediator is massive enough, the lower bound being at intermediate energy level some orders below the grand unification scale. Such a decay shows a different form of interaction between dark matter and dark energy, and the model opens a new window to investigate the dark sector from the point-of-view of particle physics.

  12. 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

  13. Role of the Bogachev - Mints Concept of Metastability of Austenite in Choosing Wear-Resistant Materials

    NASA Astrophysics Data System (ADS)

    Schastlivtsev, V. M.; Filippov, M. A.

    2005-01-01

    The significance of the Bogachev - Mints concept of metastability of austenite for the choice of strain-hardenable steel, cast iron, and facing alloys resisting mechanical kinds of wear (cavitation-, erosion-, and abrasion-induced) is discussed.

  14. Superconducting Metastable Compounds.

    PubMed

    Luo, H L; Merriam, M F; Hamilton, D C

    1964-08-07

    A number of metastable phases, germanides and tellurides of gold and silver, have been prepared, analyzed by x-ray diffraction, and investigated for superconductivity. The new superconductors and their transition temperatures are AgTe(3) (2.6 degrees K), Ag(4)Ge (0.85 degrees K), Au(3)Te(5) (1.62 degrees K), and Au(1-x)Ge(x) (0.99 degrees K-1.63 degrees K) where (0.27

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. Nanostructured metal sulfides for energy storage.

    PubMed

    Rui, Xianhong; Tan, Huiteng; Yan, Qingyu

    2014-09-07

    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.

  20. 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).

  1. Desensitization of metastable intermolecular composites

    SciTech Connect

    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.

  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. Metastable solid metallic hydrogen

    SciTech Connect

    Nellis, W. J.

    1999-04-01

    Hydrogen reaches the mimimum electrical conductivity of a metal at 140 GPa (1.4 Mbar), 0.6 g/cm3 (ninefold compression of initial liquid-H2 density), and 3000 K in the fluid phase. The quest for metallic hydrogen over the past 100 years is reviewed briefly. Possible scientific and technological uses of metastable solid metallic hydrogen (MSMH) are speculated upon in the unlikely event that the metallic fluid can be quenched to MSMH at ambient pressure and temperature: a quantum, metallic solid with novel physical properties, including room-temperature superconductivity; a very light-weight structural material; a fuel, propellant, and explosive, depending on the rate of release of stored energy; a dense fuel for higher energy yields in inertial confinement fusion; and an aid in the synthesis of novel hard materials. Some of the formidable difficulties to synthesize MSMH are discussed.

  4. 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.

  5. 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.

  6. Graphite and diamond formation via the interaction of iron carbide and Fe,Ni-sulfide under mantle P-T parameters

    NASA Astrophysics Data System (ADS)

    Bataleva, Yu. V.; Palyanov, Yu. N.; Borzdov, Yu. M.; Sobolev, N. V.

    2016-11-01

    Experimental research in the Fe3C-(Fe,Ni)S system was carried out. The objective of the investigation was to model the reactions of carbide-sulfide interaction related to graphite (diamond) formation in reduced lithosphere mantle domains. T ≤ 1200°C is the formation temperature of the Ni-cohenite + graphite assemblage coexisting with two immiscible melts such as sulfide (Fe60-Ni3-S37)L and metal-sulfide (Fe71-Ni7-S21-C1)L containing dissolved carbon. T ≥ 1300°C is the generation temperature of a unified melt such as (Fe80-Ni6-S10-C4)L characterized by graphite crystallization and diamond growth. The extraction of carbide carbon during the interaction with the sulfide melt can be considered as one of the potential mechanisms of graphite and diamond formation in the reduced mantle.

  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. 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.

  9. 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.

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

    DOE PAGES

    Toner, Brandy M.; Rouxel, Olivier J.; Santelli, Cara M.; ...

    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

  11. 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

  12. 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

  13. Catalytic performance and deactivation of precipitated iron catalyst for selective oxidation of hydrogen sulfide to elemental sulfur in the waste gas streams from coal gasification

    SciTech Connect

    Mashapa, T.N.; Rademan, J.D.; van Vuuren, M.J.J.

    2007-09-15

    The selective oxidation of hydrogen sulfide to elemental sulfur, using a commercial, precipitated silica promoted ferric oxide based catalyst, was investigated in laboratory and pilot-plant reactors. Low levels of hydrogen sulfide (1-3 vol%) can be readily removed, but a continuous slow decrease in catalyst activity was apparent. X-ray photoelectron spectroscopy showed that the loss of activity was due to the formation of ferrous sulfate, which is known to be less active than the ferric oxide. In addition, studies using a model feed showed that the propene and HCN impurities in the plant feed stocks also act as potent catalyst poisons.

  14. Point Defect Concentrations in Metastable Fe-C Alloys

    SciTech Connect

    Foerst, Clemens J.; Yip, Sidney; Slycke, Jan; Vliet, Krystyn J. van

    2006-05-05

    Point defect species and concentrations in metastable Fe-C alloys are determined using density functional theory and a constrained free-energy functional. Carbon interstitials dominate unless iron vacancies are in significant excess, whereas excess carbon causes greatly enhanced vacancy concentration. Our predictions are amenable to experimental verification; they provide a baseline for rationalizing complex microstructures known in hardened and tempered steels, and by extension other technological materials created by or subjected to extreme environments.

  15. 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

  16. 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

  17. Hydrogen sulfide

    Integrated Risk Information System (IRIS)

    EPA / 635 / R - 03 / 005 www.epa.gov / iris TOXICOLOGICAL REVIEW OF HYDROGEN SULFIDE ( CAS No . 7783 - 06 - 4 ) In Support of Summary Information on the Integrated Risk Information System ( IRIS ) June 2003 U.S . Environmental Protection Agency Washington , DC DISCLAIMER This document has been revie

  18. Metastable metallic hydrogen glass

    SciTech Connect

    Nellis, W J

    2001-02-06

    pushing the molecules together sufficiently that an electron on one molecule can delocalize and move to an adjacent molecule, if the pressure is released the system will simply revert back to a diatomic insulator. Additives will probably be necessary to produce bonding which will inhibit the reverse transformation when pressure is released. One technique for rapidly quenching metallic fluid hydrogen is to use a thin micron-thick layer of condensed hydrogen contained between metal or diamond layers, which have a high thermal conductivity to quench shock temperature before pressure is released. An appropriate planar shock wave can probably be driven by a laser or small two-stage gun to achieve the necessary pressures, temperatures, and quench rates. In this way many experiments might be performed to find the appropriate combination of materials and shock-pressure history to achieve a shock-pressure-quenched metastable metallic hydrogen glass.

  19. 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

  20. Metastable Packaging For Transient Electronics

    DTIC Science & Technology

    2014-09-01

    dated 16 Jan 09. Report contains color. 14. ABSTRACT Metastable polymeric materials were synthesized, formulated with additives and microcapsules ...photoacid generation, thermal activation, and mechanical rupture of acid-filled microcapsules -- were investigated. 15. SUBJECT TERMS transient...carbonate sulfone) (PVBCS)... 11  3.3  Thermal and Mechanical Triggered Transience of Electronic Devices via Embedded Microcapsules

  1. 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.

  2. Polar domains and charge-density waves in the acentric cerium(III) iron(II) sulfide Ce{sub 22}Fe{sub 21}S{sub 54}

    SciTech Connect

    Mills, Allison M.; Ruck, Michael

    2008-11-15

    The cerium(III) iron(II) sulfide Ce{sub 22}Fe{sub 21}S{sub 54} was synthesized through reaction of the binary sulfides C-Ce{sub 2}S{sub 3} and FeS in a LiCl/KCl flux at 1170 K, and its structure was determined by single-crystal X-ray diffraction. Ce{sub 22}Fe{sub 21}S{sub 54} crystallizes in the polar monoclinic space group Cm with a=16.3912(7) A, b=3.9554(1) A, c=62.028(3) A, {beta}=94.831(4){sup o}, and Z=2. The structure is a superstructure of the La{sub 2}Fe{sub 2}S{sub 5} structure type. Akin to the parent structure, trans-edge-sharing [FeS{sub 6}]-octahedra form linear chains, which are isotactically capped on one side by [FeS{sub 4}]-tetrahedra. The polarity of the resulting {sub {infinity}}{sup 1}[Fe{sub 2}S{sub 5}]-chains is transferred to the entire structure, as the unit cell contains two layered domains of opposite polarity with the unbalanced size ratio of 4:6. The domain walls are intrinsically centrosymmetric (layer group c 1 2/m 1). One wall consists of trigonal [FeS{sub 5}]-bipyramids, which are linked by corners and edges into a {sub {infinity}}{sup 2}[Fe{sub 2}S{sub 5}]-layer. In the other wall, the [FeS{sub 4}]-tetrahedra of two opposing {sub {infinity}}{sup 1}[Fe{sub 2}S{sub 5}]-chains share their vertices. The sulfur anions eliminated thereby are counterbalanced by vacancies in the iron sites, which follow a sinusoidal occupation modulation corresponding to a frozen charge-density wave with the wave vector k=4{pi}c*. The coordination polyhedra of all the cerium cations are bicapped trigonal prisms. - Graphical Abstract: Chains of [FeS{sub 6}]-octahedra that are isotactically capped on one side by [FeS{sub 4}]-tetrahedra dominate the acentric structure. The unit cell contains two layered domains of opposite polarity with unbalanced size ratio. Vacancies in the iron sites follow a sinusoidal occupation modulation corresponding to a frozen charge-density wave.

  3. 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.

  4. 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

  5. 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.

  6. 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.

  7. 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.

  8. High efficiency iron electrode and additives for use in rechargeable iron-based batteries

    DOEpatents

    Narayan, Sri R.; Prakash, G. K. Surya; Aniszfeld, Robert; Manohar, Aswin; Malkhandi, Souradip; Yang, Bo

    2017-02-21

    An iron electrode and a method of manufacturing an iron electrode for use in an iron-based rechargeable battery are disclosed. In one embodiment, the iron electrode includes carbonyl iron powder and one of a metal sulfide additive or metal oxide additive selected from the group of metals consisting of bismuth, lead, mercury, indium, gallium, and tin for suppressing hydrogen evolution at the iron electrode during charging of the iron-based rechargeable battery. An iron-air rechargeable battery including an iron electrode comprising carbonyl iron is also disclosed, as is an iron-air battery wherein at least one of the iron electrode and the electrolyte includes an organosulfur additive.

  9. Process for scavenging hydrogen sulfide from hydrocarbon gases

    SciTech Connect

    Fox, I.

    1981-01-20

    A process for scavenging hydrogen sulfide from hydrocarbon gases utilizes iron oxide particles of unique chemical and physical properties. These particles have large surface area, and are comprised substantially of amorphous Fe/sub 2/O/sub 3/ containing a crystalline phase of Fe/sub 2/O/sub 3/, Fe/sub 3/O/sub 4/ and combinations thereof. In scavenging hydrogen sulfide, the iron oxide particles are suspended in a liquid which enters into intimate mixing contact with hydrocarbon gases; the hydrogen sulfide is reacted at an exceptional rate and only acid-stable reaction products are formed. Thereafter, the sweetened hydrocarbon gases are collected.

  10. Metastability at the nanometer scale

    SciTech Connect

    Desre, P.J.

    1996-12-31

    Under constraints and at the nanometer scale, transitory metastable states can be generated in multicomponents materials. Examples illustrating such specific states are presented. They concern (1) the crystalline nucleation in a growing undercooled liquid droplet formed from a liquid parent phase; (2) the suppression of intermetallic nucleation in solid solutions or glasses subjected to sharp concentration gradients; (3) the nanocrystalline transitory state preceding amorphization by ball milling. In connection with this latter example, a thermodynamic model for the nanocrystal to glass transition, based on a hypothesis of a topological disorder wetting at the nanograin boundaries, is proposed.

  11. 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.

  12. 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.

  13. One-Step In Situ Growth of Iron-Nickel Sulfide Nanosheets on FeNi Alloy Foils: High-Performance and Self-Supported Electrodes for Water Oxidation.

    PubMed

    Yuan, Cheng-Zong; Sun, Zhong-Ti; Jiang, Yi-Fan; Yang, Zheng-Kun; Jiang, Nan; Zhao, Zhi-Wei; Qazi, Umair Yaqub; Zhang, Wen-Hua; Xu, An-Wu

    2017-03-10

    Efficient and durable oxygen evolution reaction (OER) catalysts are highly required for the cost-effective generation of clean energy from water splitting. For the first time, an integrated OER electrode based on one-step direct growth of metallic iron-nickel sulfide nanosheets on FeNi alloy foils (denoted as FeNi3 S2 /FeNi) is reported, and the origin of the enhanced OER activity is uncovered in combination with theoretical and experimental studies. The obtained FeNi3 S2 /FeNi electrode exhibits highly catalytic activity and long-term stability toward OER in strong alkaline solution, with a low overpotential of 282 mV at 10 mA cm(-2) and a small Tafel slope of 54 mV dec(-1) . The excellent activity and satisfactory stability suggest that the as-made electrode provides an attractive alternative to noble metal-based catalysts. Combined with density functional theory calculations, exceptional OER performance of FeNi3 S2 /FeNi results from a combination of efficient electron transfer properties, more active sites, the suitable O2 evolution kinetics and energetics benefited from Fe doping. This work not only simply constructs an excellent electrode for water oxidation, but also provides a deep understanding of the underlying nature of the enhanced OER performance, which may serve as a guide to develop highly effective and integrated OER electrodes for water splitting.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. Metastable Supersymmetry Breaking in a Cooling Universe

    SciTech Connect

    Kaplunovsky, Vadim S.

    2007-11-20

    I put metastable supersymmetry breaking in a cosmological context. I argue that under reasonable assumptions, the cooling down early Universe favors metastable SUSY-breaking vacua over the stable supersymmetric vacua. To illustrate the general argument, I analyze the early-Universe history of the Intriligator-Seiberg-Shih model.

  1. The thermodynamic scale of inorganic crystalline metastability.

    PubMed

    Sun, Wenhao; Dacek, Stephen T; Ong, Shyue Ping; Hautier, Geoffroy; Jain, Anubhav; Richards, William D; Gamst, Anthony C; Persson, Kristin A; Ceder, Gerbrand

    2016-11-01

    The space of metastable materials offers promising new design opportunities for next-generation technological materials, such as complex oxides, semiconductors, pharmaceuticals, steels, and beyond. Although metastable phases are ubiquitous in both nature and technology, only a heuristic understanding of their underlying thermodynamics exists. We report a large-scale data-mining study of the Materials Project, a high-throughput database of density functional theory-calculated energetics of Inorganic Crystal Structure Database structures, to explicitly quantify the thermodynamic scale of metastability for 29,902 observed inorganic crystalline phases. We reveal the influence of chemistry and composition on the accessible thermodynamic range of crystalline metastability for polymorphic and phase-separating compounds, yielding new physical insights that can guide the design of novel metastable materials. We further assert that not all low-energy metastable compounds can necessarily be synthesized, and propose a principle of 'remnant metastability'-that observable metastable crystalline phases are generally remnants of thermodynamic conditions where they were once the lowest free-energy phase.

  2. 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

  3. 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.

  4. Reactive iron in marine sediments

    NASA Technical Reports Server (NTRS)

    Canfield, Donald E.

    1989-01-01

    The influence of reactive iron oxides on sediment pore-water chemistry is considered in detail. A carefully calibrated extraction scheme is used to determine the depth distributions of reactive iron phases at two very different localities: the relatively iron-rich Mississippi Delta and the relatively iron-poor FOAM site in Long Island Sound. Closed system incubations are used to characterize the rates of reaction between sulfide and both naturally occurring and pure iron mineral phases. Rates of iron liberation to pore solution are measured in the presence and absence of sulfate reduction, and the origin of dissolved iron in organic-rich sediments is speculated upon.

  5. Evolution of sulfide mineralization on Mars

    SciTech Connect

    Burns, R.G.; Fisher, D.S. )

    1990-08-30

    The presence of komatiitic igneous rocks on Marks, based on geochemical evidence from SNC meteorites and Viking X ray fluorescence analyses of the regolith, suggests that massive and disseminated iron sulfide mineralization occurs near the Martian surface. Analogies are drawn between possible ultramafic Fe-Ni sulfides on Mars and terrestrial pyrrhotite-pentlandite ore deposits associated with Archean komatiites formed during early crustal development on Earth. Partial melting of the mantle as a result of high radiogenic heat production then, extrusion of turbulent high-temperature ultramafic lavas, segregation of immiscible FeS melts during cooling, gravitational settling and fractional crystallization of sulfide minerals in magma chambers or lava flows produced massive and disseminated sulfide mineralization associated with terrestrial komatiites. Comparable processes probably occurred on Mars where, on account of the inferred higher Fe/(Fe + Mg) ratio of the X ray mantle (estimated to contain {approximately}4.5 wt % S), iron-rich basaltic magmas were produced by partial melting at depths and temperatures exceeding 165 km and 1,400{degree}C, respectively. Adiabatic diapiric emplacement of these iron-rich, very low viscosity basaltic melts transported significant concentrations of dissolved sulfur as S{sup 2{minus}} and HS{sup {minus}} from the mantle. Ensuing sulfide mineralization may have been either thinly disseminated within ultramafic lavas erupting over large areas of Mars or concentrated locally at the base of structural depressions. Cumulate ore deposits several meters thick may occur at the base of intrusions or in near-surface magma chambers. The evidence for insignificant plate tectonic activity on Mars and minimal interactions of Martian mantle with crust, hydrosphere and atmosphere has restricted the evolution of sulfide ore deposits there.

  6. Instability of colliding metastable strings

    NASA Astrophysics Data System (ADS)

    Hiramatsu, Takashi; Eto, Minoru; Kamada, Kohei; Kobayashi, Tatsuo; Ookouchi, Yutaka

    2014-01-01

    The breaking of U(1) R symmetry plays a crucial role in modeling the breaking of supersymmetry (SUSY). In the models that possess both SUSY preserving and SUSY breaking vacua, tube-like cosmic strings called R-tubes, whose surfaces are constituted by domain walls interpolating a false and a true vacuum with some winding numbers, can exist. Their (in)stability can strongly constrain SUSY breaking models theirselves. In the present study, we investigate the dynamical (in)stability of two colliding metastable tube-like strings by field-theoretic simulations. From them, we find that the strings become unstable, depending on the relative collision angle and speed of two strings, and the false vacuum is eventually filled out by the true vacuum owing to rapid expansion of the strings or unstable bubbles created as remnants of the collision.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. The thermodynamic scale of inorganic crystalline metastability

    PubMed Central

    Sun, Wenhao; Dacek, Stephen T.; Ong, Shyue Ping; Hautier, Geoffroy; Jain, Anubhav; Richards, William D.; Gamst, Anthony C.; Persson, Kristin A.; Ceder, Gerbrand

    2016-01-01

    The space of metastable materials offers promising new design opportunities for next-generation technological materials, such as complex oxides, semiconductors, pharmaceuticals, steels, and beyond. Although metastable phases are ubiquitous in both nature and technology, only a heuristic understanding of their underlying thermodynamics exists. We report a large-scale data-mining study of the Materials Project, a high-throughput database of density functional theory–calculated energetics of Inorganic Crystal Structure Database structures, to explicitly quantify the thermodynamic scale of metastability for 29,902 observed inorganic crystalline phases. We reveal the influence of chemistry and composition on the accessible thermodynamic range of crystalline metastability for polymorphic and phase-separating compounds, yielding new physical insights that can guide the design of novel metastable materials. We further assert that not all low-energy metastable compounds can necessarily be synthesized, and propose a principle of ‘remnant metastability’—that observable metastable crystalline phases are generally remnants of thermodynamic conditions where they were once the lowest free-energy phase. PMID:28138514

  12. 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.

  13. 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.

  14. 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.

  15. System-Size Effects in Metastability

    NASA Astrophysics Data System (ADS)

    Schulman, L. S.

    The following sections are included: * INTRODUCTION * CALCULATION OP PV(m), THE FINITE) SIZE PROBABILITY FOR FINDING MAGNETIZATION m * HEURISTICS OF PV(m) * DYNAMIC METASTABILITY * DISCUSSION * ACKNOWLEDGEMENTS * REFERENCES

  16. 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

  17. 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...

  18. Metastability in an open quantum Ising model.

    PubMed

    Rose, Dominic C; Macieszczak, Katarzyna; Lesanovsky, Igor; Garrahan, Juan P

    2016-11-01

    We apply a recently developed theory for metastability in open quantum systems to a one-dimensional dissipative quantum Ising model. Earlier results suggest this model features either a nonequilibrium phase transition or a smooth but sharp crossover, where the stationary state changes from paramagnetic to ferromagnetic, accompanied by strongly intermittent emission dynamics characteristic of first-order coexistence between dynamical phases. We show that for a range of parameters close to this transition or crossover point the dynamics of the finite system displays pronounced metastability, i.e., the system relaxes first to long-lived metastable states before eventual relaxation to the true stationary state. From the spectral properties of the quantum master operator we characterize the low-dimensional manifold of metastable states, which are shown to be probability mixtures of two, paramagnetic and ferromagnetic, metastable phases. We also show that for long times the dynamics can be approximated by a classical stochastic dynamics between the metastable phases that is directly related to the intermittent dynamics observed in quantum trajectories and thus the dynamical phases.

  19. Metastability in an open quantum Ising model

    NASA Astrophysics Data System (ADS)

    Rose, Dominic C.; Macieszczak, Katarzyna; Lesanovsky, Igor; Garrahan, Juan P.

    2016-11-01

    We apply a recently developed theory for metastability in open quantum systems to a one-dimensional dissipative quantum Ising model. Earlier results suggest this model features either a nonequilibrium phase transition or a smooth but sharp crossover, where the stationary state changes from paramagnetic to ferromagnetic, accompanied by strongly intermittent emission dynamics characteristic of first-order coexistence between dynamical phases. We show that for a range of parameters close to this transition or crossover point the dynamics of the finite system displays pronounced metastability, i.e., the system relaxes first to long-lived metastable states before eventual relaxation to the true stationary state. From the spectral properties of the quantum master operator we characterize the low-dimensional manifold of metastable states, which are shown to be probability mixtures of two, paramagnetic and ferromagnetic, metastable phases. We also show that for long times the dynamics can be approximated by a classical stochastic dynamics between the metastable phases that is directly related to the intermittent dynamics observed in quantum trajectories and thus the dynamical phases.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. Dynamic consolidation of metastable nanocrystalline powders

    SciTech Connect

    Korth, G.E.; Williamson, R.L.

    1995-10-01

    Nanocrystalline metal powders synthesized by mechanical alloying in a ball mill resulted in micron-sized powder particles with a nanosized (5 to 25 nm) substructure. Conventional consolidation methods resulted in considerable coarsening of the metastable nanometer crystallites, but dynamic consolidation of these powders using explosive techniques produced fully dense monoliths while retaining the 5- to 25-nm substructure. Numerical modeling used to guide the experimental phase, revealed that the compression wave necessary for suitable consolidation was of order of 10 GPa for a few tenths of a microsecond. The consolidation process is described, and the retention of the metastable nanostructure is illustrated.

  9. 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.

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

    SciTech Connect

    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 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

  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. Symplectic integration approach for metastable systems

    NASA Astrophysics Data System (ADS)

    Klotins, E.

    2006-03-01

    Nonadiabatic behavior of metastable systems modeled by anharmonic Hamiltonians is reproduced by the Fokker-Planck and imaginary time Schrödinger equation scheme with subsequent symplectic integration. Example solutions capture ergodicity breaking, reassure the H-theorem of global stability [M. Shiino, Phys. Rev. A 36, 2393 (1987)], and reproduce spatially extended response under alternate source fields.

  13. 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.

  14. 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.

  15. Interstellar hydrogen sulfide.

    NASA Technical Reports Server (NTRS)

    Thaddeus, P.; Kutner, M. L.; Penzias, A. A.; Wilson, R. W.; Jefferts, K. B.

    1972-01-01

    Hydrogen sulfide has been detected in seven Galactic sources by observation of a single line corresponding to the rotational transition from the 1(sub 10) to the 1(sub 01) levels at 168.7 GHz. The observations show that hydrogen sulfide is only a moderately common interstellar molecule comparable in abundance to H2CO and CS, but somewhat less abundant than HCN and much less abundant than CO.

  16. Effect of sulfide on growth physiology and gene expression of Desulfovibrio vulgaris Hildenborough.

    PubMed

    Caffrey, Sean M; Voordouw, Gerrit

    2010-01-01

    Hydrogen sulfide, the metabolic end product of sulfate-reducing bacteria (SRB), is toxic to most life forms. This includes the SRB themselves. Although many of these are probably among the most sulfide resistant life forms, the presence of sulfide nevertheless presents a stress, which SRB must overcome. Although the response of SRB, especially the genus Desulfovibrio, to numerous stressors has been studied, their response to sulfide stress is unknown. We determined the effect of sulfide stress by comparing cells of Desulfovibrio vulgaris Hildenborough grown under conditions in which sulfide accumulated (high sulfide, 10 mM) with cells grown under conditions in which sulfide was removed by continuous gassing (low sulfide, 1 mM). High sulfide decreased the instantaneous growth rate constant and the final cell density of the culture by 52 and 33%, respectively, indicating a decreased bioenergetic fitness. Changes in gene expression caused by exposure to high sulfide were determined using full-genome D. vulgaris microarrays. The transcription of ribosomal protein-encoding genes was decreased, in agreement with the lower growth rate of D. vulgaris under high sulfide conditions. Interestingly, expression of the gene for DsrD, located downstream of the genes for dissimilatory sulfite reductase was also strongly down-regulated. In contrast, the expression of many genes involved in iron accumulation, stress response and proteolysis were increased. This indicates that high sulfide represents a significant stress condition, in which the bioavailability of metals like iron may be lowered. Overall this leads to a reduced growth rate and less efficient biomass production.

  17. 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...

  18. Use of hydrochloric acid for determinining solid-phase arsenic partitioning in sulfidic sediments.

    PubMed

    Wilkin, Richard T; Ford, Robert G

    2002-11-15

    We examined the use of room-temperature hydrochloric acid (1-6 M) and salt solutions of magnesium chloride, sodium carbonate, and sodium sulfide for the removal of arsenic from synthetic iron monosulfides and contaminated sediments containing acid-volatile sulfides (AVS). Results indicate that acid-soluble arsenic reacts with H2S released from AVS phases and precipitates at low pH as disordered orpiment or alacranite. Arsenic sulfide precipitation is consistent with geochemical modeling in that conditions during acid extraction are predicted to be oversaturated with respect to orpiment, realgar, or both. Binding of arsenic with sulfide at low pH is sufficiently strong that 6 M HCl will not keep spiked arsenic in the dissolved fraction. Over a wide range of AVS concentrations and molar [As]/[AVS] ratios, acid extraction of arsenic from sulfide-bearing sediments will give biased results that overestimate the stability or underestimate the bioavailability of sediment-bound arsenic. Alkaline solutions of sodium sulfide and sodium carbonate are efficient in removing arsenic from arsenic sulfides and mixed iron-arsenic sulfides because of the high solubility of arsenic at alkaline pH, the formation of stable arsenic complexes with sulfide or carbonate, or both.

  19. Aerosol Iron/Phytoplankton Interactions

    DTIC Science & Technology

    1994-08-16

    effect on the photocycling of able and particulate iron in the euphotic zone at iron. The TRFe levels in carboys to which catalase O0N, 140’W that...experiments without catalase (Figs. 4 filter averaged 0.05 nM in the upper 100 m and and 5). The effects of adding catalase to a carboy particulate iron... Effects on dimethyl sulfide and dimethylsulphoniopropionate production. Nightingale, P. D., Turner, S. M. Malin, G. and L1ss, P. S. Iron

  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. Metastability in bubbling AdS space

    NASA Astrophysics Data System (ADS)

    Massai, Stefano; Pasini, Giulio; Puhm, Andrea

    2015-02-01

    We study the dynamics of probe M5 branes with dissolved M2 charge in bubbling geometries with SO(4) × SO(4) symmetry. These solutions were constructed by Bena-Warner and Lin-Lunin-Maldacena and correspond to the vacua of the maximally supersymmetric mass-deformed M2 brane theory. We find that supersymmetric probe M2 branes polarize into M5 brane shells whose backreaction creates an additional bubble in the geometry. We explicitly check that the supersymmetric polarization potential agrees with the one found within the Polchinski-Strassler approximation. The main result of this paper is that probe M2 branes whose orientation is opposite to the background flux can polarize into metastable M5 brane shells. These decay to a supersymmetric configuration via brane-flux annihilation. Our findings suggest the existence of metastable states in the mass-deformed M2 brane theory.

  4. Metastable localization of diseases in complex networks

    NASA Astrophysics Data System (ADS)

    Ferreira, R. S.; da Costa, R. A.; Dorogovtsev, S. N.; Mendes, J. F. F.

    2016-12-01

    We describe the phenomenon of localization in the epidemic susceptible-infective-susceptible model on highly heterogeneous networks in which strongly connected nodes (hubs) play the role of centers of localization. We find that in this model the localized states below the epidemic threshold are metastable. The longevity and scale of the metastable outbreaks do not show a sharp localization transition; instead there is a smooth crossover from localized to delocalized states as we approach the epidemic threshold from below. Analyzing these long-lasting local outbreaks for a random regular graph with a hub, we show how this localization can be detected from the shape of the distribution of the number of infective nodes.

  5. Transient Cognitive Dynamics, Metastability, and Decision Making

    DTIC Science & Technology

    2008-05-02

    793–810. 39. Wagatsuma H, Yamaguchi Y (2007) Neural dynamics of the cognitive map in the hippocampus. Cognitive Neurodynamics 1: 119–141. 40. Kifer Y...Transient Cognitive Dynamics, Metastability, and Decision Making Mikhail I. Rabinovich1*, Ramón Huerta1,2, Pablo Varona2, Valentin S. Afraimovich3 1...Óptica, UASLP, San Luis de Potosı́, Mexico Abstract The idea that cognitive activity can be understood using nonlinear dynamics has been intensively

  6. Metastable Phase Evolution in Oxide Systems

    NASA Astrophysics Data System (ADS)

    Levi, Carlos G.

    2005-03-01

    Multi-component ceramics are often synthesized by routes that facilitate mixing at the molecular scale and subsequently generate a solid product at low homologous temperatures. Examples include chemical and physical vapor deposition, thermal spray, and pyrolytic decomposition of precursor solutions. In these processes the solid evolves rapidly from a highly energized state, typically in a temperature regime wherein long-range diffusion is largely constrained and the equilibrium configuration can be kinetically suppressed. The resulting product may exhibit various forms of metastability such as amorphization, nanocrystallinity, extended solid solubility and alternate crystalline forms. The approach allows access to novel combinations of structure and composition with unprecedented defect structures that, if reasonably durable, could have properties of potential technological interest. Understanding phase selection and evolution is facilitated by having a suitable reference framework depicting the thermodynamic hierarchy of the phases available to the system under the relevant processing conditions. When transformations are partitionless the phase menu and hierarchy can be readily derived from the relative position of the T0 curves/surfaces for the different pairs of phases. The result is a phase hierarchy map, which is an analog of the phase diagram for partitionless equilibrium. Such maps can then be used to assess the kinetic effects on the selection of metastable states and their subsequent evolution. This presentation will discuss the evolution of metastable phases in oxides, with emphasis on systems involving fluorite phases and their ordered or distorted derivatives. The concepts will be illustrated primarily with zirconia-based systems, notably those of interest in thermal barrier coatings, fuel cells and ferroelectrics (ZrO2-MO3/2, where M = Y, Sc, the lanthanides and combinations thereof, as well as ZrO2-YO3/2-TiO2, ZrO2-TiO2-PbO, etc.). Of particular

  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.

  10. 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.

  11. 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.

  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. 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.

  14. 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.

  15. Formation of dimethyl sulfide and methanethiol in anoxic freshwater sediments.

    PubMed

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

    1997-12-01

    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

  16. Microstructure of metastable metallic alloy films produced by laser breakdown chemical vapor deposition and ion implantation

    SciTech Connect

    Menon, S.K.; Jervis, T.R.; Nastasi, M.

    1986-01-01

    Thin films produced by laser breakdown chemical vapor deposition from nickel and iron carbonyls and by implanting Ni foils with varying levels of C have been characterized by transmission electron microscopy. Decomposition of Ni(CO)/sub 4/ produces polycrystalline films of fcc Ni and metastable ordered hexagonal Ni/sub 3/C. This metastable phase is identical to that produced by gas carburization, rapid solidification of Ni-C melts, and ion implantation of C into Ni at low concentrations. Increasing the H/sub 2/ content in the gas mixture during laser deposition reduces the grain size of the films significantly with grain sizes smaller than 10 nanometers produced. Laser decomposition of Fe(CO)/sub 5/ produces films with islands of fcc gamma-Fe and finely dispersed metastable Fe/sub 3/C (Cementite). In addition, the ferrous oxides Fe/sub 2/O/sub 3/ and Fe/sub 3/O/sub 4/ were found in these samples. Implants of C into pure Ni foils at 77/sup 0/K and at a concentration of 35 at. % produced amorphous layers. Implants at the same dose at room temperature did not produce amorphous layers.

  17. Metastable Krypton Beam Source via Two-Photon Pumping Technique

    SciTech Connect

    Wong, W.W.; Young, L.

    2003-01-01

    Metastable beams of rare gas atoms have wide applications in chemical analysis of samples, as well as in aiding understanding of fundamental processes and physical attributes. Most current sources of metastable rare gas atomic beams, however, are limited in their flux density, which greatly reduces their utility in applications such as low level trace analysis and precision measurements. Previous work has demonstrated feasibility of metastable krypton production via two-photon pumping, and this paper extends that possibility into beam form. Further optimization on this scheme, moreover, promises 100-fold increase of metastable krypton flux density over that of an rf-driven discharge.

  18. 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.

  19. Metastable Metal Hydrides for Hydrogen Storage

    DOE PAGES

    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

  20. Probability of metastable states in Yukawa clusters

    NASA Astrophysics Data System (ADS)

    Ludwig, Patrick; Kaehlert, Hanno; Baumgartner, Henning; Bonitz, Michael

    2008-11-01

    Finite strongly coupled systems of charged particles in external traps are of high interest in many fields. Here we analyze the occurrence probabilities of ground- and metastable states of spherical, three-dimensional Yukawa clusters by means of molecular dynamics and Monte Carlo simulations and an analytical method. We find that metastable states can occur with a higher probability than the ground state, thus confirming recent dusty plasma experiments with so-called Yukawa balls [1]. The analytical method [2], based on the harmonic approximation of the potential energy, allows for a very intuitive explanation of the probabilities when combined with the simulation results [3].[1] D. Block, S. Käding, A. Melzer, A. Piel, H. Baumgartner, and M. Bonitz, Physics of Plasmas 15, 040701 (2008)[2] F. Baletto and R. Ferrando, Reviews of Modern Physics 77, 371 (2005)[3] H. Kählert, P. Ludwig, H. Baumgartner, M. Bonitz, D. Block, S. Käding, A. Melzer, and A. Piel, submitted for publication (2008)

  1. 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 ...

  2. The relationship between seagrass ( Posidonia oceanica) decline and sulfide porewater concentration in carbonate sediments

    NASA Astrophysics Data System (ADS)

    Calleja, Maria Ll.; Marbà, Núria; Duarte, Carlos M.

    2007-07-01

    In this study we test the hypothesized negative relationship between seagrass status and porewater hydrogen sulfide (H 2S) levels, through a comparative analysis within a range of seven Posidonia oceanica meadows growing over carbonate sediments in the NW Mediterranean Sea around Mallorca Island. The studied meadows range from meadows growing on sediments with very low sulfide porewater concentrations (4.6 μM) to those growing over higher sulfide conditions (33.5 μM). Organic matter content, sulfate reduction rates and sulfide porewater concentrations in the sediments were determined concurrently with the assessment of demographic plant dynamics (specific mortality and net population growth rates). Sulfide porewater concentration increased with increasing organic matter content in the sediment, while net population growth decreased significantly with low increases of sulfide concentrations. Our results confirm the previously suspected vulnerability of seagrass meadows growing on carbonate sediments to increased sulfide levels. An excess of 10 μmols H 2S L -1 porewater is identified to already conduce P. oceanica meadows to decline, which this study identifies, particularly, as strongly sensitive to sulfides. The results reported here suggest that even moderate increases in organic carbon inputs may lead to enhancement of dissolved sulfides and may be an important factor for seagrass status in these iron-depleted carbonate sediments from the Mediterranean Sea.

  3. Sewage sludge-derived materials as efficient adsorbents for removal of hydrogen sulfide.

    PubMed

    Bagreev, A; Bashkova, S; Locke, D C; Bandosz, T J

    2001-04-01

    Sewage sludge-derived materials were used as adsorbents of hydrogen sulfide from moist air. The adsorbent obtained by carbonization at 950 degrees C has a capacity twice of that of coconut-shell-based activated carbon. The capacity of the sludge-derived materials increases with increasing carbonization temperature. It is likelythatduring carbonization at 950 degrees C a mineral-like phase is formed that consists of such catalytically active metals as iron, zinc, and copper. The results obtained demonstrate that the presence of iron oxide significantly increases the capacity of commercial carbon and activated alumina. The sludge-derived adsorbents are efficient for hydrogen sulfide removal until the pore entrances are blocked with sulfur as the product of oxidation reaction. For materials in which the catalytic effect is predominant, hydrogen sulfide is adsorbed until all pores are filled with sulfur. There is also indication that chemisorption plays a significant role in the removal of hydrogen sulfide from moist air.

  4. The role of the interaction between oxygen and catechol in the pitting corrosion of steel in alkaline sulfide solutions

    SciTech Connect

    Kannan, S.; Kelly, R.G.

    1995-12-01

    Black liquor corrosivity is shown to depend on the interaction of the chemical species present. Specifically, an interaction between oxygen and 1,2-dihydroxybenzene compounds (catechols) in alkaline sulfide solutions leads to a distinct increase in the severity of the attack. This increased corrosivity is explained in terms of the oxidation of catechol leading to increased open circuit potentials for steel. The importance of the ratio of sulfide concentration to hydroxyl concentration in the initiation of pitting is stressed. The possible role of catechol in stabilizing metastable pits is also discussed.

  5. Pulsed Nd:YAG deposition of nanostructured FeS1-x containing meta-stable phases

    NASA Astrophysics Data System (ADS)

    Křenek, T.; Karatodorov, S.; Medlín, R.; Mihailov, V.; Savková, J.

    2017-02-01

    Pulsed near-IR laser irradiation of ferrous sulfide (FeS) in a vacuum allows a non-congruent ablation and deposition of nanostructured FeS1-x thin films. Deposition has been performed on Al, Ta and Cu unheated substrate and analyzed by scanning (SEM) and high resolution transmission electron microscopy (HRTEM) and electron diffraction. Morphologically, the similar homogeneous, dark, metallic and adhesive appearanceshave been revealed for all the coats deposited on various substrates (by SEM). However, using HRTEM in agreement with electron diffraction, different phase composition on various substrates has been detected. Cubic pyrite phase (FeS2) has been detected on Ta substrate. Cubic pyrite (FeS2) and metastable rhomboedric smythite Fe9S11 have been found in case of Al substrate. Cubic pyrite (FeS2), metastable rhomboedric smythite Fe9S11 and metastable orthorhombic marcasite (FeS2m) revealed HRTEM analysis of the film on Cu substrate. In case of all deposits the detected crystalline nanograins were surrounded by amorphous matrix.

  6. 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.

  7. 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. ...

  8. Redox sensitivity of P cycling during marine black shale formation: Dynamics of sulfidic and anoxic, non-sulfidic bottom waters

    NASA Astrophysics Data System (ADS)

    März, C.; Poulton, S. W.; Beckmann, B.; Küster, K.; Wagner, T.; Kasten, S.

    2008-08-01

    A high-resolution geochemical record of a 120 cm black shale interval deposited during the Coniacian-Santonian Oceanic Anoxic Event 3 (ODP Leg 207, Site 1261, Demerara Rise) has been constructed to provide detailed insight into rapid changes in deep ocean and sediment paleo-redox conditions. High contents of organic matter, sulfur and redox-sensitive trace metals (Cd, Mo, V, Zn), as well as continuous lamination, point to deposition under consistently oxygen-free and largely sulfidic bottom water conditions. However, rapid and cyclic changes in deep ocean redox are documented by short-term (˜15-20 ka) intervals with decreased total organic carbon (TOC), S and redox-sensitive trace metal contents, and in particular pronounced phosphorus peaks (up to 2.5 wt% P) associated with elevated Fe oxide contents. Sequential iron and phosphate extractions confirm that P is dominantly bound to iron oxides and incorporated into authigenic apatite. Preservation of this Fe-P coupling in an otherwise sulfidic depositional environment (as indicated by Fe speciation and high amounts of sulfurized organic matter) may be unexpected, and provides evidence for temporarily non-sulfidic bottom waters. However, there is no evidence for deposition under oxic conditions. Instead, sulfidic conditions were punctuated by periods of anoxic, non-sulfidic bottom waters. During these periods, phosphate was effectively scavenged during precipitation of iron (oxyhydr)oxides in the upper water column, and was subsequently deposited and largely preserved at the sea floor. After ˜15-25 ka, sulfidic bottom water conditions were re-established, leading to the initial precipitation of CdS, ZnS and pyrite. Subsequently, increasing concentrations of H 2S in the water column led to extensive formation of sulfurized organic matter, which effectively scavenged particle-reactive Mo complexes (thiomolybdates). At Site 1261, sulfidic bottom waters lasted for ˜90-100 ka, followed by another period of anoxic, non-sulfidic

  9. Redox sensitivity of P cycling during marine black shale formation: Dynamics of sulfidic and anoxic, non-sulfidic bottom waters

    NASA Astrophysics Data System (ADS)

    März, C.; Poulton, S. W.; Beckmann, B.; Küster, K.; Wagner, T.; Kasten, S.

    2009-04-01

    A high-resolution geochemical record of a 120 cm black shale interval deposited during the Coniacian-Santonian Oceanic Anoxic Event 3 (ODP Leg 207, Site 1261, Demerara Rise) has been constructed to provide detailed insight into rapid changes in deep ocean and sediment paleo-redox conditions. High contents of organic matter, sulfur and redox-sensitive trace metals (Cd, Mo, V, Zn), as well as continuous lamination, point to deposition under consistently oxygen-free and largely sulfidic bottom water conditions. However, rapid and cyclic changes in deep ocean redox are documented by short-term (about 15-20 ka) intervals with decreased total organic carbon (TOC), S and redox-sensitive trace metal contents, and in particular pronounced phosphorus peaks (up to 2.5 wt% P) associated with elevated Fe oxide contents. Sequential iron and phosphate extractions confirm that P is dominantly bound to iron oxides and incorporated into authigenic apatite. Preservation of this Fe-P coupling in an otherwise sulfidic depositional environment (as indicated by Fe speciation and high amounts of sulfurized organic matter) may be unexpected, and provides evidence for temporarily non-sulfidic bottom waters. However, there is no evidence for deposition under oxic conditions. Instead, sulfidic conditions were punctuated by periods of anoxic, non-sulfidic bottom waters. During these periods, phosphate was effectively scavenged during precipitation of iron (oxyhydr)oxides in the upper water column, and was subsequently deposited and largely preserved at the sea floor. After around 15-25 ka, sulfidic bottom water conditions were re-established, leading to the initial precipitation of CdS, ZnS and pyrite. Subsequently, increasing concentrations of H2S in the water column led to extensive formation of sulfurized organic matter, which effectively scavenged particle-reactive Mo complexes (thiomolybdates). At Site 1261, sulfidic bottom waters lasted for about 90-100 ka, followed by another period of

  10. Biotreatment of refinery spent sulfidic caustics

    SciTech Connect

    Sublette, K.L.; Rajganesh, B.; Woolsey, M.; Plato, A.

    1995-12-31

    Caustics are used in petroleum refinering to remove hydrogen sulfide from various hydrocarbon streams. Spent sulfidic caustics from two Conoco refineries have been successfully biotreated on bench and pilot scale, resulting in neutralization and removal of active sulfides. Sulfides were completely oxidized to sulfate by Thiobacillus denitrificans. Microbial oxidation of sulfide produced acid, which at least partially neutralized the caustic.

  11. Suicide with hydrogen sulfide.

    PubMed

    Sams, Ralph Newton; Carver, H Wayne; Catanese, Charles; Gilson, Thomas

    2013-06-01

    This presentation will address the recent rise of suicide deaths resulting from the asphyxiation by hydrogen sulfide (H2S) gas.Hydrogen sulfide poisoning has been an infrequently encountered cause of death in medical examiner practice. Most H2S deaths that have been reported occurred in association with industrial exposure.More recently, H2S has been seen in the commission of suicide, particularly in Japan. Scattered reports of this phenomenon have also appeared in the United States.We have recently observed 2 intentional asphyxial deaths in association with H2S. In both cases, the decedents committed suicide in their automobiles. They generated H2S by combining a sulfide-containing tree spray with toilet bowl cleaner (with an active ingredient of hydrogen chloride acid). Both death scenes prompted hazardous materials team responses because of notes attached to the victims' car windows indicating the presence of toxic gas. Autopsy findings included discoloration of lividity and an accentuation of the gray matter of the brain. Toxicology testing confirmed H2S exposure with the demonstration of high levels of thiosulfate in blood.In summary, suicide with H2S appears to be increasing in the United States.

  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. 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

  14. 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.

  15. PRODUCTION OF HYDROGEN SULFIDE BY STREPTOMYCETES AND METHODS FOR ITS DETECTION.

    PubMed

    KUESTER, E; WILLIAMS, S T

    1964-01-01

    The ability of streptomycetes to produce hydrogen sulfide is generally used for taxonomic purposes. It was found that the previously used method, the blackening of Peptone Iron Agar, does not clearly indicate formation of hydrogen sulfide. It was shown that the blackening of a lead acetate strip is the most accurate indicator for H(2)S-producing streptomycetes. A great variety of organic and inorganic sulfur compounds were examined and compared, and the choice of the most suitable sulfur source and method for the detection of hydrogen sulfide is discussed.

  16. Production of Hydrogen Sulfide by Streptomycetes and Methods for its Detection

    PubMed Central

    Küster, E.; Williams, S. T.

    1964-01-01

    The ability of streptomycetes to produce hydrogen sulfide is generally used for taxonomic purposes. It was found that the previously used method, the blackening of Peptone Iron Agar, does not clearly indicate formation of hydrogen sulfide. It was shown that the blackening of a lead acetate strip is the most accurate indicator for H2S-producing streptomycetes. A great variety of organic and inorganic sulfur compounds were examined and compared, and the choice of the most suitable sulfur source and method for the detection of hydrogen sulfide is discussed. PMID:14106940

  17. 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.

  18. 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.

  19. 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.

  20. A well-structured metastable ceria surface

    SciTech Connect

    Olbrich, R.; Pieper, H. H.; Oelke, R.; Wilkens, H.; Wollschläger, J.; Reichling, M.; Zoellner, M. H.; Schroeder, T.

    2014-02-24

    By the growth of a 180 nm thick film on Si(111), we produce a metastable ceria surface with a morphology dominated by terraced pyramids with an oriented triangular base. Changes in the nanoscale surface morphology and local surface potential due to annealing at temperatures ranging from 300 K to 1150 K in the ultra-high vacuum are studied with non-contact atomic force microscopy and Kelvin probe force microscopy. As the surface is stable in the temperature range of 300 K to 850 K, it is most interesting for applications requiring regular steps with a height of one O-Ce-O triple layer.

  1. 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.

  2. Neutral atom lithography with metastable helium

    NASA Astrophysics Data System (ADS)

    Allred, Claire Shean

    In this dissertation we describe our performance of resist assisted neutral atom lithography using a bright beam of metastable 23S1 Helium (He*). Metastable Helium atoms have 20 eV of internal energy making them easy to detect and able to destroy a resist. The He* is produced by a reverse flow DC discharge source and then collimated with the bichromatic force, followed by three optical molasses velocity compression stages. The atoms in the resulting beam have a mean longitudinal velocity of 1125 m/s and a divergence of 1.1 mrad. The typical beam flux is 2 x 109 atoms/mm2s through a 0.1mm diameter aperture 70 cm away from the source. The internal energy of the atoms damages the molecules of a self assembled monolayer (SAM) of nonanethiol. The undisturbed SAM protects a 200 A layer of gold that has been evaporated onto a prepared Silicon wafer from a wet chemical etch. Two methods are used to pattern the He* atoms before they destroy the SAM. First, a Nickel micro mesh was used to protect the SAM. These experiments established an appropriate dosage and etch time for patterning. The samples were analyzed with an atomic force microscope and found to have an edge resolution of 63 nm. Then, patterning was accomplished using the dipole force the atoms experience while traversing a standing wave of lambda = 1083nm light tuned 500MHz below the 23S 1 → 23P2 transition. Depending on the intensity of the light, the He* atoms are focused or channeled into lines separated by lambda/2. The lines cover the entire exposed length of the substrate, about 3 mm. They are about 3 mm long, corresponding to about twice the beam waist of the laser standing wave. Thus there are 6 x 10 3 lines of length 5500lambda. These results agree with our numerical simulations of the experiment.

  3. 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.

  4. Method of epitaxially depositing cadmium sulfide

    NASA Technical Reports Server (NTRS)

    Hawrylo, Frank Z. (Inventor)

    1980-01-01

    A single crystal layer of either cadmium sulfide or an alloy of cadmium sulfide and indium phosphide is epitaxially deposited on a substrate of cadmium sulfide by liquid phase epitaxy using indium as the solvent.

  5. Decrease of dissolved sulfide in sewage by powdered natural magnetite and hematite.

    PubMed

    Zhang, Lehua; Verstraete, Willy; de Lourdes Mendoza, María; Lu, Zhihao; Liu, Yongdi; Huang, Guangtuan; Cai, Lankun

    2016-12-15

    Natural magnetite and hematite were explored to decrease sulfide in sewage, compared with iron salts (FeCl3 and FeSO4). A particle size of magnetite and hematite ranging from 45 to 60μm was used. The results showed that 40mgL(-1) of powdered magnetite and hematite addition decreased the sulfide in sewage by 79%and 70%, respectively. The achieved decrease of sulfide production capacities were 197.3, 210.6, 317.6 and 283.3mgSg(-1)Fe for magnetite, hematite, FeCl3 and FeSO4 at the optimal dosage of 40mgL(-1), respectively. Magnetite and hematite provided a higher decrease of sulfide production since more iron ions are capable of being released from the solid phase, not because of adsorption capacity of per gram iron. Besides, the impact on pH and oxidation-reduction potential (ORP) of hematite addition was negligible; while magnetite addition resulted in slight increase of 0.3-0.5 on pH and 10-40mV on ORP. Powdered magnetite and hematite thus appear to be suitable for sulfide decrease in sewage, for their sparing solubility, sustained-release, long reactive time in sewage as well as cost-effectiveness, compared with iron salts. Further investigation over long time periods under practical conditions are needed to evaluate the possible settlement in sewers and unwanted (toxic) metal elements presenting as impurities.

  6. How iron controls iron.

    PubMed

    Kühn, Lukas C

    2009-12-01

    Cells regulate iron homeostasis by posttranscriptional regulation of proteins responsible for iron uptake and storage. This requires RNA-binding activity of iron-regulatory proteins, IRP1 and IRP2. Two studies recently published in Science by Vashisht et al. (2009) and Salahudeen et al. (2009) reveal how cells adjust IRP2 activity.

  7. 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.

  8. 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.

  9. Oxygen and sulfur interactions with a clean iron surface and the effect of rubbing contact on these interactions

    NASA Technical Reports Server (NTRS)

    Buckley, D. H.

    1973-01-01

    An investigation was conducted to determine the nature of the chemical interactions of oxygen and sulfur with iron when surfaces are stationary and also during sliding in a vacuum environment. Various gases that contained sulfur, oxygen, or both were adsorbed to iron at 23 C. The gases included oxygen, hydrogen sulfide, methyl mercaptan, and sulfur dioxide. Friction experiments were conducted with a hemispherical rider sliding on a rotating disk. An Auger cylindrical mirror analyzer was used to monitor the iron surface chemistry. The results of this study indicate that oxygen will completely displace sulfide films from iron surfaces. Organic thiols containing sulfur, such as methyl mercaptan, adsorb to an iron surface dissociatively. Only sulfur is detected on the iron surface. Sliding inhibits the formation of sulfide films on iron with the adsorption of hydrogen sulfide and methyl mercaptan. With oxygen and sulfur dioxide, the sliding process does not affect adsorption behavior.

  10. 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.

  11. Sulfide bonded atomic radii

    NASA Astrophysics Data System (ADS)

    Gibbs, G. V.; Ross, N. L.; Cox, D. F.

    2017-03-01

    The bonded radius, r b(S), of the S atom, calculated for first- and second-row non-transition metal sulfide crystals and third-row transition metal sulfide molecules and crystals indicates that the radius of the sulfur atom is not fixed as traditionally assumed, but that it decreases systematically along the bond paths of the bonded atoms with decreasing bond length as observed in an earlier study of the bonded radius of the oxygen atom. When bonded to non-transition metal atoms, r b(S) decreases systematically with decreasing bond length from 1.68 Å when the S atom is bonded to the electropositive VINa atom to 1.25 Å when bonded to the more electronegative IVP atom. In the case of transition metal atoms, rb(S) likewise decreases with decreasing bond length from 1.82 Å when bonded to Cu and to 1.12 Å when bonded to Fe. As r b(S) is not fixed at a given value but varies substantially depending on the bond length and the field strength of the bonded atoms, it is apparent that sets of crystal and atomic sulfide atomic radii based on an assumed fixed radius for the sulfur atom are satisfactory in that they reproduce bond lengths, on the one hand, whereas on the other, they are unsatisfactory in that they fail to define the actual sizes of the bonded atoms determined in terms of the minima in the electron density between the atoms. As such, we urge that the crystal chemistry and the properties of sulfides be studied in terms of the bond lengths determined by adding the radii of either the atomic and crystal radii of the atoms but not in terms of existing sets of crystal and atomic radii. After all, the bond lengths were used to determine the radii that were experimentally determined, whereas the individual radii were determined on the basis of an assumed radius for the sulfur atom.

  12. Evaluation of long-term sulfide oxidation processes within pyrrhotite-rich tailings, Lynn Lake, Manitoba

    NASA Astrophysics Data System (ADS)

    Gunsinger, M. R.; Ptacek, C. J.; Blowes, D. W.; Jambor, J. L.

    2006-02-01

    Oxidation reactions have depleted sulfide minerals in the shallow tailings and have generated sulfate- and metal-rich pore water throughout the East Tailings Management Area (ETMA) at Lynn Lake, Manitoba, Canada. Information concerning the tailings geochemistry and mineralogy suggest the sulfide oxidation processes have reached an advanced stage in the area proximal to the point of tailings discharge. In contrast, the distal tailings, or slimes area, have a higher moisture content close to the impoundment surface, thereby impeding the ingress of oxygen and limiting sulfide oxidation. Numerical modelling of sulfide oxidation indicates the maximum rate of release for sulfate, Fe, and Ni occurred shortly after tailings deposition ceased. Although the sulfide minerals have been depleted in the very shallow tailings, the modelling suggests that sulfide oxidation will continue for hundreds and possibly thousands of years. The combination of sulfide minerals, principally pyrrhotite, that is susceptible to weathering processes and the relatively dry, coarse-grained nature of the tailings have resulted in the formation of a massive-hardpan layer in the proximal area of the ETMA. Because extensive accumulations of secondary oxyhydroxides of ferric iron are already present, remediation strategies for the ETMA should focus on mitigating the release of sulfide oxidation products rather than on preventing further oxidation.

  13. Large excitonic effects in group-IV sulfide monolayers

    NASA Astrophysics Data System (ADS)

    Tuttle, Blair R.; Alhassan, Saeed M.; Pantelides, Sokrates T.

    2015-12-01

    Large exciton binding energies are a distinguishing feature of two-dimensional semiconductors because of reduced screening, potentially leading to unique optoelectronic applications. Here we use electronic structure methods to calculate the properties of a two-dimensional material class: group-IV monosulfides including SiS, GeS, and SnS. Bulk SiS is predicted to be a metastable layered material. Quasiparticle excitations are calculated with the G0W0 method and the Bethe-Salpeter equation is are used to include electron-hole interactions. For monolayers, strongly bound excitons are found below the quasiparticle absorption edge. The predicted excitonic binding energies are as high as 0.7 eV. Due to large excitonic effects, these group-IV sulfide monolayers have great potential for nanoscale optoelectronic applications.

  14. 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 ...

  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. 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.

  17. 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.

  18. 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

  19. Modeling of metastable phase formation diagrams for sputtered thin films

    PubMed Central

    Chang, Keke; Music, Denis; to Baben, Moritz; Lange, Dennis; Bolvardi, Hamid; Schneider, Jochen M.

    2016-01-01

    Abstract A method to model the metastable phase formation in the Cu–W system based on the critical surface diffusion distance has been developed. The driver for the formation of a second phase is the critical diffusion distance which is dependent on the solubility of W in Cu and on the solubility of Cu in W. Based on comparative theoretical and experimental data, we can describe the relationship between the solubilities and the critical diffusion distances in order to model the metastable phase formation. Metastable phase formation diagrams for Cu–W and Cu–V thin films are predicted and validated by combinatorial magnetron sputtering experiments. The correlative experimental and theoretical research strategy adopted here enables us to efficiently describe the relationship between the solubilities and the critical diffusion distances in order to model the metastable phase formation during magnetron sputtering. PMID:27877871

  20. 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.

  1. Toward a Complementary Neuroscience: Metastable Coordination Dynamics of the Brain

    NASA Astrophysics Data System (ADS)

    Kelso, J. A. Scott; Tognoli, Emmanuelle

    Metastability has been proposed as a new principle of behavioral and brain function and may point the way to a truly complementary neuroscience. From elementary coordination dynamics we show explicitly that metastability is a result of a symmetry-breaking caused by the subtle interplay of two forces: the tendency of the components to couple together and the tendency of the components to express their intrinsic independent behavior. The metastable regime reconciles the well-known tendencies of specialized brain regions to express their autonomy (segregation) and the tendencies for those regions to work together as a synergy (integration). Integration ~ segregation is just one of the complementary pairs (denoted by the tilde [~] symbol) to emerge from the science of coordination dynamics. We discuss metastability in the brain by describing the favorable conditions existing for its emergence and by deriving some predictions for its empirical characterization in neurophysiological recordings.

  2. Modeling of metastable phase formation diagrams for sputtered thin films.

    PubMed

    Chang, Keke; Music, Denis; To Baben, Moritz; Lange, Dennis; Bolvardi, Hamid; Schneider, Jochen M

    2016-01-01

    A method to model the metastable phase formation in the Cu-W system based on the critical surface diffusion distance has been developed. The driver for the formation of a second phase is the critical diffusion distance which is dependent on the solubility of W in Cu and on the solubility of Cu in W. Based on comparative theoretical and experimental data, we can describe the relationship between the solubilities and the critical diffusion distances in order to model the metastable phase formation. Metastable phase formation diagrams for Cu-W and Cu-V thin films are predicted and validated by combinatorial magnetron sputtering experiments. The correlative experimental and theoretical research strategy adopted here enables us to efficiently describe the relationship between the solubilities and the critical diffusion distances in order to model the metastable phase formation during magnetron sputtering.

  3. Containerless Solidification of Hexagonal Metastable Phases from an Undercooled R3Fe5O12 Melt

    NASA Astrophysics Data System (ADS)

    Kumar, Vijaya; Kentei Yu, Yu; Kameko, Masashi; Ishikawa, Takehiko; Kuribayashi, Kazuhiko; Yoda, Shinichi

    Containerless processing is a promising technique to explore the technologically important materials using rapid solidification of an undercooled melt because it provides large undercooling prior to nucleation. In the R-Fe-O system (R=Rare-earth element), rare-earth iron garnet (R3 Fe5 O12 ) can be formed through a peritectic reaction between RFeO3 , which is a primary phase, and a melt, which contains more Fe2 O3 than the R3 Fe5 O12 composition. The iron garnet is know to become unstable with increasing ionic radius of the rare-earth ion from Lu to Sm and does not exist in a stable form in La, Pr, and Nd [1,2]. Recently, we investigated the effect of oxygen partial pressure Po2 on metastable phase formation from an undercooled RFeO3 melt through containerless solidification. On the other hand, Po2 was considered to be one of the most important thermodynamic parameters which control phase constituents during containerless processing. In the R-Fe-O system, multiferroic hexagonal RFeO3 (P63 cm) and Fe2+ -containing ferroelectric phases such as RFe2 O4 (r-R3m) and new hexagonal R3 Fe2 O7 (P63 /mmc) phases were obtained metastably with decreasing Po2 from 105 to 10-1 Pa [3,4]. However, in the R3 Fe5 O12 system, the effect of Po2 during rapid solidification has not been studied yet. The purpose of this study is to elucidate the effect of Po2 on the formation of metastable phases from an undercooled R3 Fe5 O12 melt under controlled Po2 using gas-jet levitation technique. In order to undercool the melt deeply below the melting temperature under a precisely con-trolled oxygen partial pressure, an aerodynamic levitator (ADL) combined with ZrO2 oxygen sensor was designed. A spherical R3 Fe5 O12 sample was levitated by an ADL and completely melted by a CO2 laser in an atmosphere with predetermined Po2 . The surface temperature of the levitated droplet was monitored by a two-color pyrometer. Then, the droplet was cooled by turning off the CO2 laser. Meanwhile, the recalescence

  4. Research on Sources of Gas Phase Metastable Atoms and Molecules

    DTIC Science & Technology

    1982-05-01

    PAGI(Whi DeE# WA..teod) -systems of interest to such diverse areas as gas discharge physics, chemical physics, flame chemistry and plasma physics. "A...second task involved a literature review of prior basic research meta- stable sources followed by the development and experimental testing of appro...appropriate for this phase of the program. The operation of this type of metastable source wab investigated and tested for the production of metastable argon

  5. Discovery of a metastable Al20Sm4 phase

    DOE PAGES

    Ye, Z.; Zhang, F.; Sun, Y.; ...

    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.

  6. Discovery of a metastable Al20Sm4 phase

    NASA Astrophysics Data System (ADS)

    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.; Ho, K.-M.

    2015-03-01

    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.

  7. 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.

  8. 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.

  9. Sulfides and oxides in comets

    NASA Technical Reports Server (NTRS)

    Rietmeijer, Frans J. M.

    1988-01-01

    Metal abundances associated with Sun-grazing P/comet Ikeya-Seki 1965f, the mineralogy of chrondritic interplanetary dust particles and cosmochemical affinities of Co, V, Cr, and Ni in extraterrestrial materials and probable vaporization data for nonsilicate minerals are used to evaluate the putative dearth of nonsilicates in short-period comets. It is concluded that sulfides and oxides are common, albeit minor, constituents of these comets. Sulfides and oxides can form in situ during perihelion passage in the nucleus of active short-period comets by sulfidation of Mg, Fe-silicates.

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

    PubMed

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

    2017-02-07

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

  11. 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

  12. 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.

  13. 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.

  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. 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

  16. Hydrogen sulfide in signaling pathways.

    PubMed

    Olas, Beata

    2015-01-15

    For a long time hydrogen sulfide (H₂S) was considered a toxic compound, but recently H₂S (at low concentrations) has been found to play an important function in physiological processes. Hydrogen sulfide, like other well-known compounds - nitric oxide (NO) and carbon monoxide (CO) is a gaseous intracellular signal transducer. It regulates the cell cycle, apoptosis and the oxidative stress. Moreover, its functions include neuromodulation, regulation of cardiovascular system and inflammation. In this review, I focus on the metabolism of hydrogen sulfide (including enzymatic pathways of H₂S synthesis from l- and d-cysteine) and its signaling pathways in the cardiovascular system and the nervous system. I also describe how hydrogen sulfide may be used as therapeutic agent, i.e. in the cardiovascular diseases.

  17. Sulfide oxidation by a noncanonical pathway in red blood cells generates thiosulfate and polysulfides.

    PubMed

    Vitvitsky, Victor; Yadav, Pramod K; Kurthen, Angelika; Banerjee, Ruma

    2015-03-27

    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.

  18. 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.

  19. 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

  20. Extended Neural Metastability in an Embodied Model of Sensorimotor Coupling.

    PubMed

    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

  1. Persistence of Metastability after Expansion of a Supercompressed Fluid Monolayer

    PubMed Central

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

    2012-01-01

    Fluid monolayers of 1-palmitoyl-2-oleoyl-phosphatidylcholine collapse from an air/water interface to form a three-dimensional bulk phase at the equilibrium spreading pressure (πe) of ~47 mN/m. This phase transition limits access to higher surface pressures under equilibrium conditions or during slow continuous compressions. We have shown previously that these films avoid collapse and become metastable when compressed on a captive bubble to surface pressures above 60 mN/m and that the metastability persists during expansion at least to πe. Here, we first documented the extent of this persistent metastability. Rates of isobaric collapse during expansion of the metastable films were up to 3 orders of magnitude slower than those during the initial compression to high surface pressures. Recovery of the ability to collapse depended on the surface pressure to which the films were expanded and how long they were held there. Films reverted after brief exposure to 20 mN/m and after 1 h at 35 mN/m. At πe, films remained capable of reaching high surface pressures during slow compressions after 65 h, although an increase in compressibility above 55 mN/m suggested somewhat increased rates of collapse. We also determined if the films remained metastable when they acquired sufficient free area to allow reinsertion of collapsed material. Faster isobaric expansion in the presence of more collapsed material and with further deviation below πe supported the existence of reinsertion. The persistence of metastability to πe shows that films with sufficient free area to allow reinsertion remain resistant to collapse. Observations that suggest heterogeneous reinsertion, however, argue that free area may be distributed heterogeneously and leave open the possibility that metastability persists because significant regions retain a restricted free area. PMID:15984255

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. Thermoelectric Properties of Lanthanum Sulfide

    NASA Technical Reports Server (NTRS)

    Wood, C.; Lockwood, R.; Parker, J. B.; Zoltan, A.; Zoltan, L. D.; Danielson, L.; Raag, V.

    1987-01-01

    Report describes measurement of Seebeck coefficient, electrical resistivity, thermal conductivity, and Hall effect in gamma-phase lanthanum sulfide with composition of La3-x S4. Results of study, part of search for high-temperature thermoelectric energy-conversion materials, indicate this sulfide behaves like extrinsic semiconductor over temperature range of 300 to 1,400 K, with degenerate carrier concentration controlled by stoichiometric ratio of La to S.

  7. Simultaneous release of sulfide with Fe, Mn, Ni and Zn in marine harbour sediment measured using a combined metal/sulfide DGT probe.

    PubMed

    Naylor, C; Davison, W; Motelica-Heino, M; Van Den Berg, G A; Van Der Heijdt, L M

    2004-07-26

    The technique of DGT (Diffusive Gradients in Thin Films) was further developed to allow simultaneous measurement of sulfide and trace metals at the same location in sediment. The new combined DGT probe consisted of a layer of gel impregnated with AgI, overlain by (1) a layer of gel containing Chelex, (2) a layer of gel and (3) a filter membrane. Diffusion of sulfide was controlled by layers (1) to (3), while diffusion of metals was controlled by layers (2) and (3). The Chelex gel trapped metals that were measured after elution with acid. The AgI gel trapped sulfide through the formation of Ag2S. This was then measured densitometrically as the colour changed from pale yellow to grey. Experiments demonstrated that concentrations of metal or sulfide measured by the combined device were no different to the concentrations measured by more conventional devices. The presence of Chelex in the gel did not impede the diffusion of sulfide. Deployment of a combined probe in marine sediment revealed simultaneous remobilisation of metals and sulfide at the same location. Solubility calculations indicated that some precipitation of amorphous FeS was probably occurring at the maxima in sulfide concentrations. There was general undersaturation with respect to NiS, but ZnS was supersaturated at all locations. There appeared to be localised active zones of organic matter decomposition, where reduction of manganese oxides, iron oxides and sulfate occurred simultaneously. Mass balance calculations indicated that Ni could not be supplied by release from decomposing organic matter. Manganese oxides were the most likely source, but supply from reductive dissolution of iron oxides could not be entirely discounted. Supply from either Fe or Mn oxides could account for the Zn maxima. Application of the newly developed combined probe provides new information that helps understanding of the complex nature of trace metal and sulfur chemistry in sediments.

  8. 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.

  9. Selective Medium for Hydrogen Sulfide Production by Salmonellae

    PubMed Central

    Padron, A. P.; Dockstader, W. B.

    1972-01-01

    Triple Sugar Iron Agar does not reveal hydrogen sulfide production by all Salmonella organisms nor does it permit clear-cut separation of those nonsalmonellae which produce H2S. Numerous media with varied combinations of nutrients, inhibitors, selective agents, pH levels, and metal salts were tested for H2S production of cultures of Salmonella, Citrobacter, Edwardsiella, Arizona, Proteus, Providencia, Klebsiella, and Enterobacter. An agar medium has been devised which promotes growth and H2S production (generally within 6 hr) by Salmonella, Arizona, and Edwardsiella but which inhibits hydrogen sulfide production or growth of all other gram-negative organisms tested (including Citrobacter) or inhibits both. The use of this medium should facilitate the selection and identification of Salmonella. PMID:4557561

  10. 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.

  11. A metastable liquid melted from a crystalline solid under decompression

    DOE PAGES

    Lin, Chuanlong; Smith, Jesse S.; Sinogeikin, Stanislav V.; ...

    2017-01-23

    A metastable liquid may exist under supercooling, sustaining the liquid below the melting point such as supercooled water and silicon. It may also exist as a transient state in solid–solid transitions, as demonstrated in recent studies of colloidal particles and glass-forming metallic systems. One important question is whether a crystalline solid may directly melt into a sustainable metastable liquid. By thermal heating, a crystalline solid will always melt into a liquid above the melting point. Here we report that a high-pressure crystalline phase of bismuth can melt into a metastable liquid below the melting line through a decompression process. Themore » decompression-induced metastable liquid can be maintained for hours in static conditions, and transform to crystalline phases when external perturbations, such as heating and cooling, are applied. It occurs in the pressure–temperature region similar to where the supercooled liquid Bi is observed. Finally, akin to supercooled liquid, the pressure-induced metastable liquid may be more ubiquitous than we thought.« less

  12. A metastable liquid melted from a crystalline solid under decompression

    NASA Astrophysics Data System (ADS)

    Lin, Chuanlong; Smith, Jesse S.; Sinogeikin, Stanislav V.; Kono, Yoshio; Park, Changyong; Kenney-Benson, Curtis; Shen, Guoyin

    2017-01-01

    A metastable liquid may exist under supercooling, sustaining the liquid below the melting point such as supercooled water and silicon. It may also exist as a transient state in solid-solid transitions, as demonstrated in recent studies of colloidal particles and glass-forming metallic systems. One important question is whether a crystalline solid may directly melt into a sustainable metastable liquid. By thermal heating, a crystalline solid will always melt into a liquid above the melting point. Here we report that a high-pressure crystalline phase of bismuth can melt into a metastable liquid below the melting line through a decompression process. The decompression-induced metastable liquid can be maintained for hours in static conditions, and transform to crystalline phases when external perturbations, such as heating and cooling, are applied. It occurs in the pressure-temperature region similar to where the supercooled liquid Bi is observed. Akin to supercooled liquid, the pressure-induced metastable liquid may be more ubiquitous than we thought.

  13. A metastable liquid melted from a crystalline solid under decompression

    PubMed Central

    Lin, Chuanlong; Smith, Jesse S.; Sinogeikin, Stanislav V.; Kono, Yoshio; Park, Changyong; Kenney-Benson, Curtis; Shen, Guoyin

    2017-01-01

    A metastable liquid may exist under supercooling, sustaining the liquid below the melting point such as supercooled water and silicon. It may also exist as a transient state in solid–solid transitions, as demonstrated in recent studies of colloidal particles and glass-forming metallic systems. One important question is whether a crystalline solid may directly melt into a sustainable metastable liquid. By thermal heating, a crystalline solid will always melt into a liquid above the melting point. Here we report that a high-pressure crystalline phase of bismuth can melt into a metastable liquid below the melting line through a decompression process. The decompression-induced metastable liquid can be maintained for hours in static conditions, and transform to crystalline phases when external perturbations, such as heating and cooling, are applied. It occurs in the pressure–temperature region similar to where the supercooled liquid Bi is observed. Akin to supercooled liquid, the pressure-induced metastable liquid may be more ubiquitous than we thought. PMID:28112152

  14. Origin of the metastable stability in flavylium multistate systems.

    PubMed

    Petrov, Vesselin; Slavcheva, Stoyanka; Stanimirov, Stanislav; Pina, Fernando

    2015-03-26

    Metastable states regarding the network of chemical reactions involving flavylium compounds were investigated as well as the role they may play in models for optical memories capable of write-read-erase. A necessary requirement to achieve metastable states in flavylium systems is the existence of a high cis-trans isomerization barrier, as in 4'-hydroxyflavylium described through this paper. In an optical memory, the metastable state could be the signal to be detected upon the write step. In that case the autoerase is prevented by the metastable state. Conversely, the metastable state may be the initial state and prevents the auto and unwanted write step. The compound 4'-hydroxyflavylium offers the possibility of achieving both of these two situations, depending on the sequence of the pH stimuli prior to light absorption. In this work the pH dependent distribution of the flavylium species of the network in the presence of β-cyclodextrin was calculated. Improvement of the performance of the photochromic system in the presence of β-cyclodextrin was observed.

  15. 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.

  16. 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.

  17. 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.

  18. Reaction mechanisms involved in reduction of halogenated hydrocarbons using sulfated iron

    SciTech Connect

    Hassan, S.M.; Cipollone, M.G.; Wolfe, N.L.

    1995-12-01

    Experiments were carried out to investigate the mechanisms and pathways involved in the reduction of halogenated hydrocarbons represented by trichloroethylene (TCE) and tetrachloroethylene (PCE) with sulfated iron aqueous media. Results suggested that iron sulfide acted as the dehalogenation center. Zero-valent iron acted as a generator for molecular hydrogen through its reaction with water. Results of experiments in which iron sulfide was replaced by other transition metal sulfides and experiments in which zero-valent iron was replaced by other sources of molecular hydrogen will be reported. The main reduction product of chloroethylene derivatives was ethyne which under the catalytic reaction of zero-valent iron was reduced further to ethene and finally to ethane. Intermediate products were identified using GC-MS. Mechanisms and pathways will be presented.

  19. 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.

  20. Metastable phase formation in Be-Nb intermetallic compounds

    SciTech Connect

    Brimhall, J.L.; Charlot, L.A.; Bruemmer, S.M.

    1990-11-01

    Amorphous structures or metastable crystalline phases are produced in sputter-deposited Beryllium-Niobium (Be-Nb) alloys (5-15 at. % Nb) depending on the substrate temperature. The metastable phases transform to the stable Be{sub 12}Nb, Be{sub 17}Nb{sub 2}Nb phases on annealing at temperatures >800{degree}C. No Be{sub 5}Nb phase was found and the Be{sub 17}Nb{sub 2} phase is stable to low temperature. The Be{sub 12}Nb phase appeared to have a stoichiometric range of about 5.5 to 7.7 at. % Nb. The formation of the metastable phases is consistent with current models and theories. 17 refs., 1 fig., 2 tabs.

  1. 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.

  2. Stochastic optimal velocity model and its long-lived metastability.

    PubMed

    Kanai, Masahiro; Nishinari, Katsuhiro; Tokihiro, Tetsuji

    2005-09-01

    In this paper, we propose a stochastic cellular automaton model of traffic flow extending two exactly solvable stochastic models, i.e., the asymmetric simple exclusion process and the zero range process. Moreover, it is regarded as a stochastic extension of the optimal velocity model. In the fundamental diagram (flux-density diagram), our model exhibits several regions of density where more than one stable state coexists at the same density in spite of the stochastic nature of its dynamical rule. Moreover, we observe that two long-lived metastable states appear for a transitional period, and that the dynamical phase transition from a metastable state to another metastable/stable state occurs sharply and spontaneously.

  3. 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.

  4. 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.

  5. 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.

  6. Metastability in the driven-dissipative Rabi model

    NASA Astrophysics Data System (ADS)

    Le Boité, Alexandre; Hwang, Myung-Joong; Plenio, Martin B.

    2017-02-01

    We explore the long-time dynamics of the quantum Rabi model in a driven-dissipative setting and show that, as the atom-cavity coupling strength becomes larger than the cavity frequency, a new time scale emerges. This time scale, much larger than the natural relaxation time of the atom and the cavity, leads to long-lived metastable states susceptible to being observed experimentally. By applying a Floquet-Liouville approach to the time-dependent master equation, we systematically investigate the set of possible metastable states. We find that the properties of the metastable states can differ drastically from those of the steady state and relate these properties to the energy spectrum of the Rabi Hamiltonian.

  7. An efficient magneto-optical trap of metastable krypton atoms

    NASA Astrophysics Data System (ADS)

    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.

  8. Deposition of biogenic iron minerals in a methane oxidizing microbial mat.

    PubMed

    Wrede, Christoph; Kokoschka, Sebastian; 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.

  9. 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

  10. 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.

  11. Metastable and scaling regimes of one-dimensional Kawasaki dynamics.

    PubMed

    Albarracín, F A Gómez; Rosales, H D; Grynberg, M D

    2016-04-01

    We investigate the large-time scaling regimes arising from a variety of metastable structures in a chain of Ising spins with both first- and second-neighbor couplings while subject to Kawasaki dynamics. Depending on the ratio and sign of these former, different dynamic exponents are suggested by finite-size scaling analyses of relaxation times. At low but nonzero temperatures these are calculated via exact diagonalizations of the evolution operator in finite chains under several activation barriers. In the absence of metastability the dynamics is always diffusive.

  12. Metastable and scaling regimes of one-dimensional Kawasaki dynamics

    NASA Astrophysics Data System (ADS)

    Albarracín, F. A. Gómez; Rosales, H. D.; Grynberg, M. D.

    2016-04-01

    We investigate the large-time scaling regimes arising from a variety of metastable structures in a chain of Ising spins with both first- and second-neighbor couplings while subject to Kawasaki dynamics. Depending on the ratio and sign of these former, different dynamic exponents are suggested by finite-size scaling analyses of relaxation times. At low but nonzero temperatures these are calculated via exact diagonalizations of the evolution operator in finite chains under several activation barriers. In the absence of metastability the dynamics is always diffusive.

  13. 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.

  14. New epsilon-Bi2O3 metastable polymorph.

    PubMed

    Cornei, Nicoleta; Tancret, Nathalie; Abraham, Francis; Mentré, Olivier

    2006-06-26

    The new metastable epsilon-Bi2O3 polymorph has been prepared by hydrothermal treatment and structurally characterized. It shows strong relationships with the room temperature alpha form and the metastable beta form through rearrangements of [Bi2O3] columns formed by edge-sharing OBi4 tetrahedra. Its fully ordered crystal structure yields an ionic insulating character. It irreversibly transforms at 400 degrees C to the alpha form. The chemical analysis indicates its undoped bismuth oxide nature, then leading to the fifth characterized Bi2O3 polymorph to date.

  15. Magnetic properties of metastable Fe Pd alloys by mechanical alloying

    NASA Astrophysics Data System (ADS)

    Yabe, Hiromasa; O'Handley, Robert C.; Kuji, Toshiro

    2007-03-01

    Metastable Fe-Pd powder samples with various Pd content were synthesized by mechanical alloying. Their fundamental properties, i.e., structure, magnetization and coercive fore are discussed. The saturation magnetizations of the metastable Fe-Pd powders gradually decreases with increasing Pd content. The coercive forces observed in as-milled samples are all less than 40 Oe. However, some of the heat-treated samples, notably, Pd content around 55 at% with L1 0 structure, shows Hc up to 1589 Oe.

  16. Magmatic sulfides in the porphyritic chondrules of EH enstatite chondrites

    NASA Astrophysics Data System (ADS)

    Piani, Laurette; Marrocchi, Yves; Libourel, Guy; Tissandier, Laurent

    2016-12-01

    The nature and distribution of sulfides within 17 porphyritic chondrules of the Sahara 97096 EH3 enstatite chondrite have been studied by backscattered electron microscopy and electron microprobe in order to investigate the role of gas-melt interactions in the chondrule sulfide formation. Troilite (FeS) is systematically present and is the most abundant sulfide within the EH3 chondrite chondrules. It is found either poikilitically enclosed in low-Ca pyroxenes or scattered within the glassy mesostasis. Oldhamite (CaS) and niningerite [(Mg,Fe,Mn)S] are present in ≈60% of the chondrules studied. While oldhamite is preferentially present in the mesostasis, niningerite associated with silica is generally observed in contact with troilite and low-Ca pyroxene. The Sahara 97096 chondrule mesostases contain high abundances of alkali and volatile elements (average Na2O = 8.7 wt.%, K2O = 0.8 wt.%, Cl = 7100 ppm and S = 3700 ppm) as well as silica (average SiO2 = 62.8 wt.%). Our data suggest that most of the sulfides found in EH3 chondrite chondrules are magmatic minerals that formed after the dissolution of S from a volatile-rich gaseous environment into the molten chondrules. Troilite formation occurred via sulfur solubility within Fe-poor chondrule melts followed by sulfide saturation, which causes an immiscible iron sulfide liquid to separate from the silicate melt. The FeS saturation started at the same time as or prior to the crystallization of low-Ca pyroxene during the high temperature chondrule forming event(s). Protracted gas-melt interactions under high partial pressures of S and SiO led to the formation of niningerite-silica associations via destabilization of the previously formed FeS and low-Ca pyroxene. We also propose that formation of the oldhamite occurred via the sulfide saturation of Fe-poor chondrule melts at moderate S concentration due to the high degree of polymerization and the high Na-content of the chondrule melts, which allowed the activity of Ca

  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. 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)

  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. 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.

  1. Influence of porewater sulfide on methylmercury production and partitioning in sulfate-impacted lake sediments.

    PubMed

    Bailey, Logan T; Mitchell, Carl P J; Engstrom, Daniel R; Berndt, Michael E; Coleman Wasik, Jill K; Johnson, Nathan W

    2017-02-15

    In low-sulfate and sulfate-limited freshwater sediments, sulfate loading increases the production of methylmercury (MeHg), a potent and bioaccumulative neurotoxin. Sulfate loading to anoxic sediments leads to sulfide production that can inhibit mercury methylation, but this has not been commonly observed in freshwater lakes and wetlands. In this study, sediments were collected from sulfate-impacted, neutral pH, surface water bodies located downstream from ongoing and historic mining activities to examine how chronic sulfate loading produces porewater sulfide, and influences MeHg production and transport. Sediments were collected over two years, during several seasons from lakes with a wide range of overlying water sulfate concentration. Samples were characterized for in-situ solid phase and porewater MeHg, Hg methylation potentials via incubations with enriched stable Hg isotopes, and sulfur, carbon, and iron content and speciation. Porewater sulfide reflected historic sulfur loading and was strongly related to the extractable iron content of sediment. Overall, methylation potentials were consistent with the accumulation of MeHg on the solid phase, but both methylation potentials and MeHg were significantly lower at chronically sulfate-impacted sites with a low solid-phase Fe:S ratio. At these heavily sulfate-impacted sites that also contained elevated porewater sulfide, both MeHg production and partitioning are influenced: Hg methylation potentials and sediment MeHg concentrations are lower, but occasionally porewater MeHg concentrations in sediment are elevated, particularly in the spring. The dual role of sulfide as a ligand for inorganic mercury (decreasing bioavailability) and methylmercury (increasing partitioning into porewater) means that elucidating the role of iron and sulfur loads as they define porewater sulfide is key to understanding sulfate's influence on MeHg production and partitioning in sulfate-impacted freshwater sediment.

  2. Refining thermodynamic constants for mercury(II)-sulfides in equilibrium with metacinnabar at sub-micromolar aqueous sulfide concentrations.

    PubMed

    Drott, A; Björn, E; Bouchet, S; Skyllberg, U

    2013-05-07

    An important issue in mercury (Hg) biogeochemistry is to explore the influence of aqueous Hg(II) forms on bacterial uptake, and subsequent methyl mercury formation, under iron(III) and sulfate reducing conditions. The success of this is dependent on relevant information on the thermodynamic stability of Hg-sulfides. In the present study, we determined the solubility of a commercially available HgS(s) phase, which was shown by X-ray diffraction to be a mixture of 83% metacinnabar and 17% cinnabar. At aqueous sulfide concentrations between 0.060 and 84 μM, well below levels in previous studies, we report a solubility product (log Ksp ± SE) of -36.8 ± 0.1 (HgS(s) + H(+) = Hg(2+) + HS(-), I = 0, T = 25 °C, pH 6-10, n = 20) for metacinnabar. This value is 0.7 log units higher than previous estimates. Complementing our data with data from Paquette and Helz (1997), we took advantage of a large data set (n = 65) covering a wide range of aqueous sulfide (0.06 μM-140 mM) and pH (1-11). On the basis of this, we report refined formation constants (±SE) for the three aqueous Hg(II)-sulfide species proposed by Schwarzenbach and Widmer (1963): Hg(2+) + 2HS(-) = Hg(SH)2(0); log K = 39.1 ± 0.1, Hg(2+) + 2HS(-) = HgS2H(-) + H(+); log K = 32.5 ± 0.1, Hg(2+) + 2HS(-) = HgS2(2-) + 2H(+); log K = 23.2 ± 0.1. Our refined log K values differ from previous estimates by 0.2-0.6 log units. Furthermore, at the low sulfide concentrations in our study we could rule out the value of -10.0 for the reaction HgS(s) + H2O = HgOHSH(aq) as reported by Dyrssén and Wedborg (1991). By establishing a solubility product for the most environmentally relevant HgS(s) phase, metacinnabar, and extending the range of aqueous sulfide concentrations to sub-micromolar levels, relevant for soils, sediments, and waters, this study decreases the uncertainty in stability constants for Hg-sulfides, thereby improving the basis for understanding the bioavailability and mobility of Hg(II) in the environment.

  3. Thermochemistry of sulfide liquids. I. the system O-S-Fe at 1 bar

    NASA Astrophysics Data System (ADS)

    Kress, Victor

    Recrystallized globules representing former immiscible sulfide liquids are found in a variety of igneous environments. Relatively little is known about the physical properties and thermochemistry of sulfide liquids, despite their importance in igneous systems. This study presents results of a series of experiments designed to calibrate a thermodynamic model for sulfide liquids in the system O-S-Fe at one atmosphere pressure. Sulfide liquids were equilibrated under controlled oxygen and sulfur fugacities at temperatures between 1100 and 1350° C in equilibrium with a silica mineral and a silicate melt. Experiments were quenched in a high-speed double-roller ``splat'' quencher in order to assure that measured compositions were as close to equilibrium liquid values as possible. Sulfide liquids are not stable in equilibrium with a silica-saturated silicate melt at log10(fO2) > FMQ-1 at 1250°C and log10(fS2)=-3. Iron content of the sulfide changes little with variations in oxygen and sulfur fugacity at a given temperature. Consequently, oxygen and sulfur contents are inversely correlated in these liquids. Sulfur is present entirely as sulfide. Iron appears to be present in both its ferric and ferrous states. Data from this study were combined with data compiled from the literature to calibrate an asymmetric regular solution thermodynamic mixing model for O-S-Fe liquids. This model reproduces miscibility gaps and data from this study quite well, but exhibits minor but systematic errors at the O-Fe binary. The observed inverse correlation between sulfur and oxygen is reflected in the predicted free-energy surface by a sharp energy valley running along a line of constant Fe content.

  4. CO₂ sequestration through mineral carbonation of iron oxyhydroxides.

    PubMed

    Lammers, Kristin; Murphy, Riley; Riendeau, Amber; Smirnov, Alexander; Schoonen, Martin A A; Strongin, Daniel R

    2011-12-15

    Carbon dioxide sequestration via the use of sulfide reductants and mineral carbonation of the iron oxyhydroxide polymorphs lepidocrocite, goethite, and akaganeite with supercritical CO(2) (scCO(2)) was investigated using in situ attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), X-ray diffraction (XRD), and transmission electron microscopy (TEM). The exposure of the different iron oxyhydroxides to aqueous sulfide in contact with scCO(2) at ∼70-100 °C resulted in the partial transformation of the minerals to siderite (FeCO(3)) and sulfide phases such as pyrite (FeS(2)). The relative yield of siderite to iron sulfide bearing mineral product was a strong function of the initial sulfide concentration. The order of mineral reactivity with regard to the amount of siderite formation in the scCO(2)/sulfide environment for a specific reaction time was goethite < lepidocrocite ≤ akaganeite. Given the presence of goethite in sedimentary formations, this conversion reaction may have relevance to the subsurface sequestration and geologic storage of carbon dioxide.

  5. 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...

  6. 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...

  7. 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... Safety Systems § 250.808 Hydrogen sulfide. Production operations in zones known to contain hydrogen sulfide (H2S) or in zones where the presence of H2S is unknown, as defined in § 250.490 of this...

  8. 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...

  9. 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...

  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 250.808 - 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...

  12. 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...

  13. 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...

  14. Metastable Oxygen Production by Electron-Impact of Oxygen

    NASA Astrophysics Data System (ADS)

    Hein, J. D.; Malone, C. P.; Kanik, I.; Johnson, P. V.

    2013-12-01

    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 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 incident on a cryogenically cooled rare gas matrix, where excimer production and subsequent rapid radiative de-excitation provides measurable signal that is directly related to the originating electron-impact excitation process.

  15. 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.

  16. Production of Ar metastables in a dielectric barrier discharge

    NASA Astrophysics Data System (ADS)

    Mikheyev, Pavel A.; Han, Jiande; Clark, Amanda; Sanderson, Carl; Heaven, Michael C.

    2017-01-01

    The results of experiments with a dielectric barrier discharge (DBD) are presented, where the production of metastable argon atoms was studied. The recently proposed optically pumped all-rare-gas laser (OPRGL) utilizes metastable atoms of heavier rare gases as lasing species. The required number density of metastables for efficient laser operation is 1012÷1013 cm-3 in an atmospheric pressure of He buffer gas. Recent experiments had shown that such densities are easily produced in a nanosecond pulsed discharge, even at pressures larger than atmospheric, but problems appear when one is trying to produce them in a CW regime. The reason for difficulties in the CW production of metastables at an atmospheric pressure seems to be the low value of the E/N parameter (<5-6 Td). In our experiments a 20 KHz DBD in 2-5% Ar mixture with He at an atmospheric pressure was studied. [Ar(1s5)] number density of the order of 1012 cm-3 was readily achieved. Temporal behavior of [Ar(1s5)] throughout the DBD cycle was obtained. The results demonstrate the feasibility of DBDs for OPRGL development.

  17. Metastable zirconia-yttria-alumina ceramics: Structure, processing and properties

    NASA Astrophysics Data System (ADS)

    Zhou, Xinzhang

    2002-09-01

    Metastable phases of zirconia-yttria-alumina produced by atmospheric plasma spray and subsequent quenching were studied. Two kinds of quenching methods were used: water quenching and splat quenching. Quenching rates were estimated to be 104°C/s for water quenching and between 105--107°C/s for splat quenching. Five compositions of sprayed dried powders (pure alumina, TZ3Y20A, TZ3Y57A, TZ3Y80A and pure zirconia) were plasma sprayed and quenched. The phases and microstructures of the plasma sprayed powders and thin films were investigated by XRD and FESEM. It was found that at different compositions and quenching rates, different high temperature phases formed. These phases are metastable at room temperature and can be in the form of an extended solid solution phase, an intermediate phase, or an amorphous structure. The grain sizes of the metastable phases are below 50 nm, as determined by XRD peak broadening. At the eutectic composition, zirconia-rich fibers (50 nm in diameter) uniformly distributed in an alumina-rich matrix were observed. 2-D and 3-D metastable phase diagrams were constructed to explain the metastable phase formation. Plasma spraying can be used to fabricate ceramic nanocomposites either by pressure-assisted sintering or spray forming of the metastable powders. Mechanical properties of TZ3Y20A specimens produced by plasma spray forming on steel substrates were studied. The dependence of the 4-point bend strength on plasma spray parameters was studied by a 26-2 statistical experimental design. It was found that the bend strength was sensitive to both standoff distance and scanning speed. The results of study show much promise in applications of the metastable ceramics. Firstly, homogeneous nucleation and growth of stable phases during sintering and high creep rate at elevated temperatures will result in uniformly dense nanoceramic composites. Secondly, extended solid solutions of rare earth elements in glass will greatly enhance the optical

  18. 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

  19. Nucleation of metastable aragonite CaCO3 in seawater.

    PubMed

    Sun, Wenhao; Jayaraman, Saivenkataraman; Chen, Wei; Persson, Kristin A; Ceder, Gerbrand

    2015-03-17

    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 [corrected] 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.

  20. 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.

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

    PubMed

    Sobron, Pablo; Alpers, Charles N

    2013-03-01

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

  2. 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.

  3. 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.

  4. 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.

  5. 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

  6. Metal Sulfide Cluster Complexes and their Biogeochemical Importance in the Environment

    NASA Astrophysics Data System (ADS)

    Luther, George W.; Rickard, David T.

    2005-10-01

    Aqueous clusters of FeS, ZnS and CuS constitute a major fraction of the dissolved metal load in anoxic oceanic, sedimentary, freshwater and deep ocean vent environments. Their ubiquity explains how metals are transported in anoxic environmental systems. Thermodynamic and kinetic considerations show that they have high stability in oxic aqueous environments, and are also a significant fraction of the total metal load in oxic river waters. Molecular modeling indicates that the clusters are very similar to the basic structural elements of the first condensed phase forming from aqueous solutions in the Fe-S, Zn-S and Cu-S systems. The structure of the first condensed phase is determined by the structure of the cluster in solution. This provides an alternative explanation of Ostwald's Rule, where the most soluble, metastable phases form before the stable phases. For example, in the case of FeS, we showed that the first condensed phase is nanoparticulate, metastable mackinawite with a particle size of 2 nm consisting of about 150 FeS subunits, representing the end of a continuum between aqueous FeS clusters and condensed material. These metal sulfide clusters and nanoparticles are significant in biogeochemistry. Metal sulfide clusters reduce sulfide and metal toxicity and help drive ecology. FeS cluster formation drives vent ecology and AgS cluster formation detoxifies Ag in Daphnia magna neonates. We also note a new reaction between FeS and DNA and discuss the potential role of FeS clusters in denaturing DNA.

  7. 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.

  8. Biogeochemistry of dissolved hydrogen sulfide species and carbonyl sulfide in the western North Atlantic Ocean

    NASA Astrophysics Data System (ADS)

    Radford-Knȩry, Joël; Cutter, Gregory A.

    1994-12-01

    The biogeochemistry of total sulfide dissolved in the open ocean is a poorly understood component of the global sulfur cycle. Here, the cycling of total sulfide was examined in the western North Atlantic Ocean using specially developed sampling and analytical methods. Total sulfide (particulate + dissolved sulfide) concentrations ranged from <2-550 pmol/L; concentrations were highest in the mixed layer and decreased with depth. Significant levels (up to 19 pmol/L) of free sulfide (uncomplexed sulfide) were determined in the top 50 m of the water column. Sources of total sulfide were examined. In particular, the rate of carbonyl sulfide (OCS) hydrolysis was redetermined under oceanographic conditions, and the depth distribution of OCS was examined. The patterns of near-surface enrichment (up to 150 pmol/L) and depletion at depth observed in OCS depth profiles suggest in situ production of OCS. To quantify the sources and sinks of total sulfide in the mixed layer of the Sargasso Sea, a budget was constructed. The rate of total sulfide production was 5.5 pmol L-1 h-1 (OCS hydrolysis + atmospheric input), and total sulfide removal rate was 115 pmol L -1 h-1 (oxidation + particulate sinking). The significant difference between the known sources and sinks indicates that other processes are important for the cycling of sulfide. Similarities in the depth distribution of total sulfide and chlorophyll a, and results from recent laboratory experiments argue strongly in favor of biological involvement in the production of total sulfide in the open ocean.

  9. 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.

  10. Environmental implications of the use of sulfidic back-bay sediments for dune reconstruction — Lessons learned post Hurricane Sandy

    USGS Publications Warehouse

    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; Fisher, Irene

    2016-01-01

    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).

  11. 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).

  12. 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.

  13. 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.

  14. Constraints on Meta-stable de Sitter Flux Vacua

    SciTech Connect

    Soroush, Masoud

    2007-03-05

    We consider flux compactification of type IIB string theory as the orientifold limit of an F-theory on a Calabi-Yau fourfold. We show that when supersymmetry is dominantly broken by the axion-dilaton and the contributions of the F-terms associated with complex structure moduli are small, the Hessian of the flux potential always has tachyonic modes for de Sitter vacua. This implies that there exist no meta-stable de Sitter vacua in this limit. Moreover, we find that the stability requirement imposes a relation between the values of cosmological constant and the scale of supersymmetry breaking for non-supersymmetric anti de Sitter vacua in this limit. The proof is general and does rely on the details of the geometry of the compact Calabi-Yau internal space. We finally analyze the consequences of these constraints on the statistics of meta-stable de Sitter vacua and address some other related issues.

  15. 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.

  16. Dynamic Polarizability for Metastable Helium in Debye Plasmas

    NASA Astrophysics Data System (ADS)

    Kar, Sabyasachi; Wang, Yu-Shu; Wang, Yang; Jiang, Zishi

    2017-01-01

    The dynamic dipole polarizability (DDP) for metastable helium in plasma environments has been studied recently (Kar et al. in Phys Plasmas 23:082119, 2016) by incorporating plasma screening effect on electron-nucleus interactions. In this work, we investigate the DDP for metastable helium immersed in Debye plasmas using screening effects on both electron-nucleus and electron-electron interactions. The dynamic dipole polarizabilities for the n {}1S (n=2,3) and n {}3S (n=2,3) states are reported as functions of Debye screening parameter. First tune-out wavelengths for the n {}1S (n=1,2,3) and n {}3S (n=2,3) states and magic wavelengths for the 2 {}3S → 3 {}3S transition are also reported in terms of Debye screening parameter. Magic wavelengths in screening environments are presented for the first time in the literature.

  17. Block Copolymer Metastability: Scientific Nightmare or Engineering Dream?

    NASA Astrophysics Data System (ADS)

    Bates, Frank S.

    1997-03-01

    Most experimental studies and almost all theories that deal with block copolymers, or mixtures of block copolymers and homopolymers, have been designed from an equilibrium perspective. Yet a myriad of factors conspire to retard approach to equilibrium in these systems, including: subtle features in the free energy surface that are controlled by ordered state symmetry; a coupling between microphase separation and entanglement dynamics; complex molecular architectures such as multiblock, starblock, and miktoarm. Even unentangled low molecular weight diblock copolymers, the simplest and dynamically least encumbered materials, exhibit long-lived metastable states that confound attempts to validate equilibrium theories. However, this apparent dilemma can be exploited through clever processing strategies. This lecture will address two opposing consequences of block copolymer metastability. The first is a potential nightmare: Can we ever establish universal block copolymer phase diagrams? The second is the stuff of dreams: Self-assembled thermoset nanocomposites.

  18. Coherent Atom Optics with fast metastable rare gas atoms

    SciTech Connect

    Grucker, J.; Baudon, J.; Karam, J.-C.; Perales, F.; Vassilev, G.; Ducloy, M.; Bocvarski, V.

    2006-12-01

    Coherent atom optics experiments making use of an ultra-narrow beam of fast metastable atoms generated by metastability exchange are reported. The transverse coherence of the beam (coherence radius of 1.7 {mu}m for He*, 1.2 {mu}m for Ne*, 0.87 {mu}m for Ar*) is demonstrated via the atomic diffraction by a non-magnetic 2{mu}m-period reflection grating. The combination of the non-scalar van der Waals (vdW) interaction with the Zeeman interaction generated by a static magnetic field gives rise to ''vdW-Zeeman'' transitions among Zeeman sub-levels. Exo-energetic transitions of this type are observed with Ne*(3P2) atoms traversing a copper micro-slit grating. They can be used as a tunable beam splitter in an inelastic Fresnel bi-prism atom interferometer.

  19. Iron sulfide oxidation as influenced by calcium carbonate application.

    PubMed

    Hossner, L R; Doolittle, J J

    2003-01-01

    Two overburden materials, with different FeS2 contents (1.9 and 4.1%) and low acid neutralization potential, were limed with CaCO3 at rates of 0, 25, 50, 75, 100, and 125% based on the amount of CaCO3 needed to provide an acid-base account deficit (A/Ba) of zero (A/Ba = neutralization potential--potential acidity--exchangeable acidity). The limed overburden materials were inoculated with Thiobacillus ferrooxidans and leached weekly with deionized water. Residual FeS2 and CaCO3 were determined in samples over a 378-d period. Oxidation followed zero-order kinetics with respect to FeS2 concentration at pH values greater than 4 and first-order kinetics at pH values less than 4. Zero-order oxidation rates ranged from 0.01 to 0.46 micromol g(-1) d(-1) in the overburden with 1.9% FeS2 and from 0.01 to 0.22 micromol g(-1) d(-1) in the overburden with 4.1% FeS2. Oxidation following the first-order rate law had a first-order rate constant of 0.03 d(-1) in the 1.9% FeS2 overburden and 0.01 d(-1) in the 4.1% FeS2 overburden. The calculated half-life was 23 d for the 1.9% FeS2 overburden and 69 d for the 4.1% FeS2 overburden. Additions of CaCO3 affected FeS2 oxidation by controlling the pH of the system. Liming to greater than 50% of the acid-base account deficit did not significantly affect the zero-order oxidation rate. Dissolution of the applied CaCO3 was found to be faster than the oxidation of FeS2 at pH values greater than 4. It was projected that at lime rates up to 125%, the CaCO3 would dissolve and leach out of the system before all the FeS2 oxidized, leaving the potential for acid minesoil formation.

  20. Arsenic Mobilization Influenced By Iron Reduction And Sulfidogenesis Under Dynamic Flow

    NASA Astrophysics Data System (ADS)

    Kocar, B. D.; Stewart, B. D.; Herbel, M.; Fendorf, S.

    2004-12-01

    Sulfidogenesis and iron reduction are ubiquitous processes that occur in a variety of anoxic subsurface and surface environments, which profoundly impact the cycling of arsenic. Of the iron (hydr)oxides, ferrihydrite possesses one of the highest capacities to retain arsenic, and is globally distributed within soils and sediments. Upon dissimilatory iron reduction, ferrihydrite may transform to lower surface area minerals, such as goethite and magnetite, which decreases arsenic retention, thus enhancing its transport. Here we examine how arsenic retained on ferrihydrite is mobilized under dynamic flow in the presence of Sulfurosprillum barnesii strain SES-3, a bacteria capable of reducing both As(V) and Fe(III). Ferrihydrite coated sands, loaded with 150 mg kg-1 As(V), were inoculated with S. barnesii, packed into a column and reacted with a synthetic groundwater solution. Within several days after initiation of flow, the concentration of arsenic in the column effluent increased dramatically coincident with the mineralogical transformation of ferrihydrite and As(V) reduction to As(III). Following the initial pulse of arsenic, effluent concentration then declined to less than 10 μ M. Thus, arsenic release into the aqueous phase is contingent upon the incongruent reduction of As(V) and Fe(III) as mediated by biological activity. Reaction of abiotically or biotically generated dissolved sulfide with iron (hydr)oxides may have a dramatic influence on the fate of arsenic within surface and subsurface environments. Accordingly, we examined the reaction of dissolved bisulfide and iron (hydr)oxide complexed with arsenic in both batch and column systems. Low ratios of sulfide to iron in batch reaction systems result in the formation of elemental sulfur and concomitant arsenic release from the iron (hydr)oxide surface. High sulfide to iron ratios, in contrast, appear to favor the formation of iron and arsenic sulfides. Our findings demonstrate that iron (hydr)oxides may

  1. 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.

  2. Metastable Pain-Attention Dynamics during Incremental Exhaustive Exercise

    PubMed Central

    Slapšinskaitė, Agnė; Hristovski, Robert; Razon, Selen; Balagué, Natàlia; Tenenbaum, Gershon

    2017-01-01

    Background: Pain attracts attention on the bodily regions. Attentional allocation toward pain results from the neural communication across the brain-wide network “connectome” which consists of pain-attention related circuits. Connectome is intrinsically dynamic and spontaneously fluctuating on multiple time-scales. The present study delineates the pain-attention dynamics during incremental cycling performed until volitional exhaustion and investigates the potential presence of nested metastable dynamics. Method: Fifteen young and physically active adults completed a progressive incremental cycling test and reported their discomfort and pain on a body map every 15 s. Results: The analyses revealed that the number of body locations with perceived pain and discomfort increased throughout five temporal windows reaching an average of 4.26 ± 0.59 locations per participant. A total of 37 different locations were reported and marked as painful for all participants throughout the cycling task. Significant differences in entropy were observed between all temporal windows except the fourth and fifth windows. Transient dynamics of bodily locations with perceived discomfort and pain were spanned by three principal components. The metastable dynamics of the body pain locations groupings over time were discerned by three time scales: (1) the time scale of shifts (15 s); (2) the time scale of metastable configurations (100 s), and (3) the observational time scale (1000 s). Conclusion: The results of this study indicate that body locations perceived as painful increase throughout the incremental cycling task following a switching metastable and nested dynamics. These findings support the view that human brain is intrinsically organized into active, mutually interacting complex and nested functional networks, and that subjective experiences inherent in pain perception depict identical dynamical principles to the neural tissue in the brain. PMID:28111563

  3. Topological Winding and Unwinding in Metastable Bose-Einstein Condensates

    SciTech Connect

    Kanamoto, Rina; Carr, Lincoln D.; Ueda, Masahito

    2008-02-15

    Topological winding and unwinding in a quasi-one-dimensional metastable Bose-Einstein condensate are shown to be manipulated by changing the strength of interaction or the frequency of rotation. Exact diagonalization analysis reveals that quasidegenerate states emerge spontaneously near the transition point, allowing a smooth crossover between topologically distinct states. On a mean-field level, the transition is accompanied by formation of gray solitons, or density notches, which serve as an experimental signature of this phenomenon.

  4. Modeling of diode pumped metastable rare gas lasers.

    PubMed

    Yang, Zining; Yu, Guangqi; Wang, Hongyan; Lu, Qisheng; Xu, Xiaojun

    2015-06-01

    As a new kind of optically pumped gaseous lasers, diode pumped metastable rare gas lasers (OPRGLs) show potential in high power operation. In this paper, a multi-level rate equation based model of OPRGL is established. A qualitative agreement between simulation and Rawlins et al.'s experimental result shows the validity of the model. The key parameters' influences and energy distribution characteristics are theoretically studied, which is useful for the optimized design of high efficient OPRGLs.

  5. Gauge/gravity Duality and MetastableDynamical Supersymmetry Breaking

    SciTech Connect

    Argurio, Riccardo; Bertolini, Matteo; Franco, Sebastian; Kachru, Shamit

    2006-10-24

    We engineer a class of quiver gauge theories with several interesting features by studying D-branes at a simple Calabi-Yau singularity. At weak 't Hooft coupling we argue using field theory techniques that these theories admit both supersymmetric vacua and meta-stable non-supersymmetric vacua, though the arguments indicating the existence of the supersymmetry breaking states are not decisive. At strong 't Hooft coupling we find simple candidate gravity dual descriptions for both sets of vacua.

  6. Theoretical Studies of the Lifetime of Metastable H3

    DTIC Science & Technology

    1990-11-01

    Aharonov - Bohm , MAB, metastable 21 09 lifetimes 19. ABSTRACT (Continue on reverse if necessary and identify by block number) In this report, the major steps...Molecular Aharonov - Bohm (MAB) effect (or Berry’s geometric phase). This effect has a profound influence on both the bound and scattering states of...this surface and the ground state one introduces the Molecular Aharonov - Bohm (MBA) effect 49 - 5 2 which needs special treatment, and since we also want

  7. Triggered transience of metastable poly(phthalaldehyde) for transient electronics.

    PubMed

    Hernandez, Hector Lopez; Kang, Seung-Kyun; Lee, Olivia P; Hwang, Suk-Won; Kaitz, Joshua A; Inci, Bora; Park, Chan Woo; Chung, Sangjin; Sottos, Nancy R; Moore, Jeffrey S; Rogers, John A; White, Scott R

    2014-12-03

    Triggerable transient electronics are demonstrated with the use of a metastable poly(phthalaldehyde) polymer substrate and encapsulant. The rate of degradation is controlled by the concentration of the photo-acid generator and UV irradiance. This work expands on the materials that can be used for transient electronics by demonstrating transience in response to a preselected trigger without the need for solution-based degradation.

  8. Metastable superconductivity of W/WO3 interface

    NASA Astrophysics Data System (ADS)

    Palnichenko, A. V.; Vyaselev, O. M.; Mazilkin, A. A.; Zver`kova, I. I.; Khasanov, S. S.

    2017-03-01

    Metastable W/WO3 interface has been formed at the surface of a tungsten metal bar using a solid state redox reaction of W with powdered WO3. Superconductivity at 35 ≤ T ≤ 75 K in the W/WO3 interfacial layer has been observed by means of the ac magnetic susceptibility and electrical resistance measurements. Comparative analysis of the experimental results infers that the W/WO3 interfacial layer consists of weakly linked superconducting regions.

  9. Metastable Pain-Attention Dynamics during Incremental Exhaustive Exercise.

    PubMed

    Slapšinskaitė, Agnė; Hristovski, Robert; Razon, Selen; Balagué, Natàlia; Tenenbaum, Gershon

    2016-01-01

    Background: Pain attracts attention on the bodily regions. Attentional allocation toward pain results from the neural communication across the brain-wide network "connectome" which consists of pain-attention related circuits. Connectome is intrinsically dynamic and spontaneously fluctuating on multiple time-scales. The present study delineates the pain-attention dynamics during incremental cycling performed until volitional exhaustion and investigates the potential presence of nested metastable dynamics. Method: Fifteen young and physically active adults completed a progressive incremental cycling test and reported their discomfort and pain on a body map every 15 s. Results: The analyses revealed that the number of body locations with perceived pain and discomfort increased throughout five temporal windows reaching an average of 4.26 ± 0.59 locations per participant. A total of 37 different locations were reported and marked as painful for all participants throughout the cycling task. Significant differences in entropy were observed between all temporal windows except the fourth and fifth windows. Transient dynamics of bodily locations with perceived discomfort and pain were spanned by three principal components. The metastable dynamics of the body pain locations groupings over time were discerned by three time scales: (1) the time scale of shifts (15 s); (2) the time scale of metastable configurations (100 s), and (3) the observational time scale (1000 s). Conclusion: The results of this study indicate that body locations perceived as painful increase throughout the incremental cycling task following a switching metastable and nested dynamics. These findings support the view that human brain is intrinsically organized into active, mutually interacting complex and nested functional networks, and that subjective experiences inherent in pain perception depict identical dynamical principles to the neural tissue in the brain.

  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. 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.

  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. 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.

  14. Influence of Illite and Kaolin on Chromium(VI) Reduction by Sulfide

    SciTech Connect

    Lan, Yeqing; Kim, Chulsung; Deng, Baolin; Thorton, Edward C.

    2004-03-29

    Use of hydrogen sulfide for reductive chromate immobilization requires us to understand how the minerals in the subsurface environment will affect the reaction. In this study, we examined the effects of illite and kaolin on the reduction of Cr(VI) by hydrogen sulfide under the anaerobic condition at pH ranging from 7.67 to 9.07. The results showed that extremely low concentration of iron dissolved from illite could greatly accelerate the rate of Cr(VI) reduction. An electron cycling process between Fe(II)/Fe(III) was believed to be responsible for the catalysis. The effect of iron could be completely blocked by phenanthroline that formed a strong complex with Fe(II). Elemental sulfur produced as a reaction product was also able to catalyze the reaction in the heterogeneous system. In the kaolin suspension, however, the effect of elemental sulfur could be completely eliminated because of the adsorption of elemental sulfur by kaolin.

  15. 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.

  16. Photoinduced ferrimagnetic systems in Prussian blue analogues C(I)xCo4[Fe(CN)6]y (C(I) = alkali cation). 4. Characterization of the ferrimagnetism of the photoinduced metastable state in Rb1.8Co4[Fe(CN)6]3.3-13H2O by K edges X-ray magnetic circular dichroism.

    PubMed

    Champion, G; Escax, V; Cartier Dit Moulin, C; Bleuzen, A; Villain, F; Baudelet, F; Dartyge, E; Verdaguer, M

    2001-12-19

    In Part 2 of this work, the electronic and local structure of the photoinduced metastable magnetic state of the Prussian blue analogue Rb1.8Co4[Fe(CN)6]3.3-13H2O were characterized. To determine directly the relative orientation of the magnetic moments of Co(II) and Fe(III) ions in the metastable state, and the nature of the exchange interaction between them, we performed X-ray magnetic circular dichroism (XMCD) experiments at the cobalt and iron K edges. We present the first direct experimental evidence of the antiferromagnetic interaction between the cobalt and the iron ions, leading to the ferrimagnetism of the photoinduced metastable state.

  17. 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.

  18. 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.

  19. 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

  20. 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.

  1. Chlorobaculum tepidum TLS displays a complex transcriptional response to sulfide addition.

    PubMed

    Eddie, Brian J; Hanson, Thomas E

    2013-01-01

    Chlorobaculum tepidum is a green sulfur bacterium (GSB) that is a model system for phototrophic sulfur oxidation. Despite over 2 decades of research, conspicuous gaps exist in our understanding of its electron donor metabolism and regulation. RNA sequencing (RNA-seq) was used to provide a global picture of the C. tepidum transcriptome during growth on thiosulfate as the sole electron donor and at time points following the addition of sulfide to such a culture. Following sulfide addition, 121 to 150 protein-coding genes displayed significant changes in expression depending upon the time point. These changes included a rapid decrease in expression of thiosulfate and elemental sulfur oxidation genes. Genes and gene loci with increased expression included CT1087, encoding a sulfide:quinone oxidoreductase required for growth in high sulfide concentrations; a polysulfide reductase-like complex operon, psrABC (CT0496 to CT0494); and, surprisingly, a large cluster of genes involved in iron acquisition. Finally, two genes that are conserved as a cassette in anaerobic bacteria and archaea, CT1276 and CT1277, displayed a strong increase in expression. The CT1277 gene product contains a DNA-binding domain, suggesting a role for it in sulfide-dependent gene expression changes.

  2. 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

  3. Sulfidation mechanism for zinc oxide nanoparticles and the effect of sulfidation on their solubility.

    PubMed

    Ma, Rui; Levard, Clément; Michel, F Marc; Brown, Gordon E; Lowry, Gregory V

    2013-03-19

    Environmental transformations of nanoparticles (NPs) affect their properties and toxicity potential. Sulfidation is an important transformation process affecting the fate of NPs containing metal cations with an affinity for sulfide. Here, the extent and mechanism of sulfidation of ZnO NPs were investigated, and the properties of resulting products were carefully characterized. Synchrotron X-ray absorption spectroscopy and X-ray diffraction analysis reveal that transformation of ZnO to ZnS occurs readily at ambient temperature in the presence of inorganic sulfide. The extent of sulfidation depends on sulfide concentration, and close to 100% conversion can be obtained in 5 days given sufficient addition of sulfide. X-ray diffraction and transmission electron microscopy showed formation of primarily ZnS NPs smaller than 5 nm, indicating that sulfidation of ZnO NPs occurs by a dissolution and reprecipitation mechanism. The solubility of partially sulfidized ZnO NPs is controlled by the remaining ZnO core and not quenched by a ZnS shell formed as was observed for partially sulfidized Ag NPs. Sulfidation also led to NP aggregation and a decrease of surface charge. These changes suggest that sulfidation of ZnO NPs alters the behavior, fate, and toxicity of ZnO NPs in the environment. The reactivity and fate of the resulting <5 nm ZnS particles remains to be determined.

  4. '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.

  5. Dual mode nanoparticles: CdS coated iron nanoparticles

    NASA Astrophysics Data System (ADS)

    Radwan, F. N.; Carroll, K. J.; Carpenter, E. E.

    2010-05-01

    Reverse micelles can be used in a sequential fashion to make core-shell nanoparticles. Using this technique it is possible to make a magnetic quantum dot, by coating an iron core with a cadmium sulfide shell. Transmission electron microscopy indicated core-shell morphology and narrow size distribution of the obtained particles. Collectively, x-ray powder diffraction and x-ray photoelectron spectroscopy verified the presence of cadmium sulfide on the surface of the nanoparticles. Optical properties of the coated particles were demonstrated using fluorescence spectroscopy. A vibrating sample magnetometer was used to determine magnetic properties. Dual mode cadmium sulfide coated iron core-shell nanoparticles make unique candidates for the use in biomedical applications.

  6. 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

  7. 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.

  8. 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.

  9. Rare Gas Metastable Atom Density in Diluted O2 RF Plasmas

    NASA Astrophysics Data System (ADS)

    Kitajima, Takeshi; Takahashi, Kei; Nakano, Toshiki; Makabe, Toshiaki

    Rare gas diluted O2 plasmas are gaining interests for application to high quality SiO2 film formation. The density of rare gas metastable atoms and O atom in rare gas diluted O2 radio frequency (RF) capacitively coupled plasma (CCP) was measured by optical absorption spectroscopy (OAS). Decreases of rare gas metastable densities due to addition of O2 indicate efficient O atom production by rare gas metastables via collisional quenching. Krypton metastable had highest density among four rare gas species for fixed RF power. The decrease of Ar metastable density due to O2 addition showed quantitative agreement with reported quenching rate coefficient. Detailed discussion on different gas pressures illustrates reduced O2 fraction is the key for selective production of O atoms through rare gas metastables.

  10. 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.

  11. 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.

  12. 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...

  13. 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.

  14. 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

  15. Medical Functions of Hydrogen Sulfide.

    PubMed

    Olas, Beata

    2016-01-01

    Hydrogen sulfide (H(2)S) is a gasomediator synthesized from L- and D-cysteine in various tissues. It is involved in a number of physiological and pathological processes. H(2)S exhibits antiatherosclerotic, vasodilator, and proangiogenic properties, and protects the kidney and heart from damage following ischemia/reperfusion injury. H(2)S donors may be natural or synthetic, and may be used for the safe treatment of a wide range of diseases. This review article summarizes the current state of knowledge of the therapeutic function of H(2)S.

  16. 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.

  17. 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.

  18. 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.

  19. Preservation of organic matter in sediments promoted by iron.

    PubMed

    Lalonde, Karine; Mucci, Alfonso; Ouellet, Alexandre; Gélinas, Yves

    2012-03-07

    The biogeochemical cycles of iron and organic carbon are strongly interlinked. In oceanic waters, organic ligands have been shown to control the concentration of dissolved iron. In soils, solid iron phases shelter and preserve organic carbon, but the role of iron in the preservation of organic matter in sediments has not been clearly established. Here we use an iron reduction method previously applied to soils to determine the amount of organic carbon associated with reactive iron phases in sediments of various mineralogies collected from a wide range of depositional environments. Our findings suggest that 21.5 ± 8.6 per cent of the organic carbon in sediments is directly bound to reactive iron phases. We further estimate that a global mass of (19-45) × 10(15) grams of organic carbon is preserved in surface marine sediments as a result of its association with iron. We propose that these associations between organic carbon and iron, which are formed primarily through co-precipitation and/or direct chelation, promote the preservation of organic carbon in sediments. Because reactive iron phases are metastable over geological timescales, we suggest that they serve as an efficient 'rusty sink' for organic carbon, acting as a key factor in the long-term storage of organic carbon and thus contributing to the global cycles of carbon, oxygen and sulphur.

  20. 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

  1. Structural studies of several distinct metastable forms of amorphous ice.

    PubMed

    Tulk, C A; Benmore, C J; Urquidi, J; Klug, D D; Neuefeind, J; Tomberli, B; Egelstaff, P A

    2002-08-23

    Structural changes during annealing of high-density amorphous ice were studied with both neutron and x-ray diffraction. The first diffraction peak was followed from the high- to the low-density amorphous form. Changes were observed to occur through a series of intermediate forms that appear to be metastable at each anneal temperature. Five distinct amorphous forms were studied with neutron scattering, and many more forms may be possible. Radial distribution functions indicate that the structure evolves systematically between 4 and 8 angstroms. The phase transformations in low-temperature liquid water may be much more complex than currently understood.

  2. Metastable superfluidity of repulsive fermionic atoms in optical lattices.

    PubMed

    Rosch, Achim; Rasch, David; Binz, Benedikt; Vojta, Matthias

    2008-12-31

    In the fermionic Hubbard model, doubly occupied states have an exponentially large lifetime for strong repulsive interactions U. We show that this property can be used to prepare a metastable s-wave superfluid state for fermionic atoms in optical lattices described by a large-U Hubbard model. When an initial band-insulating state is expanded, the doubly occupied sites Bose condense. A mapping to the ferromagnetic Heisenberg model in an external field allows for a reliable solution of the problem. Nearest-neighbor repulsion and pair hopping are important in stabilizing superfluidity.

  3. 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.

  4. 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.

  5. Higgs-inflaton coupling from reheating and the metastable Universe

    NASA Astrophysics Data System (ADS)

    Gross, Christian; Lebedev, Oleg; Zatta, Marco

    2016-02-01

    Current Higgs boson and top quark data favor metastability of our vacuum which raises questions as to why the Universe has chosen an energetically disfavored state and remained there during inflation. In this Letter, we point out that these problems can be solved by a Higgs-inflaton coupling which appears in realistic models of inflation. Since an inflaton must couple to the Standard Model particles either directly or indirectly, such a coupling is generated radiatively, even if absent at tree level. As a result, the dynamics of the Higgs field can change dramatically.

  6. 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.

  7. Cognitive Flexibility through Metastable Neural Dynamics Is Disrupted by Damage to the Structural Connectome.

    PubMed

    Hellyer, Peter J; Scott, Gregory; Shanahan, Murray; Sharp, David J; Leech, Robert

    2015-06-17

    Current theory proposes that healthy neural dynamics operate in a metastable regime, where brain regions interact to simultaneously maximize integration and segregation. Metastability may confer important behavioral properties, such as cognitive flexibility. It is increasingly recognized that neural dynamics are constrained by the underlying structural connections between brain regions. An important challenge is, therefore, to relate structural connectivity, neural dynamics, and behavior. Traumatic brain injury (TBI) is a pre-eminent structural disconnection disorder whereby traumatic axonal injury damages large-scale connectivity, producing characteristic cognitive impairments, including slowed information processing speed and reduced cognitive flexibility, that may be a result of disrupted metastable dynamics. Therefore, TBI provides an experimental and theoretical model to examine how metastable dynamics relate to structural connectivity and cognition. Here, we use complementary empirical and computational approaches to investigate how metastability arises from the healthy structural connectome and relates to cognitive performance. We found reduced metastability in large-scale neural dynamics after TBI, measured with resting-state functional MRI. This reduction in metastability was associated with damage to the connectome, measured using diffusion MRI. Furthermore, decreased metastability was associated with reduced cognitive flexibility and information processing. A computational model, defined by empirically derived connectivity data, demonstrates how behaviorally relevant changes in neural dynamics result from structural disconnection. Our findings suggest how metastable dynamics are important for normal brain function and contingent on the structure of the human connectome.

  8. Counting metastable states in a kinetically constrained model using a patch repetition analysis.

    PubMed

    Jack, Robert L

    2013-12-01

    We analyze metastable states in the East model, using a recently proposed patch repetition analysis based on time-averaged density profiles. The results reveal a hierarchy of states of varying lifetimes, consistent with previous studies in which the metastable states were identified and used to explain the glassy dynamics of the model. We establish a mapping between these states and configurations of systems of hard rods, which allows us to analyze both typical and atypical metastable states. We discuss connections between the complexity of metastable states and large-deviation functions of dynamical quantities, both in the context of the East model and more generally in glassy systems.

  9. 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.

  10. 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.

  11. The synthesis of cadmium sulfide nanoplatelets using a novel continuous flow sonochemical reactor

    DOE PAGES

    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

  12. The role of hydrogen sulfide in burns.

    PubMed

    Akter, Farhana

    2016-05-01

    Hydrogen sulfide is a novel gasotransmitter that has been shown to play a major role in regulating vascular tone. However, the role of hydrogen sulfide in inflammation, sepsis and burns has only recently been studied. In animal studies, hydrogen sulfide has been shown to play a role in both promoting and inhibiting inflammation. Understanding the role of H2S in sepsis and shock is particularly important due to the high mortality associated with both conditions. In animal sepsis models, hydrogen sulfide appears to increase survival. Severe burns are associated with an inflammatory response that causes increased permeability and edema. Currently, there are few studies that have examined the exact role of hydrogen sulfide in burns. However, the role of hydrogen sulfide in inflammation enables us to hypothesize its role in burns. This review highlights the role of hydrogen sulfide in the mechanisms of action underlying inflammation, wound healing and sepsis as well as examining the potential role of hydrogen sulfide in burns. The authors of this article hope that this review will stimulate research to discover the exact role of this fascinating molecule in burns.

  13. Catalyst and process for oxidizing hydrogen sulfide

    SciTech Connect

    Hass, R.H.; Ward, J.W.

    1984-04-24

    Catalysts comprising bismuth and vanadium components are highly active and stable, especially in the presence of water vapor, for oxidizing hydrogen sulfide to sulfur or SO/sub 2/. Such catalysts have been found to be especially active for the conversion of hydrogen sulfide to sulfur by reaction with oxygen or SO/sub 2/.

  14. Ferrous and Sulfide Treatment of Electroplating Wastewater.

    DTIC Science & Technology

    chromium contaminants and the precipitation of heavy metal contaminants from contaminated electroplating wastewater. The wastewater is first adjusted...to a pH of from about 8 to 10 and then treated with sodium sulfide to provide sulfide ions to effect precipitation of heavy metal contaminants followed

  15. 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...

  16. 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.

  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. 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.

  19. 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

  20. 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.

  1. Methodology for assessing thioarsenic formation potential in sulfidic landfill environments.

    PubMed

    Zhang, Jianye; Kim, Hwidong; Townsend, Timothy

    2014-07-01

    Arsenic leaching and speciation in landfills, especially those with arsenic bearing waste and drywall disposal (such as construction and demolition (C&D) debris landfills), may be affected by high levels of sulfide through the formation of thioarsenic anions. A methodology using ion chromatography (IC) with a conductivity detector was developed for the assessment of thioarsenic formation potential in sulfidic landfill environments. Monothioarsenate (H2AsSO3(-)) and dithioarsenate (H2AsS2O2(-)) were confirmed in the IC fractions of thioarsenate synthesis mixture, consistent with previous literature results. However, the observation of AsSx(-) (x=5-8) in the supposed trithioarsenate (H2AsS3O(-)) and tetrathioarsenate (H2AsS4(-)) IC fractions suggested the presence of new arsenic polysulfide complexes. All thioarsenate anions, particularly trithioarsenate and tetrathioarsenate, were unstable upon air exposure. The method developed for thioarsenate analysis was validated and successfully used to analyze several landfill leachate samples. Thioarsenate anions were detected in the leachate of all of the C&D debris landfills tested, which accounted for approximately 8.5% of the total aqueous As in the leachate. Compared to arsenite or arsenate, thioarsenates have been reported in literature to have lower adsorption on iron oxide minerals. The presence of thioarsenates in C&D debris landfill leachate poses new concerns when evaluating the impact of arsenic mobilization in such environments.

  2. Metastable Lennard-Jones fluids. II. Thermal conductivity.

    PubMed

    Baidakov, Vladimir G; Protsenko, Sergey P

    2014-06-07

    The method of equilibrium molecular dynamics with the use of the Green-Kubo formalism has been used to calculate the thermal conductivity λ in stable and metastable regions of a Lennard-Jones fluid. Calculations have been made in the range of reduced temperatures 0.4 ≤ T* = k(b)T/ε ≤ 2.0 and densities 0.01 ≤ ρ* = ρσ³ ≤ 1.2 on 15 isotherms for 234 states, 130 of which refer to metastable regions: superheated and supercooled liquids, supersaturated vapor. Equations have been built up which describe the dependence of the regular part of the thermal conductivity on temperature and density, and also on temperature and pressure. It has been found that in (p, T) variables in the region of a liquid-gas phase transition a family of lines of constant value of excess thermal conductivity Δλ = λ - λ0, where λ0 is the thermal conductivity of a dilute gas, has an envelope which coincides with the spinodal. Thus, at the approach to the spinodal of a superheated liquid and supersaturated vapor (∂Δλ/∂p)T → ∞, (∂Δλ/∂T)p → ∞.

  3. Loss Processes of Metastable Molecules in Cylindrical Cavity

    NASA Astrophysics Data System (ADS)

    Suzuki, Susumu; Itoh, Haruo

    2000-10-01

    Assuming a closed cylindrical volume, the spatiotemporal variation of the density distribution of the metastable molecules N_2(A^3Σ_u^+) in the cylindrical volume are calculated from the diffusion equation analysis under the different reflection coefficients at the flat electrode surfaces and at the cylindrical wall.(S.Suzuki, H.Itoh, N.Ikuta and H.Sekizawa:Jpn. J. Appl. Phys., 39, 1333, 2000)(S. Suzuki, H. Itoh, H. Sekizawa and N. Ikuta: Papers of Technical Meeting on Electrical Discharges, ED-98-128, 17, 1998 (in Japanese)) We solve the diffusion equation by separation of variables using the boundary condition of the third kind that is taken account of the reflection at the electrode surfaces.(S. Suzuki, H. Itoh, N. Ikuta and H. Sekizawa: J. Phys. D : Appl. Phys., 25, 1568, 1992) The obtained solution of the diffusion equation are possible to describe the density profiles along the longitudinal and the radial directions. The influence of the density distribution by the different reflection coefficient at each of electrodes and at the cylindrical wall is investigated. Furthermore, the effective lifetime of the diffusing metastable molecules is also discussed under different reflection coefficients.

  4. Metastable states in calcium phosphate - aqueous phase equilibrations

    NASA Astrophysics Data System (ADS)

    Driessens, F. C. M.; Verbeeck, R. M. H.

    1981-05-01

    A critical evaluation of the literature reveals that during equilibration of well crystallized hydroxyapatite in aqueous solutions metastable states can occur. They are characterized by a persistent supersaturation with respect to hydroxyapatite and a systematical dependence of the ion activity product of this compound on the solution composition. For products synthesized by thermal treatment it is known that they are transformed into oxyhydroxyapatite so that the theoretical solubility behaviour could be predicted from the extrapolated value of the free energy of oxyapatite at room temperature: the negative logarithm of the ionic product for hydroxyapatite should become close to that of oxyapatite during equilibration. The discrepancy with experimental data is probably due to the formation of thin layers seeming dicalcium phosphate dihydrate, octocalcium phosphate or defective hydroxyapatite as coatings on the apatite crystals. This is derived from the apparent Ca/P ratio of the solubility controlling phase. According to chemical potential plots this apparent Ca/P ratio can have values close to 1, 1.33, 1.50 or 1.67. The aqueous solutions are clearly undersaturated with respect to the more acidic calcium phosphates so that the coatings must deviate from the compositions of these compounds in their pure state. The formation of these metastable states during equilibration of oxyhydroxyapatites is compared with others occuring during precipitation and crystal growth of calcium phosphates. A model is proposed which explains the observations qualitatively.

  5. Magnetic properties of Co-Cu metastable solid solution alloys

    NASA Astrophysics Data System (ADS)

    Fan, Xu; Mashimo, Tsutomu; Huang, Xinsheng; Kagayama, Tomoko; Chiba, Akira; Koyama, Keiichi; Motokawa, Mitsuhiro

    2004-03-01

    Metastable solid solution alloy powders and bulk alloys in the cobalt(Co)-copper(Cu) (10 90 mol % Co) system, which is an almost immiscible system at the ambient state, were prepared by mechanical alloying (MA) and shock compression. All MA-treated powders showed the x-ray diffraction patterns of a single phase of fcc structure. The lattice parameter increases with Cu concentration and is fundamentally on the line with Vegard’s law. The magnetization curves of CoxCu100-x (x=20 80) metastable bulk alloys at room temperature showed ferromagnetism, while the one of Co10Cu90 system showed paramagnetism. The saturation magnetic moment (Ms) curve versus electron numbers per atom at 0 K was found to be similar to the Slater-Pauling curves of other transition-metal binary systems and decreased with increasing Cu concentration and approached zero at about 28.8 electrons per atom. The magnetoresistance ratio at room temperature increased with Cu content in the ferromagnetic region, while the one of the paramagnetic Co10Cu90 alloy was negligibly small.

  6. Extrapolating bound state data of anions into the metastable domain

    NASA Astrophysics Data System (ADS)

    Feuerbacher, Sven; Sommerfeld, Thomas; Cederbaum, Lorenz S.

    2004-10-01

    Computing energies of electronically metastable resonance states is still a great challenge. Both scattering techniques and quantum chemistry based L2 methods are very time consuming. Here we investigate two more economical extrapolation methods. Extrapolating bound states energies into the metastable region using increased nuclear charges has been suggested almost 20 years ago. We critically evaluate this attractive technique employing our complex absorbing potential/Green's function method that allows us to follow a bound state into the continuum. Using the 2Πg resonance of N2- and the 2Πu resonance of CO2- as examples, we found that the extrapolation works suprisingly well. The second extrapolation method involves increasing of bond lengths until the sought resonance becomes stable. The keystone is to extrapolate the attachment energy and not the total energy of the system. This method has the great advantage that the whole potential energy curve is obtained with quite good accuracy by the extrapolation. Limitations of the two techniques are discussed.

  7. Ultracold metastable helium: Ramsey fringes and atom interferometry

    NASA Astrophysics Data System (ADS)

    Vassen, W.; Notermans, R. P. M. J. W.; Rengelink, R. J.; van der Beek, R. F. H. J.

    2016-12-01

    We report on interference studies in the internal and external degrees of freedom of metastable triplet helium atoms trapped near quantum degeneracy in a 1.5 μm optical dipole trap. Applying a single π /2 rf pulse we demonstrate that 50% of the atoms initially in the m=+1 state can be transferred to the magnetic field insensitive m=0 state. Two π /2 pulses with varying time delay allow a Ramsey-type measurement of the Zeeman shift for a high precision measurement of the 2 ^3S_1-2 ^1S_0 transition frequency. We show that this method also allows strong suppression of mean-field effects on the measurement of the Zeeman shift, which is necessary to reach the accuracy goal of 0.1 kHz on the absolute transition frequencies. Theoretically the feasibility of using metastable triplet helium atoms in the m=0 state for atom interferometry is studied demonstrating favorable conditions, compared to the alkali atoms that are used traditionally, for a non-QED determination of the fine structure constant.

  8. Are metastable, precrystallisation, density-fluctuations a universal phenomena?

    PubMed

    Heeley, Ellen L; Poh, C Kit; Li, Wu; Maidens, Anna; Bras, Wim; Dolbnya, Igor P; Gleeson, Anthony J; Terrill, Nicolas J; Fairclough, J Patrick A; Olmsted, Peter D; Ristic, Rile I; Hounslow, Micheal J; Ryan, Anthony J

    2003-01-01

    In-situ observations of crystallisation in minerals and organic polymers have been made by simultaneous, time-resolved small angle X-ray scattering (SAXS) and wide angle X-ray scattering (WAXS) techniques. In isotactic polypropylene slow quiescent crystallisation shows the onset of large scale ordering prior to crystal growth. Rapid crystallisations studied by melt extrusion indicate the development of well resolved oriented SAXS patterns associated with long range order before the development of crystalline peaks in the WAXS region. Block copolymers self-assemble into mesophases in polymer melts above a critical chain length (or above a critical temperature) and this self-assembly process is shown to be susceptible to an incipient crystallisation. Mesophase formation is observed at anomalously high temperatures in ethylene-oxide containing block copolymers below the normal melting point of the polyoxy ethylene chains. Formation of calcium carbonate from aqueous solutions of sodium carbonate and calcium nitrate is observed to be a two-stage process and precipitation proceeds by the production of an amorphous metastable phase. This phase grows until it is volume filling and leads to the formation of the two polymorphs Calcite and Vaterite. These three sets of results suggest pre-nucleation density fluctuations, leading to a metastable phase, play an integral role in all three classes of crystallisation. In due course, this phase undergoes transformation to "normal" crystals.

  9. Deactivation of metastable single-crystal silicon hyperdoped with sulfur

    SciTech Connect

    Simmons, C. B.; Akey, Austin J.; Sullivan, Joseph T.; Buonassisi, Tonio; Krich, Jacob J.; Recht, Daniel; Aziz, Michael J.

    2013-12-28

    Silicon supersaturated with sulfur by ion implantation and pulsed laser melting exhibits broadband optical absorption of photons with energies less than silicon's band gap. However, this metastable, hyperdoped material loses its ability to absorb sub-band gap light after subsequent thermal treatment. We explore this deactivation process through optical absorption and electronic transport measurements of sulfur-hyperdoped silicon subject to anneals at a range of durations and temperatures. The deactivation process is well described by the Johnson-Mehl-Avrami-Kolmogorov framework for the diffusion-mediated transformation of a metastable supersaturated solid solution, and we find that this transformation is characterized by an apparent activation energy of E{sub A}=1.7 ± 0.1 eV. Using this activation energy, the evolution of the optical and electronic properties for all anneal duration-temperature combinations collapse onto distinct curves as a function of the extent of reaction. We provide a mechanistic interpretation of this deactivation based on short-range thermally activated atomic movements of the dopants to form sulfur complexes.

  10. A laboratory-formulated sediment incorporating synthetic acid-volatile sulfide

    SciTech Connect

    Gonzalez, A.M.

    1996-12-01

    The application of laboratory-formulated sediment (LFS) could be expanded if toxicologically significant characteristics of sediment other than particle-size distribution, organic carbon content, and pH could be manipulated. This report describes the preparation of a LFS containing synthetic acid-volatile sulfide (AVS) and shows its similarity to natural sediment AVS. Several formulations were evaluated with respect to toxicity to Hyalella azteca and chemical stability. Amphipod survival was highest (95%) in LFS formulations in which the molar iron(II)/sulfide ratio was near 1, although amphipod survival was > 80% in six of seven formulations with {le} 20% excess metal or sulfide. Synthetic AVS in the test system oxidized rapidly at the sediment surface, but AVS at depth was stable for > 30 d when isolated from air or aerated water. Oxidation-reduction potential measurements and AVS analysis of core slices revealed a vertical oxidation profile, apparently established and limited by oxygen diffusion. A formulation consisting of a 1:1 molar ratio of iron and sulfide (FeS) was evaluated with respect to complexation of copper, zinc, and nickel and to the corresponding reduction in toxicity using 10-d H. azteca toxicity texts. Amphipod mortality in metal-spiked LFS with metal/AVS molar ratios > 1 was high relative to controls. In contrast, amphipod survival in metal-spiked LFS with metal/AVS molar ratios < 1 was generally similar to amphipod survival in nonspiked LFS containing synthetic AVS. A few exceptions, where toxicity was noted when metal/AVS ratios were < 1, could be explained by high concentrations of dissolved iron, which was released by the metal + AVS displacement reaction. The LFS containing synthetic AVS appears to mimic natural sediment AVS and thus can provide consistent and controlled substrates suitable for investigating metal/sediment chemistry and toxicity and for developing realistic sediment quality criteria for metals.

  11. A new method for thioarsenate preservation in iron-rich waters by solid phase extraction.

    PubMed

    Ullrich, Maria K; Misiari, Valentina; Planer-Friedrich, Britta

    2016-10-01

    In order to preserve iron-rich samples for arsenic speciation analysis, mineral acids or EDTA are typically added to prevent oxidation and precipitation of iron. However, when sulfide is present, and thioarsenates ([HAs(V)S(-II)nO4-n](2-), n = 1-4) can form, these methods are unsuitable due to arsenic sulfide precipitation or artifact speciation changes. Here, a new method based on separating the anionic arsenic species from cationic iron in the presence of sulfide via solid phase extraction (SPE) has been investigated. Synthetic solutions containing arsenite, arsenate, monothioarsenate, and trithioarsenate were passed through the anion-exchange resin AG2-X8, after which the resin was washed, eluted, and speciation of each step analyzed by IC-ICP-MS. Retention on the resin of 96.8 ± 0.2%, 98.8 ± 0.2%, and 99.6 ± 0.3% was found for arsenate, monothioarsenate, and trithioarsenate, respectively. Cationic iron (90 μM Fe(II)) was not retained (0.4 ± 0.2%). Uncharged arsenite passed through the resin in the absence of sulfide, while 47.3% of arsenite were retained at tenfold sulfide excess via thiol groups binding to the organic resin structure. Elution with 3 × 15 mL of 0.5 M salicylate, including a soak time, resulted in quantitative recovery of all retained species. Stability of the retained species on the resin was tested with iron-rich, natural waters from a Czech mineral spring. Arsenate, monothioarsenate, dithioarsenate, and trithioarsenate were successfully separated from iron and recovered after 6 d. Thus, SPE presents a viable answer to the problem of preserving arsenic in the presence of both iron and sulfide.

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

    PubMed

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

    2015-10-09

    The first step in the mitochondrial sulfide oxidation pathway is catalyzed by sulfide quinone oxidoreductase (SQR), which belongs to the family of flavoprotein disulfide oxidoreductases. During the catalytic cycle, the flavin cofactor is intermittently reduced by sulfide and oxidized by ubiquinone, linking H2S oxidation to the electron transfer chain and to energy metabolism. Human SQR can use multiple thiophilic acceptors, including sulfide, sulfite, and glutathione, to form as products, hydrodisulfide, thiosulfate, and glutathione persulfide, respectively. In this study, we have used transient kinetics to examine the mechanism of the flavin reductive half-reaction and have determined the redox potential of the bound flavin to be -123 ± 7 mV. We observe formation of an unusually intense charge-transfer (CT) complex when the enzyme is exposed to sulfide and unexpectedly, when it is exposed to sulfite. In the canonical reaction, sulfide serves as the sulfur donor and sulfite serves as the acceptor, forming thiosulfate. We show that thiosulfate is also formed when sulfide is added to the sulfite-induced CT intermediate, representing a new mechanism for thiosulfate formation. The CT complex is formed at a kinetically competent rate by reaction with sulfide but not with sulfite. Our study indicates that sulfide addition to the active site disulfide is preferred under normal turnover conditions. However, under pathological conditions when sulfite concentrations are high, sulfite could compete with sulfide for addition to the active site disulfide, leading to attenuation of SQR activity and to an alternate route for thiosulfate formation.

  13. Sulfur and iron in shipwrecks cause conservation concerns.

    PubMed

    Fors, Yvonne; Sandström, Magnus

    2006-05-01

    Synchrotron-based sulfur X-ray absorption spectroscopy reveals considerable accumulation of organosulfur (e.g. thiols), pyrite and iron(II) sulfides in marine-archaeological wood preserved in seawater, e.g. for historical shipwrecks such as the Vasa and Mary Rose. In the museum, oxidation of the sulfur compounds in the presence of iron ions may cause severe acidity in the moist wood. This tutorial review discusses developments of conservation methods to remove acid and iron, and how to analyse and stabilise sulfur compounds in the wood.

  14. Sulfide oxidation as a process for the formation of copper-rich magmatic sulfides

    NASA Astrophysics Data System (ADS)

    Wohlgemuth-Ueberwasser, Cora C.; Fonseca, Raúl O. C.; Ballhaus, Chris; Berndt, Jasper

    2013-01-01

    Typical magmatic sulfides are dominated by pyrrhotite and pentlandite with minor chalcopyrite, and the bulk atomic Cu/Fe ratio of these sulfides is typically less than unity. However, there are rare magmatic sulfide occurrences that are dominated by Cu-rich sulfides (e.g., bornite, digenite, and chalcopyrite, sometimes coexisting with metallic Cu) with atomic Cu/Fe as high as 5. Typically, these types of sulfide assemblages occur in the upper parts of moderately to highly fractionated layered mafic-ultramafic intrusions, a well-known example being the Pd/Au reef in the Upper Middle Zone of the Skaergaard intrusion. Processes proposed to explain why these sulfides are so unusually rich in Cu include fractional crystallization of Fe/(Ni) monosulfide and infiltration of postmagmatic Cu-rich fluids. In this contribution, we explore and experimentally evaluate a third possibility: that Cu-rich magmatic sulfides may be the result of magmatic oxidation. FeS-dominated Ni/Cu-bearing sulfides were equilibrated at variable oxygen fugacities in both open and closed system. Our results show that the Cu/Fe ratio of the sulfide melt increases as a function of oxygen fugacity due to the preferential conversion of FeS into FeO and FeO1.5, and the resistance of Cu2S to being converted into an oxide component even at oxygen fugacities characteristic of the sulfide/sulfate transition (above FMQ + 1). This phenomenon will lead to an increase in the metal/S ratio of a sulfide liquid and will also depress its liquidus temperature. As such, any modeling of the sulfide liquid line of descent in magmatic sulfide complexes needs to address this issue.

  15. Influence of temperature and the role of chromium on the kinetics of sulfidation of 310 stainless steel

    NASA Technical Reports Server (NTRS)

    Rao, D. B.; Nelson, H. G.

    1977-01-01

    The sulfidation of 310 stainless steel was studied over the temperature range from 910 K to 1285 K. By adjusting the ratio of hydrogen sulfide, variations in sulfur potential were obtained. The effect of temperature on sulfidation was determined at three different sulfur potentials: 39/sqNm, 0.014/sqNm, and 0.00015/sqNm. All sulfide scales contained one or two surface layers in addition to a subscale. The second outer layer (OL-II), furthest from the alloy, contained primarily Fe-Ni-S. The first outer layer (OL-I), nearest the subscale, contained FE-Cr-S. The subscale consisted of sulfide inclusions in the metal matrix. At a given temperature and sulfur potential, the weight gain data obeyed the parabolic rate law after an initial transient period. The parabolic rate constants obtained at the sulfur potential of 39/sqNm did not show a break when the logarithm of the rate constant was plotted as a function of the inverse of absolute temperature. Sulfidation carried out at sulfur potentials below 0.02/sqNm, however, did show a break at 1145 K, which is termed as the transition temperature. This break was found to be associated with the changes which had occurred in the Fe:Cr ratio of OL-I. Below the transition temperature the activation energy was found to be approximately 125 kj/mole. Above the transition temperature the rate of sulfidation decreased with temperature but dependent on the Fe:Cr ratio in the iron-chromium-sulfide layers of the OL-I. A reaction mechanism consistent with the experimental results has been proposed.

  16. Light-induced metastable defects or light-induced metastable H atoms in a-Si:H films?

    SciTech Connect

    Godet, C.

    1997-07-01

    In hydrogenated amorphous silicon (a-Si:H) films, the increase of the metastable defect density under high-intensity illumination is usually described by an empirical two-parameter stretched-exponential time dependence (characteristic time {tau}{sub SE} and dispersion parameter {beta}). In this study, a clearly different (one-parameter) analytic function is obtained from a microscopic model based on the formation of metastable H (MSH) atoms in a-Si:H films. Assuming that MSH atoms are the only mobile species, only three chemical reactions are significant: MSH are produced from doubly hydrogenated (SiH HSi) configurations and trapped either at broken bonds or Si-H bonds, corresponding respectively to light-induced annealing (LIA) and light-induced creation (LIC) of defects. Competition between trapping sites results in a saturation of N(t) at a steady-state value N{sub ss}. A one-parameter fit of this analytical function to experimental data is generally good, indicating that the use of a statistical distribution of trap energies is not necessary.

  17. 40 CFR 425.04 - Applicability of sulfide pretreatment standards.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... hydrogen sulfide gas. (3) The characteristics of the receiving POTWs headworks, preliminary and primary... opportunities for release of hydrogen sulfide gas. (4) The occurrence of any prior sulfide related interference... 40 Protection of Environment 31 2012-07-01 2012-07-01 false Applicability of sulfide...

  18. 40 CFR 425.04 - Applicability of sulfide pretreatment standards.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... hydrogen sulfide gas. (3) The characteristics of the receiving POTWs headworks, preliminary and primary... opportunities for release of hydrogen sulfide gas. (4) The occurrence of any prior sulfide related interference... 40 Protection of Environment 30 2014-07-01 2014-07-01 false Applicability of sulfide...

  19. 40 CFR 425.04 - Applicability of sulfide pretreatment standards.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... hydrogen sulfide gas. (3) The characteristics of the receiving POTWs headworks, preliminary and primary... opportunities for release of hydrogen sulfide gas. (4) The occurrence of any prior sulfide related interference... 40 Protection of Environment 30 2011-07-01 2011-07-01 false Applicability of sulfide...

  20. 40 CFR 425.04 - Applicability of sulfide pretreatment standards.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... hydrogen sulfide gas. (3) The characteristics of the receiving POTWs headworks, preliminary and primary... opportunities for release of hydrogen sulfide gas. (4) The occurrence of any prior sulfide related interference... 40 Protection of Environment 29 2010-07-01 2010-07-01 false Applicability of sulfide...

  1. 40 CFR 425.04 - Applicability of sulfide pretreatment standards.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... hydrogen sulfide gas. (3) The characteristics of the receiving POTWs headworks, preliminary and primary... opportunities for release of hydrogen sulfide gas. (4) The occurrence of any prior sulfide related interference... 40 Protection of Environment 31 2013-07-01 2013-07-01 false Applicability of sulfide...

  2. 21 CFR 73.2995 - Luminescent zinc sulfide.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 1 2014-04-01 2014-04-01 false Luminescent zinc sulfide. 73.2995 Section 73.2995... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2995 Luminescent zinc sulfide. (a) Identity. The color additive luminescent zinc sulfide is zinc sulfide containing a copper activator....

  3. 21 CFR 73.2995 - Luminescent zinc sulfide.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Luminescent zinc sulfide. 73.2995 Section 73.2995... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2995 Luminescent zinc sulfide. (a) Identity. The color additive luminescent zinc sulfide is zinc sulfide containing a copper activator....

  4. 21 CFR 73.2995 - Luminescent zinc sulfide.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 1 2011-04-01 2011-04-01 false Luminescent zinc sulfide. 73.2995 Section 73.2995... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2995 Luminescent zinc sulfide. (a) Identity. The color additive luminescent zinc sulfide is zinc sulfide containing a copper activator....

  5. 21 CFR 73.2995 - Luminescent zinc sulfide.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 1 2012-04-01 2012-04-01 false Luminescent zinc sulfide. 73.2995 Section 73.2995... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2995 Luminescent zinc sulfide. (a) Identity. The color additive luminescent zinc sulfide is zinc sulfide containing a copper activator....

  6. 21 CFR 73.2995 - Luminescent zinc sulfide.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 1 2013-04-01 2013-04-01 false Luminescent zinc sulfide. 73.2995 Section 73.2995... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2995 Luminescent zinc sulfide. (a) Identity. The color additive luminescent zinc sulfide is zinc sulfide containing a copper activator....

  7. Metal hydrogen sulfide superconducting temperature

    NASA Astrophysics Data System (ADS)

    Kudryashov, N. A.; Kutukov, A. A.; Mazur, E. A.

    2017-01-01

    Éliashberg theory is generalized to the electronphonon (EP) systems with the not constant density of electronic states. The phonon contribution to the anomalous electron Green's function (GF) is considered. The generalized Éliashberg equations with the variable density of electronic states are resolved for the hydrogen sulphide SH3 phase under pressure. The dependence of both the real and the imaginary part of the order parameter on the frequency in the SH3 phase is obtained. The Tc = 177 K value in the hydrogen sulfide SH3 phase at the pressure P = 225 GPa has been defined. The results of the solution of the Eliashberg equations for the Im-3m (170 GPa), Im-3m (200 GPa) and R3m (120 GPa) phases are presented. A peak value Tc = 241 K of the superconducting transition temperature has been predicted.

  8. Redox biochemistry of hydrogen sulfide.

    PubMed

    Kabil, Omer; Banerjee, Ruma

    2010-07-16

    H(2)S, the most recently discovered gasotransmitter, might in fact be the evolutionary matriarch of this family, being both ancient and highly reduced. Disruption of gamma-cystathionase in mice leads to cardiovascular dysfunction and marked hypertension, suggesting a key role for this enzyme in H(2)S production in the vasculature. However, patients with inherited deficiency in gamma-cystathionase apparently do not present vascular pathology. A mitochondrial pathway disposes sulfide and couples it to oxidative phosphorylation while also exposing cytochrome c oxidase to this metabolic poison. This report focuses on the biochemistry of H(2)S biogenesis and clearance, on the molecular mechanisms of its action, and on its varied biological effects.

  9. Structural studies in limestone sulfidation

    SciTech Connect

    Fenouil, Laurent A.

    1993-05-01

    This study investigates the sulfidation of limestone at high temperatures (700--900°C) as the first step in the design of a High-Temperature Coal-Gas Clean-Up system using millimeter-size limestone particles. Several workers have found that the rate of this reaction significantly decreases after an initial 10 to 15% conversion of CaCO3 to CaS. The present work attempts to explain this feature. It is first established that millimeter-size limestone particles do not sinter at temperatures up to the CaCO3 calcination point (899°C at 1.03 bar CO2} partial pressure). It is then shown that CaS sinters rapidly at 750 to 900°C if CO2 is present in the gas phase. Scanning Electron Microscope (SEM) photographs and Electron Dispersive Spectroscopy (EDS) data reveal that the CaS product layer sinters and forms a quasi-impermeable coating around the CaCO3 grains that greatly hinders more H2S from reaching the still unreacted parts of the stone. Moreover, most of the pores initially present within the limestone structure begin to disappear or, at least, are significantly reduced in size. From then on, subsequent conversion is limited by diffusion of H2S through the CaS layer, possibly by S2- ionic diffusion. The kinetics is then adequately described by a shrinking-core model, in which a sharp front of completely converted limestone is assumed to progress toward the center of the pellet. Finally, experimental evidence and computer simulations using simple sintering models suggest that the CaS sintering, responsible for the sharp decrease in the sulfidation rate, is surface-diffusion controlled.

  10. Copper-catalyzed asymmetric oxidation of sulfides.

    PubMed

    O'Mahony, Graham E; Ford, Alan; Maguire, Anita R

    2012-04-06

    Copper-catalyzed asymmetric sulfoxidation of aryl benzyl and aryl alkyl sulfides, using aqueous hydrogen peroxide as the oxidant, has been investigated. A relationship between the steric effects of the sulfide substituents and the enantioselectivity of the oxidation has been observed, with up to 93% ee for 2-naphthylmethyl phenyl sulfoxide, in modest yield in this instance (up to 30%). The influence of variation of solvent and ligand structure was examined, and the optimized conditions were then used to oxidize a number of aryl alkyl and aryl benzyl sulfides, producing sulfoxides in excellent yields in most cases (up to 92%), and good enantiopurities in certain cases (up to 84% ee).

  11. Microbial control of hydrogen sulfide production

    SciTech Connect

    Montgomery, A.D.; Bhupathiraju, V.K.; Wofford, N.; McInerney, M.J.

    1995-12-31

    A sulfide-resistant strain of Thiobacillus denitrificans, strain F, prevented the accumulation of sulfide by Desulfovibrio desulfuricans when both organisms were grown in liquid medium. The wild-type strain of T. denitrificans did not prevent the accumulation of sulfide produced by D. desulfuricans. Strain F also prevented the accumulation of sulfide by a mixed population of sulfate-reducing bacteria enriched from an oil field brine. Fermentation balances showed that strain F stoichiometrically oxidized the sulfide produced by D. desulfuricans and the oil field brine enrichment to sulfate. The ability of a strain F to control sulfide production in an experimental system of cores and formation water from the Redfield, Iowa, natural gas storage facility was also investigated. A stable, sulfide-producing biofilm was established in two separate core systems, one of which was inoculated with strain F while the other core system (control) was treated in an identical manner, but was not inoculated with strain F. When formation water with 10 mM acetate and 5 mM nitrate was injected into both core systems, the effluent sulfide concentrations in the control core system ranged from 200 to 460 {mu}M. In the test core system inoculated with strain F, the effluent sulfide concentrations were lower, ranging from 70 to 110 {mu}M. In order to determine whether strain F could control sulfide production under optimal conditions for sulfate-reducing bacteria, the electron donor was changed to lactate and inorganic nutrients (nitrogen and phosphate sources) were added to the formation water. When nutrient-supplemented formation water with 3.1 mM lactate and 10 mM nitrate was used, the effluent sulfide concentrations of the control core system initially increased to about 3,800 {mu}M, and then decreased to about 1,100 {mu}M after 5 weeks. However, in the test core system inoculated with strain F, the effluent sulfide concentrations were much lower, 160 to 330 {mu}M.

  12. Nanostructured lead sulfide: synthesis, structure and properties

    NASA Astrophysics Data System (ADS)

    Sadovnikov, S. I.; Gusev, A. I.; Rempel, A. A.

    2016-07-01

    The theoretical and experimental results of recent studies dealing with nanostructured lead sulfide are summarized and analyzed. The key methods for the synthesis of nanostructured lead sulfide are described. The crystal structure of PbS in nanopowders and nanofilms is discussed. The influence of the size of nanostructure elements on the optical and thermal properties of lead sulfide is considered. The dependence of the band gap of PbS on the nanoparticle (crystallite) size for powders and films is illustrated. The bibliography includes 222 references.

  13. Optimization of crystal nucleation close to a metastable fluid-fluid phase transition.

    PubMed

    Wedekind, Jan; Xu, Limei; Buldyrev, Sergey V; Stanley, H Eugene; Reguera, David; Franzese, Giancarlo

    2015-06-22

    The presence of a metastable fluid-fluid critical point is thought to dramatically influence the crystallization pathway, increasing the nucleation rate by many orders of magnitude over the predictions of classical nucleation theory. We use molecular dynamics simulations to study the kinetics of crystallization in the vicinity of this metastable critical point and throughout the metastable fluid-fluid phase diagram. To quantitatively understand how the fluid-fluid phase separation affects the crystal nucleation, we evaluate accurately the kinetics and reconstruct the thermodynamic free-energy landscape of crystal formation. Contrary to expectations, we find no special advantage of the proximity of the metastable critical point on the crystallization rates. However, we find that the ultrafast formation of a dense liquid phase causes the crystallization to accelerate both near the metastable critical point and almost everywhere below the fluid-fluid spinodal line. These results unveil three different scenarios for crystallization that could guide the optimization of the process in experiments.

  14. Phase diagram with a region of liquid carbon-diamond metastable states

    NASA Astrophysics Data System (ADS)

    Basharin, A. Yu.; Dozhdikov, V. S.; Kirillin, A. V.; Turchaninov, M. A.; Fokin, L. R.

    2010-06-01

    Metastable cubic diamond has been found in the structure of solid carbon obtained by quenching of a liquid phase at a pressure (0.012 GPa) much lower than that corresponding to the existence of stable diamond. It is suggested that this metastable diamond is formed as a result of the recalescence of supercooled liquid carbon to the melting point ( T dm) of metastable diamond due to a lower energy barrier for the formation of diamond as compared to that of graphite. A comparison between the calculated Gibbs energies of metastable phases provided an estimate of T dm = 4160 ± 50 K. For the first time, metastable continuations of the curve of diamond melting at pressures of up to 0.012 GPa are constructed on the phase diagrams of carbon (according to various published data) using analytical curves described by a two-parametric Simon equation.

  15. Fragmentation of phosphorylated and singly charged peptide ions via interaction with metastable atoms

    PubMed Central

    Berkout, Vadym D.; Doroshenko, Vladimir M.

    2008-01-01

    Fragmentation of phosphorylated peptide ions via interaction with electronically excited metastable argon atoms was studied in a linear trap – time-of-flight mass spectrometer. Doubly charged ions of phosphorylated peptides from an Enolase digest were produced by electrospray ionization and subjected to a metastable atom beam in the linear trap. The metastable argon atoms were generated using a glow-discharge source. An intensive series of c- and z- ions were observed in all cases, with the phosphorylation group intact. The formation of molecular radical cations with reduced charge indicated that an electron transfer from a highly excited metastable state of argon to the peptide cation occurred. Additionally, singly charged Bradykinin, Substance P and Fibrinopeptide A molecular ions were fragmented via interaction with electronically excited metastable helium atoms. The fragmentation mechanism was different in this case and involved Penning ionization. PMID:19956340

  16. Fragmentation of phosphorylated and singly charged peptide ions via interaction with metastable atoms.

    PubMed

    Berkout, Vadym D; Doroshenko, Vladimir M

    2008-12-01

    Fragmentation of phosphorylated peptide ions via interaction with electronically excited metastable argon atoms was studied in a linear trap - time-of-flight mass spectrometer. Doubly charged ions of phosphorylated peptides from an Enolase digest were produced by electrospray ionization and subjected to a metastable atom beam in the linear trap. The metastable argon atoms were generated using a glow-discharge source. An intensive series of c- and z- ions were observed in all cases, with the phosphorylation group intact. The formation of molecular radical cations with reduced charge indicated that an electron transfer from a highly excited metastable state of argon to the peptide cation occurred. Additionally, singly charged Bradykinin, Substance P and Fibrinopeptide A molecular ions were fragmented via interaction with electronically excited metastable helium atoms. The fragmentation mechanism was different in this case and involved Penning ionization.

  17. Removal of methanethiol, dimethyl sulfide, dimethyl disulfide, and hydrogen sulfide from contaminated air by Thiobacillus thioparus TK-m

    SciTech Connect

    Kanagawa, T.; Mikami, E.

    1989-03-01

    Methanethiol, dimethyl sulfide, dimethyl disulfide, and hydrogen sulfide were efficiently removed from contaminated air by Thiobacillus thioparus TK-m and oxidized to sulfate stoichiometrically. More than 99.99% of dimethyl sulfide was removed when the load was less than 4.0 g of dimethyl sulfide per g (dry cell weight) per day.

  18. Investigation on laboratory and pilot-scale airlift sulfide oxidation reactor under varying sulfide loading rate.

    PubMed

    Pokasoowan, Chanya; Kanitchaidecha, Wilawan; K C, Bal Krishna; Annachhatre, Ajit P

    2009-01-01

    Airlift bioreactor was established for recovering sulfur from synthetic sulfide wastewater under controlled dissolved oxygen condition. The maximum recovered sulfur was 14.49 g/day when sulfide loading rate, dissolved oxygen (DO) and pH values were 2.97 kgHS(-)/m(3)-day, 0.2-1.0 mg/L and 7.2-7.8, respectively. On the other hand, the increase in recovered sulfur reduced the contact surface of sulfide oxidizing bacteria which affects the recovery process. This effect caused to reduce the conversion of sulfide to sulfur. More recovered sulfur was produced at high sulfide loading rate due to the change of metabolic pathway of sulfide-oxidizing bacteria which prevented the toxicity of sulfide in the culture. The maximum activity in this system was recorded to be about 3.28 kgS/kgVSS-day. The recovered sulfur contained organic compounds which were confirmed by the results from XRD and CHN analyzer. Afterwards, by annealing the recovered sulfur at 120 degrees C for 24 hrs under ambient Argon, the percentage of carbon reduced from 4.44% to 0.30%. Furthermore, the percentage of nitrogen and hydrogen decreased from 0.79% and 0.48% to 0.00% and 0.14%, respectively. This result showed the success in increasing the purity of recovered sulfur by using the annealing technique. The pilot-scale biological sulfide oxidation process was carried out using real wastewater from Thai Rayon Industry in Thailand. The airlift reactor successfully removed sulfide more than 90% of the influent sulfide at DO concentration of less than 0.1 mg/L, whereas the elementary sulfur production was 2.37 kgS/m(3)-day at sulfide loading rate of 2.14 kgHS(-)/m(3)-day. The sulfur production was still increasing as the reactor had not yet reached its maximum sulfide loading rate.

  19. Sulfidation of 310 stainless steel at sulfur potentials encountered in coal conversion systems

    NASA Technical Reports Server (NTRS)

    Rao, D. B.; Nelson, H. G.

    1976-01-01

    The sulfidation of SAE 310 stainless steel was carried out in gas mixtures of hydrogen and hydrogen sulfide over a range of sulfur potentials anticipated in advanced coal gasification processes. The kinetics, composition, and morphology of sulfide scale formation were studied at a fixed temperature of 1,065 K over a range of sulfur potentials from .00015 Nm to the -2nd power to 900 Nm to the -2nd power. At all sulfur potentials investigated, the sulfide scales were found to be multilayered. The relative thickness of the individual layers as well as the composition was found to depend on the sulfur potential. The reaction was found to obey the parabolic rate law after an initial transient period. Considerably longer transient periods were found to be due to unsteady state conditions resulting from compositional variations in the spinel layer. The sulfur pressure dependence on the parabolic rate constant was found to best fit the equation K sub p equals const. (P sub S2) to the 1/nth power, where n equals 3.7. The growth of the outer layers was found to be primarily due to the diffusion of metal ions, iron being the predominant species. The inner layer growth was due to the dissociation of the primary product at the alloy scale interface and depended on the activity of chromium.

  20. Influence of soil minerals on chromium(VI) reduction by sulfide under anoxic conditions.

    PubMed

    Lan, Yeqing; Deng, Baolin; Kim, Chulsung; Thornton, Edward C

    2007-04-12

    The effects of soil minerals on chromate (CrVIO42-, noted as Cr(VI)) reduction by sulfide were investigated in the pH range of 7.67 to 9.07 under the anoxic condition. The examined minerals included montmorillonite (Swy-2), illite (IMt-2), kaolinite (KGa-2), aluminum oxide (gamma-Al2O3), titanium oxide (TiO2, P-25, primarily anatase), and silica (SiO2). Based on their effects on Cr(VI) reduction, these minerals were categorized into three groups: (i) minerals catalyzing Cr(VI) reduction - illite; (ii) minerals with no effect - Al2O3; and (iii) minerals inhibiting Cr(VI) reduction- kaolinite, montmorillonite, SiO2 and TiO2 . The catalysis of illite was attributed primarily to the low concentration of iron solubilized from the mineral, which could accelerate Cr(VI) reduction by shuttling electrons from sulfide to Cr(VI). Additionally, elemental sulfur produced as the primary product of sulfide oxidation could further catalyze Cr(VI) reduction in the heterogeneous system. Previous studies have shown that adsorption of sulfide onto elemental sulfur nanoparticles could greatly increase sulfide reactivity towards Cr(VI) reduction. Consequently, the observed rate constant, kobs, increased with increasing amounts of both iron solubilized from illite and elemental sulfur produced during the reaction. The catalysis of iron, however, was found to be blocked by phenanthroline, a strong complexing agent for ferrous iron. In this case, the overall reaction rate at the initial stage of reaction was pseudo first order with respect to Cr(VI), i.e., the reaction kinetics was similar to that in the homogeneous system, because elemental sulfur exerted no effect at the initial stage prior to accumulation of elemental sulfur nanoparticles. In the suspension of kaolinite, which belonged to group (iii), an inhibitive effect to Cr(VI) reduction was observed and subsequently examined in more details. The inhibition was due to the sorption of elemental sulfur onto kaolinite, which reduced or